COMPOUNDS FOR FORMING A PATTERNING COATING AND DEVICES INCORPORATING SAME

Information

  • Patent Application
  • 20230240128
  • Publication Number
    20230240128
  • Date Filed
    June 14, 2021
    2 years ago
  • Date Published
    July 27, 2023
    10 months ago
Abstract
A phosphazene derivative compound including a chain moiety including a backbone and an attached fluorine atom and an opto-electronic device including such compound. The chain moiety includes an intermediate moiety, a terminal moiety arranged at a terminal portion of thereof bonded to the intermediate moiety, and/or a core moiety comprising a phosphazene unit attached to the chain moiety, including by a linker moiety of the chain moiety. The chain moiety attaches to the phosphorous atom of the unit and/r comprises a cyclophosphazene comprising a plurality of units. The device has two electrodes and an active region comprising a semiconducting layer bounded longitudinally by the electrodes and laterally confined to an emissive region defined thereby that lacks the compound. A device patterning coating includes the compound in a first lateral portion. The device has a deposited layer of deposited material, but the first portion lacks a closed coating of deposited material.
Description
TECHNICAL FIELD

The present disclosure relates to opto-electronic devices and in particular to a patterning coating, which may act as and/or be a nucleation-inhibiting coating (NIC), and an opto-electronic device having first and second electrodes separated by a semiconductor layer and having a conductive coating and/or an electrode patterned using a patterning coating, which may act as and/or be a nucleation-inhibiting coating (NIC) and/or such NIC.


BACKGROUND

In an opto-electronic device such as an organic light emitting diode (OLED), at least one semiconducting layer is disposed between a pair of electrodes, such as an anode and a cathode. The anode and cathode are electrically coupled with a power source and respectively generate holes and electrons that migrate toward each other through the at least one semiconducting layer. When a pair of holes and electrons combine, a photon may be emitted.


OLED display panels may comprise a plurality of (sub-) pixels, each of which has an associated pair of electrodes and at least one semiconducting layer between them. In some non-limiting examples, the (sub-) pixels may be selectively driven by a driving circuit comprising a plurality of thin-film transistor (TFT) structures electrically coupled by conductive metal lines, in some non-limiting examples, within a substrate upon which the electrodes and the at least one semiconducting layer are deposited. Various layers and coatings of such panels are typically formed by vacuum-based deposition processes.


Such display panels may be used, by way of non-limiting example, in electronic devices such as mobile phones.


In some applications, there may be an aim to provide a conductive and/or electrode coating in a pattern for each (sub-) pixel of the panel across either, or both of, a lateral and a cross-sectional aspect thereof, by selective deposition of at least one thin film of the conductive coating to form a device feature, such as, without limitation, an electrode and/or a conductive element electrically coupled therewith, during the OLED manufacturing process.


One method for doing so, in some non-limiting application, involves the interposition of a fine metal mask (FMM) during deposition of an electrode material and/or a conductive element electrically coupled therewith. However, material typically used as electrodes have relatively high evaporation temperatures, which impacts the ability to re-use the FMM and/or the accuracy of the pattern that may be achieved, with attendant increases in cost, effort, and complexity.


One method for doing so, in some non-limiting examples, involves depositing the electrode material and thereafter removing, including by a laser drilling process, unwanted regions thereof to form the pattern. However, the removal process often involves the creation and/or presence of debris, which may affect the yield of the manufacturing process.


Further, such methods may not be suitable for use in some applications and/or with some devices with certain topographical features.


In some non-limiting applications, there may be an aim to increase the transmission of photons, and/or to reduce absorption of photons, to provide an improved mechanism for along an optical path through at least a portion of the device in at least a wavelength sub-range of the electromagnetic (EM) spectrum, including, without limitation, by providing selective deposition of a conductive coating.





BRIEF DESCRIPTION OF THE DRAWINGS

Examples of the present disclosure will now be described by reference to the following figures, in which identical reference numerals in different figures indicate identical and/or in some non-limiting examples, analogous and/or corresponding elements and in which:



FIG. 1 is a simplified block diagram from a cross-sectional aspect, of an example device having a plurality of layers in a lateral aspect, formed by selective deposition of a patterning coating in a first portion of the lateral aspect, followed by deposition of a closed coating of deposited material in a second portion thereof, according to an example in the present disclosure;



FIG. 2 is a schematic diagram showing an example process for depositing a patterning coating in a pattern on an exposed layer surface of an underlying layer in an example version of the device of FIG. 1, according to an example in the present disclosure;



FIG. 3 is a schematic diagram showing an example process for depositing a deposited material in the second portion on an exposed layer surface that comprises the deposited pattern of the patterning coating of FIG. 2, where the patterning coating is a nucleation-inhibiting coating (NIC);



FIG. 4A is a schematic diagram illustrating an example version of the device of FIG. 1 in a cross-sectional view;



FIG. 4B is a schematic diagram illustrating the device of FIG. 4A in a complementary plan view;



FIG. 4C is a schematic diagram illustrating an example version of the device of FIG. 1 in a cross-sectional view;



FIG. 4D is a schematic diagram illustrating the device of FIG. 4C in a complementary plan view;



FIG. 4E is a schematic diagram illustrating an example of the device of FIG. 1 in a cross-sectional view;



FIG. 4F is a schematic diagram illustrating an example of the device of FIG. 1 in a cross-sectional view;



FIG. 4G is a schematic diagram illustrating an example of the device of FIG. 1 in a cross-sectional view;



FIGS. 5A through 5I are schematic diagrams that show various potential behaviours of an NIC at a deposition interface with a deposited layer in an example version of the device of FIG. 1, according to various examples in the present disclosure;



FIG. 6 is a block diagram from a cross-sectional aspect, of an example electro-luminescent device according to an example in the present disclosure;



FIG. 7 is a cross-sectional view of the device of FIG. 1;



FIG. 8 is a schematic diagram illustrating, in plan view, an example patterned electrode suitable for use in a version of the device of FIG. 6, according to an example in the present disclosure;



FIG. 9 is a schematic diagram illustrating an example cross-sectional view of the device of FIG. 8 taken along line 9-9;



FIG. 10A is a schematic diagram illustrating, in plan view, a plurality of example patterns of electrodes suitable for use in an example version of the device of FIG. 6, according to an example in the present disclosure;



FIG. 10B is a schematic diagram illustrating an example cross-sectional view, at an intermediate stage, of the device of FIG. 10C taken along line 10B-10B,



FIG. 10C is a schematic diagram illustrating an example cross-sectional view of the device of FIG. 10A taken along line 10C-10C;



FIG. 11 is a schematic diagram illustrating a cross-sectional view of an example version of the device of FIG. 6, having an example patterned auxiliary electrode according to an example in the present disclosure;



FIG. 12 is a schematic diagram illustrating, in plan view an example pattern of an auxiliary electrode overlaying at least one emissive region and at least one non-emissive region according to an example in the present disclosure;



FIG. 13A is a schematic diagram illustrating, in plan view, an example pattern of an example version of the device of FIG. 6, having a plurality of groups of emissive regions in a diamond configuration according to an example in the present disclosure;



FIG. 13B is a schematic diagram illustrating an example cross-sectional view of the device of FIG. 13A taken along line 13B-13B;



FIG. 13C is a schematic diagram illustrating an, example cross-sectional view of the device of FIG. 13A taken along line 13C-13C;



FIG. 14 is a schematic diagram illustrating an example cross-sectional view of an example version of the device of FIG. 7 with additional example deposition steps according to an example in the present disclosure;



FIG. 15 is a schematic diagram illustrating an example cross-sectional view of an example version of the device of FIG. 7 with additional example deposition steps according to an example in the present disclosure;



FIG. 16 is a schematic diagram illustrating an example cross-sectional view of an example version of the device of FIG. 7 with additional example deposition steps according to an example in the present disclosure;



FIG. 17 is a schematic diagram illustrating an example cross-sectional view of an example version of the device of FIG. 7 with additional example deposition steps according to an example in the present disclosure;



FIG. 18A is a schematic diagram illustrating, in plan view, an example of a transparent version of the device of FIG. 6 comprising at least one example pixel region and at least one example light-transmissive region, with at least one auxiliary electrode according to an example in the present disclosure;



FIG. 18B is a schematic diagram illustrating an example cross-sectional view of the device of FIG. 18A taken along line 18B-18B;



FIG. 19A is a schematic diagram illustrating, in plan view, an example of a transparent version of the device of FIG. 6 comprising at least one example pixel region and at least one example light-transmissive region according to an example in the present disclosure;



FIG. 19B is a schematic diagram illustrating an example cross-sectional view of the device of FIG. 19A taken along line 19-19;



FIG. 19C is a schematic diagram illustrating an example cross-sectional view of the device of FIG. 19A taken along line 19-19;



FIG. 20 is a schematic diagram that may show example stages of an example process for manufacturing an example version of the device of FIG. 7 having sub-pixel regions having a second electrode of different thickness according to an example in the present disclosure;



FIG. 21 is a schematic diagram illustrating an example cross-sectional view of an example version of the device of FIG. 6 in which a second electrode is coupled with an auxiliary electrode according to an example in the present disclosure;



FIG. 22 is a schematic diagram illustrating an example cross-sectional view of an example version of the device of FIG. 6 having a partition and a sheltered region, such as a recess, in a non-emissive region thereof according to an example in the present disclosure;



FIGS. 23A and 23B are schematic diagrams that show example cross-sectional views of an example version of the device of FIG. 6 having a partition and a sheltered region, such as an aperture, in a non-emissive region, according to various examples in the present disclosure;



FIGS. 24A, 24B, and 24C are schematic diagrams that show example stages of an example process for depositing a deposited layer in a pattern on an exposed layer surface of an example version of the device of FIG. 6, by selective deposition and subsequent removal process, according to an example in the present disclosure;



FIG. 25 is an example energy profile illustrating relative energy states of an adatom absorbed onto a surface according to an example in the present disclosure; and



FIG. 26 is a schematic diagram illustrating the formation of a film nucleus according to an example in the present disclosure.



FIGS. 27A, 27B, and 27C are graphs of the distribution of average diameter obtained from analyses of Samples III-1, III-2, and III-3, according to the examples.





In the present disclosure, a reference numeral having at least one numeric value (including without limitation, in subscript) and/or lower-case alphabetic character(s) (including without limitation, in lower-case) appended thereto, may be considered to refer to a particular instance, and/or subset thereof, of the element or feature described by the reference numeral. Reference to the reference numeral without reference to the appended value(s) and/or character(s) may, as the context dictates, refer generally to the element(s) or feature(s) described by the reference numeral, and/or to the set of all instances described thereby. Similarly, a reference numeral may have the letter “x’ in the place of a numeric digit. Reference to such reference numeral may, as the context dictates, refer generally to the element(s) or feature(s) described by the reference numeral, where the character “x” is replaced by a numeric digit, and/or to the set of all instances described thereby.


In the present disclosure, for purposes of explanation and not limitation, specific details are set forth to provide a thorough understanding of the present disclosure, including, without limitation, particular architectures, interfaces and/or techniques. In some instances, detailed descriptions of well-known systems, technologies, components, devices, circuits, methods, and applications are omitted to not obscure the description of the present disclosure with unnecessary detail.


Further, it will be appreciated that block diagrams reproduced herein can represent conceptual views of illustrative components embodying the principles of the technology.


Accordingly, the system and method components have been represented where appropriate by conventional symbols in the drawings, showing only those specific details that are pertinent to understanding the examples of the present disclosure, to not obscure the disclosure with details that will be readily apparent to those of ordinary skill in the art having the benefit of the description herein.


Any drawings provided herein may not be drawn to scale and may not be considered to limit the present disclosure in any way.


Any feature or action shown in dashed outline may in some examples be considered as optional.


SUMMARY

It is an object of the present disclosure to obviate or mitigate at least one disadvantage of the prior art.


The present disclosure discloses a phosphazene derivative compound comprising a chain moiety comprising a backbone and an attached fluorine atom and an opto-electronic device comprising such compound. The chain moiety comprises an intermediate moiety, a terminal moiety arranged at a terminal portion of thereof bonded to the intermediate moiety, and/or a core moiety comprising a phosphazene unit attached to the chain moiety, including by a linker moiety of the chain moiety. The chain moiety attaches to the phosphorous atom of the unit and/or comprises a cyclophosphazene comprising a plurality of units. The device has two electrodes and an active region comprising a semiconducting layer bounded longitudinally by the electrodes and laterally confined to an emissive region defined thereby that lacks the compound. A device patterning coating comprises the compound in a first lateral portion. The device has a deposited layer of deposited material, but the first portion lacks a closed coating of deposited material.


According to a broad aspect of the present disclosure, there is disclosed an opto-electronic device comprising a compound, the compound being a fluorine-containing phosphazene compound.


In some non-limiting examples, the compound may comprise a chain moiety, the chain moiety comprising a backbone and at least one fluorine (F) atom attached thereto. In some non-limiting examples, the backbone may be a carbon-containing backbone. In some non-limiting examples, the chain moiety may comprise an intermediate moiety.


In some non-limiting examples, the intermediate moiety may comprise at least one of: oxygen (O), ether, substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, unsubstituted fluoroalkylene, substituted cycloalkylene, unsubstituted cycloalkylene, substituted heteroarylene, and unsubstituted heteroarylene. In some non-limiting examples, the intermediate moiety may comprise a fluorine (F) atom. In some non-limiting examples, the intermediate moiety may comprise a fluoroalkylene unit. In some non-limiting examples, the intermediate moiety may comprise a CF2 unit. In some non-limiting examples, the intermediate moiety may comprise a CHF unit. In some non-limiting examples, the intermediate moiety may comprise a CH2 unit. In some non-limiting examples, the intermediate moiety may comprise saturated bonds. In some non-limiting examples, the intermediate moiety may comprise at least one of: oxygen (O), ether, substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, and unsubstituted fluoroalkylene. In some non-limiting examples, the intermediate moiety may be substantially devoid of unsaturated bonds. In some non-limiting examples, the intermediate moiety may contain up to 10 carbon atoms. In some non-limiting examples, the intermediate moiety may be represented by the formula:




embedded image


wherein: X is each independently hydrogen (H), deutero (D), fluorine (F), or CF3; a is a integer between 0 and 6; b is an integer between 0 and 12; and a sum of a and b is no more than 15.


In some non-limiting examples, the chain moiety may comprise a terminal moiety bonded to the intermediate moiety, the terminal moiety being arranged at a terminal portion of the chain moiety. In some non-limiting examples, the terminal moiety may comprise a fluorine (F) atom. In some non-limiting examples, the terminal moiety may comprise at least one of: branched alkyl, unbranched alkyl, branched fluoroalkyl, unbranched fluoroalkyl, fluorine-substituted cycloheteroalkyl, branched fluoroalkoxy; unbranched fluoroalkoxy, fluoroaryl, polyfluorosulfanyl, and fluorocycloalkyl. In some non-limiting examples, the terminal moiety may comprise fluorine (F) and hydrogen (H). In some non-limiting examples, the terminal moiety may comprise a CF2H unit. In some non-limiting examples, the terminal moiety may be represented by at least one of Formula: (EC-1), (EC-2), (EC-3), (EC-4), (EC-5), (EC-6), and (EC-7):




embedded image


In some non-limiting examples, the compound may comprise a core moiety attached to the chain moiety.


In some non-limiting examples, the chain moiety may comprise a linker moiety adapted to attach the chain moiety to the core moiety. In some non-limiting examples, the linker moiety may comprise at least one of: oxygen (O), nitrogen (N), sulfur (S), substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, unsubstituted fluoroalkylene, substituted cycloalkylene, unsubstituted cycloalkylene, substituted arylene, unsubstituted arylene, substituted heteroarylene, and unsubstituted heteroarylene. In some non-limiting examples, the linker moiety may comprise at least one of: oxygen (O), nitrogen (N), sulfur (S), substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, and unsubsituted fluoroalkylene. In some limiting examples, the linker moiety may be represented by at least one of Formula: (EA-1), (EA-2), (EA-3), (EA-4), (EA-5), and (EA-6):




embedded image


wherein: RH is selected from at least one of: hydrogen (H), deutero (D), CF3, branched alkyl, unbranched alkyl, branched fluoroalkyl, unbranched fluoroalkyl, fluorine-substituted cycloheteroalkyl, branched fluoroalkoxy, unbranched fluoroalkoxy, fluoroaryl, polyfluorosulfanyl, and fluorocycloalkyl.


In some non-limiting examples, the core moiety may comprise a phosphazene unit. In some non-limiting examples, the chain moiety may be attached to the phosphorus (P) atom of the phosphazene unit. In some non-limiting examples, the chain moiety may comprise a cyclophosphazene. In some non-limiting examples, the cyclophosphazene may be provided by a plurality of phosphazene units. In some non-limiting examples, the cyclophosphazene may be provided by a number of phosphazene units selected from 3 and 4.


In some non-limiting examples, the chain moiety may comprise a branching moiety attached to at least three moieties selected from: an intermediate moiety, a terminal moiety, and a linker moiety. In some non-limiting examples, the branching moiety may comprise at least one of: nitrogen (N), amine, substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, unsubstituted fluoroalkylene, substituted cycloalkylene, unsubstituted cycloalkylene, substituted cycloheteroalkylene, unsubstituted cycloheteroalkylene, substituted arylene, unsubstituted arylene, substituted heteroarylene, and unsubstituted heteroarylene. In some non-limiting examples, the branching moiety may comprise at least one of: nitrogen (N), amine, substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, and unsubstituted fluoroalkylene.


In some non-limiting examples, the compound may exhibit light absorption at a wavelength other than a visible portion of an electromagnetic spectrum. In some non-limiting examples, the compound may exhibit photoluminescence at a wavelength other than a visible portion of an electromagnetic spectrum. In some non-limiting examples, the compound may have an optical gap that exceeds at least one of about: 3.4 eV, 3.5 eV, 4.1 eV, 5 eV, and 6.2. In some non-limiting examples, the compound may have a melting temperature that exceeds about 100° C. In some non-limiting examples, the compound may have a sublimation temperature that exceeds about 100° C. In some non-limiting examples, the compound may have a characteristic surface energy that is less than at least one of about: 25 dynes/cm, 21 dynes/cm, 20 dynes/cm, 19 dynes/cm, 18 dynes/cm, 17 dynes/cm, 16 dynes/cm, 15 dynes/cm, 14 dynes/cm, 13 dynes/cm, 12 dynes/cm, 11 dynes/cm, and 10 dynes/cm. In some non-limiting examples, the compound may have a refractive index of no more than at least one of about: 1.5, 1.45, 1.4, 1.35, 1.3, and 1.25.


In some non-limiting examples, the device may further comprise first and second electrodes, and an active region comprising at least one semiconducting layer and bounded, in a transverse aspect, by the electrodes and confined, in a lateral aspect, to an emissive region defined by the electrodes, wherein the active region is substantially devoid of the compound. In some non-limiting examples, the device may further comprise: a patterning coating comprising the compound, the patterning coating being disposed on a first layer surface of an underlying layer in a first portion of a lateral aspect thereof; and a deposited layer comprised of a deposited material, disposed on a second layer surface; wherein the first portion is substantially devoid of a closed coating of the deposited material. In some non-limiting examples, the first portion may exclude a lateral aspect of the emissive region. In some non-limiting examples, the second electrode may comprise at least a part of the deposited layer as a layer thereof. In some non-limiting examples, the first portion may include a lateral aspect of the emissive region. In some non-limiting examples, the device may further comprise an auxiliary electrode comprising the deposited layer as a layer thereof. In some non-limiting examples, the device may further comprise a conductor electrically coupled with the second electrode.


According to a broad aspect of the present disclosure, there is disclosed an opto-electronic device comprising a compound, the compound comprising a terminal moiety comprising a CF2H unit.


In some non-limiting examples, the compound may comprise a chain moiety, wherein the terminal moiety is arranged at a terminal portion of the chain moiety. In some non-limiting examples, the chain moiety may comprise a backbone and at least one fluorine (F) atom attached thereto. In some non-limiting examples, the chain moiety may comprise an intermediate moiety attached to the terminal moiety.


In some non-limiting examples, the intermediate moiety may comprise at least one of: oxygen (O), ether, substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, unsubstituted fluoroalkylene, substituted cycloalkylene, unsubstituted cycloalkylene, substituted heteroarylene, and unsubstituted heteroarylene. In some non-limiting examples, the intermediate moiety may comprise a fluorine (F) atom. In some non-limiting examples, the intermediate moiety may comprise a CF2 unit. In some non-limiting examples, the intermediate moiety may comprise a CH2 unit. In some non-limiting examples, the intermediate moiety may comprise a fluoroalkylene unit.


In some non-limiting examples, the compound may comprise a core moiety attached to the chain moiety.


In some non-limiting examples, the chain moiety may comprise a linker moiety adapted to attach the chain moiety to the core moiety. In some non-limiting examples, the linker moiety may comprise at least one of: oxygen (O), nitrogen (N), sulfur (S), substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, unsubsituted fluoroalkylene, substituted cycloalkylene, unsubstituted cycloalkylene, substituted arylene, unsubstituted arylene, substituted heteroarylene, and unsubstituted heteroarylene.


In some non-limiting examples, the core moiety may comprise a phosphazene unit. In some non-limiting examples, the chain moiety may be attached to the phosphorus (P) atom of the phosphazene unit. In some non-limiting examples, the core moiety may comprise a cyclophosphazene. In some non-limiting examples, the cyclophosphazene may be provided by a plurality of phosphazene units. In some non-limiting examples, the cyclophosphazene may be provided by a number of phosphazene units selected from 3 and 4.


In some non-limiting examples, the chain moiety may be selected such that an equivalent precursor form of the chain moiety, derived by cleaving a bond between the linker moiety and the core moiety and attaching a hydrogen (H) atom to the cleaved linker moiety, has a melting temperature that exceeds about 60° C.


In some non-limiting examples, the chain moiety may comprise a branching moiety attached to at least three moieties selected from: an intermediate moiety, a terminal moiety, and a linker moiety. In some non-limiting examples, the branching moiety may comprise at least one of: nitrogen (N), substituted alkylene, unsubstituted alkylene, substituted fluoroalkylene, unsubstituted fluoroalkylene, substituted cycloalkylene, unsubstituted cycloalkylene, substituted cycloheteroalkylene, unsubstituted cycloheteroalkylene, substituted arylene, unsubstituted arylene, substituted heteroarylene, and unsubstituted heteroarylene.


In some non-limiting examples, the compound may exhibit light absorption at a wavelength other than a visible portion of an electromagnetic spectrum. In some non-limiting examples, the compound may exhibit photoluminescence at a wavelength other than a visible portion of an electromagnetic spectrum. In some non-limiting examples, the compound may have an optical gap that exceeds at least one of about: 3.4 eV, 3.5 eV, 4.1 eV, 5 eV, and 6.2 eV. In some non-limiting examples, the compound may have a melting temperature that exceeds about 100° C. In some non-limiting examples, the compound may have a sublimation temperature that exceeds about 100° C. In some non-limiting examples, the compound may have a characteristic surface energy that is less than at least one of about: 25 dynes/cm, 21 dynes/cm, 20 dynes/cm, 19 dynes/cm, 18 dynes/cm, 17 dynes/cm, 16 dynes/cm, 15 dynes/cm, 14 dynes/cm, 13 dynes/cm, 12 dynes/cm, 11 dynes/cm, and 10 dynes/cm. In some non-limiting examples, the compound may have a refractive index of no more than at least one of about: 1.5, 1.45, 1.4, 1.35, 1.3, and 1.25.


In some non-limiting examples, the chain moiety may be devoid of a continuous perfluorinated unit longer than at least one of: 8, 7, and 6 carbon (C) atoms.


In some non-limiting examples, the device may further comprise first and second electrodes, and an active region comprising at least one semiconducting layer and bounded in a transverse aspect by the electrodes and confined, in a lateral aspect, to an emissive region defined by the electrodes, wherein the active region is substantially devoid of the compound. In some non-limiting examples, the device may further comprise: a patterning coating comprising the compound, the patterning coating being disposed on a first layer surface of an underlying layer in a first portion of a lateral aspect thereof; and a deposited layer comprised of a deposited material, disposed on a second layer surface; wherein the first portion is substantially devoid of a closed coating of the deposited material. In some non-limiting examples, the first portion may exclude a lateral aspect of the emissive region. In some non-limiting examples, the second electrode may comprise at least a part of the deposited layer as a layer thereof. In some non-limiting examples, the first portion may include a lateral aspect of the emissive region. In some non-limiting examples, the device may further comprise an auxiliary electrode comprising the deposited layer as a layer thereof. In some non-limiting examples, the device may further comprise a conductor electrically coupled with the second electrode.


According to a broad aspect of the present disclosure, there is disclosed a phosphazene derivative compound comprising first and second chain moieties, each comprising a backbone and a fluorine (F) atom attached thereto, wherein the first chain moiety is different from the second chain moiety.


In some non-limiting examples, the compound may further comprise a phosphazene unit, wherein each of the first chain moiety and the second chain moiety may be attached to a phosphorus (P) atom of the phosphazene unit. In some non-limiting examples, the first chain moiety and the second chain moiety may be attached to a common phosphorus (P) atom. In some non-limiting examples, at least one of the first and second chain moieties may comprise at least one of a CF2 unit, a CH2 unit, and a fluoroalkylene unit. In some non-limiting examples, a ratio of a number of carbon (C) atoms in the first chain moiety to a number of carbon (C) atoms in the second chain moiety may be at least one of about: 1:8, 1:6, 2:6, 2:4, 2:3, and 1:3. In some non-limiting examples, a ratio of a number of fluorine (F) atoms in the first chain moiety to a number of fluorine (F) atoms sin the second chain moiety may be at least one of about: 1:16, 1:12, 2:12, 4:12, 4:8. 4:6, and 2:6.


In some non-limiting examples, the first chain moiety may be represented by the formula:





*—O—(CH2)t(CF2)uZ


wherein: t represents an integer between 1 and 3; u represents an integer between 5 and 12; and Z represents at least one of hydrogen (H), deutero (D), and fluorine (F).


In some non-limiting examples, the second chain moiety may be represented by the formula:





*—O—(CH2)v(CF2)wZ


wherein: v represents an integer between 1 and 3; w represents an integer between 5 and 12; and Z represents at least one of hydrogen (H), deutero (D), and fluorine (F).


In some non-limiting examples, the compound may be represented by Formula (X):




embedded image


wherein: t and v each represent an integer between 1 and 3; u and w each represent an integer between 5 and 12; y represents an integer between 2 and 6; and Z individually represents at least one of hydrogen (H), deutero (D), and fluorine (F).


In some non-limiting examples, u and v may be different. In some non-limiting examples, t and v may be both 1. In some non-limiting examples, y may be at least one of 3 and 4. In some non-limiting examples, u may be 8. In some non-limiting examples, w may be 10.


According to a broad aspect of the present disclosure, there is disclosed a compound comprising a moiety according to Formula (PX-1):




embedded image


wherein: R1 and R2 each independently represents at least one of: a substituted alkyl, unsubstituted alkyl, substituted alkoxy, unsubstituted alkoxy, and a chain moiety comprising a backbone and a fluorine (F) atom attached thereto; and R1 and R2 are different.


DESCRIPTION
Layered Device

The present disclosure relates generally to layered devices, and more specifically, to opto-electronic devices. An opto-electronic device may generally encompass any device that converts electrical signals into photons and vice versa.


Those having ordinary skill in the relevant art will appreciate that, while the present disclosure is directed to opto-electronic devices, the principles thereof may be applicable to any panel having a plurality of layers, including without limitation, at least one layer of conductive deposited material 331 (FIG. 3), including as a thin film, and in some non-limiting examples, through which electromagnetic (EM) signals may pass, entirely or partially, at an angle relative to a plane of at least one of the layers.


Turning now to FIG. 1, there may be shown a cross-sectional view of an example layered device 100a. In some non-limiting examples, as shown in greater detail in FIG. 10, the device 100 may comprise a plurality of layers deposited upon a substrate 10.


A lateral axis, identified as the X-axis, may be shown, together with a longitudinal axis, identified as the Z-axis. A second lateral axis, identified as the Y-axis, may be shown as being substantially transverse to both the X-axis and the Z-axis. At least one of the lateral axes may define a lateral aspect 710 (FIG. 7) of the device 100. The longitudinal axis may define a transverse aspect of the device 100. Some figures herein may be shown in plan. In such plan view(s), a pair of lateral axes, identified as the X-axis and Y-axis respectively, which in some non-limiting examples may be substantially transverse to one another, are shown. At least one of these lateral axes may define a lateral aspect 710 of the device 100.


The layers of the device 100 may extend in the lateral aspect 710 substantially parallel to a plane defined by the lateral axes. Those having ordinary skill in the relevant art will appreciate that the substantially planar representation shown in FIG. 1 may be, in some non-limiting examples, an abstraction for purposes of illustration. In some non-limiting examples, there may be, across a lateral extent of the device 100, localized substantially planar strata of different thicknesses and dimension, including, in some non-limiting examples, the substantially complete absence of a layer, and/or layer(s) separated by non-planar transition regions (including lateral gaps and even discontinuities).


Thus, while for illustrative purposes, the device 100 may be shown in its cross-sectional aspect as a substantially stratified structure of substantially parallel planar layers, such display panel may illustrate locally, a diverse topography to define features, each of which may substantially exhibit the stratified profile discussed in the cross-sectional aspect.


In some non-limiting examples, a lateral aspect 710 of an exposed layer surface 11 of the device 100 may comprise a first portion 101 and a second portion 102. In some non-limiting examples, the second portion 102 may comprise that part of the exposed layer surface 11 of the underlying layer of the device 100 that lies beyond the first portion 101.


In some non-limiting examples, in the first portion 101, a nucleation inhibiting coating (NIC) 110, comprising an NIC material, may be selectively deposited as a closed coating 140 on the exposed layer surface 11 of an underlying layer, including without limitation, a substrate 10, of the device 100, only in the first portion 101. However, in the second portion 102, the exposed layer surface 11 of the underlying layer may be substantially devoid of a closed coating 140 of the NIC material.


NICs

The NIC 110 may comprise an NIC material. In some non-limiting examples, the NIC 110 may comprise a closed coating 140 of the NIC material.


The NIC 110 may provide an exposed layer surface 11 with a relatively low initial sticking probability S0 (in some non-limiting examples, under the conditions identified in the dual QCM technique described by Walker et al.) against the deposition of deposited material 331, which, in some non-limiting examples, may be substantially less than the initial sticking probability S0 against the deposition of the deposited material 331 of the exposed layer surface 11 of the underlying layer of the device 100, upon which the NIC 110 has been deposited.


Because of the low initial sticking probability S0 of the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, against the deposition of the deposited material 331, the first portion 101 comprising the NIC 110 may be substantially devoid of a closed coating 140 of the deposited material 331.


In some non-limiting examples, the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, may have an initial sticking probability S0 against the deposition of the deposited material 331, that is less than about: 0.9, 0.3, 0.2, 0.15, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0.008, 0.005, 0.003, 0.001, 0.0008, 0.0005, 0.0003, or 0.0001.


In some non-limiting examples, the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, may have an initial sticking probability S0 against the deposition of silver (Ag), and/or magnesium (Mg) that is less than about: 0.9, 0.3, 0.2, 0.15, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0.008, 0.005, 0.003, 0.001, 0.0008, 0.0005, 0.0003, or 0.0001.


In some non-limiting examples, the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, may have an initial sticking probability S0 against the deposition of a deposited material 331 of between about: 0.15-0.0001, 0.1-0.0003, 0.08-0.0005, 0.08-0.0008, 0.05-0.001, 0.03-0.0001, 0.03-0.0003, 0.03-0.0005, 0.03-0.0008, 0.03-0.001, 0.03-0.005, 0.03-0.008, 0.03-0.01, 0.02-0.0001, 0.02-0.0003, 0.02-0.0005, 0.02-0.0008, 0.02-0.001, 0.02-0.005, 0.02-0.008, 0.02-0.01, 0.01-0.0001, 0.01-0.0003, 0.01-0.0005, 0.01-0.0008, 0.01-0.001, 0.01-0.005, 0.01-0.008, 0.008-0.0001, 0.008-0.0003, 0.008-0.0005, 0.008-0.0008, 0.008-0.001, 0.008-0.005, 0.005-0.0001, 0.005-0.0003, 0.005-0.0005, 0.005-0.0008, or 0.005-0.001.


In some non-limiting examples, the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, may have an initial sticking probability S0 that is less than a threshold value against the deposition of a plurality of deposited materials 531. In some non-limiting examples, such threshold value may be about: 0.3, 0.2, 0.18, 0.15, 0.13, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0.008, 0.005, 0.003, or 0.001.


In some non-limiting examples, the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, may have an initial sticking probability S0 that is less than such threshold value against the deposition of a plurality of deposition materials 531 selected from: Ag, Mg, ytterbium (Yb), cadmium (Cd), and zinc (Zn). In some further non-limiting examples, the NIC 110 may exhibit S0 of or below such threshold value against the deposition of a plurality of deposition materials 531 selected from: Ag, Mg, and Yb.


In some non-limiting examples, the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, may exhibit an initial sticking probability S0 against the deposition of a first deposited material 331 of, or below, a first threshold value, and an initial sticking probability S0 against the deposition of a second deposited material 331 of, or below, a second threshold value. In some non-limiting examples, the first deposited material 331 may be Ag, and the second deposited material 331 may be Mg. In some other non-limiting examples, the first deposited material 331 may be Ag, and the second deposited material 331 may be Yb. In some other non-limiting examples, the first deposited material 331 may be Yb, and the second deposited material 331 may be Mg. In some non-limiting examples, the first threshold value may exceed the second threshold value.


In some non-limiting examples, the NIC 110, and/or the NIC material, in some non-limiting examples, when deposited as a film, and/or coating in a form, and under similar circumstances to the deposition of the NIC 110 within the device 100, may have an extinction coefficient k that may be less than about 0.01 for photons at a wavelength that exceeds at least one of about: 600 nm, 500 nm, 460 nm, 420 nm, or 410 nm.


In some non-limiting examples, the NIC 110 may have and/or provide, including without limitation, because of the NIC material 311 used and/or the deposition environment, at least one nucleation site for the deposited material 331.


In some non-limiting examples, the NIC 110 may act as an optical coating. In some non-limiting examples, the NIC 110 may modify at least one property, and/or characteristic of EM radiation, including without limitation, in the form of photons, emitted by the device 100. In some non-limiting examples, the NIC 110 may exhibit a degree of haze, causing emitted light to be scattered. In some non-limiting examples, the NIC 110 may comprise a crystalline material for causing light transmitted therethrough to be scattered. Such scattering of light may facilitate enhancement of the outcoupling of light from the device in some non-limiting examples. In some non-limiting examples, the NIC 110 may initially be deposited as a substantially non-crystalline, including without limitation, substantially amorphous, coating, whereupon, after deposition thereof, the NIC 110 may become crystallized and thereafter serve as an optical coupling.


In some non-limiting examples, the NIC 810 and/or patterning coating includes a compound containing a core moiety and a chain moiety attached to the core moiety. In some further non-limiting examples, the compound contains a plurality of the chain moieties attached to the core moiety.


In some non-limiting examples, the at least one chain moiety includes a backbone and one or more fluorine atom(s) attached to the backbone. In some non-limiting examples, the backbone is a carbon-containing backbone. In some non-limiting examples, the backbone contains a heteroatom, which by way of non-limiting example may be silicon. In some non-limiting examples, the chain moiety includes a linker moiety, RB, an intermediate moiety, RD, and a terminal moiety, RT. In some further non-limiting examples, the chain moiety further includes a branching moiety, RE. In some non-limiting examples, the chain moiety includes saturated bonds. In some non-limiting examples, the bonds of the chain moiety are substantially comprised of saturated bonds, such that the chain moiety is a saturated moiety. In such non-limiting examples, various moieties of the chain moiety, including but not limited to RB, RD, RT, and/or RE, are saturated moieties.


Without wishing to be bound by any particular theory, it is postulated that the presence of multiple ether units within a single chain moiety may decrease the melting point of the compound, which may be undesirable in at least certain applications. Accordingly, in some non-limiting examples, the chain moiety includes less than or equal to 4, less than or equal to 3, less than or equal to 2, or a single ether unit.


The linker moiety, RB, corresponds to a terminal portion of the chain moiety proximal to the core moiety, and includes the atom(s) which attach the chain moiety to the core moiety. In some non-limiting examples, RB includes: O, N, S, a substituted or unsubstituted alkylene, substituted or unsubstituted fluoroalkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, and/or a substituted or unsubstituted heteroarylene. In some non-limiting examples, RB includes P═N, or a phosphazene group, in addition to the aforementioned groups. In some non-limiting examples, RB includes O, N, S, a substituted or unsubstituted alkylene, and/or a substituted or unsubstituted fluoroalkylene. In some non-limiting examples, RB includes: O, N, S, a substituted or unsubstituted alkylene, and/or a substituted or unsubstituted fluoroalkylene. In some non-limiting examples, RB includes at least one of: O, N, S, an alkylene, a fluoromethylene, and a difluoromethylene.


The intermediate moiety, RD, generally corresponds to a portion of the chain moiety arranged between the linker moiety and the terminal moiety. In some non-limiting examples, RD includes: O, an ether, a substituted or unsubstituted alkylene, a substituted or unsubstituted fluoroalkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted arylene, and/or a substituted or unsubstituted heteroarylene. In some non-limiting examples, RD includes a fluorine atom. In some non-limiting examples, RD includes a fluoroalkylene unit. In some non-limiting examples, RD contains a CF2 unit, a CFH unit, and/or a CH2 unit. In some further non-limiting examples, RD includes two or more CF2 units bonded together to form a fluoroalkylene or a portion thereof. In some non-limiting examples, RD includes at least one CH2 unit and at least one CF2 unit. In some non-limiting examples, RD includes an ether unit. In some non-limiting examples, RD includes saturated bonds. In some further non-limiting examples, RD does not substantially contain any unsaturated bonds. In some non-limiting examples, RD contains up to about 15, 13, 12, or 10 carbon atoms. In some non-limiting examples, RD includes 0, an ether, a substituted or unsubstituted alkylene, and/or a substituted or unsubstituted fluoroalkylene.


The terminal moiety, RT, corresponds to a terminal portion of the chain moiety, which may for example be the distal portion of the chain moiety with respect to the core moiety. For example, the terminal portion may correspond to the terminal portion of the chain moiety opposite to the linker moiety. In some non-limiting examples, RT includes a fluorine atom. In some non-limiting examples, RT includes a branched or unbranched alkyl, a branched or unbranched fluoroalkyl, a substituted or unsubstituted cycloheteroalkyl, a branched or unbranched fluoroalkoxy, a fluoroaryl, a polyfluorosulfanyl, and/or a fluorocycloalkyl. In some non-limiting examples, RT includes a branched or unbranched alkyl, a branched or unbranched fluoroalkyl, and/or a branched or unbranched fluoroalkoxy. “Cycloheteroalkyl” as described herein refers to cycloalkyl groups in which one or more constituent carbon atoms have been replaced by corresponding number of heteroatoms, including without limitation oxygen, nitrogen, and/or sulfur. Non-limiting examples of cycloheteroalkyl groups include those which contain a morpholine unit, a piperidine unit, a pyrrolidine unit, an azepane unit, and/or a piperazine unit. In some non-limiting examples, RT contains up to about 8, 6, 5, 3, 2, or 1 carbon atom(s).


The branching moiety, RE, generally corresponds to a portion of the chain moiety from which two or more branches of the backbone extend. In other words, RE may act as a branching point of the backbone. For example, branching may occur by bonding three or more of the other moieties forming the chain moiety to RE. By way of example, RE may be arranged in various configurations and/or positions of the chain moiety, and be bonded to RB, RD, and/or RT. Three or more moieties bonded to RE may be different or same moieties as one another. By way of non-limiting example, RE may be bonded to two or more RD and/or two or more RT in examples where the chain moiety includes two or more RD and/or RT. In some non-limiting examples, RE includes: O, N, S, an amine, a substituted or unsubstituted alkylene, a substituted or unsubstituted fluoroalkylene, a substituted or unsubstituted cycloalkylene, a substituted or unsubstituted cycloheteroalkylene, a substituted or unsubstituted arylene, and/or a substituted or unsubstituted heteroarylene. In some non-limiting examples, RE includes: O, N, S, an amine, a substituted or unsubstituted alkylene, and/or a substituted or unsubstituted fluoroalkylene. In some non-limiting examples, RE contains up to about 8, 6, 5, 3, 2, or 1 carbon atom(s). In some non-limiting examples, RE does not contain any carbon atoms.


The core moiety, according to some non-limiting examples, includes a substituted or unsubstituted organophosphate, a substituted or unsubstituted alkyl, a substituted or unsubstituted heteroalkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloheteroalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted cyclosiloxane, and/or an organometallic. Non-limiting examples of the core moiety include those containing a phosphazene, a cyclophosphazene, a triazene, a cyclohexane, an adamantane, a branched or unbranched alkyl, an organo-metallic complex, a phenyl, a naphthyl, and/or a cyclosiloxane. In some non-limiting examples, the core moiety includes an unsaturated bond. In some non-limiting examples, the core moiety is an unsaturated moiety.


In some non-limiting examples, the chain moiety is represented by Formula (E-1):




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wherein * indicates a point of attachment within the compound, RB represents the linker moiety, RD represents the intermediate moiety, and RT represents the terminal moiety.


In some non-limiting examples, RB in Formula (E-1) is represented by Formula (EA-1), (EA-2), (EA-3), (EA-4), (EA-5) or (EA-6):




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wherein, in Formula (EA-2), RH is H, D (deutero), CF3, or a secondary chain moiety containing an intermediate moiety, RD, and a terminal moiety, RT. The terminal moiety is bonded to the intermediate moiety of the secondary chain moiety. In some non-limiting examples, the secondary chain moiety is represented by Formula (ED-1):




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In some non-limiting examples, RD and RT of the secondary chain moiety are identical in molecular structure to RD and RT, for example of those in Formula (E-1), of the chain moiety. In some other non-limiting examples, at least one of RD and RT of the secondary chain moiety is different from those of the chain moiety. As would be appreciated, descriptions regarding various non-limiting examples of RD and RT provided herein in relation to the chain moiety may also similarly apply to RD and RT of the secondary chain moiety.


In some non-limiting examples, RD in Formula (E-1) is represented by Formula (EB-1):




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wherein X is each independently H, D (deutero), F, or CF3; a is an integer of 0 to 6; and b is an integer of 0 to 12. In some non-limiting examples, the sum of a and b is less than or equal to 15, less than or equal to 12, less than or equal to 10, or less than or equal to 9.


Non-limiting examples of RD according to the Formula (EB-1) include the following:




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In some non-limiting examples, a is an integer of 1 to 4 and b is an integer of 4 to 9, and the sum of a and b is an integer of 6 to 13. In some non-limiting examples, a is an integer of 2 to 4 and b is an integer of 5 to 9, and the sum of a and b is an integer of 6 to 13.


In some non-limiting examples, RT in Formula (E-1) is represented by Formula (EC-1), (EC-2), (EC-3), (EC-4), (EC-5), (EC-6), or (EC-7).




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In some non-limiting examples, the chain moiety includes a branching moiety, RE. Non-limiting examples of such chain moiety include the following:




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In some non-limiting examples, the chain moiety includes a carbon-containing backbone in a closed ring configuration, for example to form a cyclic structure. Non-limiting examples of such cyclic structure include those containing fluorocycloalkyl, such as perfluorocyclopentyl and perfluorocyclohexyl.


It will be appreciated that various descriptions of RB, RD, RE, and RT would generally apply to various non-limiting examples of the chain moiety, including to those of Formulae (E-2), (E-3), and (E-4). It will be understood that, in examples where the chain moiety includes two or more of the same moieties, for example two or more RB, two or more RD, two or more RE, and/or two or more RT, each such moiety may be selected independently upon each occurrence according to various non-limiting examples described herein.


In some non-limiting examples, the compound contains a chain moiety selected from Formula (F-1) to (F-294):




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In some non-limiting examples, the chain moiety is selected according to one or more properties of an equivalent precursor form of the chain moiety. In some non-limiting examples, the equivalent precursor form is derived by cleaving a bond between the linker moiety and the core moiety and attaching a hydrogen (H) atom to the cleaved linker moiety. By way of non-limiting examples, the equivalent precursor form of a chain moiety containing 0 as the linker moiety may be an alcohol, and the equivalent precursor form of a chain moiety containing N as the linker moiety may be an amine. In some non-limiting examples, the chain moiety is selected such that the equivalent precursor form of the chain moiety has a melting temperature that exceeds about 60° C., 80° C., or 100° C. In some non-limiting examples, the chain moiety is selected such that the equivalent precursor form of the chain moiety has a refractive index of no greater than about 1.4, 1.35, or 1.3. In some non-limiting examples, the chain moiety is selected such that the equivalent precursor form of the chain moiety has a surface energy of no greater than about 25 dynes/cm, 24 dynes/cm, 23 dynes/cm, 22 dynes/cm, 21 dynes/cm, or 20 dynes/cm.


Without wishing to be bound by any particular theory, it is postulated that selecting the chain moiety such that the equivalent precursor form has: (i) a relatively high melting temperature exceeding, by way of non-limiting example, 60° C., (ii) a relatively low refractive index of, by way of non-limiting example, no greater than about 1.4, and (iii) a relatively low surface energy of, by way of non-limiting example, no greater than about 23 dynes/cm, the compound may exhibit one or more properties which are advantageous for certain applications, including in opto-electronic devices.


The surface energy of a material, including that of a thin film formed by depositing a compound, may be measured through experiments such as the sessile drop test or estimated through the use of Parachor. The Parachor is an additive property. In some non-limiting examples, the Parachor value may be derived through additions based on the atomic composition of the compound. In some other non-limiting examples, the Parachor may be derived through additions based on functional groups and/or various moieties of the compound. The Parachor and surface energy are related through the following equation:






γ
=



(

P
V

)

4

=


(

P

M
/
ρ


)

4






Wherein y is the surface energy, P is the Parachor, V is the molar volume, M is the molecular weight and p is the density. In some non-limiting examples, the molar volume may be measured experimentally or may be estimated using various group contribution methods. References for values of Parachor and molar volume may be found, by way of non-limiting example, in Fedors, R. F. (1974) Polymer Engineering and Science, 14(2), 147-154, and Knotts et al. (2001) J. Chem. Eng. Data, 46, 1007-1012.


It has now been found by the inventors that it may be particularly desirable for certain moieties of the compound to have a relatively low Parachor value and a relatively low molar volume associated therewith to reduce the surface energy contribution by such moieties. In some non-limiting examples, a quotient of the Parachor (P) to the molar volume (V), which may also be expressed as “P/V”, of the chain moiety is less than at least one of about: 3, 2.5, 2, 1.8, 1.6, and 1.5. In some non-limiting examples, P/V of the plurality of chain moieties is less than at least one of about: 3, 2.5, 2, 1.8, 1.6, and 1.5.


Without wishing to be bound by any particular theory, it is postulated that a compound containing a core moiety having a relatively high P/V and a chain moiety having a relatively low P/V may be particularly desirable for use in at least certain applications. Accordingly, in some non-limiting examples, the compound contains a core moiety having P/V of at least about 6, 8, 10, 12, 15, 20, 30, or 40, and a chain moiety having P/V of less than about 3, 2.5, 2, 1.8, 1.6, or 1.5.


By way of non-limiting example, reference values of Parachor, molar volume, and P/V values for certain functional groups are summarized in the table below. The example reference values in the table below are based on data presented in Fedors (1974) and Knotts et al. (2001).

















Moiety or
Parachor
Molar Volume



Type
Functional Group
Contribution
Contribution
PV



















Alphalic
C
15.76
−19.2
−0.82



CH
28.9
−1
−28.9



CH2
40.11
16.1
2.49



CH3
55.25
33.5
1.65



CF
37.57
−1.2
−31.3



CFH
50.71
17
2.98



CF2
48.42
23
2.11



CF2H
72.52
39
1.86



CF3
70.23
57.5
1.22



O
20
3.8
5.26



Si
28.64
0
N/A


Aromatic
F
66.3
18
3.68



C - fused
19.73
−5.5
−3.59



C branched
16.07
−5.5
−2.92



6-Membered Rings
6.1
16
0.38



Additional Double
23.2
−2.2
−10.55



bonds






CH-Phenyl
34.36
13.5
2.55



Si - ring
28.64
0
N/A



(P═N)3
226.3
21.4
10.57



(P═N)4
293.6
7.2
40.78









In some non-limiting examples, the NIC 810 and/or patterning coating includes a compound containing a plurality of chain moieties. In some non-limiting examples, each chain moiety of the plurality of chain moieties is selected independently of the other chain moieties. In some non-limiting examples, the plurality of chain moieties is identical.


In some non-limiting examples, a sum of the molar mass of the plurality of chain moieties exceeds about 90%, 92%, or 95% of the molar mass of the compound. In some non-limiting examples, a sum of the molar mass of the plurality of chain moieties exceeds about 10 times the molar mass of the core moiety.


In some non-limiting examples, the molar mass of each chain moiety is about 200-900 g/mol, 300-800 g/mol, or 350-650 g/mol.


In some non-limiting examples, the chain moiety is devoid of a continuous perfluorinated unit which exceeds: 8, 7, or 6 carbon (C) atoms. By way of non-limiting example, a perfluorinated unit may be considered to be formed as a continuous unit, if the perfluorinated carbon atoms of the perfluorinated unit are bonded to one another continuously without any non-perfluorinated carbon or heteroatoms being present therebetween.


In some non-limiting examples, the NIC 810 and/or patterning coating includes a compound containing a phosphazene unit represented by Formula (PU-1):




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wherein R independently represents, upon each occurrence, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, or a chain moiety. In some non-limiting examples, at least one R corresponds to the chain moiety is represented by Formula (E-1), (E-2), (E-3), or (E-4).


In some non-limiting examples, the compound contains two or more phosphazene units. For example, the compound may contain two or more phosphazene units bonded end-to-end to form, by way of non-limiting example, an oligomer, represented by Formula (A-1):




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where n is an integer greater than 2, and R independently represents, upon each occurrence, F, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, or a chain moiety. In some non-limiting examples, at least one R corresponds to the chain moiety is represented by Formula (E-1), (E-2), (E-3), or (E-4).


In some non-limiting examples, the compound is a polymer in which n is greater than about 20. By way of non-limiting example, in such polymers, n may be an integer of about 21-60, 21-50, 21-40, or 21-30.


In some non-limiting examples, the compound is an oligomer in which n is less than about 20. By way of non-limiting example, in such oligomers, n may be an integer of about 2 to 20, 2 to 18, 2 to 15, 2 to 13, 2 to 10, 2 to 8, 2 to 7, 2 to 5, 3 to 5, or 3 to 4. The oligomer may be linear, branched, cyclic, cyclo-linear, and/or cross-linked.


In some non-limiting examples, the compound is an oligomeric phosphazene compound. In some non-limiting examples, the compound is a cyclic oligomeric phosphazene.


In some non-limiting examples, the two R groups attached to the phosphorus of a phosphazene unit may be fused to each other to form a cyclic structure. In some non-limiting examples, such compound may be represented by the Formula (A-2):




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wherein Rcy represents the cyclic structure formed by fusing the two R groups to each other. For example, Rey may include various moieties for forming the chain moiety described in various examples herein, including for example RB, RD, RE and/or RT. In some non-limiting examples, Rcy is represented by Formula (CB-1), (CB-2), or (CB-3):




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in which k is an integer of 2 to 9, 2 to 6, 2 to 5, or 2 to 3; j is an integer of 1 to 5, 1 to 3, or 1 to 2; and I is an integer of 1 to 5, 1 to 3, or 1 to 2.


In some non-limiting examples, the compound contains two or more phosphazene units which are arranged to form a cyclophosphazene. Such compound may be represented, for example, by Formula (CA-1) or (CA-2):




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In Formula (CA-1), m is an integer of 2 to 7.


In Formula (CA-2), r and s each represents an integer of 1 to 6, and the sum of r and s equals 2, 3, 4, 5, 6, or 7. In some non-limiting examples, RA, RB, RC, and RD each independently represents R, the description of which is provided above in various non-limiting examples. In some non-limiting examples, RA, RB, RD, and RD are selected such that at least one of RA and RB differs from RC and RD.


Referring again to Formula (CA-2), in some non-limiting examples where r and s each represents an integer of 2 or greater, the phosphazene units —N═PRARB— (represented as “A”) and —RCRDP═N— (represented as “B”) may be bonded in various cyclic configurations with respect to one another. Some non-limiting examples of such bonding arrangements include but are not limited to: AABB, ABAB, ABBA, AAABB, ABABA, AABAB, ABAAB, BBBAA, BABAB, BBABA, BABBA, AAABBB, AABBAB, ABABAB, and ABABBA.


In some non-limiting examples, the cyclophosphazene is represented by Formula (C-1), (C-2), (C-3), (C-4), (C-5), or (C-6) which are shown below.




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The descriptions of R provided above in various non-limiting examples, including but not limited to those provided in relation to Formula (PU-1), is also applicable with regards each occurrence of R in Formula (C-1), (C-2), (C-3), (C-4), (C-5), and (C-6). In some non-limiting examples, R is selected independently upon each occurrence in each of Formula (C-1), (C-2), (C-3), (C-4), (C-5), and (C-6). In some other non-limiting examples, all R represented in each given Formula are identical to one another.


In some non-limiting examples, the NIC 810 and/or patterning coating includes a compound containing a cyclophosphazene according to Formula (C-2), wherein at least one R corresponds to the chain moiety represented by Formula (E-1), (E-2), (E-3), or (E-4). In some further non-limiting examples, at least one R is represented by any one of Formulae (F-1) to (F-294). In some further non-limiting examples, the compound includes two or more different species of chain moiety selected from Formulae (F-1) to (F-294).


Non-limiting examples of compound according to Formula (C-3) include those in which at least one R is represented by any one of Formulae (F-156), (F-157), (F-165), (F-169), (F-209) to (F-239). In some non-limiting examples, all R groups within the compound are identical.


Non-limiting examples of compound according to Formula (C-2) include those in which at least one R is represented by any one of Formulae (F-153) to (F-172), and (F-209) to (F-279). In some non-limiting examples, all R groups within the compound are identical.


In some non-limiting examples, the NIC 810 and/or patterning coating includes a compound containing a cyclophosphazene according to Formulae (C-1), (C-2), (C-3), (C-4), (C-5), and/or (C-6), wherein at least one R includes a linker moiety containing O, N, S, a substituted or unsubstituted alkylene, fluoromethylene, and/or difluoromethylene. In some non-limiting examples, the at least one R includes an intermediate moiety containing a substituted or unsubstituted alkylene, and/or substituted or unsubstituted fluoroalkylene.


In some non-limiting examples, a phosphazene derivative compound is provided. The compound includes a first chain moiety and a second chain moiety. Each of the first chain moiety and the second chain moiety includes a backbone and a fluorine atom attached to the backbone. The first chain moiety is different from the second chain moiety.


In some non-limiting examples, the NIC 810 and/or the patterning coating includes, or is formed by, the phosphazene derivative compound containing the first chain moiety and the second chain moiety. It will be appreciated that descriptions of the chain moiety according to various non-limiting examples herein may be applicable for each of the first chain moiety and the second chain moiety.


In some non-limiting examples, wherein a difference between the molar mass of the first chain moiety and the molar mass of the second chain moiety is less than about: 600 g/mol, 500 g/mol, 450 g/mol, 300 g/mol, or 200 g/mol.


In some non-limiting examples, at least one of the first and second chain moieties includes at least one of a CF2 unit, a CH2 unit, and a fluoroalkylene unit.


In some non-limiting examples, the number of carbon (C) atoms contained in the first chain moiety differs from the number of carbon atoms contained in the second chain moiety by about 1 to 8 C atoms, 1 to 6 C atoms, 2 to 6 C atoms, 2 to 4 C atoms, 2 to 3 C atoms, or 1 to 3 C atoms. In some non-limiting examples, the number of fluorine (F) atoms contained in the first chain moiety differs from the number of fluorine atoms contained in the second chain moiety by about 1 to 16 F atoms, 1 to 12 F atoms, 2 to 12 F atoms, 4 to 12 F atoms, 4 to 8 F atoms, 4 to 6 F atoms, or 2 to 6 F atoms.


In some non-limiting examples, the compound includes a phosphazene unit according to Formula (PX-1):




embedded image


Wherein R1 and R2 represents the first chain moiety and the second chain moiety, respectively.


In some non-limiting examples, the compound is a cyclophosphazene derivative represented by the following formula:




embedded image


In the above formula: A represents an integer between 3 and 7; R1 represents the first chain moiety; B represents an integer between 1 and 13; R2 represents the second chain moiety; C represents an integer of 1 to 13; and the sum of B and C is no more than twice the value of A. In the above formula, each chain moiety of the first and second chain moieties may be bonded to a phosphorous atom of the phosphazene units constituting the core moiety, which is represented as [P═N]A in the above formula.


In some non-limiting examples, up to two chain moieties are bonded to each phosphorous atom of the phosphazene units constituting the core moiety. In some non-limiting examples, B and C are equal. In some further non-limiting examples, each phosphorous atom of the core moiety is bonded to a first chain moiety and a second chain moiety.


In some non-limiting examples, the compound according to Formula (XA-1) has A of 3, B of 1 to 5, and C of 1 to 5. In some further non-limiting examples, B is 3 and C is 3. Non-limiting examples of molecular structures according to Formula (XA-1) in which A is 3 include, but are not limited to the following:




embedded image


In some non-limiting examples, the compound according to Formula (XA-1) has A of 4, B of 1 to 7, and C of 1 to 7. In some further non-limiting examples, B is 4 and C is 4. Non-limiting examples of molecular structures according to Formula (XA-1) in which A is 4 include, but are not limited to the following:




embedded image


In some non-limiting examples, the first chain moiety and the second chain moiety are attached to a common phosphorus (P) atom.


In some non-limiting examples, the first chain moiety is represented by the formula:





*—O—(CH2)t(CF2)uZ


In the above formula: t represents an integer between 1 and 3; u represents an integer between 5 and 12; and Z represents hydrogen (H), deutero (D), or fluorine (F).


In some non-limiting examples, the second chain moiety is represented by the formula:





*—O—(CH2)v(CF2)wZ


In the above formula: v represents an integer between 1 and 3; w represents an integer between 5 and 12; and Z represents hydrogen (H), deutero (D), or fluorine (F).


In some non-limiting examples, the compound is represented by the following formula:




embedded image


In Formula (XA-2): t and v each represent an integer between 1 and 3; u and w each represent an integer between 5 and 12; y represents an integer between 2 and 7; and Z individually represents hydrogen (H), deutero (D), or fluorine (F).


In some non-limiting examples, in Formula (XA-2), the values of u and w are different. In some non-limiting examples, t and v are both 1. In some non-limiting examples, y is 3 or 4. In some non-limiting examples, u is 8. In some non-limiting examples, w is 10.


Non-limiting examples of compounds according to Formula (XA-1) include those derived according to the table below. In the table below, the values of A, B, and C, and the formula identifier for each of the first chain moiety, R1, and the second chain moiety, R2, for each derivative compound are provided.
















A
R1
R2
B
C







3
(F-32)
(F-35)
1
5


3
(F-32)
(F-38)
1
5


3
(F-32)
(F-44)
1
5


3
(F-32)
(F-47)
1
5


3
(F-32)
(F-50)
1
5


3
(F-32)
(F-41)
1
5


3
(F-32)
(F-287)
1
5


3
(F-32)
(F-289)
1
5


3
(F-32)
(F-291)
1
5


3
(F-32)
(F-293)
1
5


3
(F-35)
(F-32)
1
5


3
(F-35)
(F-38)
1
5


3
(F-35)
(F-44)
1
5


3
(F-35)
(F-47)
1
5


3
(F-35)
(F-50)
1
5


3
(F-35)
(F-41)
1
5


3
(F-35)
(F-287)
1
5


3
(F-35)
(F-289)
1
5


3
(F-35)
(F-291)
1
5


3
(F-35)
(F-293)
1
5


3
(F-38)
(F-32)
1
5


3
(F-38)
(F-35)
1
5


3
(F-38)
(F-44)
1
5


3
(F-38)
(F-47)
1
5


3
(F-38)
(F-50)
1
5


3
(F-38)
(F-41)
1
5


3
(F-38)
(F-287)
1
5


3
(F-38)
(F-289)
1
5


3
(F-38)
(F-291)
1
5


3
(F-38)
(F-293)
1
5


3
(F-44)
(F-32)
1
5


3
(F-44)
(F-35)
1
5


3
(F-44)
(F-38)
1
5


3
(F-44)
(F-47)
1
5


3
(F-44)
(F-50)
1
5


3
(F-44)
(F-41)
1
5


3
(F-44)
(F-287)
1
5


3
(F-44)
(F-289)
1
5


3
(F-44)
(F-291)
1
5


3
(F-44)
(F-293)
1
5


3
(F-47)
(F-32)
1
5


3
(F-47)
(F-35)
1
5


3
(F-47)
(F-38)
1
5


3
(F-47)
(F-44)
1
5


3
(F-47)
(F-50)
1
5


3
(F-47)
(F-41)
1
5


3
(F-47)
(F-287)
1
5


3
(F-47)
(F-289)
1
5


3
(F-47)
(F-291)
1
5


3
(F-47)
(F-293)
1
5


3
(F-50)
(F-32)
1
5


3
(F-50)
(F-35)
1
5


3
(F-50)
(F-38)
1
5


3
(F-50)
(F-44)
1
5


3
(F-50)
(F-47)
1
5


3
(F-50)
(F-41)
1
5


3
(F-50)
(F-287)
1
5


3
(F-50)
(F-289)
1
5


3
(F-50)
(F-291)
1
5


3
(F-50)
(F-293)
1
5


3
(F-41)
(F-32)
1
5


3
(F-41)
(F-35)
1
5


3
(F-41)
(F-38)
1
5


3
(F-41)
(F-44)
1
5


3
(F-41)
(F-47)
1
5


3
(F-41)
(F-50)
1
5


3
(F-41)
(F-287)
1
5


3
(F-41)
(F-289)
1
5


3
(F-41)
(F-291)
1
5


3
(F-41)
(F-293)
1
5


3
(F-287)
(F-32)
1
5


3
(F-287)
(F-35)
1
5


3
(F-287)
(F-38)
1
5


3
(F-287)
(F-44)
1
5


3
(F-287)
(F-47)
1
5


3
(F-287)
(F-50)
1
5


3
(F-287)
(F-41)
1
5


3
(F-287)
(F-289)
1
5


3
(F-287)
(F-291)
1
5


3
(F-287)
(F-293)
1
5


3
(F-289)
(F-32)
1
5


3
(F-289)
(F-35)
1
5


3
(F-289)
(F-38)
1
5


3
(F-289)
(F-44)
1
5


3
(F-289)
(F-47)
1
5


3
(F-289)
(F-50)
1
5


3
(F-289)
(F-41)
1
5


3
(F-289)
(F-287)
1
5


3
(F-289)
(F-291)
1
5


3
(F-289)
(F-293)
1
5


3
(F-291)
(F-32)
1
5


3
(F-291)
(F-35)
1
5


3
(F-291)
(F-38)
1
5


3
(F-291)
(F-44)
1
5


3
(F-291)
(F-47)
1
5


3
(F-291)
(F-50)
1
5


3
(F-291)
(F-41)
1
5


3
(F-291)
(F-287)
1
5


3
(F-291)
(F-289)
1
5


3
(F-291)
(F-293)
1
5


3
(F-293)
(F-32)
1
5


3
(F-293)
(F-35)
1
5


3
(F-293)
(F-38)
1
5


3
(F-293)
(F-44)
1
5


3
(F-293)
(F-47)
1
5


3
(F-293)
(F-50)
1
5


3
(F-293)
(F-41)
1
5


3
(F-293)
(F-287)
1
5


3
(F-293)
(F-289)
1
5


3
(F-293)
(F-291)
1
5


3
(F-32)
(F-35)
2
4


3
(F-32)
(F-38)
2
4


3
(F-32)
(F-44)
2
4


3
(F-32)
(F-47)
2
4


3
(F-32)
(F-50)
2
4


3
(F-32)
(F-41)
2
4


3
(F-32)
(F-287)
2
4


3
(F-32)
(F-289)
2
4


3
(F-32)
(F-291)
2
4


3
(F-32)
(F-293)
2
4


3
(F-35)
(F-32)
2
4


3
(F-35)
(F-38)
2
4


3
(F-35)
(F-44)
2
4


3
(F-35)
(F-47)
2
4


3
(F-35)
(F-50)
2
4


3
(F-35)
(F-41)
2
4


3
(F-35)
(F-287)
2
4


3
(F-35)
(F-289)
2
4


3
(F-35)
(F-291)
2
4


3
(F-35)
(F-293)
2
4


3
(F-38)
(F-32)
2
4


3
(F-38)
(F-35)
2
4


3
(F-38)
(F-44)
2
4


3
(F-38)
(F-47)
2
4


3
(F-38)
(F-50)
2
4


3
(F-38)
(F-41)
2
4


3
(F-38)
(F-287)
2
4


3
(F-38)
(F-289)
2
4


3
(F-38)
(F-291)
2
4


3
(F-38)
(F-293)
2
4


3
(F-44)
(F-32)
2
4


3
(F-44)
(F-35)
2
4


3
(F-44)
(F-38)
2
4


3
(F-44)
(F-47)
2
4


3
(F-44)
(F-50)
2
4


3
(F-44)
(F-41)
2
4


3
(F-44)
(F-287)
2
4


3
(F-44)
(F-289)
2
4


3
(F-44)
(F-291)
2
4


3
(F-44)
(F-293)
2
4


3
(F-47)
(F-32)
2
4


3
(F-47)
(F-35)
2
4


3
(F-47)
(F-38)
2
4


3
(F-47)
(F-44)
2
4


3
(F-47)
(F-50)
2
4


3
(F-47)
(F-41)
2
4


3
(F-47)
(F-287)
2
4


3
(F-47)
(F-289)
2
4


3
(F-47)
(F-291)
2
4


3
(F-47)
(F-293)
2
4


3
(F-50)
(F-32)
2
4


3
(F-50)
(F-35)
2
4


3
(F-50)
(F-38)
2
4


3
(F-50)
(F-44)
2
4


3
(F-50)
(F-47)
2
4


3
(F-50)
(F-41)
2
4


3
(F-50)
(F-287)
2
4


3
(F-50)
(F-289)
2
4


3
(F-50)
(F-291)
2
4


3
(F-50)
(F-293)
2
4


3
(F-41)
(F-32)
2
4


3
(F-41)
(F-35)
2
4


3
(F-41)
(F-38)
2
4


3
(F-41)
(F-44)
2
4


3
(F-41)
(F-47)
2
4


3
(F-41)
(F-50)
2
4


3
(F-41)
(F-287)
2
4


3
(F-41)
(F-289)
2
4


3
(F-41)
(F-291)
2
4


3
(F-41)
(F-293)
2
4


3
(F-287)
(F-32)
2
4


3
(F-287)
(F-35)
2
4


3
(F-287)
(F-38)
2
4


3
(F-287)
(F-44)
2
4


3
(F-287)
(F-47)
2
4


3
(F-287)
(F-50)
2
4


3
(F-287)
(F-41)
2
4


3
(F-287)
(F-289)
2
4


3
(F-287)
(F-291)
2
4


3
(F-287)
(F-293)
2
4


3
(F-289)
(F-32)
2
4


3
(F-289)
(F-35)
2
4


3
(F-289)
(F-38)
2
4


3
(F-289)
(F-44)
2
4


3
(F-289)
(F-47)
2
4


3
(F-289)
(F-50)
2
4


3
(F-289)
(F-41)
2
4


3
(F-289)
(F-287)
2
4


3
(F-289)
(F-291)
2
4


3
(F-289)
(F-293)
2
4


3
(F-291)
(F-32)
2
4


3
(F-291)
(F-35)
2
4


3
(F-291)
(F-38)
2
4


3
(F-291)
(F-44)
2
4


3
(F-291)
(F-47)
2
4


3
(F-291)
(F-50)
2
4


3
(F-291)
(F-41)
2
4


3
(F-291)
(F-287)
2
4


3
(F-291)
(F-289)
2
4


3
(F-291)
(F-293)
2
4


3
(F-293)
(F-32)
2
4


3
(F-293)
(F-35)
2
4


3
(F-293)
(F-38)
2
4


3
(F-293)
(F-44)
2
4


3
(F-293)
(F-47)
2
4


3
(F-293)
(F-50)
2
4


3
(F-293)
(F-41)
2
4


3
(F-293)
(F-287)
2
4


3
(F-293)
(F-289)
2
4


3
(F-293)
(F-291)
2
4


3
(F-32)
(F-35)
3
3


3
(F-32)
(F-38)
3
3


3
(F-32)
(F-44)
3
3


3
(F-32)
(F-47)
3
3


3
(F-32)
(F-50)
3
3


3
(F-32)
(F-41)
3
3


3
(F-32)
(F-287)
3
3


3
(F-32)
(F-289)
3
3


3
(F-32)
(F-291)
3
3


3
(F-32)
(F-293)
3
3


3
(F-35)
(F-32)
3
3


3
(F-35)
(F-38)
3
3


3
(F-35)
(F-44)
3
3


3
(F-35)
(F-47)
3
3


3
(F-35)
(F-50)
3
3


3
(F-35)
(F-41)
3
3


3
(F-35)
(F-287)
3
3


3
(F-35)
(F-289)
3
3


3
(F-35)
(F-291)
3
3


3
(F-35)
(F-293)
3
3


3
(F-38)
(F-32)
3
3


3
(F-38)
(F-35)
3
3


3
(F-38)
(F-44)
3
3


3
(F-38)
(F-47)
3
3


3
(F-38)
(F-50)
3
3


3
(F-38)
(F-41)
3
3


3
(F-38)
(F-287)
3
3


3
(F-38)
(F-289)
3
3


3
(F-38)
(F-291)
3
3


3
(F-38)
(F-293)
3
3


3
(F-44)
(F-32)
3
3


3
(F-44)
(F-35)
3
3


3
(F-44)
(F-38)
3
3


3
(F-44)
(F-47)
3
3


3
(F-44)
(F-50)
3
3


3
(F-44)
(F-41)
3
3


3
(F-44)
(F-287)
3
3


3
(F-44)
(F-289)
3
3


3
(F-44)
(F-291)
3
3


3
(F-44)
(F-293)
3
3


3
(F-47)
(F-32)
3
3


3
(F-47)
(F-35)
3
3


3
(F-47)
(F-38)
3
3


3
(F-47)
(F-44)
3
3


3
(F-47)
(F-50)
3
3


3
(F-47)
(F-41)
3
3


3
(F-47)
(F-287)
3
3


3
(F-47)
(F-289)
3
3


3
(F-47)
(F-291)
3
3


3
(F-47)
(F-293)
3
3


3
(F-50)
(F-32)
3
3


3
(F-50)
(F-35)
3
3


3
(F-50)
(F-38)
3
3


3
(F-50)
(F-44)
3
3


3
(F-50)
(F-47)
3
3


3
(F-50)
(F-41)
3
3


3
(F-50)
(F-287)
3
3


3
(F-50)
(F-289)
3
3


3
(F-50)
(F-291)
3
3


3
(F-50)
(F-293)
3
3


3
(F-41)
(F-32)
3
3


3
(F-41)
(F-35)
3
3


3
(F-41)
(F-38)
3
3


3
(F-41)
(F-44)
3
3


3
(F-41)
(F-47)
3
3


3
(F-41)
(F-50)
3
3


3
(F-41)
(F-287)
3
3


3
(F-41)
(F-289)
3
3


3
(F-41)
(F-291)
3
3


3
(F-41)
(F-293)
3
3


3
(F-287)
(F-32)
3
3


3
(F-287)
(F-35)
3
3


3
(F-287)
(F-38)
3
3


3
(F-287)
(F-44)
3
3


3
(F-287)
(F-47)
3
3


3
(F-287)
(F-50)
3
3


3
(F-287)
(F-41)
3
3


3
(F-287)
(F-289)
3
3


3
(F-287)
(F-291)
3
3


3
(F-287)
(F-293)
3
3


3
(F-289)
(F-32)
3
3


3
(F-289)
(F-35)
3
3


3
(F-289)
(F-38)
3
3


3
(F-289)
(F-44)
3
3


3
(F-289)
(F-47)
3
3


3
(F-289)
(F-50)
3
3


3
(F-289)
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4
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4
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4
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4
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5


4
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4
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4
4


4
(F-32)
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4
4


4
(F-32)
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4
4


4
(F-32)
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4
4


4
(F-32)
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4
4


4
(F-32)
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4
4


4
(F-32)
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4
4


4
(F-32)
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4
4


4
(F-32)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-35)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-44)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
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4
4


4
(F-41)
(F-293)
4
4


4
(F-287)
(F-32)
4
4


4
(F-287)
(F-35)
4
4


4
(F-287)
(F-38)
4
4


4
(F-287)
(F-44)
4
4


4
(F-287)
(F-47)
4
4


4
(F-287)
(F-50)
4
4


4
(F-287)
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4
4


4
(F-287)
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4
4


4
(F-287)
(F-291)
4
4


4
(F-287)
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4
4


4
(F-289)
(F-32)
4
4


4
(F-289)
(F-35)
4
4


4
(F-289)
(F-38)
4
4


4
(F-289)
(F-44)
4
4


4
(F-289)
(F-47)
4
4


4
(F-289)
(F-50)
4
4


4
(F-289)
(F-41)
4
4


4
(F-289)
(F-287)
4
4


4
(F-289)
(F-291)
4
4


4
(F-289)
(F-293)
4
4


4
(F-291)
(F-32)
4
4


4
(F-291)
(F-35)
4
4


4
(F-291)
(F-38)
4
4


4
(F-291)
(F-44)
4
4


4
(F-291)
(F-47)
4
4


4
(F-291)
(F-50)
4
4


4
(F-291)
(F-41)
4
4


4
(F-291)
(F-287)
4
4


4
(F-291)
(F-289)
4
4


4
(F-291)
(F-293)
4
4


4
(F-293)
(F-32)
4
4


4
(F-293)
(F-35)
4
4


4
(F-293)
(F-38)
4
4


4
(F-293)
(F-44)
4
4


4
(F-293)
(F-47)
4
4


4
(F-293)
(F-50)
4
4


4
(F-293)
(F-41)
4
4


4
(F-293)
(F-287)
4
4


4
(F-293)
(F-289)
4
4


4
(F-293)
(F-291)
4
4


3
(F-34)
(F-37)
1
5


3
(F-34)
(F-40)
1
5


3
(F-34)
(F-43)
1
5


3
(F-34)
(F-46)
1
5


3
(F-34)
(F-49)
1
5


3
(F-34)
(F-280)
1
5


3
(F-34)
(F-282)
1
5


3
(F-34)
(F-283)
1
5


3
(F-34)
(F-285)
1
5


3
(F-37)
(F-34)
1
5


3
(F-37)
(F-40)
1
5


3
(F-37)
(F-43)
1
5


3
(F-37)
(F-46)
1
5


3
(F-37)
(F-49)
1
5


3
(F-37)
(F-280)
1
5


3
(F-37)
(F-282)
1
5


3
(F-37)
(F-283)
1
5


3
(F-37)
(F-285)
1
5


3
(F-40)
(F-34)
1
5


3
(F-40)
(F-37)
1
5


3
(F-40)
(F-43)
1
5


3
(F-40)
(F-46)
1
5


3
(F-40)
(F-49)
1
5


3
(F-40)
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1
5


3
(F-40)
(F-282)
1
5


3
(F-40)
(F-283)
1
5


3
(F-40)
(F-285)
1
5


3
(F-43)
(F-34)
1
5


3
(F-43)
(F-37)
1
5


3
(F-43)
(F-40)
1
5


3
(F-43)
(F-46)
1
5


3
(F-43)
(F-49)
1
5


3
(F-43)
(F-280)
1
5


3
(F-43)
(F-282)
1
5


3
(F-43)
(F-283)
1
5


3
(F-43)
(F-285)
1
5


3
(F-46)
(F-34)
1
5


3
(F-46)
(F-37)
1
5


3
(F-46)
(F-40)
1
5


3
(F-46)
(F-43)
1
5


3
(F-46)
(F-49)
1
5


3
(F-46)
(F-280)
1
5


3
(F-46)
(F-282)
1
5


3
(F-46)
(F-283)
1
5


3
(F-46)
(F-285)
1
5


3
(F-49)
(F-34)
1
5


3
(F-49)
(F-37)
1
5


3
(F-49)
(F-40)
1
5


3
(F-49)
(F-43)
1
5


3
(F-49)
(F-46)
1
5


3
(F-49)
(F-280)
1
5


3
(F-49)
(F-282)
1
5


3
(F-49)
(F-283)
1
5


3
(F-49)
(F-285)
1
5


3
(F-280)
(F-34)
1
5


3
(F-280)
(F-37)
1
5


3
(F-280)
(F-40)
1
5


3
(F-280)
(F-43)
1
5


3
(F-280)
(F-46)
1
5


3
(F-280)
(F-49)
1
5


3
(F-280)
(F-282)
1
5


3
(F-280)
(F-283)
1
5


3
(F-280)
(F-285)
1
5


3
(F-282)
(F-34)
1
5


3
(F-282)
(F-37)
1
5


3
(F-282)
(F-40)
1
5


3
(F-282)
(F-43)
1
5


3
(F-282)
(F-46)
1
5


3
(F-282)
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1
5


3
(F-282)
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1
5


3
(F-282)
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1
5


3
(F-282)
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1
5


3
(F-283)
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1
5


3
(F-283)
(F-37)
1
5


3
(F-283)
(F-40)
1
5


3
(F-283)
(F-43)
1
5


3
(F-283)
(F-46)
1
5


3
(F-283)
(F-49)
1
5


3
(F-283)
(F-280)
1
5


3
(F-283)
(F-282)
1
5


3
(F-283)
(F-285)
1
5


3
(F-285)
(F-34)
1
5


3
(F-285)
(F-37)
1
5


3
(F-285)
(F-40)
1
5


3
(F-285)
(F-43)
1
5


3
(F-285)
(F-46)
1
5


3
(F-285)
(F-49)
1
5


3
(F-285)
(F-280)
1
5


3
(F-285)
(F-282)
1
5


3
(F-285)
(F-283)
1
5


3
(F-34)
(F-37)
2
4


3
(F-34)
(F-40)
2
4


3
(F-34)
(F-43)
2
4


3
(F-34)
(F-46)
2
4


3
(F-34)
(F-49)
2
4


3
(F-34)
(F-280)
2
4


3
(F-34)
(F-282)
2
4


3
(F-34)
(F-283)
2
4


3
(F-34)
(F-285)
2
4


3
(F-37)
(F-34)
2
4


3
(F-37)
(F-40)
2
4


3
(F-37)
(F-43)
2
4


3
(F-37)
(F-46)
2
4


3
(F-37)
(F-49)
2
4


3
(F-37)
(F-280)
2
4


3
(F-37)
(F-282)
2
4


3
(F-37)
(F-283)
2
4


3
(F-37)
(F-285)
2
4


3
(F-40)
(F-34)
2
4


3
(F-40)
(F-37)
2
4


3
(F-40)
(F-43)
2
4


3
(F-40)
(F-46)
2
4


3
(F-40)
(F-49)
2
4


3
(F-40)
(F-280)
2
4


3
(F-40)
(F-282)
2
4


3
(F-40)
(F-283)
2
4


3
(F-40)
(F-285)
2
4


3
(F-43)
(F-34)
2
4


3
(F-43)
(F-37)
2
4


3
(F-43)
(F-40)
2
4


3
(F-43)
(F-46)
2
4


3
(F-43)
(F-49)
2
4


3
(F-43)
(F-280)
2
4


3
(F-43)
(F-282)
2
4


3
(F-43)
(F-283)
2
4


3
(F-43)
(F-285)
2
4


3
(F-46)
(F-34)
2
4


3
(F-46)
(F-37)
2
4


3
(F-46)
(F-40)
2
4


3
(F-46)
(F-43)
2
4


3
(F-46)
(F-49)
2
4


3
(F-46)
(F-280)
2
4


3
(F-46)
(F-282)
2
4


3
(F-46)
(F-283)
2
4


3
(F-46)
(F-285)
2
4


3
(F-49)
(F-34)
2
4


3
(F-49)
(F-37)
2
4


3
(F-49)
(F-40)
2
4


3
(F-49)
(F-43)
2
4


3
(F-49)
(F-46)
2
4


3
(F-49)
(F-280)
2
4


3
(F-49)
(F-282)
2
4


3
(F-49)
(F-283)
2
4


3
(F-49)
(F-285)
2
4


3
(F-280)
(F-34)
2
4


3
(F-280)
(F-37)
2
4


3
(F-280)
(F-40)
2
4


3
(F-280)
(F-43)
2
4


3
(F-280)
(F-46)
2
4


3
(F-280)
(F-49)
2
4


3
(F-280)
(F-282)
2
4


3
(F-280)
(F-283)
2
4


3
(F-280)
(F-285)
2
4


3
(F-282)
(F-34)
2
4


3
(F-282)
(F-37)
2
4


3
(F-282)
(F-40)
2
4


3
(F-282)
(F-43)
2
4


3
(F-282)
(F-46)
2
4


3
(F-282)
(F-49)
2
4


3
(F-282)
(F-280)
2
4


3
(F-282)
(F-283)
2
4


3
(F-282)
(F-285)
2
4


3
(F-283)
(F-34)
2
4


3
(F-283)
(F-37)
2
4


3
(F-283)
(F-40)
2
4


3
(F-283)
(F-43)
2
4


3
(F-283)
(F-46)
2
4


3
(F-283)
(F-49)
2
4


3
(F-283)
(F-280)
2
4


3
(F-283)
(F-282)
2
4


3
(F-283)
(F-285)
2
4


3
(F-285)
(F-34)
2
4


3
(F-285)
(F-37)
2
4


3
(F-285)
(F-40)
2
4


3
(F-285)
(F-43)
2
4


3
(F-285)
(F-46)
2
4


3
(F-285)
(F-49)
2
4


3
(F-285)
(F-280)
2
4


3
(F-285)
(F-282)
2
4


3
(F-285)
(F-283)
2
4


3
(F-34)
(F-37)
3
3


3
(F-34)
(F-40)
3
3


3
(F-34)
(F-43)
3
3


3
(F-34)
(F-46)
3
3


3
(F-34)
(F-49)
3
3


3
(F-34)
(F-280)
3
3


3
(F-34)
(F-282)
3
3


3
(F-34)
(F-283)
3
3


3
(F-34)
(F-285)
3
3


3
(F-37)
(F-34)
3
3


3
(F-37)
(F-40)
3
3


3
(F-37)
(F-43)
3
3


3
(F-37)
(F-46)
3
3


3
(F-37)
(F-49)
3
3


3
(F-37)
(F-280)
3
3


3
(F-37)
(F-282)
3
3


3
(F-37)
(F-283)
3
3


3
(F-37)
(F-285)
3
3


3
(F-40)
(F-34)
3
3


3
(F-40)
(F-37)
3
3


3
(F-40)
(F-43)
3
3


3
(F-40)
(F-46)
3
3


3
(F-40)
(F-49)
3
3


3
(F-40)
(F-280)
3
3


3
(F-40)
(F-282)
3
3


3
(F-40)
(F-283)
3
3


3
(F-40)
(F-285)
3
3


3
(F-43)
(F-34)
3
3


3
(F-43)
(F-37)
3
3


3
(F-43)
(F-40)
3
3


3
(F-43)
(F-46)
3
3


3
(F-43)
(F-49)
3
3


3
(F-43)
(F-280)
3
3


3
(F-43)
(F-282)
3
3


3
(F-43)
(F-283)
3
3


3
(F-43)
(F-285)
3
3


3
(F-46)
(F-34)
3
3


3
(F-46)
(F-37)
3
3


3
(F-46)
(F-40)
3
3


3
(F-46)
(F-43)
3
3


3
(F-46)
(F-49)
3
3


3
(F-46)
(F-280)
3
3


3
(F-46)
(F-282)
3
3


3
(F-46)
(F-283)
3
3


3
(F-46)
(F-285)
3
3


3
(F-49)
(F-34)
3
3


3
(F-49)
(F-37)
3
3


3
(F-49)
(F-40)
3
3


3
(F-49)
(F-43)
3
3


3
(F-49)
(F-46)
3
3


3
(F-49)
(F-280)
3
3


3
(F-49)
(F-282)
3
3


3
(F-49)
(F-283)
3
3


3
(F-49)
(F-285)
3
3


3
(F-280)
(F-34)
3
3


3
(F-280)
(F-37)
3
3


3
(F-280)
(F-40)
3
3


3
(F-280)
(F-43)
3
3


3
(F-280)
(F-46)
3
3


3
(F-280)
(F-49)
3
3


3
(F-280)
(F-282)
3
3


3
(F-280)
(F-283)
3
3


3
(F-280)
(F-285)
3
3


3
(F-282)
(F-34)
3
3


3
(F-282)
(F-37)
3
3


3
(F-282)
(F-40)
3
3


3
(F-282)
(F-43)
3
3


3
(F-282)
(F-46)
3
3


3
(F-282)
(F-49)
3
3


3
(F-282)
(F-280)
3
3


3
(F-282)
(F-283)
3
3


3
(F-282)
(F-285)
3
3


3
(F-283)
(F-34)
3
3


3
(F-283)
(F-37)
3
3


3
(F-283)
(F-40)
3
3


3
(F-283)
(F-43)
3
3


3
(F-283)
(F-46)
3
3


3
(F-283)
(F-49)
3
3


3
(F-283)
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3
3


3
(F-283)
(F-282)
3
3


3
(F-283)
(F-285)
3
3


3
(F-285)
(F-34)
3
3


3
(F-285)
(F-37)
3
3


3
(F-285)
(F-40)
3
3


3
(F-285)
(F-43)
3
3


3
(F-285)
(F-46)
3
3


3
(F-285)
(F-49)
3
3


3
(F-285)
(F-280)
3
3


3
(F-285)
(F-282)
3
3


3
(F-285)
(F-283)
3
3


4
(F-34)
(F-37)
1
7


4
(F-34)
(F-40)
1
7


4
(F-34)
(F-43)
1
7


4
(F-34)
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1
7


4
(F-34)
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1
7


4
(F-34)
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1
7


4
(F-34)
(F-282)
1
7


4
(F-34)
(F-283)
1
7


4
(F-34)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-40)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-46)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-280)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-283)
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1
7


4
(F-283)
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1
7


4
(F-283)
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1
7


4
(F-283)
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1
7


4
(F-283)
(F-46)
1
7


4
(F-283)
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1
7


4
(F-283)
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1
7


4
(F-283)
(F-282)
1
7


4
(F-283)
(F-285)
1
7


4
(F-285)
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1
7


4
(F-285)
(F-37)
1
7


4
(F-285)
(F-40)
1
7


4
(F-285)
(F-43)
1
7


4
(F-285)
(F-46)
1
7


4
(F-285)
(F-49)
1
7


4
(F-285)
(F-280)
1
7


4
(F-285)
(F-282)
1
7


4
(F-285)
(F-283)
1
7


4
(F-34)
(F-37)
2
6


4
(F-34)
(F-40)
2
6


4
(F-34)
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2
6


4
(F-34)
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2
6


4
(F-34)
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2
6


4
(F-34)
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2
6


4
(F-34)
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2
6


4
(F-34)
(F-283)
2
6


4
(F-34)
(F-285)
2
6


4
(F-37)
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2
6


4
(F-37)
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2
6


4
(F-37)
(F-43)
2
6


4
(F-37)
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2
6


4
(F-37)
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2
6


4
(F-37)
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2
6


4
(F-37)
(F-282)
2
6


4
(F-37)
(F-283)
2
6


4
(F-37)
(F-285)
2
6


4
(F-40)
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2
6


4
(F-40)
(F-37)
2
6


4
(F-40)
(F-43)
2
6


4
(F-40)
(F-46)
2
6


4
(F-40)
(F-49)
2
6


4
(F-40)
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2
6


4
(F-40)
(F-282)
2
6


4
(F-40)
(F-283)
2
6


4
(F-40)
(F-285)
2
6


4
(F-43)
(F-34)
2
6


4
(F-43)
(F-37)
2
6


4
(F-43)
(F-40)
2
6


4
(F-43)
(F-46)
2
6


4
(F-43)
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2
6


4
(F-43)
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2
6


4
(F-43)
(F-282)
2
6


4
(F-43)
(F-283)
2
6


4
(F-43)
(F-285)
2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
(F-46)
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2
6


4
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2
6


4
(F-49)
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2
6


4
(F-49)
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2
6


4
(F-49)
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2
6


4
(F-49)
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2
6


4
(F-49)
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2
6


4
(F-49)
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2
6


4
(F-49)
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2
6


4
(F-49)
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2
6


4
(F-280)
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2
6


4
(F-280)
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2
6


4
(F-280)
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2
6


4
(F-280)
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2
6


4
(F-280)
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2
6


4
(F-280)
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2
6


4
(F-280)
(F-282)
2
6


4
(F-280)
(F-283)
2
6


4
(F-280)
(F-285)
2
6


4
(F-282)
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2
6


4
(F-282)
(F-37)
2
6


4
(F-282)
(F-40)
2
6


4
(F-282)
(F-43)
2
6


4
(F-282)
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2
6


4
(F-282)
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2
6


4
(F-282)
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2
6


4
(F-282)
(F-283)
2
6


4
(F-282)
(F-285)
2
6


4
(F-283)
(F-34)
2
6


4
(F-283)
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2
6


4
(F-283)
(F-40)
2
6


4
(F-283)
(F-43)
2
6


4
(F-283)
(F-46)
2
6


4
(F-283)
(F-49)
2
6


4
(F-283)
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2
6


4
(F-283)
(F-282)
2
6


4
(F-283)
(F-285)
2
6


4
(F-285)
(F-34)
2
6


4
(F-285)
(F-37)
2
6


4
(F-285)
(F-40)
2
6


4
(F-285)
(F-43)
2
6


4
(F-285)
(F-46)
2
6


4
(F-285)
(F-49)
2
6


4
(F-285)
(F-280)
2
6


4
(F-285)
(F-282)
2
6


4
(F-285)
(F-283)
2
6


4
(F-34)
(F-37)
3
5


4
(F-34)
(F-40)
3
5


4
(F-34)
(F-43)
3
5


4
(F-34)
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3
5


4
(F-34)
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3
5


4
(F-34)
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3
5


4
(F-34)
(F-282)
3
5


4
(F-34)
(F-283)
3
5


4
(F-34)
(F-285)
3
5


4
(F-37)
(F-34)
3
5


4
(F-37)
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3
5


4
(F-37)
(F-43)
3
5


4
(F-37)
(F-46)
3
5


4
(F-37)
(F-49)
3
5


4
(F-37)
(F-280)
3
5


4
(F-37)
(F-282)
3
5


4
(F-37)
(F-283)
3
5


4
(F-37)
(F-285)
3
5


4
(F-40)
(F-34)
3
5


4
(F-40)
(F-37)
3
5


4
(F-40)
(F-43)
3
5


4
(F-40)
(F-46)
3
5


4
(F-40)
(F-49)
3
5


4
(F-40)
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3
5


4
(F-40)
(F-282)
3
5


4
(F-40)
(F-283)
3
5


4
(F-40)
(F-285)
3
5


4
(F-43)
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3
5


4
(F-43)
(F-37)
3
5


4
(F-43)
(F-40)
3
5


4
(F-43)
(F-46)
3
5


4
(F-43)
(F-49)
3
5


4
(F-43)
(F-280)
3
5


4
(F-43)
(F-282)
3
5


4
(F-43)
(F-283)
3
5


4
(F-43)
(F-285)
3
5


4
(F-46)
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3
5


4
(F-46)
(F-37)
3
5


4
(F-46)
(F-40)
3
5


4
(F-46)
(F-43)
3
5


4
(F-46)
(F-49)
3
5


4
(F-46)
(F-280)
3
5


4
(F-46)
(F-282)
3
5


4
(F-46)
(F-283)
3
5


4
(F-46)
(F-285)
3
5


4
(F-49)
(F-34)
3
5


4
(F-49)
(F-37)
3
5


4
(F-49)
(F-40)
3
5


4
(F-49)
(F-43)
3
5


4
(F-49)
(F-46)
3
5


4
(F-49)
(F-280)
3
5


4
(F-49)
(F-282)
3
5


4
(F-49)
(F-283)
3
5


4
(F-49)
(F-285)
3
5


4
(F-280)
(F-34)
3
5


4
(F-280)
(F-37)
3
5


4
(F-280)
(F-40)
3
5


4
(F-280)
(F-43)
3
5


4
(F-280)
(F-46)
3
5


4
(F-280)
(F-49)
3
5


4
(F-280)
(F-282)
3
5


4
(F-280)
(F-283)
3
5


4
(F-280)
(F-285)
3
5


4
(F-282)
(F-34)
3
5


4
(F-282)
(F-37)
3
5


4
(F-282)
(F-40)
3
5


4
(F-282)
(F-43)
3
5


4
(F-282)
(F-46)
3
5


4
(F-282)
(F-49)
3
5


4
(F-282)
(F-280)
3
5


4
(F-282)
(F-283)
3
5


4
(F-282)
(F-285)
3
5


4
(F-283)
(F-34)
3
5


4
(F-283)
(F-37)
3
5


4
(F-283)
(F-40)
3
5


4
(F-283)
(F-43)
3
5


4
(F-283)
(F-46)
3
5


4
(F-283)
(F-49)
3
5


4
(F-283)
(F-280)
3
5


4
(F-283)
(F-282)
3
5


4
(F-283)
(F-285)
3
5


4
(F-285)
(F-34)
3
5


4
(F-285)
(F-37)
3
5


4
(F-285)
(F-40)
3
5


4
(F-285)
(F-43)
3
5


4
(F-285)
(F-46)
3
5


4
(F-285)
(F-49)
3
5


4
(F-285)
(F-280)
3
5


4
(F-285)
(F-282)
3
5


4
(F-285)
(F-283)
3
5


4
(F-34)
(F-37)
4
4


4
(F-34)
(F-40)
4
4


4
(F-34)
(F-43)
4
4


4
(F-34)
(F-46)
4
4


4
(F-34)
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4
4


4
(F-34)
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4
4


4
(F-34)
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4
4


4
(F-34)
(F-283)
4
4


4
(F-34)
(F-285)
4
4


4
(F-37)
(F-34)
4
4


4
(F-37)
(F-40)
4
4


4
(F-37)
(F-43)
4
4


4
(F-37)
(F-46)
4
4


4
(F-37)
(F-49)
4
4


4
(F-37)
(F-280)
4
4


4
(F-37)
(F-282)
4
4


4
(F-37)
(F-283)
4
4


4
(F-37)
(F-285)
4
4


4
(F-40)
(F-34)
4
4


4
(F-40)
(F-37)
4
4


4
(F-40)
(F-43)
4
4


4
(F-40)
(F-46)
4
4


4
(F-40)
(F-49)
4
4


4
(F-40)
(F-280)
4
4


4
(F-40)
(F-282)
4
4


4
(F-40)
(F-283)
4
4


4
(F-40)
(F-285)
4
4


4
(F-43)
(F-34)
4
4


4
(F-43)
(F-37)
4
4


4
(F-43)
(F-40)
4
4


4
(F-43)
(F-46)
4
4


4
(F-43)
(F-49)
4
4


4
(F-43)
(F-280)
4
4


4
(F-43)
(F-282)
4
4


4
(F-43)
(F-283)
4
4


4
(F-43)
(F-285)
4
4


4
(F-46)
(F-34)
4
4


4
(F-46)
(F-37)
4
4


4
(F-46)
(F-40)
4
4


4
(F-46)
(F-43)
4
4


4
(F-46)
(F-49)
4
4


4
(F-46)
(F-280)
4
4


4
(F-46)
(F-282)
4
4


4
(F-46)
(F-283)
4
4


4
(F-46)
(F-285)
4
4


4
(F-49)
(F-34)
4
4


4
(F-49)
(F-37)
4
4


4
(F-49)
(F-40)
4
4


4
(F-49)
(F-43)
4
4


4
(F-49)
(F-46)
4
4


4
(F-49)
(F-280)
4
4


4
(F-49)
(F-282)
4
4


4
(F-49)
(F-283)
4
4


4
(F-49)
(F-285)
4
4


4
(F-280)
(F-34)
4
4


4
(F-280)
(F-37)
4
4


4
(F-280)
(F-40)
4
4


4
(F-280)
(F-43)
4
4


4
(F-280)
(F-46)
4
4


4
(F-280)
(F-49)
4
4


4
(F-280)
(F-282)
4
4


4
(F-280)
(F-283)
4
4


4
(F-280)
(F-285)
4
4


4
(F-282)
(F-34)
4
4


4
(F-282)
(F-37)
4
4


4
(F-282)
(F-40)
4
4


4
(F-282)
(F-43)
4
4


4
(F-282)
(F-46)
4
4


4
(F-282)
(F-49)
4
4


4
(F-282)
(F-280)
4
4


4
(F-282)
(F-283)
4
4


4
(F-282)
(F-285)
4
4


4
(F-283)
(F-34)
4
4


4
(F-283)
(F-37)
4
4


4
(F-283)
(F-40)
4
4


4
(F-283)
(F-43)
4
4


4
(F-283)
(F-46)
4
4


4
(F-283)
(F-49)
4
4


4
(F-283)
(F-280)
4
4


4
(F-283)
(F-282)
4
4


4
(F-283)
(F-285)
4
4


4
(F-285)
(F-34)
4
4


4
(F-285)
(F-37)
4
4


4
(F-285)
(F-40)
4
4


4
(F-285)
(F-43)
4
4


4
(F-285)
(F-46)
4
4


4
(F-285)
(F-49)
4
4


4
(F-285)
(F-280)
4
4


4
(F-285)
(F-282)
4
4


4
(F-285)
(F-283)
4
4


3
(F-32)
(F-34)
1
5


3
(F-32)
(F-37)
1
5


3
(F-32)
(F-40)
1
5


3
(F-32)
(F-43)
1
5


3
(F-32)
(F-46)
1
5


3
(F-32)
(F-49)
1
5


3
(F-32)
(F-280)
1
5


3
(F-32)
(F-282)
1
5


3
(F-32)
(F-283)
1
5


3
(F-32)
(F-285)
1
5


3
(F-35)
(F-34)
1
5


3
(F-35)
(F-37)
1
5


3
(F-35)
(F-40)
1
5


3
(F-35)
(F-43)
1
5


3
(F-35)
(F-46)
1
5


3
(F-35)
(F-49)
1
5


3
(F-35)
(F-280)
1
5


3
(F-35)
(F-282)
1
5


3
(F-35)
(F-283)
1
5


3
(F-35)
(F-285)
1
5


3
(F-38)
(F-34)
1
5


3
(F-38)
(F-37)
1
5


3
(F-38)
(F-40)
1
5


3
(F-38)
(F-43)
1
5


3
(F-38)
(F-46)
1
5


3
(F-38)
(F-49)
1
5


3
(F-38)
(F-280)
1
5


3
(F-38)
(F-282)
1
5


3
(F-38)
(F-283)
1
5


3
(F-38)
(F-285)
1
5


3
(F-44)
(F-34)
1
5


3
(F-44)
(F-37)
1
5


3
(F-44)
(F-40)
1
5


3
(F-44)
(F-43)
1
5


3
(F-44)
(F-46)
1
5


3
(F-44)
(F-49)
1
5


3
(F-44)
(F-280)
1
5


3
(F-44)
(F-282)
1
5


3
(F-44)
(F-283)
1
5


3
(F-44)
(F-285)
1
5


3
(F-47)
(F-34)
1
5


3
(F-47)
(F-37)
1
5


3
(F-47)
(F-40)
1
5


3
(F-47)
(F-43)
1
5


3
(F-47)
(F-46)
1
5


3
(F-47)
(F-49)
1
5


3
(F-47)
(F-280)
1
5


3
(F-47)
(F-282)
1
5


3
(F-47)
(F-283)
1
5


3
(F-47)
(F-285)
1
5


3
(F-50)
(F-34)
1
5


3
(F-50)
(F-37)
1
5


3
(F-50)
(F-40)
1
5


3
(F-50)
(F-43)
1
5


3
(F-50)
(F-46)
1
5


3
(F-50)
(F-49)
1
5


3
(F-50)
(F-280)
1
5


3
(F-50)
(F-282)
1
5


3
(F-50)
(F-283)
1
5


3
(F-50)
(F-285)
1
5


3
(F-41)
(F-34)
1
5


3
(F-41)
(F-37)
1
5


3
(F-41)
(F-40)
1
5


3
(F-41)
(F-43)
1
5


3
(F-41)
(F-46)
1
5


3
(F-41)
(F-49)
1
5


3
(F-41)
(F-280)
1
5


3
(F-41)
(F-282)
1
5


3
(F-41)
(F-283)
1
5


3
(F-41)
(F-285)
1
5


3
(F-287)
(F-34)
1
5


3
(F-287)
(F-37)
1
5


3
(F-287)
(F-40)
1
5


3
(F-287)
(F-43)
1
5


3
(F-287)
(F-46)
1
5


3
(F-287)
(F-49)
1
5


3
(F-287)
(F-280)
1
5


3
(F-287)
(F-282)
1
5


3
(F-287)
(F-283)
1
5


3
(F-287)
(F-285)
1
5


3
(F-289)
(F-34)
1
5


3
(F-289)
(F-37)
1
5


3
(F-289)
(F-40)
1
5


3
(F-289)
(F-43)
1
5


3
(F-289)
(F-46)
1
5


3
(F-289)
(F-49)
1
5


3
(F-289)
(F-280)
1
5


3
(F-289)
(F-282)
1
5


3
(F-289)
(F-283)
1
5


3
(F-289)
(F-285)
1
5


3
(F-291)
(F-34)
1
5


3
(F-291)
(F-37)
1
5


3
(F-291)
(F-40)
1
5


3
(F-291)
(F-43)
1
5


3
(F-291)
(F-46)
1
5


3
(F-291)
(F-49)
1
5


3
(F-291)
(F-280)
1
5


3
(F-291)
(F-282)
1
5


3
(F-291)
(F-283)
1
5


3
(F-291)
(F-285)
1
5


3
(F-293)
(F-34)
1
5


3
(F-293)
(F-37)
1
5


3
(F-293)
(F-40)
1
5


3
(F-293)
(F-43)
1
5


3
(F-293)
(F-46)
1
5


3
(F-293)
(F-49)
1
5


3
(F-293)
(F-280)
1
5


3
(F-293)
(F-282)
1
5


3
(F-293)
(F-283)
1
5


3
(F-293)
(F-285)
1
5


3
(F-32)
(F-34)
2
4


3
(F-32)
(F-37)
2
4


3
(F-32)
(F-40)
2
4


3
(F-32)
(F-43)
2
4


3
(F-32)
(F-46)
2
4


3
(F-32)
(F-49)
2
4


3
(F-32)
(F-280)
2
4


3
(F-32)
(F-282)
2
4


3
(F-32)
(F-283)
2
4


3
(F-32)
(F-285)
2
4


3
(F-35)
(F-34)
2
4


3
(F-35)
(F-37)
2
4


3
(F-35)
(F-40)
2
4


3
(F-35)
(F-43)
2
4


3
(F-35)
(F-46)
2
4


3
(F-35)
(F-49)
2
4


3
(F-35)
(F-280)
2
4


3
(F-35)
(F-282)
2
4


3
(F-35)
(F-283)
2
4


3
(F-35)
(F-285)
2
4


3
(F-38)
(F-34)
2
4


3
(F-38)
(F-37)
2
4


3
(F-38)
(F-40)
2
4


3
(F-38)
(F-43)
2
4


3
(F-38)
(F-46)
2
4


3
(F-38)
(F-49)
2
4


3
(F-38)
(F-280)
2
4


3
(F-38)
(F-282)
2
4


3
(F-38)
(F-283)
2
4


3
(F-38)
(F-285)
2
4


3
(F-44)
(F-34)
2
4


3
(F-44)
(F-37)
2
4


3
(F-44)
(F-40)
2
4


3
(F-44)
(F-43)
2
4


3
(F-44)
(F-46)
2
4


3
(F-44)
(F-49)
2
4


3
(F-44)
(F-280)
2
4


3
(F-44)
(F-282)
2
4


3
(F-44)
(F-283)
2
4


3
(F-44)
(F-285)
2
4


3
(F-47)
(F-34)
2
4


3
(F-47)
(F-37)
2
4


3
(F-47)
(F-40)
2
4


3
(F-47)
(F-43)
2
4


3
(F-47)
(F-46)
2
4


3
(F-47)
(F-49)
2
4


3
(F-47)
(F-280)
2
4


3
(F-47)
(F-282)
2
4


3
(F-47)
(F-283)
2
4


3
(F-47)
(F-285)
2
4


3
(F-50)
(F-34)
2
4


3
(F-50)
(F-37)
2
4


3
(F-50)
(F-40)
2
4


3
(F-50)
(F-43)
2
4


3
(F-50)
(F-46)
2
4


3
(F-50)
(F-49)
2
4


3
(F-50)
(F-280)
2
4


3
(F-50)
(F-282)
2
4


3
(F-50)
(F-283)
2
4


3
(F-50)
(F-285)
2
4


3
(F-41)
(F-34)
2
4


3
(F-41)
(F-37)
2
4


3
(F-41)
(F-40)
2
4


3
(F-41)
(F-43)
2
4


3
(F-41)
(F-46)
2
4


3
(F-41)
(F-49)
2
4


3
(F-41)
(F-280)
2
4


3
(F-41)
(F-282)
2
4


3
(F-41)
(F-283)
2
4


3
(F-41)
(F-285)
2
4


3
(F-287)
(F-34)
2
4


3
(F-287)
(F-37)
2
4


3
(F-287)
(F-40)
2
4


3
(F-287)
(F-43)
2
4


3
(F-287)
(F-46)
2
4


3
(F-287)
(F-49)
2
4


3
(F-287)
(F-280)
2
4


3
(F-287)
(F-282)
2
4


3
(F-287)
(F-283)
2
4


3
(F-287)
(F-285)
2
4


3
(F-289)
(F-34)
2
4


3
(F-289)
(F-37)
2
4


3
(F-289)
(F-40)
2
4


3
(F-289)
(F-43)
2
4


3
(F-289)
(F-46)
2
4


3
(F-289)
(F-49)
2
4


3
(F-289)
(F-280)
2
4


3
(F-289)
(F-282)
2
4


3
(F-289)
(F-283)
2
4


3
(F-289)
(F-285)
2
4


3
(F-291)
(F-34)
2
4


3
(F-291)
(F-37)
2
4


3
(F-291)
(F-40)
2
4


3
(F-291)
(F-43)
2
4


3
(F-291)
(F-46)
2
4


3
(F-291)
(F-49)
2
4


3
(F-291)
(F-280)
2
4


3
(F-291)
(F-282)
2
4


3
(F-291)
(F-283)
2
4


3
(F-291)
(F-285)
2
4


3
(F-293)
(F-34)
2
4


3
(F-293)
(F-37)
2
4


3
(F-293)
(F-40)
2
4


3
(F-293)
(F-43)
2
4


3
(F-293)
(F-46)
2
4


3
(F-293)
(F-49)
2
4


3
(F-293)
(F-280)
2
4


3
(F-293)
(F-282)
2
4


3
(F-293)
(F-283)
2
4


3
(F-293)
(F-285)
2
4


3
(F-32)
(F-34)
3
3


3
(F-32)
(F-37)
3
3


3
(F-32)
(F-40)
3
3


3
(F-32)
(F-43)
3
3


3
(F-32)
(F-46)
3
3


3
(F-32)
(F-49)
3
3


3
(F-32)
(F-280)
3
3


3
(F-32)
(F-282)
3
3


3
(F-32)
(F-283)
3
3


3
(F-32)
(F-285)
3
3


3
(F-35)
(F-34)
3
3


3
(F-35)
(F-37)
3
3


3
(F-35)
(F-40)
3
3


3
(F-35)
(F-43)
3
3


3
(F-35)
(F-46)
3
3


3
(F-35)
(F-49)
3
3


3
(F-35)
(F-280)
3
3


3
(F-35)
(F-282)
3
3


3
(F-35)
(F-283)
3
3


3
(F-35)
(F-285)
3
3


3
(F-38)
(F-34)
3
3


3
(F-38)
(F-37)
3
3


3
(F-38)
(F-40)
3
3


3
(F-38)
(F-43)
3
3


3
(F-38)
(F-46)
3
3


3
(F-38)
(F-49)
3
3


3
(F-38)
(F-280)
3
3


3
(F-38)
(F-282)
3
3


3
(F-38)
(F-283)
3
3


3
(F-38)
(F-285)
3
3


3
(F-44)
(F-34)
3
3


3
(F-44)
(F-37)
3
3


3
(F-44)
(F-40)
3
3


3
(F-44)
(F-43)
3
3


3
(F-44)
(F-46)
3
3


3
(F-44)
(F-49)
3
3


3
(F-44)
(F-280)
3
3


3
(F-44)
(F-282)
3
3


3
(F-44)
(F-283)
3
3


3
(F-44)
(F-285)
3
3


3
(F-47)
(F-34)
3
3


3
(F-47)
(F-37)
3
3


3
(F-47)
(F-40)
3
3


3
(F-47)
(F-43)
3
3


3
(F-47)
(F-46)
3
3


3
(F-47)
(F-49)
3
3


3
(F-47)
(F-280)
3
3


3
(F-47)
(F-282)
3
3


3
(F-47)
(F-283)
3
3


3
(F-47)
(F-285)
3
3


3
(F-50)
(F-34)
3
3


3
(F-50)
(F-37)
3
3


3
(F-50)
(F-40)
3
3


3
(F-50)
(F-43)
3
3


3
(F-50)
(F-46)
3
3


3
(F-50)
(F-49)
3
3


3
(F-50)
(F-280)
3
3


3
(F-50)
(F-282)
3
3


3
(F-50)
(F-283)
3
3


3
(F-50)
(F-285)
3
3


3
(F-41)
(F-34)
3
3


3
(F-41)
(F-37)
3
3


3
(F-41)
(F-40)
3
3


3
(F-41)
(F-43)
3
3


3
(F-41)
(F-46)
3
3


3
(F-41)
(F-49)
3
3


3
(F-41)
(F-280)
3
3


3
(F-41)
(F-282)
3
3


3
(F-41)
(F-283)
3
3


3
(F-41)
(F-285)
3
3


3
(F-287)
(F-34)
3
3


3
(F-287)
(F-37)
3
3


3
(F-287)
(F-40)
3
3


3
(F-287)
(F-43)
3
3


3
(F-287)
(F-46)
3
3


3
(F-287)
(F-49)
3
3


3
(F-287)
(F-280)
3
3


3
(F-287)
(F-282)
3
3


3
(F-287)
(F-283)
3
3


3
(F-287)
(F-285)
3
3


3
(F-289)
(F-34)
3
3


3
(F-289)
(F-37)
3
3


3
(F-289)
(F-40)
3
3


3
(F-289)
(F-43)
3
3


3
(F-289)
(F-46)
3
3


3
(F-289)
(F-49)
3
3


3
(F-289)
(F-280)
3
3


3
(F-289)
(F-282)
3
3


3
(F-289)
(F-283)
3
3


3
(F-289)
(F-285)
3
3


3
(F-291)
(F-34)
3
3


3
(F-291)
(F-37)
3
3


3
(F-291)
(F-40)
3
3


3
(F-291)
(F-43)
3
3


3
(F-291)
(F-46)
3
3


3
(F-291)
(F-49)
3
3


3
(F-291)
(F-280)
3
3


3
(F-291)
(F-282)
3
3


3
(F-291)
(F-283)
3
3


3
(F-291)
(F-285)
3
3


3
(F-293)
(F-34)
3
3


3
(F-293)
(F-37)
3
3


3
(F-293)
(F-40)
3
3


3
(F-293)
(F-43)
3
3


3
(F-293)
(F-46)
3
3


3
(F-293)
(F-49)
3
3


3
(F-293)
(F-280)
3
3


3
(F-293)
(F-282)
3
3


3
(F-293)
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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6


4
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6


4
(F-85)
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6


4
(F-85)
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6


4
(F-85)
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6


4
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6


4
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5


4
(F-65)
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5


4
(F-65)
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
(F-80)
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
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4
(F-80)
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4
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4
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4
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3
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3
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3
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3
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3
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3
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3
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3
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3
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3
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3
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3
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3
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3
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5


3
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5


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5


3
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5


3
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5


3
(F-133)
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1
5


3
(F-89)
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1
5


3
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1
5


3
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1
5


3
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1
5


3
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1
5


3
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1
5


3
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1
5


3
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1
5


3
(F-116)
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1
5


3
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5


3
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5


3
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3
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3
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5


3
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3
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3
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5


3
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3
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3
(F-105)
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5


3
(F-116)
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5


3
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3
3


3
(F-97)
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3
3


3
(F-97)
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3
3


3
(F-97)
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3
3


3
(F-97)
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3
3


3
(F-97)
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3
3


3
(F-97)
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3
3


3
(F-111)
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3
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3
(F-111)
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3
3


3
(F-111)
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3
3


3
(F-111)
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3
3


3
(F-111)
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3
3


3
(F-111)
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3
3


3
(F-111)
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3
3


3
(F-133)
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3


3
(F-133)
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3
3


3
(F-133)
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3
3


3
(F-133)
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3
3


3
(F-133)
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3
3


3
(F-133)
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3
3


3
(F-133)
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3
3


3
(F-89)
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3
3


3
(F-89)
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3
3


3
(F-89)
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3
3


3
(F-89)
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3
3


3
(F-89)
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3
3


3
(F-89)
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3
3


3
(F-89)
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3
3


3
(F-105)
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3


3
(F-105)
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3


3
(F-105)
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3


3
(F-105)
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3


3
(F-105)
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3
(F-105)
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3
(F-105)
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3
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3
(F-116)
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3
(F-116)
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3
(F-116)
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3
(F-116)
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3


3
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3


3
(F-116)
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3
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3
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3
(F-133)
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3
(F-89)
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3
(F-105)
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3


3
(F-116)
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3


3
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3


3
(F-111)
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3


3
(F-133)
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3


3
(F-89)
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3


3
(F-105)
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3


3
(F-116)
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3
3


3
(F-97)
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3
3


3
(F-111)
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3


3
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3


3
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3


3
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3
(F-116)
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3
(F-97)
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3
(F-111)
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3


3
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3


3
(F-89)
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3
3


3
(F-105)
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3
3


3
(F-116)
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3
3


4
(F-97)
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1
7


4
(F-97)
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1
7


4
(F-97)
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1
7


4
(F-97)
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1
7


4
(F-97)
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1
7


4
(F-97)
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1
7


4
(F-97)
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1
7


4
(F-111)
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1
7


4
(F-111)
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1
7


4
(F-111)
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1
7


4
(F-111)
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1
7


4
(F-111)
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1
7


4
(F-111)
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1
7


4
(F-111)
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1
7


4
(F-133)
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1
7


4
(F-133)
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1
7


4
(F-133)
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1
7


4
(F-133)
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1
7


4
(F-133)
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1
7


4
(F-133)
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1
7


4
(F-133)
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1
7


4
(F-89)
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1
7


4
(F-89)
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1
7


4
(F-89)
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1
7


4
(F-89)
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1
7


4
(F-89)
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1
7


4
(F-89)
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1
7


4
(F-89)
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1
7


4
(F-105)
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1
7


4
(F-105)
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1
7


4
(F-105)
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1
7


4
(F-105)
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1
7


4
(F-105)
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1
7


4
(F-105)
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1
7


4
(F-105)
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1
7


4
(F-116)
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1
7


4
(F-116)
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1
7


4
(F-116)
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1
7


4
(F-116)
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1
7


4
(F-116)
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1
7


4
(F-116)
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1
7


4
(F-116)
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1
7


4
(F-97)
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1
7


4
(F-111)
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1
7


4
(F-133)
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1
7


4
(F-89)
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1
7


4
(F-105)
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1
7


4
(F-116)
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1
7


4
(F-97)
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1
7


4
(F-111)
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1
7


4
(F-133)
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1
7


4
(F-89)
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1
7


4
(F-105)
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1
7


4
(F-116)
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1
7


4
(F-97)
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1
7


4
(F-111)
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1
7


4
(F-133)
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1
7


4
(F-89)
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1
7


4
(F-105)
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1
7


4
(F-116)
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1
7


4
(F-97)
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1
7


4
(F-111)
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1
7


4
(F-133)
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1
7


4
(F-89)
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1
7


4
(F-105)
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1
7


4
(F-116)
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1
7


4
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4
4


4
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4
4


4
(F-97)
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4
4


4
(F-97)
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4
4


4
(F-97)
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4


4
(F-97)
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4
4


4
(F-97)
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4
4


4
(F-111)
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4
4


4
(F-111)
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4
4


4
(F-111)
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4
4


4
(F-111)
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4
4


4
(F-111)
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4
4


4
(F-111)
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4
4


4
(F-111)
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4
4


4
(F-133)
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4
4


4
(F-133)
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4
4


4
(F-133)
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4
4


4
(F-133)
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4
4


4
(F-133)
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4
4


4
(F-133)
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4
4


4
(F-133)
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4
4


4
(F-89)
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4
4


4
(F-89)
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4
4


4
(F-89)
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4
4


4
(F-89)
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4
4


4
(F-89)
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4
4


4
(F-89)
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4
4


4
(F-89)
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4
4


4
(F-105)
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4
4


4
(F-105)
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4
4


4
(F-105)
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4
4


4
(F-105)
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4
4


4
(F-105)
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4
4


4
(F-105)
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4
4


4
(F-105)
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4
4


4
(F-116)
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4
4


4
(F-116)
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4
4


4
(F-116)
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4
4


4
(F-116)
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4
4


4
(F-116)
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4
4


4
(F-116)
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4
4


4
(F-116)
(F-37)
4
4


4
(F-97)
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4
4


4
(F-111)
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4
4


4
(F-133)
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4
4


4
(F-89)
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4
4


4
(F-105)
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4
4


4
(F-116)
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4
4


4
(F-97)
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4
4


4
(F-111)
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4
4


4
(F-133)
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4
4


4
(F-89)
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4
4


4
(F-105)
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4
4


4
(F-116)
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4
4


4
(F-97)
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4
4


4
(F-111)
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4
4


4
(F-133)
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4
4


4
(F-89)
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4
4


4
(F-105)
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4
4


4
(F-116)
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4
4


4
(F-97)
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4
4


4
(F-111)
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4
4


4
(F-133)
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4
4


4
(F-89)
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4
4


4
(F-105)
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4
4


4
(F-116)
(F-285)
4
4


3
(F-155)
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1
5


3
(F-155)
(F-162)
1
5


3
(F-155)
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1
5


3
(F-155)
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1
5


3
(F-156)
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1
5


3
(F-156)
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1
5


3
(F-156)
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1
5


3
(F-156)
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1
5


3
(F-162)
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1
5


3
(F-162)
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1
5


3
(F-162)
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1
5


3
(F-162)
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1
5


3
(F-220)
(F-155)
1
5


3
(F-220)
(F-156)
1
5


3
(F-220)
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1
5


3
(F-220)
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1
5


3
(F-238)
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1
5


3
(F-238)
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1
5


3
(F-238)
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1
5


3
(F-238)
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1
5


3
(F-155)
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3
3


3
(F-155)
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3
3


3
(F-155)
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3
3


3
(F-155)
(F-238)
3
3


3
(F-156)
(F-155)
3
3


3
(F-156)
(F-162)
3
3


3
(F-156)
(F-220)
3
3


3
(F-156)
(F-238)
3
3


3
(F-162)
(F-155)
3
3


3
(F-162)
(F-156)
3
3


3
(F-162)
(F-220)
3
3


3
(F-162)
(F-238)
3
3


3
(F-220)
(F-155)
3
3


3
(F-220)
(F-156)
3
3


3
(F-220)
(F-162)
3
3


3
(F-220)
(F-238)
3
3


3
(F-238)
(F-155)
3
3


3
(F-238)
(F-156)
3
3


3
(F-238)
(F-162)
3
3


3
(F-238)
(F-220)
3
3


4
(F-155)
(F-156)
1
7


4
(F-155)
(F-162)
1
7


4
(F-155)
(F-220)
1
7


4
(F-155)
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1
7


4
(F-156)
(F-155)
1
7


4
(F-156)
(F-162)
1
7


4
(F-156)
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1
7


4
(F-156)
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1
7


4
(F-162)
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1
7


4
(F-162)
(F-156)
1
7


4
(F-162)
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1
7


4
(F-162)
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1
7


4
(F-220)
(F-155)
1
7


4
(F-220)
(F-156)
1
7


4
(F-220)
(F-162)
1
7


4
(F-220)
(F-238)
1
7


4
(F-238)
(F-155)
1
7


4
(F-238)
(F-156)
1
7


4
(F-238)
(F-162)
1
7


4
(F-238)
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1
7


4
(F-155)
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4
4


4
(F-155)
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4
4


4
(F-155)
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4
4


4
(F-155)
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4
4


4
(F-156)
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4
4


4
(F-156)
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4
4


4
(F-156)
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4
4


4
(F-156)
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4
4


4
(F-162)
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4
4


4
(F-162)
(F-156)
4
4


4
(F-162)
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4
4


4
(F-162)
(F-238)
4
4


4
(F-220)
(F-155)
4
4


4
(F-220)
(F-156)
4
4


4
(F-220)
(F-162)
4
4


4
(F-220)
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4
4


4
(F-238)
(F-155)
4
4


4
(F-238)
(F-156)
4
4


4
(F-238)
(F-162)
4
4


4
(F-238)
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4
4


3
(F-32)
(F-155)
1
5


3
(F-32)
(F-156)
1
5


3
(F-32)
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1
5


3
(F-32)
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1
5


3
(F-32)
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1
5


3
(F-35)
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1
5


3
(F-35)
(F-156)
1
5


3
(F-35)
(F-162)
1
5


3
(F-35)
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1
5


3
(F-35)
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1
5


3
(F-38)
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1
5


3
(F-38)
(F-156)
1
5


3
(F-38)
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1
5


3
(F-38)
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1
5


3
(F-38)
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1
5


3
(F-44)
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1
5


3
(F-44)
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1
5


3
(F-44)
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1
5


3
(F-44)
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1
5


3
(F-44)
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1
5


3
(F-47)
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1
5


3
(F-47)
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1
5


3
(F-47)
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1
5


3
(F-47)
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1
5


3
(F-47)
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1
5


3
(F-50)
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1
5


3
(F-50)
(F-156)
1
5


3
(F-50)
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1
5


3
(F-50)
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1
5


3
(F-50)
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1
5


3
(F-41)
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1
5


3
(F-41)
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1
5


3
(F-41)
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1
5


3
(F-41)
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1
5


3
(F-41)
(F-238)
1
5


3
(F-287)
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1
5


3
(F-287)
(F-156)
1
5


3
(F-287)
(F-162)
1
5


3
(F-287)
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1
5


3
(F-287)
(F-238)
1
5


3
(F-289)
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1
5


3
(F-289)
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1
5


3
(F-289)
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1
5


3
(F-289)
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1
5


3
(F-289)
(F-238)
1
5


3
(F-291)
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1
5


3
(F-291)
(F-156)
1
5


3
(F-291)
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1
5


3
(F-291)
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1
5


3
(F-291)
(F-238)
1
5


3
(F-293)
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1
5


3
(F-293)
(F-156)
1
5


3
(F-293)
(F-162)
1
5


3
(F-293)
(F-220)
1
5


3
(F-293)
(F-238)
1
5


3
(F-32)
(F-155)
3
3


3
(F-32)
(F-156)
3
3


3
(F-32)
(F-162)
3
3


3
(F-32)
(F-220)
3
3


3
(F-32)
(F-238)
3
3


3
(F-35)
(F-155)
3
3


3
(F-35)
(F-156)
3
3


3
(F-35)
(F-162)
3
3


3
(F-35)
(F-220)
3
3


3
(F-35)
(F-238)
3
3


3
(F-38)
(F-155)
3
3


3
(F-38)
(F-156)
3
3


3
(F-38)
(F-162)
3
3


3
(F-38)
(F-220)
3
3


3
(F-38)
(F-238)
3
3


3
(F-44)
(F-155)
3
3


3
(F-44)
(F-156)
3
3


3
(F-44)
(F-162)
3
3


3
(F-44)
(F-220)
3
3


3
(F-44)
(F-238)
3
3


3
(F-47)
(F-155)
3
3


3
(F-47)
(F-156)
3
3


3
(F-47)
(F-162)
3
3


3
(F-47)
(F-220)
3
3


3
(F-47)
(F-238)
3
3


3
(F-50)
(F-155)
3
3


3
(F-50)
(F-156)
3
3


3
(F-50)
(F-162)
3
3


3
(F-50)
(F-220)
3
3


3
(F-50)
(F-238)
3
3


3
(F-41)
(F-155)
3
3


3
(F-41)
(F-156)
3
3


3
(F-41)
(F-162)
3
3


3
(F-41)
(F-220)
3
3


3
(F-41)
(F-238)
3
3


3
(F-287)
(F-155)
3
3


3
(F-287)
(F-156)
3
3


3
(F-287)
(F-162)
3
3


3
(F-287)
(F-220)
3
3


3
(F-287)
(F-238)
3
3


3
(F-289)
(F-155)
3
3


3
(F-289)
(F-156)
3
3


3
(F-289)
(F-162)
3
3


3
(F-289)
(F-220)
3
3


3
(F-289)
(F-238)
3
3


3
(F-291)
(F-155)
3
3


3
(F-291)
(F-156)
3
3


3
(F-291)
(F-162)
3
3


3
(F-291)
(F-220)
3
3


3
(F-291)
(F-238)
3
3


3
(F-293)
(F-155)
3
3


3
(F-293)
(F-156)
3
3


3
(F-293)
(F-162)
3
3


3
(F-293)
(F-220)
3
3


3
(F-293)
(F-238)
3
3


3
(F-35)
(F-189)
1
5


3
(F-35)
(F-272)
1
5


3
(F-35)
(F-273)
1
5


3
(F-35)
(F-275)
1
5


3
(F-35)
(F-190)
1
5


3
(F-38)
(F-189)
1
5


3
(F-38)
(F-272)
1
5


3
(F-38)
(F-273)
1
5


3
(F-38)
(F-275)
1
5


3
(F-38)
(F-190)
1
5


3
(F-47)
(F-189)
1
5


3
(F-47)
(F-272)
1
5


3
(F-47)
(F-273)
1
5


3
(F-47)
(F-275)
1
5


3
(F-47)
(F-190)
1
5


3
(F-50)
(F-189)
1
5


3
(F-50)
(F-272)
1
5


3
(F-50)
(F-273)
1
5


3
(F-50)
(F-275)
1
5


3
(F-50)
(F-190)
1
5


3
(F-287)
(F-189)
1
5


3
(F-287)
(F-272)
1
5


3
(F-287)
(F-273)
1
5


3
(F-287)
(F-275)
1
5


3
(F-287)
(F-190)
1
5


3
(F-291)
(F-189)
1
5


3
(F-291)
(F-272)
1
5


3
(F-291)
(F-273)
1
5


3
(F-291)
(F-275)
1
5


3
(F-291)
(F-190)
1
5


3
(F-37)
(F-189)
1
5


3
(F-37)
(F-272)
1
5


3
(F-37)
(F-273)
1
5


3
(F-37)
(F-275)
1
5


3
(F-37)
(F-190)
1
5


3
(F-43)
(F-189)
1
5


3
(F-43)
(F-272)
1
5


3
(F-43)
(F-273)
1
5


3
(F-43)
(F-275)
1
5


3
(F-43)
(F-190)
1
5


3
(F-49)
(F-189)
1
5


3
(F-49)
(F-272)
1
5


3
(F-49)
(F-273)
1
5


3
(F-49)
(F-275)
1
5


3
(F-49)
(F-190)
1
5


3
(F-282)
(F-189)
1
5


3
(F-282)
(F-272)
1
5


3
(F-282)
(F-273)
1
5


3
(F-282)
(F-275)
1
5


3
(F-35)
(F-189)
3
3


3
(F-35)
(F-272)
3
3


3
(F-35)
(F-273)
3
3


3
(F-35)
(F-275)
3
3


3
(F-35)
(F-190)
3
3


3
(F-38)
(F-189)
3
3


3
(F-38)
(F-272)
3
3


3
(F-38)
(F-273)
3
3


3
(F-38)
(F-275)
3
3


3
(F-38)
(F-190)
3
3


3
(F-47)
(F-189)
3
3


3
(F-47)
(F-272)
3
3


3
(F-47)
(F-273)
3
3


3
(F-47)
(F-275)
3
3


3
(F-47)
(F-190)
3
3


3
(F-50)
(F-189)
3
3


3
(F-50)
(F-272)
3
3


3
(F-50)
(F-273)
3
3


3
(F-50)
(F-275)
3
3


3
(F-50)
(F-190)
3
3


3
(F-287)
(F-189)
3
3


3
(F-287)
(F-272)
3
3


3
(F-287)
(F-273)
3
3


3
(F-287)
(F-275)
3
3


3
(F-287)
(F-190)
3
3


3
(F-291)
(F-189)
3
3


3
(F-291)
(F-272)
3
3


3
(F-291)
(F-273)
3
3


3
(F-291)
(F-275)
3
3


3
(F-291)
(F-190)
3
3


3
(F-37)
(F-189)
3
3


3
(F-37)
(F-272)
3
3


3
(F-37)
(F-273)
3
3


3
(F-37)
(F-275)
3
3


3
(F-37)
(F-190)
3
3


3
(F-43)
(F-189)
3
3


3
(F-43)
(F-272)
3
3


3
(F-43)
(F-273)
3
3


3
(F-43)
(F-275)
3
3


3
(F-43)
(F-190)
3
3


3
(F-49)
(F-189)
3
3


3
(F-49)
(F-272)
3
3


3
(F-49)
(F-273)
3
3


3
(F-49)
(F-275)
3
3


3
(F-49)
(F-190)
3
3


3
(F-282)
(F-189)
3
3


3
(F-282)
(F-272)
3
3


3
(F-282)
(F-273)
3
3


3
(F-282)
(F-275)
3
3


4
(F-35)
(F-189)
1
7


4
(F-35)
(F-272)
1
7


4
(F-35)
(F-273)
1
7


4
(F-35)
(F-275)
1
7


4
(F-35)
(F-190)
1
7


4
(F-38)
(F-189)
1
7


4
(F-38)
(F-272)
1
7


4
(F-38)
(F-273)
1
7


4
(F-38)
(F-275)
1
7


4
(F-38)
(F-190)
1
7


4
(F-47)
(F-189)
1
7


4
(F-47)
(F-272)
1
7


4
(F-47)
(F-273)
1
7


4
(F-47)
(F-275)
1
7


4
(F-47)
(F-190)
1
7


4
(F-50)
(F-189)
1
7


4
(F-50)
(F-272)
1
7


4
(F-50)
(F-273)
1
7


4
(F-50)
(F-275)
1
7


4
(F-50)
(F-190)
1
7


4
(F-287)
(F-189)
1
7


4
(F-287)
(F-272)
1
7


4
(F-287)
(F-273)
1
7


4
(F-287)
(F-275)
1
7


4
(F-287)
(F-190)
1
7


4
(F-291)
(F-189)
1
7


4
(F-291)
(F-272)
1
7


4
(F-291)
(F-273)
1
7


4
(F-291)
(F-275)
1
7


4
(F-291)
(F-190)
1
7


4
(F-37)
(F-189)
1
7


4
(F-37)
(F-272)
1
7


4
(F-37)
(F-273)
1
7


4
(F-37)
(F-275)
1
7


4
(F-37)
(F-190)
1
7


4
(F-43)
(F-189)
1
7


4
(F-43)
(F-272)
1
7


4
(F-43)
(F-273)
1
7


4
(F-43)
(F-275)
1
7


4
(F-43)
(F-190)
1
7


4
(F-49)
(F-189)
1
7


4
(F-49)
(F-272)
1
7


4
(F-49)
(F-273)
1
7


4
(F-49)
(F-275)
1
7


4
(F-49)
(F-190)
1
7


4
(F-282)
(F-189)
1
7


4
(F-282)
(F-272)
1
7


4
(F-282)
(F-273)
1
7


4
(F-282)
(F-275)
1
7


4
(F-35)
(F-189)
4
4


4
(F-35)
(F-272)
4
4


4
(F-35)
(F-273)
4
4


4
(F-35)
(F-275)
4
4


4
(F-35)
(F-190)
4
4


4
(F-38)
(F-189)
4
4


4
(F-38)
(F-272)
4
4


4
(F-38)
(F-273)
4
4


4
(F-38)
(F-275)
4
4


4
(F-38)
(F-190)
4
4


4
(F-47)
(F-189)
4
4


4
(F-47)
(F-272)
4
4


4
(F-47)
(F-273)
4
4


4
(F-47)
(F-275)
4
4


4
(F-47)
(F-190)
4
4


4
(F-50)
(F-189)
4
4


4
(F-50)
(F-272)
4
4


4
(F-50)
(F-273)
4
4


4
(F-50)
(F-275)
4
4


4
(F-50)
(F-190)
4
4


4
(F-287)
(F-189)
4
4


4
(F-287)
(F-272)
4
4


4
(F-287)
(F-273)
4
4


4
(F-287)
(F-275)
4
4


4
(F-287)
(F-190)
4
4


4
(F-291)
(F-189)
4
4


4
(F-291)
(F-272)
4
4


4
(F-291)
(F-273)
4
4


4
(F-291)
(F-275)
4
4


4
(F-291)
(F-190)
4
4


4
(F-37)
(F-189)
4
4


4
(F-37)
(F-272)
4
4


4
(F-37)
(F-273)
4
4


4
(F-37)
(F-275)
4
4


4
(F-37)
(F-190)
4
4


4
(F-43)
(F-189)
4
4


4
(F-43)
(F-272)
4
4


4
(F-43)
(F-273)
4
4


4
(F-43)
(F-275)
4
4


4
(F-43)
(F-190)
4
4


4
(F-49)
(F-189)
4
4


4
(F-49)
(F-272)
4
4


4
(F-49)
(F-273)
4
4


4
(F-49)
(F-275)
4
4


4
(F-49)
(F-190)
4
4


4
(F-282)
(F-189)
4
4


4
(F-282)
(F-272)
4
4


4
(F-282)
(F-273)
4
4


4
(F-282)
(F-275)
4
4


3
(F-35)
(F-52)
1
5


3
(F-35)
(F-61)
1
5


3
(F-35)
(F-12)
1
5


3
(F-35)
(F-27)
1
5


3
(F-35)
(F-194)
1
5


3
(F-35)
(F-281)
1
5


3
(F-35)
(F-284)
1
5


3
(F-38)
(F-52)
1
5


3
(F-38)
(F-61)
1
5


3
(F-38)
(F-12)
1
5


3
(F-38)
(F-27)
1
5


3
(F-38)
(F-194)
1
5


3
(F-38)
(F-281)
1
5


3
(F-38)
(F-284)
1
5


3
(F-47)
(F-52)
1
5


3
(F-47)
(F-61)
1
5


3
(F-47)
(F-12)
1
5


3
(F-47)
(F-27)
1
5


3
(F-47)
(F-194)
1
5


3
(F-47)
(F-281)
1
5


3
(F-47)
(F-284)
1
5


3
(F-50)
(F-52)
1
5


3
(F-50)
(F-61)
1
5


3
(F-50)
(F-12)
1
5


3
(F-50)
(F-27)
1
5


3
(F-50)
(F-194)
1
5


3
(F-50)
(F-281)
1
5


3
(F-50)
(F-284)
1
5


3
(F-287)
(F-52)
1
5


3
(F-287)
(F-61)
1
5


3
(F-287)
(F-12)
1
5


3
(F-287)
(F-27)
1
5


3
(F-287)
(F-194)
1
5


3
(F-287)
(F-281)
1
5


3
(F-287)
(F-284)
1
5


3
(F-291)
(F-52)
1
5


3
(F-291)
(F-61)
1
5


3
(F-291)
(F-12)
1
5


3
(F-291)
(F-27)
1
5


3
(F-291)
(F-194)
1
5


3
(F-291)
(F-281)
1
5


3
(F-291)
(F-284)
1
5


3
(F-37)
(F-52)
1
5


3
(F-37)
(F-61)
1
5


3
(F-37)
(F-12)
1
5


3
(F-37)
(F-27)
1
5


3
(F-37)
(F-194)
1
5


3
(F-37)
(F-281)
1
5


3
(F-37)
(F-284)
1
5


3
(F-43)
(F-52)
1
5


3
(F-43)
(F-61)
1
5


3
(F-43)
(F-12)
1
5


3
(F-43)
(F-27)
1
5


3
(F-43)
(F-194)
1
5


3
(F-43)
(F-281)
1
5


3
(F-43)
(F-284)
1
5


3
(F-49)
(F-52)
1
5


3
(F-49)
(F-61)
1
5


3
(F-49)
(F-12)
1
5


3
(F-49)
(F-27)
1
5


3
(F-49)
(F-194)
1
5


3
(F-49)
(F-281)
1
5


3
(F-49)
(F-284)
1
5


3
(F-282)
(F-52)
1
5


3
(F-282)
(F-61)
1
5


3
(F-282)
(F-12)
1
5


3
(F-282)
(F-27)
1
5


3
(F-282)
(F-194)
1
5


3
(F-282)
(F-281)
1
5


3
(F-282)
(F-284)
1
5


3
(F-285)
(F-52)
1
5


3
(F-285)
(F-61)
1
5


3
(F-285)
(F-12)
1
5


3
(F-285)
(F-27)
1
5


3
(F-285)
(F-194)
1
5


3
(F-285)
(F-281)
1
5


3
(F-285)
(F-284)
1
5


3
(F-35)
(F-52)
3
3


3
(F-35)
(F-61)
3
3


3
(F-35)
(F-12)
3
3


3
(F-35)
(F-27)
3
3


3
(F-35)
(F-194)
3
3


3
(F-35)
(F-281)
3
3


3
(F-35)
(F-284)
3
3


3
(F-38)
(F-52)
3
3


3
(F-38)
(F-61)
3
3


3
(F-38)
(F-12)
3
3


3
(F-38)
(F-27)
3
3


3
(F-38)
(F-194)
3
3


3
(F-38)
(F-281)
3
3


3
(F-38)
(F-284)
3
3


3
(F-47)
(F-52)
3
3


3
(F-47)
(F-61)
3
3


3
(F-47)
(F-12)
3
3


3
(F-47)
(F-27)
3
3


3
(F-47)
(F-194)
3
3


3
(F-47)
(F-281)
3
3


3
(F-47)
(F-284)
3
3


3
(F-50)
(F-52)
3
3


3
(F-50)
(F-61)
3
3


3
(F-50)
(F-12)
3
3


3
(F-50)
(F-27)
3
3


3
(F-50)
(F-194)
3
3


3
(F-50)
(F-281)
3
3


3
(F-50)
(F-284)
3
3


3
(F-287)
(F-52)
3
3


3
(F-287)
(F-61)
3
3


3
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3
3


3
(F-287)
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3
3


3
(F-287)
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3
3


3
(F-287)
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3
3


3
(F-287)
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3
3


3
(F-291)
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3
3


3
(F-291)
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3
3


3
(F-291)
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3
3


3
(F-291)
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3
3


3
(F-291)
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3
3


3
(F-291)
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3
3


3
(F-291)
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3
3


3
(F-37)
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3
3


3
(F-37)
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3
3


3
(F-37)
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3
3


3
(F-37)
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3
3


3
(F-37)
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3
3


3
(F-37)
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3
3


3
(F-37)
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3
3


3
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3
3


3
(F-43)
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3
3


3
(F-43)
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3
3


3
(F-43)
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3
3


3
(F-43)
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3
3


3
(F-43)
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3
3


3
(F-43)
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3
3


3
(F-49)
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3
3


3
(F-49)
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3
3


3
(F-49)
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3
3


3
(F-49)
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3
3


3
(F-49)
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3
3


3
(F-49)
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3
3


3
(F-49)
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3
3


3
(F-282)
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3
3


3
(F-282)
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3
3


3
(F-282)
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3
3


3
(F-282)
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3
3


3
(F-282)
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3
3


3
(F-282)
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3
3


3
(F-282)
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3
3


3
(F-285)
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3
3


3
(F-285)
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3
3


3
(F-285)
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3
3


3
(F-285)
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3
3


3
(F-285)
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3
3


3
(F-285)
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3
3


3
(F-285)
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3
3


4
(F-35)
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1
7


4
(F-35)
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1
7


4
(F-35)
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1
7


4
(F-35)
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1
7


4
(F-35)
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1
7


4
(F-35)
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1
7


4
(F-35)
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1
7


4
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1
7


4
(F-38)
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1
7


4
(F-38)
(F-12)
1
7


4
(F-38)
(F-27)
1
7


4
(F-38)
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1
7


4
(F-38)
(F-281)
1
7


4
(F-38)
(F-284)
1
7


4
(F-47)
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1
7


4
(F-47)
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1
7


4
(F-47)
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1
7


4
(F-47)
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1
7


4
(F-47)
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1
7


4
(F-47)
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1
7


4
(F-47)
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1
7


4
(F-50)
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1
7


4
(F-50)
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1
7


4
(F-50)
(F-12)
1
7


4
(F-50)
(F-27)
1
7


4
(F-50)
(F-194)
1
7


4
(F-50)
(F-281)
1
7


4
(F-50)
(F-284)
1
7


4
(F-287)
(F-52)
1
7


4
(F-287)
(F-61)
1
7


4
(F-287)
(F-12)
1
7


4
(F-287)
(F-27)
1
7


4
(F-287)
(F-194)
1
7


4
(F-287)
(F-281)
1
7


4
(F-287)
(F-284)
1
7


4
(F-291)
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1
7


4
(F-291)
(F-61)
1
7


4
(F-291)
(F-12)
1
7


4
(F-291)
(F-27)
1
7


4
(F-291)
(F-194)
1
7


4
(F-291)
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1
7


4
(F-291)
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1
7


4
(F-37)
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1
7


4
(F-37)
(F-61)
1
7


4
(F-37)
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1
7


4
(F-37)
(F-27)
1
7


4
(F-37)
(F-194)
1
7


4
(F-37)
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1
7


4
(F-37)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-43)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
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1
7


4
(F-49)
(F-27)
1
7


4
(F-49)
(F-194)
1
7


4
(F-49)
(F-281)
1
7


4
(F-49)
(F-284)
1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
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1
7


4
(F-282)
(F-284)
1
7


4
(F-285)
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1
7


4
(F-285)
(F-61)
1
7


4
(F-285)
(F-12)
1
7


4
(F-285)
(F-27)
1
7


4
(F-285)
(F-194)
1
7


4
(F-285)
(F-281)
1
7


4
(F-285)
(F-284)
1
7


4
(F-35)
(F-52)
4
4


4
(F-35)
(F-61)
4
4


4
(F-35)
(F-12)
4
4


4
(F-35)
(F-27)
4
4


4
(F-35)
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4
4


4
(F-35)
(F-281)
4
4


4
(F-35)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
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4
4


4
(F-38)
(F-284)
4
4


4
(F-47)
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4
4


4
(F-47)
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4
4


4
(F-47)
(F-12)
4
4


4
(F-47)
(F-27)
4
4


4
(F-47)
(F-194)
4
4


4
(F-47)
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4
4


4
(F-47)
(F-284)
4
4


4
(F-50)
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4
4


4
(F-50)
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4
4


4
(F-50)
(F-12)
4
4


4
(F-50)
(F-27)
4
4


4
(F-50)
(F-194)
4
4


4
(F-50)
(F-281)
4
4


4
(F-50)
(F-284)
4
4


4
(F-287)
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4
4


4
(F-287)
(F-61)
4
4


4
(F-287)
(F-12)
4
4


4
(F-287)
(F-27)
4
4


4
(F-287)
(F-194)
4
4


4
(F-287)
(F-281)
4
4


4
(F-287)
(F-284)
4
4


4
(F-291)
(F-52)
4
4


4
(F-291)
(F-61)
4
4


4
(F-291)
(F-12)
4
4


4
(F-291)
(F-27)
4
4


4
(F-291)
(F-194)
4
4


4
(F-291)
(F-281)
4
4


4
(F-291)
(F-284)
4
4


4
(F-37)
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4
4


4
(F-37)
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4
4


4
(F-37)
(F-12)
4
4


4
(F-37)
(F-27)
4
4


4
(F-37)
(F-194)
4
4


4
(F-37)
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4
4


4
(F-37)
(F-284)
4
4


4
(F-43)
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4
4


4
(F-43)
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4
4


4
(F-43)
(F-12)
4
4


4
(F-43)
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4
4


4
(F-43)
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4
4


4
(F-43)
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4
4


4
(F-43)
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4
4


4
(F-49)
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4
4


4
(F-49)
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4
4


4
(F-49)
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4
4


4
(F-49)
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4
4


4
(F-49)
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4
4


4
(F-49)
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4
4


4
(F-49)
(F-284)
4
4


4
(F-282)
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4
4


4
(F-282)
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4
4


4
(F-282)
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4
4


4
(F-282)
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4
4


4
(F-282)
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4
4


4
(F-282)
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4
4


4
(F-282)
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4
4


4
(F-285)
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4
4


4
(F-285)
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4
4


4
(F-285)
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4
4


4
(F-285)
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4
4


4
(F-285)
(F-194)
4
4


4
(F-285)
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4
4


4
(F-285)
(F-284)
4
4


3
(F-35)
(F-189)
5
1


3
(F-35)
(F-272)
5
1


3
(F-35)
(F-273)
5
1


3
(F-35)
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5
1


3
(F-35)
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5
1


3
(F-38)
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5
1


3
(F-38)
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5
1


3
(F-38)
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5
1


3
(F-38)
(F-275)
5
1


3
(F-38)
(F-190)
5
1


3
(F-47)
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5
1


3
(F-47)
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5
1


3
(F-47)
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5
1


3
(F-47)
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5
1


3
(F-47)
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5
1


3
(F-50)
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5
1


3
(F-50)
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5
1


3
(F-50)
(F-273)
5
1


3
(F-50)
(F-275)
5
1


3
(F-50)
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5
1


3
(F-287)
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5
1


3
(F-287)
(F-272)
5
1


3
(F-287)
(F-273)
5
1


3
(F-287)
(F-275)
5
1


3
(F-287)
(F-190)
5
1


3
(F-291)
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5
1


3
(F-291)
(F-272)
5
1


3
(F-291)
(F-273)
5
1


3
(F-291)
(F-275)
5
1


3
(F-291)
(F-190)
5
1


3
(F-37)
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5
1


3
(F-37)
(F-272)
5
1


3
(F-37)
(F-273)
5
1


3
(F-37)
(F-275)
5
1


3
(F-37)
(F-190)
5
1


3
(F-43)
(F-189)
5
1


3
(F-43)
(F-272)
5
1


3
(F-43)
(F-273)
5
1


3
(F-43)
(F-275)
5
1


3
(F-43)
(F-190)
5
1


3
(F-49)
(F-189)
5
1


3
(F-49)
(F-272)
5
1


3
(F-49)
(F-273)
5
1


3
(F-49)
(F-275)
5
1


3
(F-49)
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5
1


3
(F-282)
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5
1


3
(F-282)
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5
1


3
(F-282)
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5
1


3
(F-282)
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5
1


3
(F-282)
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5
1


3
(F-285)
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5
1


3
(F-285)
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5
1


3
(F-285)
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5
1


3
(F-285)
(F-275)
5
1


3
(F-285)
(F-190)
5
1


3
(F-35)
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3
3


3
(F-35)
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3
3


3
(F-35)
(F-273)
3
3


3
(F-35)
(F-275)
3
3


3
(F-35)
(F-190)
3
3


3
(F-38)
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3
3


3
(F-38)
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3
3


3
(F-38)
(F-273)
3
3


3
(F-38)
(F-275)
3
3


3
(F-38)
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3
3


3
(F-47)
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3
3


3
(F-47)
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3
3


3
(F-47)
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3
3


3
(F-47)
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3
3


3
(F-47)
(F-190)
3
3


3
(F-50)
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3
3


3
(F-50)
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3
3


3
(F-50)
(F-273)
3
3


3
(F-50)
(F-275)
3
3


3
(F-50)
(F-190)
3
3


3
(F-287)
(F-189)
3
3


3
(F-287)
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3
3


3
(F-287)
(F-273)
3
3


3
(F-287)
(F-275)
3
3


3
(F-287)
(F-190)
3
3


3
(F-291)
(F-189)
3
3


3
(F-291)
(F-272)
3
3


3
(F-291)
(F-273)
3
3


3
(F-291)
(F-275)
3
3


3
(F-291)
(F-190)
3
3


3
(F-37)
(F-189)
3
3


3
(F-37)
(F-272)
3
3


3
(F-37)
(F-273)
3
3


3
(F-37)
(F-275)
3
3


3
(F-37)
(F-190)
3
3


3
(F-43)
(F-189)
3
3


3
(F-43)
(F-272)
3
3


3
(F-43)
(F-273)
3
3


3
(F-43)
(F-275)
3
3


3
(F-43)
(F-190)
3
3


3
(F-49)
(F-189)
3
3


3
(F-49)
(F-272)
3
3


3
(F-49)
(F-273)
3
3


3
(F-49)
(F-275)
3
3


3
(F-49)
(F-190)
3
3


3
(F-282)
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3
3


3
(F-282)
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3
3


3
(F-282)
(F-273)
3
3


3
(F-282)
(F-275)
3
3


3
(F-282)
(F-190)
3
3


3
(F-285)
(F-189)
3
3


3
(F-285)
(F-272)
3
3


3
(F-285)
(F-273)
3
3


3
(F-285)
(F-275)
3
3


3
(F-285)
(F-190)
3
3


4
(F-35)
(F-189)
7
1


4
(F-35)
(F-272)
7
1


4
(F-35)
(F-273)
7
1


4
(F-35)
(F-275)
7
1


4
(F-35)
(F-190)
7
1


4
(F-38)
(F-189)
7
1


4
(F-38)
(F-272)
7
1


4
(F-38)
(F-273)
7
1


4
(F-38)
(F-275)
7
1


4
(F-38)
(F-190)
7
1


4
(F-47)
(F-189)
7
1


4
(F-47)
(F-272)
7
1


4
(F-47)
(F-273)
7
1


4
(F-47)
(F-275)
7
1


4
(F-47)
(F-190)
7
1


4
(F-50)
(F-189)
7
1


4
(F-50)
(F-272)
7
1


4
(F-50)
(F-273)
7
1


4
(F-50)
(F-275)
7
1


4
(F-50)
(F-190)
7
1


4
(F-287)
(F-189)
7
1


4
(F-287)
(F-272)
7
1


4
(F-287)
(F-273)
7
1


4
(F-287)
(F-275)
7
1


4
(F-287)
(F-190)
7
1


4
(F-291)
(F-189)
7
1


4
(F-291)
(F-272)
7
1


4
(F-291)
(F-273)
7
1


4
(F-291)
(F-275)
7
1


4
(F-291)
(F-190)
7
1


4
(F-37)
(F-189)
7
1


4
(F-37)
(F-272)
7
1


4
(F-37)
(F-273)
7
1


4
(F-37)
(F-275)
7
1


4
(F-37)
(F-190)
7
1


4
(F-43)
(F-189)
7
1


4
(F-43)
(F-272)
7
1


4
(F-43)
(F-273)
7
1


4
(F-43)
(F-275)
7
1


4
(F-43)
(F-190)
7
1


4
(F-49)
(F-189)
7
1


4
(F-49)
(F-272)
7
1


4
(F-49)
(F-273)
7
1


4
(F-49)
(F-275)
7
1


4
(F-49)
(F-190)
7
1


4
(F-282)
(F-189)
7
1


4
(F-282)
(F-272)
7
1


4
(F-282)
(F-273)
7
1


4
(F-282)
(F-275)
7
1


4
(F-282)
(F-190)
7
1


4
(F-285)
(F-189)
7
1


4
(F-285)
(F-272)
7
1


4
(F-285)
(F-273)
7
1


4
(F-285)
(F-275)
7
1


4
(F-285)
(F-190)
7
1


4
(F-35)
(F-189)
4
4


4
(F-35)
(F-272)
4
4


4
(F-35)
(F-273)
4
4


4
(F-35)
(F-275)
4
4


4
(F-35)
(F-190)
4
4


4
(F-38)
(F-189)
4
4


4
(F-38)
(F-272)
4
4


4
(F-38)
(F-273)
4
4


4
(F-38)
(F-275)
4
4


4
(F-38)
(F-190)
4
4


4
(F-47)
(F-189)
4
4


4
(F-47)
(F-272)
4
4


4
(F-47)
(F-273)
4
4


4
(F-47)
(F-275)
4
4


4
(F-47)
(F-190)
4
4


4
(F-50)
(F-189)
4
4


4
(F-50)
(F-272)
4
4


4
(F-50)
(F-273)
4
4


4
(F-50)
(F-275)
4
4


4
(F-50)
(F-190)
4
4


4
(F-287)
(F-189)
4
4


4
(F-287)
(F-272)
4
4


4
(F-287)
(F-273)
4
4


4
(F-287)
(F-275)
4
4


4
(F-287)
(F-190)
4
4


4
(F-291)
(F-189)
4
4


4
(F-291)
(F-272)
4
4


4
(F-291)
(F-273)
4
4


4
(F-291)
(F-275)
4
4


4
(F-291)
(F-190)
4
4


4
(F-37)
(F-189)
4
4


4
(F-37)
(F-272)
4
4


4
(F-37)
(F-273)
4
4


4
(F-37)
(F-275)
4
4


4
(F-37)
(F-190)
4
4


4
(F-43)
(F-189)
4
4


4
(F-43)
(F-272)
4
4


4
(F-43)
(F-273)
4
4


4
(F-43)
(F-275)
4
4


4
(F-43)
(F-190)
4
4


4
(F-49)
(F-189)
4
4


4
(F-49)
(F-272)
4
4


4
(F-49)
(F-273)
4
4


4
(F-49)
(F-275)
4
4


4
(F-49)
(F-190)
4
4


4
(F-282)
(F-189)
4
4


4
(F-282)
(F-272)
4
4


4
(F-282)
(F-273)
4
4


4
(F-282)
(F-275)
4
4


4
(F-282)
(F-190)
4
4


4
(F-285)
(F-189)
4
4


4
(F-285)
(F-272)
4
4


4
(F-285)
(F-273)
4
4


4
(F-285)
(F-275)
4
4


4
(F-285)
(F-190)
4
4









In various non-limiting examples described herein, molecular formulae showing fragment(s) or part(s) of a compound may include one or more bonds connected to an asterisks denoted by the symbol *, which are used to indicate the bonds to another atom (not shown) of the compound to which such fragment(s) or part(s) is attached.


In various non-limiting examples of R groups described herein, a backbone having one or more fluorine atoms attached thereto is provided. In some non-limiting examples, one or more such fluorine atoms may be replaced with a chlorine instead and still impart substantially similar properties at least for some applications. In various non-limiting examples, one or more H present in a molecule may optionally be replaced with a corresponding number of D (deuterium).


Various compounds described herein may be synthesised by carrying out various chemical reactions known in the art. Non-limiting example of such reaction includes but is not limited to those in which chlorine-substituted phosphazene is reacted with an alcohol (e.g. HO—R) in the presence of potassium hydroxide at an elevated temperature to form ether bridges between phosphorus and carbon of the R group. Non-limiting example of such reaction scheme used to produce a cyclotriphosphazene-containing compound is schematically illustrated below.




embedded image


In some other non-limiting examples, mixed substituent compounds (e.g. phosphazene derivatives containing two or more different substituents) may be produced by following a similar synthesis procedure as above, except alcohol reactants with the desired substituent groups may be added in the desired proportions and in sequence to result in compounds containing mixed substituents.


Various examples of synthesis methods for phosphazene derivatives are described, by way of non-limiting example, in Allcock, Harry R. Chemistry and applications of polyphosphazenes. Wiley-Interscience, 2003. and Allcock, H. Phosphorus-nitrogen compounds: cyclic, linear, and high polymeric systems. Elsevier, 2012.


It has now been found, somewhat surprisingly, that at least some of the compounds described above exhibit a relatively low critical surface tension. It is postulated that low energy surfaces formed by such compounds may exhibit relatively low initial sticking probabilities, and may thus be particularly suitable for forming the NIC 810 and/or the patterning coating. Without wishing to be bound by any particular theory, it is postulated that, especially for low surface energy surfaces, the critical surface tension may positively correlate with the surface energy. For example, a surface exhibiting a relatively low critical surface tension may also exhibit a relatively low surface energy, and a surface exhibiting a relatively high critical surface tension may also exhibit a relatively high surface energy. According to some models of surface energy, the critical surface tension of a surface may equate to, or substantially equate to, the surface energy of such surface. In reference to Young's equation described above, a lower surface energy may result in a greater contact angle, θ, while also lowering the ysv, thus enhancing the likelihood of such surface having low wettability and low initial sticking probability with respect to the material for forming the conductive coating 830.


In some non-limiting examples, the surface of the NIC 810 and/or patterning coating containing the compounds described herein exhibits a critical surface tension of less than about 20 dynes/cm, less than about 18 dynes/cm, less than about 16 dynes/cm, less than about 15 dynes/cm, less than about 13 dynes/cm, less than about 12 dynes/cm, less than about 11 dynes/cm, less than about 10 dynes/cm, less than about 9 dynes/cm, less than about 8 dynes/cm, or less than about 7 dynes/cm. For example, the critical surface tension values in various non-limiting examples herein may correspond to such values measured at around normal temperature and pressure (NTP), which corresponds to a temperature of 20° C., and an absolute pressure of 1 atm. In some non-limiting examples, the critical surface tension of a surface may be determined according to the Zisman method, as further detailed in W. A. Zisman, Advances in Chemistry 43 (1964), P. 1-51.


It has also now been found, somewhat surprisingly, that NIC 810 formed by a compound exhibiting a relatively low critical surface tension may also exhibit a relatively low refractive index, n.


In some non-limiting examples, the refractive index, n, of the NIC 810 and/or the compound is less than or equal to about 1.7. For example, the refractive index of the NIC 810 may be less than or equal to about 1.6, less than or equal to about 1.5, less than or equal to about 1.4, or less than or equal to about 1.3. In some non-limiting examples, n of the NIC 810 is about 1.2 to about 1.6, about 1.2 to about 1.5, or about 1.25 to about 1.45. As further described in various non-limiting examples above, the NIC 810 exhibiting relatively low refractive index may be particularly desirable for enhancing the optical properties and/or performance of the device, for example, by enhancing the outcoupling of light emitted by the opto-electronic device.


In some non-limiting examples, the NIC 810 and/or the compound exhibits a critical surface tension of less than or equal to about 25 dynes/cm and a refractive index of less than or equal to about 1.45. In some non-limiting examples, the NIC 810 includes a material exhibiting a critical surface tension of less than or equal to about 20 dynes/cm and a refractive index of less than or equal to about 1.4. In some non-limiting examples, the NIC 810 includes a material exhibiting a critical surface tension of less than or equal to about 20 dynes/cm and a refractive index of less than or equal to about 1.35, or less than or equal to about 1.3.


In some non-limiting examples, the NIC 810 and/or the compound is substantially transparent and/or light-transmissive. For example, the NIC 810 and/or the compound may exhibit an extinction coefficient, K, of less than or equal to about 0.1, less than or equal to about 0.08, less than or equal to about 0.05, less than or equal to about 0.03, or less than or equal to about 0.01 in at least a portion of the visible light spectrum. In some non-limiting examples, the NIC 810 does not exhibit light absorption at any wavelength corresponding to the visible portion of the electromagnetic spectrum.


In some non-limiting examples, the NIC 810 and/or the compound does not exhibit photoluminescence at any wavelength corresponding to the visible portion of the electromagnetic spectrum. In some non-limiting examples, the NIC 810 and/or the compound does not exhibit photoluminescence upon being subjected to a radiation having a wavelength of, or a wavelength longer than, about 300 nm, 320 nm, 350 nm, and/or 365 nm. By way of non-limiting example, the NIC 810 and/or the compound may exhibit insignificant and/or no detectable amount of absorption when subjected to such radiation.


In some non-limiting examples, the NIC 810 and/or the compound has an optical gap greater than about 3.4 eV, greater than about 3.5 eV, greater than about 4.1 eV, greater than about 5 eV, or greater than about 6.2 eV.


It will be appreciated that the refractive index, extinction coefficient, and/or absorption values described herein may correspond to such value(s) measured at a wavelength in the visible range of the electromagnetic spectrum. In some non-limiting examples, the refractive index and/or extinction coefficient value may correspond to the value measured at wavelength(s) of about 456 nm which may correspond to the peak emission wavelength of a blue subpixel, about 528 nm which may correspond to the peak emission wavelength of a green subpixel, and/or about 624 nm which may correspond to the peak emission wavelength of a red subpixel. In some non-limiting examples, the refractive index and/or extinction coefficient value described herein may correspond to the value measured at a wavelength of about 589 nm, which approximately corresponds to the Fraunhofer D-line.


As would be appreciated by persons skilled in the art, NIC 810 exhibiting a combination of: (i) a relatively low critical surface tension, for example of less than or equal to about 20 dynes/cm or less than or equal to about 15 dynes/cm; (ii) a relatively low refractive index, for example of less than or equal to about 1.35 or less than or equal to about 1.3; and (iii) a relatively low attenuation coefficient, for example of less than or equal to about 0.05 or less than or equal to about 0.01, may be particularly useful in at least certain applications.


In some non-limiting examples, the NIC 810 and/or the compound thereof has a melting temperature greater than about 90° C., 100° C., 110° C., 120° C., 140° C., 150° C. or about 180° C.


In some non-limiting examples, the NIC 810 and/or the compound thereof has a sublimation temperature of about 100° C. to 300° C., 100° C. to 250° C., 120° C. to 230° C., 130° C. to 220° C., 140° C. to 210° C., 140° C. to 200° C., or 140° C. to 190° C.


The sublimation temperature of a material may be determined using various known methods in the art. By way of non-limiting example, the sublimation temperature may be determined by heating the material under high vacuum in a crucible and determining the required temperature to observe the start of deposition of the material on a quartz crystal microbalance mounted a fixed distance from the source. In some non-limiting examples, the quartz crystal microbalance may be mounted about 65 cm away from the source for the purpose of determining the sublimation temperature. In some non-limiting examples, the sublimation temperature may be determined by heating the material under high vacuum in a crucible and measuring the required temperature to observe a specific deposition rate, by way of non-limiting example of 0.1 A/sec, on a quartz crystal microbalance mounted away from the crucible at a fixed distance, by way of non-limiting example, of about 65 cm from the source. In some non-limiting examples, the sublimation temperature may be determined by heating the material under high vacuum in a crucible and determining the required temperature to reach a threshold vapor pressure of the material. By way of non-limiting example, the threshold vapor pressure may be about 10E-4 Torr or 10E-5 Torr. In some non-limiting examples, the sublimation temperature of a material may be determined by heating the material in an evaporation source under a high vacuum environment of about 10E-4 Torr, and measuring the temperature required to cause the material to evaporate, thus generating a vapor flux sufficient to cause deposition of the material onto a surface positioned about 65 cm away from the evaporation source at a rate of about 0.1 angstrom/sec. The rate of deposition may be measured, by way of non-limiting example, using a quartz crystal microbalance which is positioned about 65 cm away from the evaporation source.


For example, the presence of various elements in thin films may be detected using a variety of techniques, including but not limited to x-ray photoelectron spectroscopy (XPS). Using XPS for example, the core-level binding energy and associated intensities may be determined. The measured binding energy may then be compared against reference binding energies of known elements in various forms and oxidation states to determine the species present in the measured sample. Non-limiting examples of reference core-level binding energy for phosphorus and nitrogen are summarized in the table below.

















Element
Core Level
Binding Energy (eV)









P
2 p
132-135



N
1 s
397-400










While the binding energies are provided as ranges in the above table, it will be appreciated that specific reference binding energy values falling within or outside of these ranges may be found in various sources. Examples of such sources include but are not limited to: BV Crist. (1999). Handbook of The Elements and Native Oxides. XPS International, Inc.; A. V. Naumkin et al., NIST X-ray Photoelectron Spectroscopy Database, NIST Standard Reference Database 20, Version 4.1, NIST; and J. F. Moulder et al. (1992). Handbook of X-ray Photoelectron Spectroscopy. Perkin-Elmer Corporation.


In some non-limiting examples, the contact angle θ of water on the surface of the NIC 810 and/or patterning coating may be greater or equal to about 90 degrees, greater or equal to about 100 degrees, greater or equal to about 110 degrees, greater or equal to about 120 degrees, greater or equal to about 130 degrees, greater or equal to about 140 degrees, or greater or equal to about 150 degrees. Various methods may be used to measure such contact angle θ, including but not limited to the static or dynamic sessile drop method and the pendant drop method.


Various methods and theories for determining the surface energy of a solid are known. For example, the surface energy may be calculated or derived based on a series of contact angle measurements, in which various liquids are brought into contact with a surface of a solid to measure the contact angle between the liquid-vapor interface and the surface. In some non-limiting examples, the surface energy of a solid surface is equal to the surface tension of a liquid with the highest surface tension which completely wets the surface. For example, a Zisman plot may be used to determine the highest surface tension value which would result in complete wetting (i.e. contact angle of 0°) of the surface.


In some non-limiting examples, the molecular weight of the compound is less than or equal to about 5000 g/mol. For example, the molecular weight of the compound may be less than or equal to about 4500 g/mol, less than or equal to about 4000 g/mol, less than or equal to about 3800 g/mol, or less than or equal to about 3500 g/mol.


In some non-limiting examples, the molecular weight of the compound is greater than or equal to about 1500 g/mol. For example, the molecular weight of the compound may be greater than or equal to about 1700, greater than or equal to about 2000, greater than or equal to about 2200, or greater than or equal to about 2500.


In some non-limiting examples, the percentage of the molar weight of the compound which is attributed to the presence of the fluorine atoms is about 40%-90%, 45%-85%, 50%-80%, 55%-75%, or 60%-75%. In some non-limiting examples, fluorine atoms constitute a majority of the molar weight of the compound.


For example, the ratio of the number of fluorine atoms to the number of carbon atoms in a given molecular structure of a compound may be referred to as “fluorine: carbon” ratio or as “F:C”. In some non-limiting examples, the compound has an F:C of between about 9:4 and about 1:1.


In some non-limiting examples, an opto-electronic device is provided. The opto-electronic device includes a compound containing a terminal moiety. The terminal moiety includes a CF2H unit.


It has now been found that compounds in which the terminal moiety includes a CF2H unit may be particularly useful in at least some applications. In particular, while a compound having a CF3 unit as a terminal moiety may be adapted to form a surface with a lower surface energy in comparison to a compound of a similar molecular structure except in that it contains a CF2H unit as a terminal moiety, the compound having the CF2H unit as the terminal moiety may exhibit other properties which may be desirable, including but not limited to a higher melting temperature and a higher sublimation temperature. Accordingly, in at least some applications, it may be desirable to provide a compound having a terminal moiety which includes a CF2H unit.


In some non-limiting examples, the compound includes a chain moiety, and the terminal moiety containing the CF2H unit is arranged at a terminal portion of the chain moiety. Various non-limiting examples of the chain moiety described herein may be applicable with respect to the compound containing the CF2H unit as a terminal moiety. In some non-limiting examples, the compound is a phosphazene derivative. In some non-limiting examples, the compound includes a core moiety which includes a phosphazene unit. In some further non-limiting examples, the chain moiety is attached to the phosphorous (P) atom of the phosphazene unit.


Deposited Layer

In some non-limiting examples, in the second portion 102 of the lateral aspect 710 of the device 100, a deposited layer 130 comprising a deposited material 331 may be disposed as a closed coating 140 on an exposed layer surface 11 of an underlying layer, including without limitation, the substrate 10.


In some non-limiting examples, the deposited layer 130 may comprise a deposited material 331 (FIG. 3).


In some non-limiting examples, the deposited material 331 may comprise an element selected from: potassium (K), sodium (Na), lithium (Li), barium (Ba), cesium (Cs), Yb, Ag, gold (Au), copper (Cu), aluminum (Al), Mg, Zn, Cd, tin (Sn), or yttrium (Y). In some non-limiting examples, the element may comprise K, Na, Li, Ba, Cs, Yb, Ag, Au, Cu, Al, and/or Mg. In some non-limiting examples, the element may comprise Cu, Ag, and/or Au. In some non-limiting examples, the element may be Cu. In some non-limiting examples, the element may be Al. In some non-limiting examples, the element may comprise Mg, Zn, Cd, or Yb. In some non-limiting examples, the element may comprise Mg, Ag, Al, Yb, or Li. In some non-limiting examples, the element may comprise Mg, Ag, or Yb. In some non-limiting examples, the element may comprise Mg, or Ag. In some non-limiting examples, the element may be Ag.


In some non-limiting examples, the deposited material 331 may comprise a pure metal. In some non-limiting examples, the deposited material 331 may be a pure metal. In some non-limiting examples, the deposited material 331 may be pure Ag or substantially pure Ag. In some non-limiting examples, the substantially pure Ag may have a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, or 99.9995%. In some non-limiting examples, the deposited material 331 may be pure Mg or substantially pure Mg. In some non-limiting examples, the substantially pure Mg may have a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, or 99.9995%.


In some non-limiting examples, the deposited material 331 may comprise an alloy. In some non-limiting examples, the alloy may be an Ag-containing alloy, an Mg-containing alloy, or an AgMg-containing alloy. In some non-limiting examples, the AgMg-containing alloy may have an alloy composition that may range from about 1:10 (Ag:Mg) to about 10:1 by volume.


In some non-limiting examples, the deposited material 331 may comprise other metals in place of, and/or in combination with, Ag. In some non-limiting examples, the deposited material 331 may comprise an alloy of Ag with at least one other metal. In some non-limiting examples, the deposited material 331 may comprise an alloy of Ag with Mg, and/or Yb. In some non-limiting examples, such alloy may be a binary alloy having a composition between about 5-95 vol. % Ag, with the remainder being the other metal. In some non-limiting examples, the deposited material 331 may comprise Ag and Mg. In some non-limiting examples, the deposited material 331 may comprise an Ag:Mg alloy having a composition between about 1:10-10:1 by volume. In some non-limiting examples, the deposited material 331 may comprise Ag and Yb. In some non-limiting examples, the deposited material 331 may comprise a Yb:Ag alloy having a composition between about 1:20-10:1 by volume. In some non-limiting examples, the deposited material 331 may comprise Mg and Yb. In some non-limiting examples, the deposited material 331 may comprise an Mg:Yb alloy. In some non-limiting examples, the deposited material 331 may comprise Ag, Mg, and Yb. In some non-limiting examples, the deposited layer 130 may comprise an Ag:Mg:Yb alloy.


In some non-limiting examples, the deposited layer 130 may comprise at least one additional element. In some non-limiting examples, such additional element may be a non-metallic element. In some non-limiting examples, the non-metallic element may be O, S, N, or C. It will be appreciated by those having ordinary skill in the relevant art that, in some non-limiting examples, such additional element(s) may be incorporated into the deposited layer 130 as a contaminant, due to the presence of such additional element(s) in the source material, equipment used for deposition, and/or the vacuum chamber environment. In some non-limiting examples, the concentration of such additional element(s) may be limited to be below a threshold concentration. In some non-limiting examples, such additional element(s) may form a compound together with other element(s) of the deposited layer 130. In some non-limiting examples, a concentration of the non-metallic element in the deposited material 331 may be less than about: 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, or 0.0000001%. In some non-limiting examples, the deposited layer 130 may have a composition in which a combined amount of O and C therein is less than about: 10%, 5%, 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, or 0.0000001%.


It has now been found, somewhat surprisingly, that reducing a concentration of certain non-metallic elements in the deposited layer 130, particularly in cases wherein the deposited layer 130 is substantially comprised of metal(s), and/or metal alloy(s), may facilitate selective deposition of the deposited layer 130. Without wishing to be bound by any particular theory, it may be postulated that certain non-metallic elements, such as, by way of non-limiting examples, O, or C, when present in the vapor flux 332 (FIG. 3) of the deposited layer 130, and/or in the deposition chamber, and/or environment, may be deposited onto the surface of the NIC 110 to act as nucleation sites for the metallic element(s) of the deposited layer 130. It may be postulated that reducing a concentration of such non-metallic elements that could act as nucleation sites may facilitate reducing an amount of deposited material 331 deposited on the exposed layer surface 11 of the NIC 110.


In some non-limiting examples, the deposited material 331 in the first portion 101 and the underlying layer thereunder may comprise a common metal.


In some non-limiting examples, the deposited layer 130 may comprise a plurality of layers of the deposited material 331. In some non-limiting examples, the deposited material 331 of a first one of the plurality of layers may be different from the deposited material 331 of a second one of the plurality of layers. In some non-limiting examples, the deposited layer 130 may comprise a multilayer coating. In some non-limiting examples, such multilayer coating may be Yb/Ag, Yb/Mg, Yb/Mg:Ag, Yb/Yb:Ag, Yb/Ag/Mg, or Yb/Mg/Ag.


In some non-limiting examples, the deposited material 331 may comprise a metal having a bond dissociation energy, of no more than about: 300 kJ/mol, 200 kJ/mol, 165 kJ/mol, 150 kJ/mol, 100 kJ/mol, 50 kJ/mol, or 20 kJ/mol.


In some non-limiting examples, the deposited material 331 may comprise a metal having an electronegativity that is no more than about: 1.4, 1.3, or 1.2.


In some non-limiting examples, a sheet resistance R2 of the deposited layer 130 may generally correspond to a sheet resistance of the deposited layer 130, measured or determined in isolation from other components, layers, and/or parts of the device 100. In some non-limiting examples, the deposited layer 130 may be formed as a thin film.


Accordingly, in some non-limiting examples, the characteristic sheet resistance R for the deposited layer 130 may be determined, and/or calculated based on the composition, thickness, and/or morphology of such thin film. In some non-limiting examples, the sheet resistance R2 may be no more than about: 10Ω/□, 5Ω/□, 1Ω/□, 0.5Ω/□, 0.2Ω/□, or 0.1 Ω/□.


In some non-limiting examples, the deposited layer 130 may be disposed in a pattern that may be defined by at least one region therein that is substantially devoid of a closed coating 140 of the deposited layer 130. In some non-limiting examples, the at least one region may separate the deposited layer 130 into a plurality of discrete fragments thereof. In some non-limiting examples, each discrete fragment of the deposited layer 130 may be a distinct second portion 102. In some non-limiting examples, the plurality of discrete fragments of the deposited layer 130 may be physically spaced apart from one another in the lateral aspect thereof. In some non-limiting examples, at least two of such plurality of discrete fragments of the deposited layer 130 may be electrically coupled. In some non-limiting examples, at least two of such plurality of discrete fragments of the deposited layer 130 may be each electrically coupled with a common conductive layer or coating, including without limitation, the underlying surface, to allow the flow of electrical current between them. In some non-limiting examples, at least two of such plurality of discrete fragments of the deposited layer 130 may be electrically insulated from one another.


Selective Deposition Using Patterning Coatings


FIG. 2 is an example schematic diagram illustrating a non-limiting example of an evaporative deposition process, shown generally at 200, in a chamber 20, for selectively depositing a patterning coating 210, including without limitation, an NIC 110 or an NPC 520, onto a first portion 101 of an exposed layer surface 11 of the underlying layer.


In the process 200, a quantity of a patterning material 211, including without limitation, an NIC material, and/or an NPC material is heated under vacuum, to evaporate, and/or sublime the patterning material 211. In some non-limiting examples, the patterning material 211 may comprise entirely, and/or substantially, a material used to form the patterning coating 210. In some non-limiting examples, such material may comprise an organic material.


An evaporated flux 212 of the patterning material 211 may flow through the chamber 20, including in a direction indicated by arrow 21, toward the exposed layer surface 11. When the evaporated flux 212 is incident on the exposed layer surface 11, the patterning coating 210 may be formed thereon.


In some non-limiting examples, as shown in the figure for the process 200, the patterning coating 210 may be selectively deposited only onto a portion, in the example illustrated, the first portion 101, of the exposed layer surface 11, by the interposition, between the evaporated flux 212 and the exposed layer surface 11, of a shadow mask 215, which in some non-limiting examples, may be a fine metal mask (FMM). In some non-limiting examples, such a shadow mask 215 may, in some non-limiting examples, be used to form relatively small features, with a feature size on the order of tens of microns or smaller.


The shadow mask 215 may have at least one aperture 216 extending therethrough such that a part of the evaporated flux 212 passes through the aperture 216 and may be incident on the exposed layer surface 11 to form the patterning coating 210. Where the evaporated flux 212 does not pass through the aperture 216 but is incident on the surface 217 of the shadow mask 215, it is precluded from being disposed on the exposed layer surface 11 to form the patterning coating 210. In some non-limiting examples, the shadow mask 215 may be configured such that the evaporated flux 212 that passes through the aperture 216 may be incident on the first portion 101 but not the second portion 102. The second portion 102 of the exposed layer surface 11 may thus be substantially devoid of the patterning coating 210. In some non-limiting examples (not shown), the patterning material 211 that is incident on the shadow mask 215 may be deposited on the surface 217 thereof.


Accordingly, a patterned surface may be produced upon completion of the deposition of the patterning coating 210.


In some non-limiting examples, the patterning coating 210 employed in FIG. 2 may be an NIC 110.



FIG. 3 is an example schematic diagram illustrating a non-limiting example of a result of an evaporative process, shown generally at 300a, in a chamber 20, for selectively depositing a closed coating 140 of a deposited layer 130 onto the second portion 102 of an exposed layer surface 11 of the underlying layer that is substantially devoid of the NIC 110 that was selectively deposited onto the first portion 101, including without limitation, by the evaporative process 200 of FIG. 2.


In some non-limiting examples, the deposited layer 130 may be comprised of a deposited material 331, in some non-limiting examples, comprising at least one metal. It will be appreciated by those having ordinary skill in the relevant art that typically, the vaporization temperature of an organic material is low relative to the vaporization temperature of metals, such as may be employed as a deposited material 331.


Thus, in some non-limiting examples, there may be fewer constraints in employing a shadow mask 215 to selectively deposit a patterning coating 210, such as an NIC 110 in a pattern, relative to directly patterning the deposited layer 130 using such shadow mask 215.


Once the NIC 110 has been deposited on the first portion 101 of the exposed layer surface 11 of the underlying layer, a closed coating 140 of the deposited material 331 may be deposited, on the second portion 102 of the exposed layer surface 11 that is substantially devoid of the NIC 110, as the deposited layer 130.


In the process 300a, a quantity of the deposited material 331 may be heated under vacuum, to evaporate, and/or sublime the deposited material 331. In some non-limiting examples, the deposited material 331 may comprise entirely, and/or substantially, a material used to form the deposited layer 130.


An evaporated flux 332 of the deposited material 331 may be directed inside the chamber 20, including in a direction indicated by arrow 31, toward the exposed layer surface 11 of the first portion 101 and of the second portion 102. When the evaporated flux 332 is incident on the second portion 102 of the exposed layer surface 11, a closed coating 140 of the deposited material 331 may be formed thereon as the deposited layer 130.


In some non-limiting examples, deposition of the deposited material 331 may be performed using an open mask and/or mask-free deposition process.


It will be appreciated by those having ordinary skill in the relevant art that, contrary to that of a shadow mask 215, the feature size of an open mask may be generally comparable to the size of a device 100 being manufactured.


It will be appreciated by those having ordinary skill in the relevant art that, in some non-limiting examples, the use of an open mask may be omitted. In some non-limiting examples, an open mask deposition process described herein may alternatively be conducted without the use of an open mask, such that an entire target exposed layer surface 11 may be exposed.


Indeed, as shown in FIG. 3, the evaporated flux 332 may be incident both on an exposed layer surface 11 of the NIC 110 across the first portion 101 as well as the exposed layer surface 11 of the underlying layer across the second portion 102 that is substantially devoid of the NIC 110.


Since the exposed layer surface 11 of the NIC 110 in the first portion 101 may exhibit a relatively low initial sticking probability S0 against the deposition of the deposited layer 130 relative to the exposed layer surface 11 of the underlying layer in the second portion 102, the deposited layer 130 may be selectively deposited substantially only on the exposed layer surface 11, of the underlying layer in the second portion 102, that is substantially devoid of the NIC 110. By contrast, the evaporated flux 332 incident on the exposed layer surface 11 of the NIC 110 across the first portion 101 may tend to not be deposited (as shown 533), and the exposed layer surface 11 of the NIC 110 across the first portion 101 may be substantially devoid of a closed coating 140 of the deposited layer 130.


In some non-limiting examples, an initial deposition rate, of the evaporated flux 332 on the exposed layer surface 11 of the underlying layer in the second portion 102, may exceed about: 200 times, 550 times, 900 times, 1,000 times, 1,500 times, 1,900 times, or 2,000 times an initial deposition rate of the evaporated flux 332 on the exposed layer surface 11 of the NIC 110 in the first portion 101.


Thus, the combination of the selective deposition of an NIC 110 as the patterning coating 210 in FIG. 2 using a shadow mask 215 and the open mask and/or mask-free deposition of the deposited material 331 may result in a version 100a of the device 100, shown in FIG. 1.


After selective deposition of the NIC 110 across the first portion 101, a closed coating 140 of the deposited material 331 may be deposited over the device 100a as the deposited layer 130, in some non-limiting examples, using an open mask and/or a mask-free deposition process, but may remain substantially only within the second portion 102, which is substantially devoid of the NIC 110.


The NIC 110 may provide, within the first portion 101, an exposed layer surface 11 with a relatively low initial sticking probability S0, against the deposition of the deposited material 331, and that is substantially less than the initial sticking probability S0, against the deposition of the deposited material 331, of the exposed layer surface 11 of the underlying material of the device 100a within the second portion 102.


Thus, the first portion 101 may be substantially devoid of a closed coating 140 of the deposited material 331.


While the present disclosure contemplates the patterned deposition of the selective coating 210 by an evaporative deposition process, involving a shadow mask 215, those having ordinary skill in the relevant art will appreciate that, in some non-limiting examples, this may be achieved by any suitable deposition process, including without limitation, a micro-contact printing process.


While the present disclosure contemplates the patterning coating 210 being an NIC 110, those having ordinary skill in the relevant art will appreciate that, in some non-limiting examples, the patterning coating 210 may be an NPC 520. In such examples, the portion (such as, without limitation, the first portion 301) in which the NPC 520 has been deposited may, in some non-limiting examples, have a closed coating 140 of the deposited material 331, while the other portion (such as, without limitation, the second portion 302) may be substantially devoid of a closed coating 140 of the deposited material 331.


In some non-limiting examples, a thickness of the patterning coating 210, including without limitation, an NIC 110, and of the deposited layer 130 deposited thereafter may be varied according to a variety of parameters, including without limitation, a given application and given performance characteristics. In some non-limiting examples, the thickness of the NIC 110 may be comparable to, and/or substantially less than a thickness of the deposited layer 130 deposited thereafter. Use of a relatively thin NIC 110 to achieve selective patterning of a deposited layer 130 may be suitable to provide flexible devices 100. In some non-limiting examples, a relatively thin NIC 110 may provide a relatively planar surface on which a barrier coating 1050 (FIG. 10C) or other thin film encapsulation (TFE) layer, may be deposited. In some non-limiting examples, providing such a relatively planar surface for application of such barrier coating 1050 may increase adhesion thereof to such surface.


Edge Effects

NIC Transition Region


Turning to FIG. 4A, there may be shown a version 400a of the device 100 of FIG. 1 that may show in exaggerated form, an interface between the NIC 110 in the first portion 101 and the deposited layer 130 in the second portion 102. FIG. 4B may show the device 400a in plan.


As may be better seen in FIG. 4B, in some non-limiting examples, the NIC 110 in the first portion 101 may be surrounded on all sides by the deposited layer 130 in the second portion 102, such that the first portion 101 may have a boundary that is defined by the further extent or edge 415 of the NIC 110 in the lateral aspect along each lateral axis. In some non-limiting examples, the NIC edge 415 in the lateral aspect may be defined by a perimeter of the first portion 101 in such aspect.


In some non-limiting examples, the first portion 101 may comprise at least one NIC transition region 101t, in the lateral aspect, in which a thickness of the NIC 110 may transition from a maximum thickness to a reduced thickness. The extent of the first portion 101 that does not exhibit such a transition is identified as an NIC non-transition part loin of the first portion 101. In some non-limiting examples, the NIC 110 may form a substantially closed coating 140 in the NIC non-transition part 101n of the first portion 101.


In some non-limiting examples, the NIC transition region 101t may extend, in the lateral aspect, between the NIC non-transition part 101n of the first portion 101 and the NIC edge 415.


In some non-limiting examples, in plan, the NIC transition region 101t may surround, and/or extend along a perimeter of, the non-transition part 101n of the first portion 101.


In some non-limiting examples, along at least one lateral axis, the NIC non-transition part 101n may occupy the entirety of the first portion 101, such that there is no NIC transition region 101t between it and a second portion 102.


As illustrated in FIG. 4A, in some non-limiting examples, the NIC 110 may have an average film thickness d2 in the NIC non-transition part 101n of the first portion 101 that may be in a range of between about: 1-100 nm, 2-50 nm, 3-30 nm, 4-20 nm, 5-15 nm, 5-10 nm, or 1-10 nm. In some non-limiting examples, the average film thickness d2 of the NIC 110 in the NIC non-transition part loin of the first portion 101 may be substantially the same, or constant, thereacross. In some non-limiting examples, a thickness of the NIC 110 may remain, within the NIC non-transition part 101n, within about: 95%, or 90% of the average film thickness d2 of the NIC 110.


In some non-limiting examples, the average film thickness d2 may be less than about: 80 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 15 nm, or 10 nm. In some non-limiting examples, the average film thickness d2 of the NIC 110 may exceed about: 3 nm, 5 nm, or 8 nm.


In some non-limiting examples, the average film thickness d2 of the NIC 110 in the NIC non-transition part 101n of the first portion 101 may be less than about 10 nm. Without wishing to be bound by any particular theory, it has been found, somewhat surprisingly, that an average film thickness d2 of the NIC 110 that exceeds zero and is no more than about 10 nm may, at least in some non-limiting examples, provide certain advantages for achieving, by way of non-limiting example, enhanced patterning contrast of the deposited layer 130, relative to an NIC 110 having an average film thickness d2 in the NIC non-transition part 101n of the first portion 101 in excess of 10 nm.


In some non-limiting examples, the NIC 110 may have an NIC thickness that decreases from a maximum to a minimum within the NIC transition region 101t. In some non-limiting examples, the maximum may be at, and/or proximate to, the boundary between the NIC transition region 101t and the NIC non-transition part 101n of the first portion 101. In some non-limiting examples, the minimum may be at, and/or proximate to, the NIC edge 415. In some non-limiting examples, the maximum may be the average film thickness d2 in the NIC non-transition part 101n of the first portion 101. In some non-limiting examples, the maximum may be no more than about: 95% or 90% of the average film thickness d2 in the NIC non-transition part 101n of the first portion 101. In some non-limiting examples, the minimum may be in a range of between about 0-0.1 nm.


In some non-limiting examples, a profile of the NIC thickness in the NIC transition region 101t may be sloped, and/or follow a gradient. In some non-limiting examples, such profile may be tapered. In some non-limiting examples, the taper may follow a linear, non-linear, parabolic, and/or exponential decaying profile.


In some non-limiting examples, the NIC 110 may completely cover the underlying surface in the NIC transition region 101t. In some non-limiting examples, at least a part of the underlying surface may be left uncovered by the NIC 110 in the NIC transition region 101t. In some non-limiting examples, the NIC 110 may comprise a substantially closed coating 140 in at least a part of the NIC transition region 101t.


In some non-limiting examples, the NIC 110 may comprise a discontinuous layer 440 (FIG. 4C) in at least a part of the NIC transition region 101t.


In some non-limiting examples, at least a part of the NIC 110 in the first portion 101 may be substantially devoid of a closed coating 140 of the deposited layer 130. In some non-limiting examples, at least a part of the exposed layer surface 11 of the first portion 101 may be substantially devoid of the deposited layer 130 or of the deposited material 331.


In some non-limiting examples, along at least one lateral axis, including without limitation, the X-axis, the NIC non-transition region 101n may have a width of and the NIC transition part 101t may have a width of w2. In some non-limiting examples, the NIC non-transition region 101n may have a cross-sectional area that, in some non-limiting examples, may be approximated by multiplying the average film thickness d2 by the width w1. In some non-limiting examples, the NIC transition part 101t may have a cross-sectional area that, in some non-limiting examples, may be approximated by multiplying an average film thickness across the NIC transition part 101t by the width WI.


In some non-limiting examples, w1 may exceed w2. In some non-limiting examples, a quotient of w1/w2 may be at least about: 5, 10, 20, 50, 100, 500, 1,000, 1,500, 5,000, 10,000, 50,000, or 100,000.


In some non-limiting examples, at least one of w1 and w2 may exceed the average film thickness d1 of the underlying layer.


In some non-limiting examples, at least one of w1 and w2 may exceed d2. In some non-limiting examples, both w1 and w2 may exceed d2. In some non-limiting examples, w1 and w2 both may exceed d1, and d1 may exceed d2.


Deposited Layer Transition Region


As may be better seen in FIG. 4B, in some non-limiting examples, the NIC 110 in the first portion 101 may be surrounded by the deposited layer 130 in the second portion 102 such that the second portion 102 has a boundary that is defined by the further extent or edge 435 of the deposited layer 130 in the lateral aspect along each lateral axis. In some non-limiting examples, the deposited layer edge 435 in the lateral aspect may be defined by a perimeter of the second portion 102 in such aspect.


In some non-limiting examples, the second portion 102 may comprise at least one deposited layer transition region 102t, in the lateral aspect, in which a thickness of the deposited layer 130 may transition from a maximum thickness to a reduced thickness. The extent of the second portion 102 that does not exhibit such a transition is identified as a deposited layer non-transition part 102n of the second portion 102. In some non-limiting examples, the deposited layer 130 may form a substantially closed coating 140 in the deposited layer non-transition part 102n of the second portion 102.


In some non-limiting examples, in plan, the deposited layer transition region 102t may extend, in the lateral aspect, between the deposited layer non-transition part 102n of the second portion 102 and the deposited layer edge 435.


In some non-limiting examples, in plan, the deposited layer transition region 102t may surround, and/or extend along a perimeter of, the deposited layer non-transition part 102n of the second portion 102.


In some non-limiting examples, along at least one lateral axis, the deposited layer non-transition part 102n of the second portion 102 may occupy the entirety of the second portion 102, such that there is no deposited layer transition region 102t between it and the first portion 101.


As illustrated in FIG. 4A, in some non-limiting examples, the deposited layer 130 may have an average film thickness d3 in the deposited layer non-transition part 102n of the second portion 102 that may be in a range of between about: 1-500 nm, 5-200 nm, 5-40 nm, 10-30 nm, or 10-100 nm. In some non-limiting examples, d3 may exceed about: 10 nm, 50 nm, or 100 nm. In some non-limiting examples, the average film thickness d3 of the deposited layer 130 in the deposited layer non-transition part 102t of the second portion 102 may be substantially the same, or constant, thereacross.


In some non-limiting examples, d3 may exceed the average film thickness d1 of the underlying layer.


In some non-limiting examples, a quotient d3/d1 may be at least about: 1.5, 2, 5, 10, 20, 50, or 100. In some non-limiting examples, the quotient d3/d/may be in a range of between about: 0.1-10, or 0.2-40.


In some non-limiting examples, d3 may exceed an average film thickness d2 of the NIC 110.


In some non-limiting examples, a quotient d3/d2 may be at least about: 1.5, 2, 5, 10, 20, 50, or 100. In some non-limiting examples, the quotient d3/d2 may be in a range of between about: 0.2-10, or 0.5-40.


In some non-limiting examples, d3 may exceed d2 and d2 may exceed d1. In some other non-limiting examples, d3 may exceed d1 and d1 may exceed d2.


In some non-limiting examples, a quotient d2/d1 may be between about: 0.2-3, or 0.1-5.


In some non-limiting examples, along at least one lateral axis, including without limitation, the X-axis, the deposited layer non-transition region 102n of the second portion 102 may have a width of w3. In some non-limiting examples, the deposited layer non-transition region 102n of the second portion 102 may have a cross-sectional area a3 that, in some non-limiting examples, may be approximated by multiplying the average film thickness d3 by the width w3.


In some non-limiting examples, w3 may exceed the width w1 of the NIC non-transition region 101n. In some non-limiting examples, w1 may exceed w3.


In some non-limiting examples, a quotient w1/w3 may be in a range of between about: 0.1-10, 0.2-5, 0.3-3, or 0.4-2. In some non-limiting examples, a quotient w3/w1 may be at least: 1, 2, 3, or 4.


In some non-limiting examples, w3 may exceed the average film thickness d3 of the deposited layer 130.


In some non-limiting examples, a quotient w3/d3 may be at least about: 10, 50, 100, or 500. In some non-limiting examples, the quotient w3/d3 may be less than about 100,000.


In some non-limiting examples, the deposited layer 130 may have a thickness that decreases from a maximum to a minimum within the deposited layer transition region 102t. In some non-limiting examples, the maximum may be at, and/or proximate to, the boundary between the deposited layer transition region 102t and the non-transition part 102n of the second portion 102. In some non-limiting examples, the minimum may be at, and/or proximate to, the deposited layer edge 435. In some non-limiting examples, the maximum may be the average film thickness d3 in the deposited layer non-transition part 102n of the second portion 102. In some non-limiting examples, the minimum may be in a range of between about 0-0.1 nm. In some non-limiting examples, the minimum may be the average film thickness d3 in the deposited layer non-transition part 102n of the second portion 102.


In some non-limiting examples, a profile of the thickness in the deposited layer transition region 102t may be sloped, and/or follow a gradient. In some non-limiting examples, such profile may be tapered. In some non-limiting examples, the taper may follow a linear, non-linear, parabolic, and/or exponential decaying profile.


In some non-limiting examples, as shown by way of non-limiting example in the example version 400e in FIG. 4E of the device 100, the deposited layer 130 may completely cover the underlying surface in the deposited layer transition region 102t. In some non-limiting examples, at least a part of the underlying surface may be uncovered by the deposited layer 130 in the deposited layer transition region 102t. In some non-limiting examples, the deposited layer 130 may comprise a substantially closed coating 140 in at least a part of the deposited layer transition region 102t.


In some non-limiting examples, the deposited layer 130 may comprise a discontinuous layer 440 in at least a part of the deposited layer transition region 102t.


Those having ordinary skill in the relevant art will appreciate that, while not explicitly illustrated, the NIC material may also be present to some extent at an interface between the deposited layer 130 and an underlying layer. Such material may be deposited as a result of a shadowing effect, in which a deposited pattern is not identical to a pattern of a mask and may, in some non-limiting examples, result in some evaporated NIC material being deposited on a masked part of a target exposed layer surface 11. By way of non-limiting examples, such material may form as particle structures 441 (FIG. 4C) and/or as a thin film having a thickness that may be substantially less than an average thickness of the NIC 110.


Overlap


In some non-limiting examples, the deposited layer edge 435 may be spaced apart, in the lateral aspect from the NIC non-transition part 101n of the first portion 101, such that there is no overlap between the first portion 101 and the second portion 102 in the lateral aspect.


In some non-limiting examples, at least a part of the first portion 101 and at least a part of the second portion 102 may overlap in the lateral aspect. Such overlap may be identified by an overlap portion 403, such as may be shown by way of non-limiting example in FIG. 4A, in which at least a part of the second portion 102 overlaps at least a part of the first portion 101.


In some non-limiting examples, as shown by way of non-limiting example in FIG. 4F, at least a part of the deposited layer transition region 102t may be disposed over at least a part of the NIC transition region 101t. In some non-limiting examples, at least a part of the NIC transition region 101t may be substantially devoid of the deposited layer 130, and/or the deposited material 331. In some non-limiting examples, the deposited material 331 may form a discontinuous layer 440 on an exposed layer surface 11 of at least a part of the NIC transition region 101t.


In some non-limiting examples, as shown by way of non-limiting example in FIG. 4G, at least a part of the deposited layer transition region 102t may be disposed over at least a part of the NIC non-transition part 101n of the first portion 101.


Although not shown, those having ordinary skill in the relevant art will appreciate that, in some non-limiting examples, the overlap portion 903 may reflect a scenario in which at least a part of the first portion 101 overlaps at least a part of the second portion 102.


Thus, in some non-limiting examples, at least a part of the NIC transition region 101t may be disposed over at least a part of the deposited layer transition region 102t. In some non-limiting examples, at least a part of the deposited layer transition region 102t may be substantially devoid of the NIC 110, and/or the NIC material. In some non-limiting examples, the NIC material may form a discontinuous layer 440 on an exposed layer surface of at least a part of the deposited layer transition region 102t.


In some non-limiting examples, at least a part of the NIC transition region 101t may be disposed over at least a part of the non-transition part 102n of the second portion 102.


In some non-limiting examples, the NIC edge 415 may be spaced apart, in the lateral aspect, from the non-transition part 102n of the second portion 102.


In some non-limiting examples, the deposited layer 130 may be formed as a single monolithic coating across both the non-transition part 102n and the deposited layer transition region 102t of the second portion 102.


Edge Effects of NICs and Deposited Layers



FIGS. 5A-5I describe various potential behaviours of NICs 110 at a deposition interface with deposited layers 130.


Turning to FIG. 5A, there may be shown a first example of a part of an example version 500 of the device 100 at an NIC deposition boundary. The device 500 may comprise a substrate 10 having an exposed layer surface 11. An NIC 110 may be deposited over a first portion 101 of the exposed layer surface 11. A deposited layer 130 may be deposited over a second portion 102 of the exposed layer surface 11. As shown, by way of non-limiting example, the first portion 101 and the second portion 102 may be distinct and non-overlapping parts of the exposed layer surface 11.


The deposited layer 130 may comprise a first part 130a and a remaining part 130b. As shown, by way of non-limiting example, the first part 130a of the deposited layer 130 may substantially cover the second portion 102 and the second part 130b of the deposited layer 130 may partially project over, and/or overlap a first part of the NIC 110.


In some non-limiting examples, since the NIC 110 may be formed such that its exposed layer surface 11 exhibits a relatively low initial sticking probability S0 against deposition of the deposited material 331, there may be a gap 529 formed between the projecting, and/or overlapping second part 130b of the deposited layer 130 and the exposed layer surface 11 of the NIC 110. As a result, the second part 130b may not be in physical contact with the NIC 110 but may be spaced-apart therefrom by the gap 529 in a cross-sectional aspect. In some non-limiting examples, the first part 130a of the deposited layer 130 may be in physical contact with the NIC 110 at an interface, and/or boundary between the first portion 101 and the second portion 102.


In some non-limiting examples, the projecting, and/or overlapping second part 130b of the deposited layer 130 may extend laterally over the NIC 110 by a comparable extent as a thickness t1 of the deposited layer 130. By way of non-limiting example, as shown, a width w2 of the second part 130b may be comparable to the thickness t1. In some non-limiting examples, a ratio off w2:t1 may be in a range of between about: 1:1-1:3, 1:1-1:1.5, or 1:1-1:2. While the thickness t1 may in some non-limiting examples be relatively uniform across the deposited layer 130, in some non-limiting examples, the extent to which the second part 130b may project, and/or overlap with the NIC 110 (namely w2) may vary to some extent across different parts of the exposed layer surface 11.


Turning now to FIG. 5B, the deposited layer 130 may be shown to include a third part 130c disposed between the second part 130b and the NIC 110. As shown, the second part 130b of the deposited layer 130 may extend laterally over and is spaced apart from the third part 130c of the deposited layer 130 and the third part 130c may be in physical contact with the exposed layer surface 11 of the NIC 110. A thickness t3 of the third part 130c of the deposited layer 130 may be less and in some non-limiting examples, substantially less than the thickness t1 of the first part 130a thereof. In some non-limiting examples, a width w3 of the third part 130c may exceed the width w2 of the second part 130b. In some non-limiting examples, the third part 130c may extend laterally to overlap the NIC 110 to a greater extent than the second part 130b. In some non-limiting examples, a ratio of w3:t1 may be in a range of about: 1:2-3:1, or 1:1.2-2.5:1. While the thickness t1 may in some non-limiting examples be relatively uniform across the deposited layer 130, in some non-limiting examples, the extent to which the third part 130c may project, and/or overlap with the NIC 110 (namely w3) may vary to some extent across different parts of the exposed layer surface 11.


The thickness t3 of the third part 130c may not exceed about 5% of the thickness t3 of the first part 130a. By way of non-limiting example, t3 may be less than about: 4%, 3%, 2%, 1%, or 0.5% of t1. Instead of, and/or in addition to, the third part 130c being formed as a thin film, as shown, the material of the deposited layer 130 may form as particle structures 441 on a part of the NIC 110. By way of non-limiting example, such particle structures 441 may comprise features that are physically separated from one another, such that they do not form a continuous layer.


Turning now to FIG. 5C, an NPC 520 may be disposed between the substrate 10 and the deposited layer 130. The NPC 520 may be disposed between the first part 130a of the deposited layer 130 and the second portion 102 of the substrate 10. The NPC 520 is illustrated as being disposed on the second portion 102 and not on the first portion 101, where the NIC 110 has been deposited. The NPC 520 may be formed such that, at an interface, and/or boundary between the NPC 520 and the deposited layer 130, a surface of the NPC 520 may exhibit a relatively high initial sticking probability S0 against deposition of the deposited material 331. As such, the presence of the NPC 520 may promote the formation, and/or growth of the deposited layer 130 during deposition.


Turning now to FIG. 5D, the NPC 520 may be disposed on both the first portion 101 and the second portion 102 of the substrate 10 and the NIC 110 may cover a part of the NPC 520 disposed on the first portion 101. Another part of the NPC 520 may be substantially devoid of the NIC 110 and the deposited layer 130 covers such part of the NPC 520.


Turning now to FIG. 5E, the deposited layer 130 may be shown to partially overlap a part of the NIC 110 in a third portion 503 of the substrate 10. In some non-limiting examples, in addition to the first part 130a and the second part 130b, the deposited layer 130 may further include a fourth part 130d. As shown, the fourth part 130d of the deposited layer 130 may be disposed between the first part 130a and the second part 130b of the deposited layer 130 and the fourth part 130d may be in physical contact with the exposed layer surface 11 of the NIC 110. In some non-limiting examples, the overlap in the third portion 503 may be formed as a result of lateral growth of the deposited layer 130 during an open mask and/or mask-free deposition process. In some non-limiting examples, while the exposed layer surface 11 of the NIC 110 may exhibit a relatively low initial sticking probability S0 against deposition of the deposited material 331, and thus the probability of the material nucleating the exposed layer surface 11 may be low, as the deposited layer 130 grows in thickness, the deposited layer 130 may also grow laterally and may cover a subset of the NIC 110 as shown.


Turning now to FIG. 5F the first portion 101 of the substrate 10 may be coated with the NIC 110 and the second portion 102 adjacent thereto may be coated with the deposited layer 130. In some non-limiting examples, it has been observed that conducting an open mask and/or mask-free deposition of the deposited layer 130 may result in the deposited layer 130 exhibiting a tapered cross-sectional profile at, and/or near an interface between the deposited layer 130 and the NIC 110.


In some non-limiting examples, a thickness of the deposited layer 130 at, and/or near the interface may be less than an average thickness of the deposited layer 130. While such tapered profile may be shown as being curved, and/or arched, in some non-limiting examples, the profile may, in some non-limiting examples be substantially linear, and/or non-linear. By way of non-limiting example, the thickness of the deposited layer 130 may decrease, without limitation, in a substantially linear, exponential, and/or quadratic fashion in a region proximal to the interface.


It has been observed that a contact angle θc of the deposited layer 130 at, and/or near the interface between the deposited layer 130 and the NIC 110 may vary, depending on properties of the NIC 110, such as a relative initial sticking probability S0. It may be further postulated that the contact angle θc of the nuclei may, in some non-limiting examples, dictate the thin film contact angle of the deposited layer 130 formed by deposition. Referring to FIG. 5F by way of non-limiting example, the contact angle θc may be determined by measuring a slope of a tangent of the deposited layer 130 at or near the interface between the deposited layer 130 and the NIC 110. In some non-limiting examples, where the cross-sectional taper profile of the deposited layer 130 may be substantially linear, the contact angle θc may be determined by measuring the slope of the deposited layer 130 at, and/or near the interface. As will be appreciated by those having ordinary skill in the relevant art, the contact angle θc may be generally measured relative to an angle of the underlying surface. In the present disclosure, for purposes of simplicity of illustration, the NIC 110 and the deposited layer 130 may be shown deposited on a planar surface. However, those having ordinary skill in the relevant art will appreciate that the NIC 110 and the deposited layer 130 may be deposited on non-planar surfaces.


In some non-limiting examples, the contact angle θc of the deposited layer 130 may exceed about 90°. Referring now to FIG. 5G, by way of non-limiting example, the deposited layer 130 may be shown as including a part extending past the interface between the NIC 110 and the deposited layer 130 and may be spaced apart from the NIC by a gap 529. In such non-limiting scenario, the contact angle θc may, in some non-limiting examples, exceed 90°.


In some non-limiting examples, it may be advantageous to form a deposited layer 130 exhibiting a relatively high contact angle θc. By way of non-limiting example, the contact angle θc may exceed about: 10°, 15°, 20°, 25°, 30°, 35°, 40°, 50°, 70°, 75°, or 80°. By way of non-limiting example, a deposited layer 130 having a relatively high contact angle θc may allow for creation of finely patterned features while maintaining a relatively high aspect ratio. By way of non-limiting example, there may be an aim to form a deposited layer 130 exhibiting a contact angle θc greater than about 90°. By way of non-limiting example, the contact angle θc may exceed about: 90°, 95°, 100°, 105°, 110° 120°, 130°, 135°, 140°, 145°, 150°, or 170°.


Turning now to FIGS. 5H-5I, the deposited layer 130 may partially overlap a part of the NIC 110 in the third portion 503 of the substrate 10, which may be disposed between the first portion 101 and the second portion 102 thereof. As shown, the subset of the deposited layer 130 partially overlapping a subset of the NIC 110 may be in physical contact with the exposed layer surface 11 thereof. In some non-limiting examples, the overlap in the third region 3130 may be formed because of lateral growth of the deposited layer 130 during an open mask and/or mask-free deposition process. In some non-limiting examples, while the exposed layer surface 11 of the NIC 110 may exhibit a relatively low affinity or initial sticking probability S0 against deposition of the deposited material 331 and thus the probability of the material nucleating on the exposed layer surface 11 is low, as the deposited layer 130 grows in thickness, the deposited layer 130 may also grow laterally and may cover a subset of the NIC 110.


In the case of FIGS. 5H-5I, the contact angle θc of the deposited layer 130 may be measured at an edge thereof near the interface between it and the NIC 110, as shown. In FIG. 51, the contact angle θc may exceed about 90°, which may in some non-limiting examples result in a subset of the deposited layer 130 being spaced apart from the NIC 110 by the gap 529.


Particle

In some non-limiting examples, such as may be shown in FIG. 4C, there may be at least one particle, including without limitation, a nanoparticle (NP), an island, a plate, a disconnected cluster, and/or a network (collectively particle structure 441) disposed on an exposed layer surface 11 of an underlying layer. In some non-limiting examples, the underlying layer may be the NIC 110 in the first portion 101. In some non-limiting examples, the at least one particle structure 441 may be disposed on an exposed layer surface 11 of the NIC 110. In some non-limiting examples, there may be a plurality of such particle structures 441.


In some non-limiting examples, the at least one particle structure 441 may comprise a particle structure material. In some non-limiting examples, the particle structure material may be the same as the deposited material 331 in the deposited layer.


In some non-limiting examples, the particle structure material in the discontinuous layer 440 in the first portion 101, the deposited material 331 in the deposited layer 130, and/or a material of which the underlying layer thereunder may be comprised, may comprise a common metal.


In some non-limiting examples, the particle structure material may comprise an element selected from K, Na, Li, Ba, Cs, Yb, Ag, Au, Cu, Al, Mg, Zn, Cd, Sn, or Y. In some non-limiting examples, the element may comprise K, Na, Li, Ba, Cs, Yb, Ag, Au, Cu, Al, or Mg. In some non-limiting examples, the element may comprise Cu, Ag, or Au. In some non-limiting examples, the element may be Cu. In some non-limiting examples, the element may be Al. In some non-limiting examples, the element may comprise Mg, Zn, Cd, or Yb. In some non-limiting examples, the element may comprise Mg, Ag, Al, Yb, or Li. In some non-limiting examples, the element may comprise Mg, Ag, or Yb. In some non-limiting examples, the element may comprise Mg, or Ag. In some non-limiting examples, the element may be Ag.


In some non-limiting examples, the particle structure material may comprise a pure metal. In some non-limiting examples, the at least one particle structure 441 may be a pure metal. In some non-limiting examples, the at least one particle structure 441 may be pure Ag or substantially pure Ag. In some non-limiting examples, the substantially pure Ag may have a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, or 99.9995%. In some non-limiting examples, the at least one particle structure 441 may be pure Mg or substantially pure Mg. In some non-limiting examples, the substantially pure Mg may have a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, or 99.9995%.


In some non-limiting examples, the at least one particle structure 441 may comprise an alloy. In some non-limiting examples, the alloy may be an Ag-containing alloy, and Mg-containing alloy, or an AgMg-containing alloy. In some non-limiting examples, the AgMg-containing alloy may have an alloy composition that may range from about 1:10 (Ag:Mg) to about 10:1 by volume.


In some non-limiting examples, the particle structure material may comprise other metals in place of, or in combination with Ag. In some non-limiting examples, the particle structure material may comprise an alloy of Ag with at least one other metal. In some non-limiting examples, the particle structure material may comprise an alloy of Ag with Mg, or Yb. In some non-limiting examples, such alloy may be a binary alloy having a composition of between about: 5-95 vol. % Ag, with the remainder being the other metal. In some non-limiting examples, the particle structure material may comprise Ag and Mg. In some non-limiting examples, the particle structure material may comprise an Ag:Mg alloy having a composition of between about 1:10-10:1 by volume. In some non-limiting examples, the particle structure material may comprise Ag and Yb. In some non-limiting examples, the particle structure material may comprise a Yb:Ag alloy having a composition of between about 1:20-10:1 by volume. In some non-limiting examples, the particle structure material may comprise Mg and Yb. In some non-limiting examples, the particle structure material may comprise an Mg:Yb alloy. In some non-limiting examples, the particle structure material may comprise an Ag:Mg:Yb alloy.


In some non-limiting examples, the at least one particle structure 441 may comprise at least one additional element. In some non-limiting examples, such additional element may be a non-metallic element. In some non-limiting examples, the non-metallic material may be O, S, N, or C. It will be appreciated by those having ordinary skill in the relevant art that, in some non-limiting examples, such additional element(s) may be incorporated into the at least one particle structure 441 as a contaminant, due to the presence of such additional element(s) in the source material, equipment used for deposition, and/or the vacuum chamber environment. In some non-limiting examples, such additional element(s) may form a compound together with other element(s) of the at least one particle structure 441. In some non-limiting examples, a concentration of the non-metallic element in the deposited material 331 may be less than about: 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, or 0.0000001%. In some non-limiting examples, the at least one particle structure 441 may have a composition in which a combined amount of O and C therein is less than about: 10%, 5%, 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, or 0.0000001%.


In some non-limiting examples, the presence of the at least one particle structure 441, including without limitation, NPs, including without limitation, in a discontinuous layer 440, on an exposed layer surface 11 of the NIC 110 may affect some optical properties of the device 400.


In some non-limiting examples, such plurality of particle structures 441 may form a discontinuous layer 440.


Without wishing to be limited to any particular theory, it may be postulated that, while the formation of a closed coating 140 of the deposited material 331 may be substantially inhibited on the NIC 110, in some non-limiting examples, when the NIC 110 is exposed to deposition of the deposited material 331 thereon, some vapor monomers 332 of the deposited material 331 may ultimately form at least one particle structure 441 of the deposited material 331 thereon.


In some non-limiting examples, at least some of the particle structures 441 may be disconnected from one another. In other words, in some non-limiting examples, the discontinuous layer 440 may comprise features, including particle structures 441, that may be physically separated from one another, such that the particle structures 441 do not form a closed coating 140. Accordingly, such discontinuous layer 440 may, in some non-limiting examples, thus comprise a thin disperse layer of deposited material 331 formed as particle structures 441, inserted at, and substantially across the lateral extent of, an interface between the NIC 110 and at least one covering layer in the device 100.


In some non-limiting examples, at least one of the particle structures 441 of deposited material 331 may be in physical contact with an exposed layer surface 11 of the NIC 110. In some non-limiting examples, substantially all of the particle structures 441 of deposited material 331 may be in physical contact with the exposed layer surface 11 of the NIC 110.


Without wishing to be bound by any particular theory, it has been found, somewhat surprisingly, that the presence of such a thin, disperse discontinuous layer 440 of deposited material 331, including without limitation, at least one particle structure 441, including without limitation, metal particle structures 441, on an exposed layer surface 11 of the NIC 110, may exhibit at least one varied characteristics and concomitantly, varied behaviours, including without limitation, optical effects and properties of the device 100, as discussed herein. In some non-limiting examples, such effects and properties may be controlled to some extent by judicious selection of the characteristic size S1, size distribution, shape, surface coverage C1, configuration, deposited density, and/or dispersity D of the particle structures 441 on the NIC 110.


In some non-limiting examples, the formation of at least one of the characteristic size S1, size distribution, shape, surface coverage C1, configuration, deposited density, and/or dispersity D of such discontinuous layer 440 may be controlled, in some non-limiting examples, by judicious selection of at least one of: at least one characteristic of the NIC material, the average film thickness d2 of the NIC 110, the introduction of heterogeneities in the NIC 110, and/or a deposition environment, including without limitation, a temperature, pressure, duration, deposition rate, and/or deposition process for the NIC 110.


In some non-limiting examples, the formation of at least one of the characteristic size S1, size distribution, shape, surface coverage_C1, configuration, deposited density, and/or dispersity D of such discontinuous layer 440 may be controlled, in some non-limiting examples, by judicious selection of at least one of: at least one characteristic of the particle structure material (which may be the deposited material 331), an extent to which the NIC 110 may be exposed to deposition of the particle structure material (which, in some non-limiting examples may be specified in terms of a thickness of the corresponding discontinuous layer 440), and/or a deposition environment, including without limitation, a temperature, pressure, duration, deposition rate, and/or method of deposition for the particle structure material.


In some non-limiting examples, the discontinuous layer 440 may be deposited in a pattern across the lateral extent of the NIC 110.


In some non-limiting examples, the discontinuous layer 440 may be disposed in a pattern that may be defined by at least one region therein that is substantially devoid of of the at least one particle structure 441.


In some non-limiting examples, the characteristics of such discontinuous layer 440 may be assessed, in some non-limiting examples, somewhat arbitrarily, according to at least one of several criteria, including without limitation, a characteristic size S1, size distribution, shape, configuration, surface coverage C1, deposited distribution, dispersity D, and/or a presence, and/or extent of aggregation instances of the particle structure material, formed on a portion of the exposed layer surface 11 of the underlying layer.


In some non-limiting examples, an assessment of the discontinuous layer 440 according to such at least one criterion, may be performed on, including without limitation, by measuring, and/or calculating, at least one attribute of the discontinuous layer 440, using a variety of imaging techniques, including without limitation, transmission electron microscopy (TEM), atomic force microscopy (AFM), and/or scanning electron microscopy (SEM).


Those having ordinary skill in the relevant art will appreciate that such an assessment of the discontinuous layer 440 may depend, to a greater, and/or lesser extent, by the extent, of the exposed layer surface 11 under consideration, which in some non-limiting examples may comprise an area, and/or region thereof. In some non-limiting examples, the discontinuous layer 440 may be assessed across the entire extent, in a first lateral aspect, and/or a second lateral aspect that is substantially transverse thereto, of the exposed layer surface 11. In some non-limiting examples, the discontinuous layer 440 may be assessed across an extent that comprises at least one observation window applied against (a part of) the discontinuous layer 440.


In some non-limiting examples, the at least one observation window may be located at a perimeter, interior location, and/or grid coordinate of the lateral aspect of the exposed layer surface 11. In some non-limiting examples, a plurality of the at least one observation windows may be used in assessing the discontinuous layer 440.


In some non-limiting examples, the observation window may correspond to a field of view of an imaging technique applied to assess the discontinuous layer 440, including without limitation, TEM, AFM, and/or SEM. In some non-limiting examples, the observation window may correspond to a given level of magnification, including without limitation: 2.00 μm, 1.00 μm, 500 nm, or 200 nm.


In some non-limiting examples, the assessment of the discontinuous layer 440, including without limitation, at least one observation window used, of the exposed layer surface 11 thereof, may involve calculating, and/or measuring, by any number of mechanisms, including without limitation, manual counting, and/or known estimation techniques, which may, in some non-limiting examples, may comprise curve, polygon, and/or shape fitting techniques.


In some non-limiting examples, the assessment of the discontinuous layer 440, including without limitation, at least one observation window used, of the exposed layer surface 11 thereof, may involve calculating, and/or measuring an average, median, mode, maximum, minimum, and/or other probabilistic, statistical, and/or data manipulation of a value of the calculation, and/or measurement.


In some non-limiting examples, one of the at least one criterion by which such discontinuous layer 440 may be assessed, may be a surface coverage C1 of the deposited material 331 on such (part of the) discontinuous layer 440. In some non-limiting examples, the surface coverage C1 may be represented by a (non-zero) percentage coverage by such deposited material 331 of such (part of the) discontinuous layer 440. In some non-limiting examples, the percentage coverage may be compared to a maximum threshold percentage coverage.


In some non-limiting examples, a (part of a) discontinuous layer 440 having surface coverage C1 that may be substantially no more than the maximum threshold percentage coverage, may result in a manifestation of different optical characteristics that may be imparted by such part of the discontinuous layer 440, to photons passing therethrough, whether transmitted entirely through the device 100, and/or emitted thereby, relative to photons passing through a part of the discontinuous layer 440 having a surface coverage C1 that substantially exceeds the maximum threshold percentage coverage.


In some non-limiting examples, one measure of a surface coverage C1 of an amount of an electrically conductive material on a surface may be a (light) transmittance, since in some non-limiting examples, electrically conductive materials, including without limitation, metals, including without limitation: Ag, Mg, or Yb, attenuate, and/or absorb photons.


Those having ordinary skill in the relevant art will appreciate that in some non-limiting examples, surface coverage C1 may be understood to encompass one or both of particle size, and deposited density. Thus, in some non-limiting examples, plurality of these three criteria may be positively correlated. Indeed, in some non-limiting examples, a criterion of low surface coverage C1 may comprise some combination of a criterion of low deposited density with a criterion of low particle size.


In some non-limiting examples, one of the at least one criterion by which such discontinuous layer 440 may be assessed, may be a characteristic size S1 of the constituent particle structures 441.


In some non-limiting examples, the at least one particle structure 441 of the discontinuous layer 440, may have a characteristic size S1 that is no more than a maximum threshold size. Non-limiting examples of the characteristic size S1 may include height, width, length, and/or diameter.


In some non-limiting examples, substantially all of the particle structures 441, of the discontinuous layer 440 may have a characteristic size S1 that lies within a specified range.


In some non-limiting examples, such characteristic size S1 may be characterized by a characteristic length, which in some non-limiting examples, may be considered a maximum value of the characteristic size S1. In some non-limiting examples, such maximum value may extend along a major axis of the particle structure 441. In some non-limiting examples, the major axis may be understood to be a first dimension extending in a plane defined by the plurality of lateral axes. In some non-limiting examples, a characteristic width may be identified as the value of the characteristic size S1 of the particle structure 441 that may extend along a minor axis of the particle structure 441. In some non-limiting examples, the minor axis may be understood to be a second dimension extending in the same plane but substantially transverse to the major axis.


In some non-limiting examples, the characteristic length of the at least one particle structure 441, along the first dimension, may be less than the maximum threshold size.


In some non-limiting examples, the characteristic width of the at least one particle structure 441, along the second dimension, may be less than the maximum threshold size.


In some non-limiting examples, the size of the constituent particle structures 441, in the (part of the) discontinuous layer 440, may be assessed by calculating, and/or measuring a characteristic size S1 of such at least one particle structure 441, including without limitation, a mass, volume, length of a diameter, perimeter, major, and/or minor axis thereof.


In some non-limiting examples, one of the at least one criterion by which such discontinuous layer 440 may be assessed, may be a deposited density thereof.


In some non-limiting examples, the characteristic size S1 of the particle structure 441 may be compared to a maximum threshold size.


In some non-limiting examples, the deposited density of the particle structures 441 may be compared to a maximum threshold deposited density.


In some non-limiting examples, at least one of such criteria may be quantified by a numerical metric. In some non-limiting examples, such a metric may be a calculation of a dispersity D that describes the distribution of particle (area) sizes in a deposited layer 320 of particles 60, in which:







D
=



S
s

_



S
n

_






where
:







S
s

_

=








i
=
1

n



S
i
2









i
=
1

n



S
i




,



S
n

_

=








i
=
1

n



S
i


n


,





n is the number of particles 60 in a sample area,


Si is the (area) size of the ith particle 60,



S
n is the number average of the particle (area) sizes and



S
s is the (area) size average of the particle (area) sizes.


Those having ordinary skill in the relevant art will appreciate that the dispersity D is roughly analogous to a polydispersity index (PDI) and that these averages are roughly analogous to the concepts of number average molecular weight and weight average molecular weight familiar in organic chemistry, but applied to an (area) size, as opposed to a molecular weight of a sample particle 60.


Those having ordinary skill in the relevant will also appreciate that while the concept of dispersity D may, in some non-limiting examples, be considered a three-dimensional volumetric concept, in some non-limiting examples, the dispersity D may be considered to be a two-dimensional concept. As such, the concept of dispersity D may be used in connection with viewing and analyzing two-dimensional images of the deposited layer 320, such as may be obtained by using a variety of imaging techniques, including without limitation, TEM, AFM and/or SEM. It is in such a two-dimensional context, that the equations set out above are defined.


In some non-limiting examples, the dispersity D and/or the number average of the particle (area) size and the (area) size average of the particle (area) size may involve a calculation of at least one of the number average of the particle diameters and the (area) size average of the particle diameters:









d
n

_

=

2





s
n

_

π




,



d
s

_

=

2





s
s

_

π








In some non-limiting examples, the deposited material, including without limitation as particle structures 61, of the at least one deposited layer 320, may be deposited by a mask-free and/or open mask deposition process.


In some non-limiting examples, the particle structures 441 may have a substantially round shape. In some non-limiting examples, the particle structures 441 may have a substantially spherical shape.


For purposes of simplification, in some non-limiting examples, it may be assumed that the longitudinal extent of each particle structure 441 may be substantially the same (and, in any event, may not be directly measured from a plan view SEM image) so that the (area) size of the particle structure 441 may be represented as a two-dimensional area coverage along the pair of lateral axes. In the present disclosure, a reference to an (area) size may be understood to refer to such two-dimensional concept, and to be differentiated from a size (without the prefix “area”) that may be understood to refer to a one-dimensional concept, such as a linear dimension.


Indeed, in some early investigations, it appears that, in some non-limiting examples, the longitudinal extent, along the longitudinal axis, of such particle structures 441, may tend to be small relative to the lateral extent (along at least one of the lateral axes), such that the volumetric contribution of the longitudinal extent thereof may be much less than that of such lateral extent. In some non-limiting examples, this may be expressed by an aspect ratio (a ratio of a longitudinal extent to a lateral extent) that may be less than 1. In some non-limiting examples, such aspect ratio may be about: 1:10, 1:20, 1:50, 1:75, or 1:300.


In this regard, the assumption set out above (that the longitudinal extent is substantially the same and can be ignored) to represent the particle structure 441 as a two-dimensional area coverage may be appropriate.


Those having ordinary skill in the relevant art will appreciate, having regard to the non-determinative nature of the deposition process, especially in the presence of defects, and/or anomalies on the exposed layer surface 11 of the underlying material, including without limitation, heterogeneities, including without limitation, a step edge, a chemical impurity, a bonding site, a kink, and/or a contaminant thereon, and consequently the formation of particle structures 441 thereon, the non-uniform nature of coalescence thereof as the deposition process continues, and in view of the uncertainty in the size, and/or position of observation windows, as well as the intricacies and variability inherent in the calculation, and/or measurement of their characteristic size S1, spacing, deposited density, degree of aggregation, and the like, there may be considerable variability in terms of the features, and/or topology within observation windows.


In the present disclosure, for purposes of simplicity of illustration, certain details of deposited materials 531, including without limitation, thickness profiles, and/or edge profiles of layer(s) have been omitted.


Those having ordinary skill in the relevant art will appreciate that certain metal NPs, whether or not as part of a discontinuous layer 440 of deposited material 331, including without limitation, at least one particle structure 441, may exhibit surface plasmon (SP) excitations, and/or coherent oscillations of free electrons, with the result that such NPs may absorb, and/or scatter light in a range of the EM spectrum, including without limitation, the visible light spectrum, and/or a sub-range thereof. The optical response, including without limitation, the (sub-)range of the EM spectrum over which absorption may be concentrated (absorption spectrum), refractive index n, and/or extinction spectrum k, of such localized SP (LSP) excitations, and/or coherent oscillations, may be tailored by varying properties of such NPs, including without limitation, a characteristic size S1, size distribution, shape, surface coverage C1, configuration, deposition density, dispersity D, and/or property, including without limitation, material, and/or degree of aggregation, of the nanostructures, and/or a medium proximate thereto.


Such optical response, in respect of photon-absorbing coatings, may include absorption of photons incident thereon, thereby reducing reflection. In some non-limiting examples, the absorption may be concentrated in a range of the EM spectrum, including without limitation, the visible light spectrum, and/or a sub-range thereof. In some non-limiting examples, employing a photon-absorbing layer as part of an opto-electronic device may reduce reliance on a polarizer therein.


It has been reported in Fusella et al., “Plasmonic enhancement of stability and brightness in organic light-emitting devices”, Nature 2020, 585, at 379-382 (“Fusella et al.”), that the stability of an optical light-emitting diode (OLED) device may be enhanced by incorporating an NP-based out-coupling layer above the cathode layer to extract energy from the plasmon modes. The NP-based out-coupling layer was fabricated by spin-casting cubic Ag NPs on top of an organic layer on top of a cathode. However, since most commercial OLED devices are fabricated using vacuum-based processing, spin-casting from solution may not constitute an appropriate mechanism for forming such an NP-based out-coupling layer above the cathode.


It has been discovered that such an NP-based out-coupling layer above the cathode may be fabricated in vacuum (and thus, may be suitable for use in a commercial OLED fabrication process), by depositing a metal deposited material 331 in a discontinuous layer 440 onto a NIC 110, which in some non-limiting examples, may be, and/or be deposited on, the cathode. Such process may avoid the use of solvents or other wet chemicals that may cause damage to the OLED device, and/or may adversely impact device reliability.


In some non-limiting examples, the presence of such a discontinuous layer 440 of deposited material 331, including without limitation, at least one particle structure 441, may contribute to enhanced light extraction, performance, stability, reliability, and/or lifetime of the device.


In some non-limiting examples, the existence, in a layered device 100, of at least one discontinuous layer 440, on, and/or proximate to the exposed layer surface 11 of a NIC 110, and/or, in some non-limiting examples, and/or proximate to the interface of such NIC 110 with at least one covering layer, may impart optical effects to photons, and/or EM signals emitted by the device, and/or transmitted therethrough.


Those having ordinary skill in the relevant art will appreciate that, while a simplified model of the optical effects is presented herein, other models, and/or explanations may be applicable.


In some non-limiting examples, the presence of such a discontinuous layer 440 of the deposited material 331, including without limitation, at least one particle structure 441, may reduce, and/or mitigate crystallization of thin film layers, and/or coatings disposed adjacent in the longitudinal aspect, including without limitation, the NIC 110, and/or at least one covering layer, thereby stabilizing the property of the thin film(s) disposed adjacent thereto, and, in some non-limiting examples, reducing scattering. In some non-limiting examples, such thin film may be, and/or comprise at least one layer of an outcoupling, and/or encapsulating coating of the device, including without limitation, a capping layer (CPL).


In some non-limiting examples, the presence of such a discontinuous layer 440 of deposited material 331, including without limitation, at least one particle structure 441, may provide an enhanced absorption in at least a part of the UV spectrum. In some non-limiting examples, controlling the characteristics of such particle structures 441, including without limitation, characteristic size S1, size distribution, shape, surface coverage C1, configuration, deposited density, dispersity D, deposited material 331, and refractive index n, of the particle structures 441, may facilitate controlling the degree of absorption, wavelength range and peak wavelength λmax of the absorption spectrum, including in the UV spectrum. Enhanced absorption of light in at least a part of the UV spectrum may be advantageous, for example, for improving device performance, stability, reliability, and/or lifetime.


In some non-limiting examples, the optical effects may be described in terms of its impact on the transmission, and/or absorption wavelength spectrum, including a wavelength range, and/or peak intensity thereof.


Additionally, while the model presented may suggest certain effects imparted on the transmission, and/or absorption of photons passing through such discontinuous layer 440, in some non-limiting examples, such effects may reflect local effects that may not be reflected on a broad, observable basis.


In some non-limiting examples, the NIC 110 may be doped, covered, and/or supplemented with another material that may act as a seed or heterogeneity, to act as such a nucleation site for the deposited material 331. In some non-limiting examples, such other material may comprise a nucleation promoting coating (NPC) 520 (FIG. 5C) material. In some non-limiting examples, such other material may comprise an organic material, such as by way of non-limiting example, a polycyclic aromatic compound, and/or a material containing a non-metallic element such as, without limitation, oxygen (O), sulfur (S), nitrogen (N), or carbon (C), whose presence might otherwise be a contaminant in the source material, equipment used for deposition, and/or the vacuum chamber environment. In some non-limiting examples, such other material may be deposited in a layer thickness that is a fraction of a monolayer, to avoid forming a closed coating 140 thereof. Rather, the monomers of such other material will tend to be spaced apart in the lateral aspect so as form discrete nucleation sites for the deposited material, thereby forming the particles.


Opto-Electronic Device


FIG. 6 is a simplified block diagram from a cross-sectional aspect, of an example electro-luminescent device 600 according to the present disclosure. In some non-limiting examples, the device 600 is an OLED.


The device 600 may comprise a substrate 10, upon which a frontplane 610, comprising a plurality of layers, respectively, a first electrode 620, at least one semiconducting layer 630, and a second electrode 640, are disposed. In some non-limiting examples, the frontplane 610 may provide mechanisms for photon emission, and/or manipulation of emitted photons.


In some non-limiting examples, the deposited layer 130 and the underlying surface may together form at least a part of at least one of the first electrode 620 and the second electrode 640 of the device 600. In some non-limiting examples, the deposited layer 130 and the underlying layer thereunder may together form at least a part of a cathode of the device 600.


In some non-limiting examples, the device 600 may be electrically coupled with a power source 605. When so coupled, the device 600 may emit photons as described herein.


Substrate


In some examples, the substrate 10 may comprise a base substrate 612. In some examples, the base substrate 612 may be formed of material suitable for use thereof, including without limitation, an inorganic material, including without limitation, silicon (Si), glass, metal (including without limitation, a metal foil), sapphire, and/or other inorganic material, and/or an organic material, including without limitation, a polymer, including without limitation, a polyimide, and/or a silicon-based polymer. In some examples, the base substrate 612 may be rigid or flexible. In some examples, the substrate 10 may be defined by at least one planar surface. In some non-limiting examples, the substrate 10 may have at least one surface that supports the remaining frontplane 610 components of the device 600, including without limitation, the first electrode 620, the at least one semiconducting layer 630, and/or the second electrode 640.


In some non-limiting examples, such surface may be an organic surface, and/or an inorganic surface.


In some examples, the substrate 10 may comprise, in addition to the base substrate 612, at least one additional organic, and/or inorganic layer (not shown nor specifically described herein) supported on an exposed layer surface 11 of the base substrate 612.


In some non-limiting examples, such additional layers may comprise, and/or form at least one organic layers, which may comprise, replace, and/or supplement at least one of the at least one semiconducting layers 630.


In some non-limiting examples, such additional layers may comprise at least one inorganic layers, which may comprise, and/or form at least one electrode, which in some non-limiting examples, may comprise, replace, and/or supplement the first electrode 620, and/or the second electrode 640.


In some non-limiting examples, such additional layers may comprise, and/or be formed of, and/or as a backplane 615. In some non-limiting examples, the backplane 615 may contain power circuitry, and/or switching elements for driving the device 600, including without limitation, electronic TFT structure(s) 701 (FIG. 7), and/or component(s) thereof, that may be formed by a photolithography process, which may not be provided under, and/or may precede the introduction of low pressure (including without limitation, a vacuum) environment.


Backplane and TFT Structure(s) Embodied Therein


In some non-limiting examples, the backplane 1015 of the substrate 10 may comprise at least one electronic, and/or opto-electronic component, including without limitation, transistors, resistors, and/or capacitors, such as which may support the device 600 acting as an active-matrix, and/or a passive matrix device. In some non-limiting examples, such structures may be a thin-film transistor (TFT) structure 701.


Non-limiting examples of TFT structures 701 include top-gate, bottom-gate, n-type and/or p-type TFT structures 701. In some non-limiting examples, the TFT structure 701 may incorporate any at least one of amorphous Si (a-Si), indium gallium zinc (Zn) oxide (IGZO), and/or low-temperature polycrystalline Si (LIPS).


First Electrode


The first electrode 620 may be deposited over the substrate 10. In some non-limiting examples, the first electrode 620 may be electrically coupled with a terminal of the power source 605, and/or to ground. In some non-limiting examples, the first electrode 620 may be so coupled through at least one driving circuit which in some non-limiting examples, may incorporate at least one TFT structure 701 in the backplane 1015 of the substrate 10.


In some non-limiting examples, the first electrode 620 may comprise an anode, and/or a cathode. In some non-limiting examples, the first electrode 620 may be an anode.


In some non-limiting examples, the first electrode 620 may be formed by depositing at least one thin conductive film, over (a portion of) the substrate 10. In some non-limiting examples, there may be a plurality of first electrodes 620, disposed in a spatial arrangement over a lateral aspect of the substrate 10. In some non-limiting examples, at least one of such at least one first electrode 620 may be deposited over (a part of) a TFT insulating layer 709 (FIG. 7) disposed in a lateral aspect in a spatial arrangement. If so, in some non-limiting examples, at least one of such at least one first electrode 620 may extend through an opening of the corresponding TFT insulating layer 709 to be electrically coupled with an electrode of the TFT structures 701 in the backplane 1015.


In some non-limiting examples, the at least one first electrode 620, and/or at least one thin film thereof, may comprise various materials, including without limitation, at least one metallic materials, including without limitation, Mg, Al, calcium (Ca), Zn, Ag, Cd, Ba, or Yb, or combinations of any plurality thereof, including without limitation, alloys containing any of such materials, at least one metal oxide, including without limitation, a transparent conducting oxide (TOO), including without limitation, ternary compositions such as, without limitation, fluorine tin oxide (FTO), indium zinc oxide (IZO), or indium tin oxide (ITO), or combinations of any plurality thereof, or in varying proportions, or combinations of any plurality thereof in at least one layer, any at least one of which may be, without limitation, a thin film.


Second Electrode


The second electrode 640 may be deposited over the at least one semiconducting layer 630. In some non-limiting examples, the second electrode 640 may be electrically coupled with a terminal of the power source 605, and/or with ground. In some non-limiting examples, the second electrode 640 may be so coupled through at least one driving circuit, which in some non-limiting examples, may incorporate at least one TFT structure 701 in the backplane 1015 of the substrate 10.


In some non-limiting examples, the second electrode 640 may comprise an anode, and/or a cathode. In some non-limiting examples, the second electrode 1030 may be a cathode.


In some non-limiting examples, the second electrode 640 may be formed by depositing a deposited layer 130, in some non-limiting examples, as at least one thin film, over (a part of) the at least one semiconducting layer 630. In some non-limiting examples, there may be a plurality of second electrodes 640, disposed in a spatial arrangement over a lateral aspect of the at least one semiconducting layer 630.


In some non-limiting examples, the at least one second electrode 640 may comprise various materials, including without limitation, at least one metallic materials, including without limitation, Mg, Al, Ca, Zn, Ag, Cd, Ba, or Yb, or combinations of any plurality thereof, including without limitation, alloys containing any of such materials, at least one metal oxides, including without limitation, a TCO, including without limitation, ternary compositions such as, without limitation, FTO, IZO, or ITO, or combinations of any plurality thereof, or in varying proportions, or zinc oxide (ZnO), or other oxides containing indium (In), or Zn, or combinations of any plurality thereof in at least one layer, and/or at least one non-metallic materials, any at least one of which may be, without limitation, a thin conductive film. In some non-limiting examples, for a Mg:Ag alloy, such alloy composition may range between about 1:9-9:1 by volume.


In some non-limiting examples, the deposition of the second electrode 640 may be performed using an open mask and/or a mask-free deposition process.


In some non-limiting examples, the second electrode 640 may comprise a plurality of such layers, and/or coatings. In some non-limiting examples, such layers, and/or coatings may be distinct layers, and/or coatings disposed on top of one another.


In some non-limiting examples, the second electrode 640 may comprise a Yb/Ag bi-layer coating. By way of non-limiting examples, such bi-layer coating may be formed by depositing a Yb coating, followed by an Ag coating. In some non-limiting examples, a thickness of such Ag coating may exceed a thickness of the Yb coating.


In some non-limiting examples, the second electrode 640 may be a multi-layer electrode 640 comprising at least one metallic layer, and/or at least one oxide layer.


In some non-limiting examples, the second electrode 640 may comprise a fullerene and Mg.


By way of non-limiting examples, such coating may be formed by depositing a fullerene coating followed by an Mg coating. In some non-limiting examples, a fullerene may be dispersed within the Mg coating to form a fullerene-containing Mg alloy coating. Non-limiting examples of such coatings are described in United States Patent Application Publication No. 2015/0287846 published 8 Oct. 2015, and/or in PCT International Application No. PCT/IB2017/054970 filed 15 Aug. 2017 and published as WO2018/033860 on 22 Feb. 2018.


Semiconducting Layer


In some non-limiting examples, the at least one semiconducting layer 630 may comprise a plurality of layers 631, 633, 635, 637, 639, any of which may be disposed, in some non-limiting examples, in a thin film, in a stacked configuration, which may include, without limitation, at least one of a hole injection layer (HIL) 631, a hole transport layer (HTL) 633, an emissive layer (EML) 635, an electron transport layer (ETL) 637, and/or an electron injection layer (EIL) 639.


In some non-limiting examples, the at least one semiconducting layer 630 may form a “tandem” structure comprising a plurality of EMLs 635. In some non-limiting examples, such tandem structure may also comprise at least one charge generation layer (CGL).


Those having ordinary skill in the relevant art will readily appreciate that the structure of the device 600 may be varied by omitting, and/or combining at least one of the semiconductor layers 631, 633, 635, 637, 639.


Further, any of the layers 631, 633, 635, 637, 639 of the at least one semiconducting layer 630 may comprise any number of sub-layers. Still further, any of such layers 631, 633, 635, 637, 639, and/or sub-layer(s) thereof may comprise various mixture(s), and/or composition gradient(s). In addition, those having ordinary skill in the relevant art will appreciate that the device 600 may comprise at least one layer comprising inorganic, and/or organometallic materials and may not be necessarily limited to devices comprised solely of organic materials. By way of non-limiting example, the device 600 may comprise at least one QD.


In some non-limiting examples, the HIL 631 may be formed using a hole injection material, which may facilitate injection of holes by the anode.


In some non-limiting examples, the HTL 633 may be formed using a hole transport material, which may, in some non-limiting examples, exhibit high hole mobility.


In some non-limiting examples, the ETL 637 may be formed using an electron transport material, which may, in some non-limiting examples, exhibit high electron mobility.


In some non-limiting examples, the EIL 639 may be formed using an electron injection material, which may facilitate injection of electrons by the cathode.


In some non-limiting examples, the EML 635 may be formed, by way of non-limiting example, by doping a host material with at least one emitter material. In some non-limiting examples, the emitter material may be a fluorescent emitter, a phosphorescent emitter, a thermally activated delayed fluorescence (TADF) emitter, and/or a plurality of any combination of these.


In some non-limiting examples, the device 600 may be an OLED in which the at least one semiconducting layer 630 comprises at least an EML 635 interposed between conductive thin film electrodes 620, 640, whereby, when a potential difference is applied across them, holes may be injected into the at least one semiconducting layer 630 through the anode and electrons may be injected into the at least one semiconducting layer 630 through the cathode, migrate toward the EML 635 and combine to emit EM radiation in the form of photons.


In some non-limiting examples, the device 600 may be an electro-luminescent QD device in which the at least one semiconducting layer 630 may comprise an active layer comprising at least one QD. When current may be provided by the power source 605 to the first electrode 620 and second electrode 640, photons may be emitted from the active layer comprising the at least one semiconducting layer 630 between them.


Those having ordinary skill in the relevant art will readily appreciate that the structure of the device 600 may be varied by the introduction of at least one additional layer (not shown) at appropriate position(s) within the at least one semiconducting layer 630 stack, including without limitation, a hole blocking layer (not shown), an electron blocking layer (not shown), an additional charge transport layer (not shown), and/or an additional charge injection layer (not shown).


In some non-limiting examples, including where the OLED device 600 comprises a lighting panel, an entire lateral aspect of the device 600 may correspond to a single lighting element. As such, the substantially planar cross-sectional profile shown in FIG. 6 may extend substantially along the entire lateral aspect of the device 600, such that photons are emitted from the device 600 substantially along the entirety of the lateral extent thereof. In some non-limiting examples, such single lighting element may be driven by a single driving circuit of the device 600.


In some non-limiting examples, including where the OLED device 600 comprises a display module, the lateral aspect of the device 600 may be sub-divided into a plurality of emissive regions 1210 (FIG. 12) of the device 600, in which the cross-sectional aspect of the device structure 1000, within each of the emissive region(s) 1210 shown, without limitation, in FIG. 6 may cause photons to be emitted therefrom when energized.


Emissive Regions

In some non-limiting examples, such as may be shown by way of non-limiting example in FIG. 7, an active region 730 of an emissive region 1210 may be defined to be bounded, in the transverse aspect, by the first electrode 620 and the second electrode 640, and to be confined, in the lateral aspect, to an emissive region 1210 defined by the first electrode 620 and the second electrode 640. Those having ordinary skill in the relevant art will appreciate that the lateral extent of the emissive region 1210, and thus the lateral boundaries of the active region 730, may not correspond to the entire lateral aspect of either, or both, of the first electrode 620 and the second electrode 640. Rather, the lateral extent of the emissive region may be substantially less than the lateral extent of either the first electrode 620 and the second electrode 640. By way of non-limiting example, parts of the first electrode 620 may be covered by the pixel definition layer(s) (PDL) 740 (FIG. 7) and/or parts of the second electrode 640 may not be disposed on the at least one semiconducting layer 630, with the result, in either, or both, scenarios, that the emissive region 1210 may be laterally constrained.


In some non-limiting examples, individual emissive regions 1210 of the device 600 may be laid out in a lateral pattern. In some non-limiting examples, the pattern may extend along a first lateral direction. In some non-limiting examples, the pattern may also extend along a second lateral direction, which in some non-limiting examples, may be substantially normal to the first lateral direction. In some non-limiting examples, the pattern may have a number of elements in such pattern, each element being characterized by at least one feature thereof, including without limitation, a wavelength of light emitted by the emissive region 1210 thereof, a shape of such emissive region 1210, a dimension (along either, or both of, the first, and/or second lateral direction(s)), an orientation (relative to either, and/or both of the first, and/or second lateral direction(s)), and/or a spacing (relative to either, or both of, the first, and/or second lateral direction(s)) from a previous element in the pattern. In some non-limiting examples, the pattern may repeat in either, or both of, the first and/or second lateral direction(s).


In some non-limiting examples, each individual emissive region 1210 of the device 600 may be associated with, and driven by, a corresponding driving circuit within the backplane 1015 of the device 600, for driving an OLED structure for the associated emissive region 1210. In some non-limiting examples, including without limitation, where the emissive regions 1210 may be laid out in a regular pattern extending in both the first (row) lateral direction and the second (column) lateral direction, there may be a signal line in the backplane 1015, corresponding to each row of emissive regions 1210 extending in the first lateral direction and a signal line, corresponding to each column of emissive regions 1210 extending in the second lateral direction. In such a non-limiting configuration, a signal on a row selection line may energize the respective gates of the switching TFT(s) electrically coupled therewith and a signal on a data line may energize the respective sources of the switching TFT(s) electrically coupled therewith, such that a signal on a row selection line/data line pair may electrically couple and energise, by the positive terminal of the power source 605, the anode of the OLED structure of the emissive region 1210 associated with such pair, causing the emission of a photon therefrom, the cathode thereof being electrically coupled with the negative terminal of the power source 605.


In some non-limiting examples, each emissive region 1210 of the device 600 may correspond to a single display pixel 1810 (FIG. 18A). In some non-limiting examples, each pixel 1810 may emit light at a given wavelength spectrum. In some non-limiting examples, the wavelength spectrum may correspond to a colour in, without limitation, the visible spectrum.


In some non-limiting examples, each emissive region 1210 of the device 600 may correspond to a sub-pixel 134x (FIG. 13A) of a display pixel 1810. In some non-limiting examples, a plurality of sub-pixels 134x may combine to form, or to represent, a single display pixel 1810.


In some non-limiting examples, a single display pixel 1810 may be represented by three sub-pixels 134x. In some non-limiting examples, the three sub-pixels 134x may be denoted as, respectively, R(ed) sub-pixels 1341, G(reen) sub-pixels 1342, and/or B(lue) sub-pixels 1343. In some non-limiting examples, a single display pixel 1810 may be represented by four sub-pixels 134x, in which three of such sub-pixels 134x may be denoted as R, G and B sub-pixels 134x and the fourth sub-pixel 134x may be denoted as a W(hite) sub-pixel 134x. In some non-limiting examples, the emission spectrum of the light emitted by a given sub-pixel 134x may correspond to the colour by which the sub-pixel 134x is denoted. In some non-limiting examples, the wavelength of the light may not correspond to such colour, but further processing may be performed, in a manner apparent to those having ordinary skill in the relevant art, to transform the wavelength to one that does so correspond.


Since the wavelength of sub-pixels 134x of different colours may be different, the optical characteristics of such sub-pixels 134x may differ, especially if a common electrode 620, 640 having a substantially uniform thickness profile may be employed for sub-pixels 134x of different colours.


When a common electrode 620, 640 having a substantially uniform thickness may be provided as the second electrode 640 in a device 600, the optical performance of the device 600 may not be readily be fine-tuned according to an emission spectrum associated with each (sub-)pixel 1810/134x. The second electrode 640 used in such OLED devices 600 may in some non-limiting examples, be a common electrode 620, 640 coating a plurality of (sub-)pixels 1810/134x. By way of non-limiting example, such common electrode 620, 640 may be a relatively thin conductive film having a substantially uniform thickness across the device 600. While efforts have been made in some non-limiting examples, to tune the optical microcavity effects associated with each (sub-)pixel 1810/134x color by varying a thickness of organic layers disposed within different (sub-) pixel(s) 1810/134x, such approach may, in some non-limiting examples, provide a significant degree of tuning of the optical microcavity effects in at least some cases. In addition, in some non-limiting examples, such approach may be difficult to implement in an OLED display production environment.


As a result, the presence of optical interfaces created by numerous thin-film layers and coatings with different refractive indices, such as may in some non-limiting examples be used to construct opto-electronic devices including without limitation OLED devices 600, may create different optical microcavity effects for sub-pixels 134x of different colours.


Some factors that may impact an observed microcavity effect in a device 600 include, without limitation, a total path length (which in some non-limiting examples may correspond to a total thickness of the device 600 through which photons emitted therefrom will travel before being outcoupled) and the refractive indices n of various layers and coatings.


In some non-limiting examples, modulating a thickness of an electrode 620, 640 in and across a lateral aspect 710 of emissive region(s) 1210 of a (sub-) pixel 1810/134x may impact the microcavity effect observable. In some non-limiting examples, such impact may be attributable to a change in the total optical path length.


In some non-limiting examples, a change in a thickness of the electrode 620, 640 may also change the refractive index n of light passing therethrough, in some non-limiting examples, in addition to a change in the total optical path length. In some non-limiting examples, this may be particularly the case where the electrode 620, 640 may be formed of at least one deposited layer 130.


In some non-limiting examples, the optical properties of the device 600, and/or in some non-limiting examples, across the lateral aspect 710 of emissive region(s) 1210 of a (sub-) pixel 1810/134x that may be varied by modulating at least one optical microcavity effect, may include, without limitation, the emission spectrum, the intensity (including without limitation, luminous intensity), and/or angular distribution of emitted light, including without limitation, an angular dependence of a brightness, and/or color shift of the emitted light.


In some non-limiting examples, a sub-pixel 134x may be associated with a first set of other sub-pixels 134x to represent a first display pixel 1810 and also with a second set of other sub-pixels 134x to represent a second display pixel 1810, so that the first and second display pixels 340 may have associated therewith, the same sub-pixel(s) 134x.


The pattern, and/or organization of sub-pixels 134x into display pixels 340 continues to develop. All present and future patterns, and/or organizations are considered to fall within the scope of the present disclosure.


Non-Emissive Regions

In some non-limiting examples, the various emissive regions 1210 of the device 600 may be substantially surrounded and separated by, in at least one lateral direction, at least one non-emissive region 1220 (FIG. 12), in which the structure, and/or configuration along the cross-sectional aspect, of the device structure 600 shown, without limitation, in FIG. 6, may be varied, to substantially inhibit photons to be emitted therefrom.


In some non-limiting examples, the non-emissive regions 1220 may comprise those regions in the lateral aspect, that are substantially devoid of an emissive region 1210.


Thus, as shown in the cross-sectional view of FIG. 7, the lateral topology of the various layers of the at least one semiconducting layer 630 may be varied to define at least one emissive region 1210, surrounded (at least in one lateral direction) by at least one non-emissive region 1220.


In some non-limiting examples, the emissive region 1210 corresponding to a single display (sub-) pixel 1810/134x may be understood to have a lateral aspect 710, surrounded in at least one lateral direction by at least one non-emissive region 1220 having a lateral aspect 720.


A non-limiting example of an implementation of the cross-sectional aspect of the device 600 as applied to an emissive region 1210 corresponding to a single display (sub-) pixel 1810/134x of an OLED display 600 will now be described. While features of such implementation are shown to be specific to the emissive region 1210, those having ordinary skill in the relevant art will appreciate that in some non-limiting examples, more than one emissive region 1210 may encompass common features.


In some non-limiting examples, the first electrode 620 may be disposed over an exposed layer surface 11 of the device 600, in some non-limiting examples, within at least a part of the lateral aspect 710 of the emissive region 1210. In some non-limiting examples, at least within the lateral aspect 710 of the emissive region 1210 of the (sub-) pixel(s) 1810/134x, the exposed layer surface 11, may, at the time of deposition of the first electrode 620, comprise the TFT insulating layer 709 of the various TFT structures 701 that make up the driving circuit for the emissive region 1210 corresponding to a single display (sub-) pixel 1810/134x.


In some non-limiting examples, the TFT insulating layer 709 may be formed with an opening extending therethrough to permit the first electrode 620 to be electrically coupled with one of the TFT electrodes 705, 707, 708, including, without limitation, as shown in FIG. 7, the TFT drain electrode 708.


Those having ordinary skill in the relevant art will appreciate that the driving circuit comprises a plurality of TFT structures 701. In FIG. 7, for purposes of simplicity of illustration, only one TFT structure 701 may be shown, but it will be appreciated by those having ordinary skill in the relevant art, that such TFT structure 701 may be representative of such plurality thereof that comprise the driving circuit.


In a cross-sectional aspect, the configuration of each emissive region 1210 may, in some non-limiting examples, be defined by the introduction of at least one PDL 740 substantially throughout the lateral aspects 720 of the surrounding non-emissive region(s) 1220. In some non-limiting examples, the PDLs 740 may comprise an insulating organic, and/or inorganic material.


In some non-limiting examples, the PDLs 740 may be deposited substantially over the TFT insulating layer 709, although, as shown, in some non-limiting examples, the PDLs 740 may also extend over at least a part of the deposited first electrode 620, and/or its outer edges.


In some non-limiting examples, as shown in FIG. 7, the cross-sectional thickness, and/or profile of the PDLs 740 may impart a substantially valley-shaped configuration to the emissive region 1210 of each (sub-) pixel 1810/134x by a region of increased thickness along a boundary of the lateral aspect 720 of the surrounding non-emissive region 1220 with the lateral aspect 710 of the surrounded emissive region 1210, corresponding to a (sub-) pixel 1810/134x.


In some non-limiting examples, the profile of the PDLs 740 may have a reduced thickness beyond such valley-shaped configuration, including without limitation, away from the boundary between the lateral aspect 720 of the surrounding non-emissive region 1220 and the lateral aspect 710 of the surrounded emissive region 1210, in some non-limiting examples, substantially well within the lateral aspect 720 of such non-emissive region 1220.


While the PDL(s) 740 have been generally illustrated as having a linearly sloped surface to form a valley-shaped configuration that define the emissive region(s) 1210 surrounded thereby, those having ordinary skill in the relevant art will appreciate that in some non-limiting examples, at least one of the shape, aspect ratio, thickness, width, and/or configuration of such PDL(s) 740 may be varied. By way of non-limiting example, a PDL 740 may be formed with a steeper or more gradually sloped part. In some non-limiting examples, such PDL(s) 740 may be configured to extend substantially normally away from a surface on which it is deposited, that may cover at least one edges of the first electrode 620. In some non-limiting examples, such PDL(s) 740 may be configured to have deposited thereon at least one semiconducting layer 630 by a solution-processing technology, including without limitation, by printing, including without limitation, ink-jet printing.


In some non-limiting examples, the at least one semiconducting layer 630 may be deposited over the exposed layer surface 11 of the device 600, including at least a part of the lateral aspect 710 of such emissive region 1210 of the (sub-) pixel(s) 1810/134x. In some non-limiting examples, at least within the lateral aspect 710 of the emissive region 1210 of the (sub-) pixel(s) 1810/134x, such exposed layer surface 11, may, at the time of deposition of the at least one semiconducting layer 630 (and/or layers 631, 633, 635, 637, 639 thereof), comprise the first electrode 620.


In some non-limiting examples, the at least one semiconducting layer 630 may also extend beyond the lateral aspect 710 of the emissive region 1210 of the (sub-) pixel(s) 1810/134x and at least partially within the lateral aspects 720 of the surrounding non-emissive region(s) 1220. In some non-limiting examples, such exposed layer surface 11 of such surrounding non-emissive region(s) 1220 may, at the time of deposition of the at least one semiconducting layer 630, comprise the PDL(s) 740.


In some non-limiting examples, the second electrode 640 may be disposed over an exposed layer surface 11 of the device 600, including at least a part of the lateral aspect 710 of the emissive region 1210 of the (sub-) pixel(s) 1810/134x. In some non-limiting examples, at least within the lateral aspect 710 of the emissive region 1210 of the (sub-) pixel(s) 1810/134x, such exposed layer surface 11, may, at the time of deposition of the second electrode 620, comprise the at least one semiconducting layer 630.


In some non-limiting examples, the second electrode 640 may also extend beyond the lateral aspect 710 of the emissive region 1210 of the (sub-) pixel(s) 1810/134x and at least partially within the lateral aspects 720 of the surrounding non-emissive region(s) 1220. In some non-limiting examples, such exposed layer surface 11 of such surrounding non-emissive region(s) 1220 may, at the time of deposition of the second electrode 640, comprise the PDL(s) 740.


In some non-limiting examples, the second electrode 640 may extend throughout substantially all or a substantial part of the lateral aspects 720 of the surrounding non-emissive region(s) 1220.


Selective Deposition of Patterned Electrode

In some non-limiting examples, the ability to achieve selective deposition of the deposited material 331 in an open mask and/or mask-free deposition process by the prior selective deposition of a patterning coating 210, including without limitation, an NIC 110, may be employed to achieve the selective deposition of a patterned electrode 620, 640, 1150, and/or at least one layer thereof, of an opto-electronic device, including without limitation, an OLED device 600, and/or a conductive element electrically coupled therewith.


In this fashion, the selective deposition of an NIC 110 as the patterning coating 210 in FIG. 2 using a shadow mask 215, and the open mask and/or mask-free deposition of the deposited material 331, may be combined to effect the selective deposition of at least one deposited layer 130 to form a device feature, including without limitation, a patterned electrode 620, 640, 1150, and/or at least one layer thereof, and/or a conductive element electrically coupled therewith, in the device 100a shown in FIG. 1, without employing shadow mask 215 within the deposition process for forming the deposited layer 130. In some non-limiting examples, such patterning may permit, and/or enhance the transmissivity of the device 100a.


A number of non-limiting examples of such patterned electrodes 620, 640, 1150, and/or at least one layer thereof, and/or a conductive element electrically coupled therewith, to impart various structural and/or performance capabilities to such devices 600 will now be described.


As a result of the foregoing, there may be an aim to selectively deposit, across the lateral aspect 710 of the emissive region 1210 of a (sub-) pixel 1810/134x, and/or the lateral aspect 720 of the non-emissive region(s) 1220 surrounding the emissive region 1210, a device feature, including without limitation, at least one of the first electrode 620, the second electrode 640, the auxiliary electrode 1150, and/or a conductive element electrically coupled therewith, in a pattern, on an exposed layer surface 11 of a frontplane 610 of the device 600. In some non-limiting examples, the first electrode 620, the second electrode 640, and/or the auxiliary electrode 1150, may be deposited in at least one of a plurality of deposited layers 130.



FIG. 8 may show an example patterned electrode 800 in plan view, in the figure, the second electrode 640 suitable for use in an example version 900 (FIG. 9) of the device 600. The electrode 800 may be formed in a pattern 810 that comprises a single continuous structure, having or defining a patterned plurality of apertures 820 therewithin, in which the apertures 820 may correspond to regions of the device 600 where there is no cathode.


In the figure, by way of non-limiting example, the pattern 810 may be disposed across the entire lateral extent of the device 900, without differentiation between the lateral aspect(s) 710 of emissive region(s) 1210 corresponding to (sub-) pixel(s) 1810/134x and the lateral aspect(s) 720 of non-emissive region(s) 1220 surrounding such emissive region(s) 1210. Thus, the example illustrated may correspond to a device 900 that may be substantially transmissive relative to light incident on an external surface thereof, such that a substantial part of such externally-incident light may be transmitted through the device 900, in addition to the emission (in a top-emission, bottom-emission, and/or double-sided emission) of photons generated internally within the device 900 as disclosed herein.


The transmittivity of the device 900 may be adjusted, and/or modified by altering the pattern 810 employed, including without limitation, an average size of the apertures 820, and/or a spacing, and/or density of the apertures 820.


Turning now to FIG. 9, there may be shown a cross-sectional view of the device 900, taken along line 9-9 in FIG. 8. In the figure, the device 900 may be shown as comprising the substrate 10, the first electrode 620 and the at least one semiconducting layer 630.


An NIC 110 may be selectively disposed in a pattern substantially corresponding to the pattern 810 on the exposed layer surface 11 of the underlying layer.


A deposited layer 130 suitable for forming the patterned electrode 800, which in the figure is the second electrode 640, may be disposed on substantially all of the exposed layer surface 11 of the underlying layer, using an open mask and/or a mask-free deposition process. The underlying layer may comprise both regions of the NIC 110, disposed in the pattern 1810, and regions of the at least one semiconducting layer 630, in the pattern 810 where the NIC 110 has not been deposited. In some non-limiting examples, the regions of the NIC 110 may correspond substantially to a first portion 101 comprising the apertures 820 shown in the pattern 810.


Because of the nucleation-inhibiting properties of those regions of the pattern 810 where the NIC 110 was disposed (corresponding to the apertures 820), the deposited material 331 disposed on such regions may tend to not remain, resulting in a pattern of selective deposition of the deposited layer 130, that may correspond substantially to the remainder of the pattern 810, leaving those regions of the first portion 101 of the pattern 810 corresponding to the apertures 820 substantially devoid of a closed coating 140 of the deposited layer 130.


In other words, the deposited layer 130 that will form the cathode may be selectively deposited substantially only on a second portion 102 comprising those regions of the at least one semiconducting layer 630 that surround but do not occupy the apertures 820 in the pattern 810.



FIG. 10A may show, in plan view, a schematic diagram showing a plurality of patterns 1020, 1040 of electrodes 620, 640, 1150.


In some non-limiting examples, the first pattern 1020 may comprise a plurality of elongated, spaced-apart regions that extend in a first lateral direction. In some non-limiting examples, the first pattern 1020 may comprise a plurality of first electrodes 620. In some non-limiting examples, a plurality of the regions that comprise the first pattern 1020 may be electrically coupled.


In some non-limiting examples, the second pattern 1040 may comprise a plurality of elongated, spaced-apart regions that extend in a second lateral direction. In some non-limiting examples, the second lateral direction may be substantially normal to the first lateral direction. In some non-limiting examples, the second pattern 1040 may comprise a plurality of second electrodes 640. In some non-limiting examples, a plurality of the regions that comprise the second pattern 1040 may be electrically coupled.


In some non-limiting examples, the first pattern 1020 and the second pattern 1040 may form part of an example version, shown generally at 1000 of the device 600.


In some non-limiting examples, the lateral aspect(s) 710 of emissive region(s) 1810 corresponding to (sub-) pixel(s) 1810/134x may be formed where the first pattern 1020 overlaps the second pattern 1040. In some non-limiting examples, the lateral aspect(s) 720 of non-emissive region 1220 may correspond to any lateral aspect other than the lateral aspect(s) 710.


In some non-limiting examples, a first terminal, which, in some non-limiting examples, may be a positive terminal, of the power source 605, may be electrically coupled with at least one electrode 620, 640, 1150 of the first pattern 1020. In some non-limiting examples, the first terminal may be coupled with the at least one electrode 620, 640, 1150 of the first pattern 1020 through at least one driving circuit. In some non-limiting examples, a second terminal, which, in some non-limiting examples, may be a negative terminal, of the power source 605, may be electrically coupled with at least one electrode 620, 640, 1150 of the second pattern 1040. In some non-limiting examples, the second terminal may be coupled with the at least one electrode 620, 640, 1150 of the second pattern 1040 through the at least one driving circuit.


Turning now to FIG. 10B, there may be shown a cross-sectional view of the device 1000, at a deposition stage 1000b, taken along line 10B-10B in FIG. 10A. In the figure, the device 1000 at the stage 1000b may be shown as comprising the substrate 10.


An NIC 110 may be selectively disposed in a pattern substantially corresponding to the inverse of the first pattern 1020 on the exposed layer surface 11 of the underlying layer, which, as shown in the figure, may be the substrate 10.


A deposited layer 130 suitable for forming the first pattern 1020 of electrodes 620, 640, 1150, which in the figure is the first electrode 620, may be disposed on substantially all of the exposed layer surface 11 of the underlying layer, using an open mask and/or a mask-free deposition process. The underlying layer may comprise both regions of the NIC 110, disposed in the inverse of the first pattern 1020, and regions of the substrate 10, disposed in the first pattern 1020 where the NIC 110 has not been deposited. In some non-limiting examples, the regions of the substrate 10 may correspond substantially to the elongated spaced-apart regions of the first pattern 1020, while the regions of the NIC 110 may correspond substantially to a first portion 101 comprising the gaps therebetween.


Because of the nucleation-inhibiting properties of those regions of the first pattern 1020 where the NIC 110 was disposed (corresponding to the gaps therebetween), the deposited layer 130 disposed on such regions may tend to not remain, resulting in a pattern of selective deposition of the deposited layer 130, that may correspond substantially to elongated spaced-apart regions of the first pattern 1020, leaving a first portion 101 comprising the gaps therebetween substantially devoid of a closed coating 140 of the deposited layer 130.


In other words, the deposited layer 130 that may form the first pattern 1020 of electrodes 620, 640, 1150 may be selectively deposited substantially only on a second portion 102 comprising those regions of the substrate 10 that define the elongated spaced-apart regions of the first pattern 1020.


Turning now to FIG. 10C, there may be shown a cross-sectional view 1000c of the device 1000, taken along line 10C-10C in FIG. 10A. In the figure, the device 1000 may be shown as comprising the substrate 10; the first pattern 1020 of electrodes 620 deposited as shown in FIG. 10B, and the at least one semiconducting layer(s) 630.


In some non-limiting examples, the at least one semiconducting layer(s) 630 may be provided as a common layer across substantially all of the lateral aspect(s) of the device 1000.


An NIC 110 may be selectively disposed in a pattern substantially corresponding to the second pattern 1040 on the exposed layer surface 11 of the underlying layer, which, as shown in the figure, is the at least one semiconducting layer 630.


A deposited layer 130 suitable for forming the second pattern 1040 of electrodes 620, 640, 1150, which in the figure is the second electrode 640, may be disposed on substantially all of the exposed layer surface 11 of the underlying layer, using an open mask and/or a mask-free deposition process. The underlying layer may comprise both regions of the NIC 110, disposed in the inverse of the second pattern 1040, and regions of the at least one semiconducting layer(s) 630, in the second pattern 1040 where the NIC 110 has not been deposited. In some non-limiting examples, the regions of the at least one semiconducting layer(s) 630 may correspond substantially to a first portion 101 comprising the elongated spaced-apart regions of the second pattern 1040, while the regions of the NIC 110 may correspond substantially to the gaps therebetween.


Because of the nucleation-inhibiting properties of those regions of the second pattern 1040 where the NIC 110 was disposed (corresponding to the gaps therebetween), the deposited layer 130 disposed on such regions may tend not to remain, resulting in a pattern of selective deposition of the deposited layer 130, that may correspond substantially to elongated spaced-apart regions of the second pattern 1040, leaving the first portion 101 comprising the gaps therebetween substantially devoid of a closed coating 140 of the deposited layer 130.


In other words, the deposited layer 130 that may form the second pattern 1040 of electrodes 620, 640, 1150 may be selectively deposited substantially only on a second portion 102 comprising those regions of the NPC 520 that define the elongated spaced-apart regions of the second pattern 1040.


In some non-limiting examples, a thickness of the NIC 110 and of the deposited layer 130 deposited thereafter for forming either, or both, of the first pattern 1020, and/or the second pattern 1040 of electrodes 620, 640, 1150 may be varied according to a variety of parameters, including without limitation, a given application and given performance characteristics. In some non-limiting examples, the thickness of the NIC 110 may be comparable to, and/or substantially less than a thickness of the deposited layer 130 deposited thereafter. Use of a relatively thin NIC 110 to achieve selective patterning of a deposited layer 130 deposited thereafter may be suitable to provide flexible devices 600. In some non-limiting examples, a relatively thin NIC 110 may provide a relatively planar surface on which a barrier coating 1050 may be deposited. In some non-limiting examples, providing such a relatively planar surface for application of the barrier coating 1050 may increase adhesion of the barrier coating 1050 to such surface.


At least one of the first pattern 1020 of electrodes 620, 640, 1150 and at least one of the second pattern 1040 of electrodes 620, 640, 1150 may be electrically coupled with the power source 605, whether directly, and/or, in some non-limiting examples, through their respective driving circuit(s) 1200 to control photon emission from the lateral aspect(s) 710 of the emissive region(s) 1810 corresponding to (sub-) pixel(s) 1810/134x.


Auxiliary Electrode

Those having ordinary skill in the relevant art will appreciate that the process of forming the second electrode 640 in the second pattern 1040 shown in FIGS. 10A-10C may, in some non-limiting examples, be used in similar fashion to form an auxiliary electrode 1150 for the device 1000. In some non-limiting examples, the second electrode 640 thereof may comprise a common electrode, and the auxiliary electrode 1150 may be deposited in the second pattern 1040, in some non-limiting examples, above or in some non-limiting examples below, the second electrode 640 and electrically coupled therewith. In some non-limiting examples, the second pattern 1040 for such auxiliary electrode 1150 may be such that the elongated spaced-apart regions of the second pattern 1040 lie substantially within the lateral aspect(s) 720 of non-emissive region(s) 1820 surrounding the lateral aspect(s) 710 of emissive region(s) 1810 corresponding to (sub-) pixel(s) 1810/134x. In some non-limiting examples, the second pattern 1040 for such auxiliary electrodes 1150 may be such that the elongated spaced-apart regions of the second pattern 1040 lie substantially within the lateral aspect(s) 710 of emissive region(s) 1810 corresponding to (sub-) pixel(s) 1810/134x, and/or the lateral aspect(s) 720 of non-emissive region(s) 1820 surrounding them.



FIG. 11 may show an example cross-sectional view of an example version 1100 of the device 600 that is substantially similar thereto, but further may comprise at least one auxiliary electrode 1150 disposed in a pattern above and electrically coupled (not shown) with the second electrode 640.


The auxiliary electrode 1150 may be electrically conductive. In some non-limiting examples, the auxiliary electrode 1150 may be formed by at least one metal, and/or metal oxide. Non-limiting examples of such metals include Cu, Al, molybdenum (Mo), or Ag. By way of non-limiting examples, the auxiliary electrode 1150 may comprise a multi-layer metallic structure, including without limitation, one formed by Mo/Al/Mo. Non-limiting examples of such metal oxides include ITO, ZnO, IZO, or other oxides containing In, or Zn. In some non-limiting examples, the auxiliary electrode 1150 may comprise a multi-layer structure formed by a combination of at least one metal and at least one metal oxide, including without limitation, Ag/ITO, Mo/ITO, ITO/Ag/ITO, or ITO/Mo/ITO. In some non-limiting examples, the auxiliary electrode 1150 comprises a plurality of such electrically conductive materials.


The device 1100 may be shown as comprising the substrate 10, the first electrode 620 and the at least one semiconducting layer 630.


The second electrode 640 may be disposed on substantially all of the exposed layer surface 11 of the at least one semiconducting layer 630.


In some non-limiting examples, particularly in a top-emission device 1100, the second electrode 640 may be formed by depositing a relatively thin conductive film layer (not shown) in order, by way of non-limiting example, to reduce optical interference (including, without limitation, attenuation, reflections, and/or diffusion) related to the presence of the second electrode 640. In some non-limiting examples, as discussed elsewhere, a reduced thickness of the second electrode 640, may generally increase a sheet resistance R of the second electrode 640, which may, in some non-limiting examples, reduce the performance, and/or efficiency of the device 1100. By providing the auxiliary electrode 1150 that may be electrically coupled with the second electrode 640, the sheet resistance Rand thus, the IR drop associated with the second electrode 640, may, in some non-limiting examples, be decreased.


In some non-limiting examples, the device 1100 may be a bottom-emission, and/or double-sided emission device 1100. In such examples, the second electrode 640 may be formed as a relatively thick conductive layer without substantially affecting optical characteristics of such a device 1100. Nevertheless, even in such scenarios, the second electrode 640 may nevertheless be formed as a relatively thin conductive film layer (not shown), by way of non-limiting example, so that the device 1100 may be substantially transmissive relative to light incident on an external surface thereof, such that a substantial part such externally-incident light may be transmitted through the device 1100, in addition to the emission of photons generated internally within the device 1100 as disclosed herein.


An NIC 110 may be selectively disposed in a pattern on the exposed layer surface 11 of the underlying layer, which, as shown in the figure, may be the at least one semiconducting layer 630. In some non-limiting examples, as shown in the figure, the NIC 110 may be disposed, in a first portion of the pattern, as a series of parallel rows 1120.


A deposited layer 130 suitable for forming the patterned auxiliary electrode 1150, may be disposed on substantially all of the exposed layer surface 11 of the underlying layer, using an open mask and/or a mask-free deposition process. The underlying layer may comprise both regions of the NIC 110, disposed in the pattern of rows 1120, and regions of the at least one semiconducting layer 630 where the NIC 110 has not been deposited.


Because of the nucleation-inhibiting properties of those rows 1120 where the NIC 110 was disposed, the deposited layer 130 disposed on such rows 1120 may tend to not remain, resulting in a pattern of selective deposition of the deposited layer 130, that may correspond substantially to at least one second portion 102 of the pattern, leaving the first portion 101 comprising the rows 1120 substantially devoid of a closed coating 140 of the deposited layer 130.


In other words, the deposited layer 130 that may form the auxiliary electrode 1150 may be selectively deposited substantially only on a second portion 102 comprising those regions of the at least one semiconducting layer 630, that surround but do not occupy the rows 1120.


In some non-limiting examples, selectively depositing the auxiliary electrode 1150 to cover only certain rows 1120 of the lateral aspect of the device 1100, while other regions thereof remain uncovered, may control, and/or reduce optical interference related to the presence of the auxiliary electrode 1150.


In some non-limiting examples, the auxiliary electrode 1150 may be selectively deposited in a pattern that may not be readily detected by the naked eye from a typical viewing distance.


In some non-limiting examples, the auxiliary electrode 1150 may be formed in devices other than OLED devices, including for decreasing an effective resistance of the electrodes of such devices.


The ability to pattern electrodes 620, 640, 1150, 5050 including without limitation, the second electrode 640, and/or the auxiliary electrode 1150 without employing a shadow mask 215 during the high-temperature deposited layer 130 deposition process by employing a selective coating 210, including without limitation, the process depicted in FIG. 2, may allow numerous configurations of auxiliary electrodes 1150 to be deployed.


In some non-limiting examples, the auxiliary electrode 1150 may be disposed between neighbouring emissive regions 1210 (FIG. 12) and electrically coupled with the second electrode 640. In non-limiting examples, a width of the auxiliary electrode 1150 may be less than a separation distance between the neighbouring emissive regions 1120. As a result, there may exist a gap within the at least one non-emissive region 1220 (FIG. 12) on each side of the auxiliary electrode 1150. In some non-limiting examples, such an arrangement may reduce a likelihood that the auxiliary electrode 1150 would interfere with an optical output of the device 1100, in some non-limiting examples, from at least one of the emissive regions 1110. In some non-limiting examples, such an arrangement may be appropriate where the auxiliary electrode 1150 is relatively thick (in some non-limiting examples, greater than several hundred nm, and/or on the order of a few microns in thickness). In some non-limiting examples, an aspect ratio of the auxiliary electrode 1150 may exceed about 0.05, such as about at least: 0.1, 0.2, 0.5, 0.8, 1, or 2. By way of non-limiting example, a height (thickness) of the auxiliary electrode 1150 may exceed about 50 nm, such as at least about: 80 nm, 100 nm, 200 nm, 500 nm, 700 nm, 1,000 nm, 1,500 nm, 1,700 nm, or 2,000 nm.



FIG. 12 may show, in plan view, a schematic diagram showing an example of a pattern 1250 of the auxiliary electrode 1150 formed as a grid that may be overlaid over both the lateral aspects 710 of emissive regions 1210, which may correspond to (sub-) pixel(s) 1810/134x of an example version 1200 of device 600, and the lateral aspects 720 of non-emissive regions 1220 surrounding the emissive regions 1210.


In some non-limiting examples, the auxiliary electrode pattern 1250 may extend substantially only over some but not all of the lateral aspects 720 of non-emissive regions 1220, to not substantially cover any of the lateral aspects 710 of the emissive regions 1210.


Those having ordinary skill in the relevant art will appreciate that while, in the figure, the auxiliary electrode pattern 1250 may be shown as being formed as a continuous structure such that all elements thereof are both physically connected to and electrically coupled with one another and electrically coupled with at least one electrode 620, 640, 1150, which in some non-limiting examples may be the first electrode 620, and/or the second electrode 640, in some non-limiting examples, the auxiliary electrode pattern 1250 may be provided as a plurality of discrete elements of the auxiliary electrode pattern 1250 that, while remaining electrically coupled with one another, may not be physically connected to one another. Even so, such discrete elements of the auxiliary electrode pattern 1250 may still substantially lower a sheet resistance R of the at least one electrode 620, 640, 1150 with which they are electrically coupled, and consequently of the device 1200, to increase an efficiency of the device 1200 without substantially interfering with its optical characteristics.


In some non-limiting examples, auxiliary electrodes 1150 may be employed in devices 600 with a variety of arrangements of (sub-) pixel(s) 1810/134x. In some non-limiting examples, the (sub-) pixel 1810/134x arrangement may be substantially diamond-shaped.


By way of non-limiting example, FIG. 13A may show, in plan view, in an example version 1300 of device 600, a plurality of groups 1341-1343 of emissive regions 1210 each corresponding to a sub-pixel 134x, surrounded by the lateral aspects of a plurality of non-emissive regions 1320 comprising PDLs 740 in a diamond configuration. In some non-limiting examples, the configuration may be defined by patterns 1341-1343 of emissive regions 1210 and PDLs 740 in an alternating pattern of first and second rows.


In some non-limiting examples, the lateral aspects 720 of the non-emissive regions 1220 comprising PDLs 740 may be substantially elliptically shaped. In some non-limiting examples, the major axes of the lateral aspects 720 of the non-emissive regions 1220 in the first row may be aligned and substantially normal to the major axes of the lateral aspects 720 of the non-emissive regions 1220 in the second row. In some non-limiting examples, the major axes of the lateral aspects 720 of the non-emissive regions 1220 in the first row may be substantially parallel to an axis of the first row.


In some non-limiting examples, a first group 1341 of emissive regions 1210 may correspond to sub-pixels 134x that emit light at a first wavelength, in some non-limiting examples the sub-pixels 134x of the first group 1341 may correspond to R(ed) sub-pixels 1341. In some non-limiting examples, the lateral aspects 710 of the emissive regions 1210 of the first group 1341 may have a substantially diamond-shaped configuration. In some non-limiting examples, the emissive regions 1210 of the first group 1341 may lie in the pattern of the first row, preceded and followed by PDLs 740. In some non-limiting examples, the lateral aspects 710 of the emissive regions 1210 of the first group 1341 may slightly overlap the lateral aspects 720 of the preceding and following non-emissive regions 1220 comprising PDLs 740 in the same row, as well as of the lateral aspects 720 of adjacent non-emissive regions 1220 comprising PDLs 740 in a preceding and following pattern of the second row.


In some non-limiting examples, a second group 1342 of emissive regions 1210 may correspond to sub-pixels 134x that emit light at a second wavelength, in some non-limiting examples the sub-pixels 134x of the second group 1342 may correspond to G(reen) sub-pixels 1342. In some non-limiting examples, the lateral aspects 710 of the emissive regions 1210 of the second group 1341 may have a substantially elliptical configuration. In some non-limiting examples, the emissive regions 1210 of the second group 1341 may lie in the pattern of the second row, preceded and followed by PDLs 740. In some non-limiting examples, the major axis of some of the lateral aspects 710 of the emissive regions 1210 of the second group 1341 may be at a first angle, which in some non-limiting examples, may be 45° relative to an axis of the second row. In some non-limiting examples, the major axis of others of the lateral aspects 710 of the emissive regions 1210 of the second group 1341 may be at a second angle, which in some non-limiting examples may be substantially normal to the first angle. In some non-limiting examples, the emissive regions 1210 of the first group 1341, whose lateral aspects 710 may have a major axis at the first angle, may alternate with the emissive regions 1210 of the first group 1341, whose lateral aspects 710 may have a major axis at the second angle.


In some non-limiting examples, a third group 1343 of emissive regions 1210 may correspond to sub-pixels 134x that emit light at a third wavelength, in some non-limiting examples the sub-pixels 134x of the third group 1343 may correspond to B(lue) sub-pixels 1343. In some non-limiting examples, the lateral aspects 710 of the emissive regions 1210 of the third group 1343 may have a substantially diamond-shaped configuration. In some non-limiting examples, the emissive regions 1210 of the third group 1343 may lie in the pattern of the first row, preceded and followed by PDLs 740. In some non-limiting examples, the lateral aspects 710 of the emissive regions 1210 of the third group 1343 may slightly overlap the lateral aspects 710 of the preceding and following non-emissive regions 1220 comprising PDLs 740 in the same row, as well as of the lateral aspects 720 of adjacent non-emissive regions 1220 comprising PDLs 740 in a preceding and following pattern of the second row. In some non-limiting examples, the pattern of the second row may comprise emissive regions 1210 of the first group 1341 alternating emissive regions 1210 of the third group 1343, each preceded and followed by PDLs 740.


Turning now to FIG. 13B, there may be shown an example cross-sectional view of the device 1300, taken along line 13B-13B in FIG. 13A. In the figure, the device 1300 may be shown as comprising a substrate 10 and a plurality of elements of a first electrode 620, formed on an exposed layer surface 11 thereof. The substrate 10 may comprise the base substrate 612 (not shown for purposes of simplicity of illustration), and/or at least one TFT structure 701, corresponding to and for driving each sub-pixel 134x. PDLs 740 may be formed over the substrate 10 between elements of the first electrode 620, to define emissive region(s) 1210 over each element of the first electrode 620, separated by non-emissive region(s) 1220 comprising the PDL(s) 740. In the figure, the emissive region(s) 1210 may all correspond to the second group 1342.


In some non-limiting examples, at least one semiconducting layer 630 may be deposited on each element of the first electrode 620, between the surrounding PDLs 740.


In some non-limiting examples, a second electrode 640, which in some non-limiting examples, may be a common cathode, may be deposited over the emissive region(s) 1210 of the second group 1342 to form the G(reen) sub-pixel(s) 1342 thereof and over the surrounding PDLs 740.


In some non-limiting examples, an NIC 110 may be selectively deposited over the second electrode 640 across the lateral aspects 710 of the emissive region(s) 1210 of the second group 1342 of G(reen) sub-pixels 1342 to allow selective deposition of a deposited layer 130 over parts of the second electrode 640 that may be substantially devoid of the NIC 110, namely across the lateral aspects 720 of the non-emissive region(s) 1220 comprising the PDLs 740. In some non-limiting examples, the deposited layer 130 may tend to accumulate along the substantially planar parts of the PDLs 740, as the deposited layer 130 may tend to not remain on the inclined parts of the PDLs 740 but may tend to descend to a base of such inclined parts, which may be coated with the NIC 110. In some non-limiting examples, the deposited layer 130 on the substantially planar parts of the PDLs 740 may form at least one auxiliary electrode 1150 that may be electrically coupled with the second electrode 640.


In some non-limiting examples, the device 1300 may comprise a CPL, and/or an outcoupling layer. By way of non-limiting example, such CPL, and/or outcoupling layer may be provided directly on a surface of the second electrode 640, and/or a surface of the NIC 110. In some non-limiting examples, such CPL, and/or outcoupling layer may be provided across the lateral aspect 710 of at least one emissive region 1210 corresponding to a (sub-) pixel 1810/134x.


In some non-limiting examples, the NIC 110 may also act as an index-matching coating. In some non-limiting examples, the NIC 110 may also act as an outcoupling layer.


In some non-limiting examples, the device 1300 may comprise an encapsulation layer. Non-limiting examples of such encapsulation layer include a glass cap, a barrier film, a barrier adhesive, a barrier coating 1050, and/or a TFE layer 1350 such as shown in dashed outline in the figure, provided to encapsulate the device 1300. In some non-limiting examples, the TFE layer 1350 may be considered a type of barrier coating 1050.


In some non-limiting examples, the encapsulation layer may be arranged above at least one of the second electrode 640, and/or the NIC 110. In some non-limiting examples, the device 1300 may comprise additional optical, and/or structural layers, coatings, and components, including without limitation, a polarizer, a color filter, an anti-reflection coating, an anti-glare coating, cover glass, and/or an optically clear adhesive (OCA).


Turning now to FIG. 13C, there may be shown an example cross-sectional view of the device 1300, taken along line 13C-13C in FIG. 13A. In the figure, the device 1300 may be shown as comprising a substrate 10 and a plurality of elements of a first electrode 620, formed on an exposed layer surface 11 thereof. PDLs 740 may be formed over the substrate 10 between elements of the first electrode 620, to define emissive region(s) 1210 over each element of the first electrode 620, separated by non-emissive region(s) 1220 comprising the PDL(s) 740. In the figure, the emissive region(s) 1210 may correspond to the first group 1341 and to the third group 1343 in alternating fashion.


In some non-limiting examples, at least one semiconducting layer 630 may be deposited on each element of the first electrode 620, between the surrounding PDLs 740.


In some non-limiting examples, a second electrode 640, which in some non-limiting examples, may be a common cathode, may be deposited over the emissive region(s) 1210 of the first group 1341 to form the R(ed) sub-pixel(s) 1341 thereof, over the emissive region(s) 1210 of the third group 1343 to form the B(lue) sub-pixel(s) 1343 thereof, and over the surrounding PDLs 740.


In some non-limiting examples, an NIC 110 may be selectively deposited over the second electrode 640 across the lateral aspects 710 of the emissive region(s) 1210 of the first group 1341 of R(ed) sub-pixels 1341 and of the third group 1343 of B(lue) sub-pixels 1343 to allow selective deposition of a deposited layer 130 over parts of the second electrode 640 that may be substantially devoid of the NIC 110, namely across the lateral aspects 720 of the non-emissive region(s) 1220 comprising the PDLs 740. In some non-limiting examples, the deposited layer 130 may tend to accumulate along the substantially planar parts of the PDLs 740, as the deposited layer 130 may tend to not remain on the inclined parts of the PDLs 740 but may tend to descend to a base of such inclined parts, which are coated with the NIC 110. In some non-limiting examples, the deposited layer 130 on the substantially planar parts of the PDLs 740 may form at least one auxiliary electrode 1150 that may be electrically coupled with the second electrode 640.


Turning now to FIG. 14, there may be shown an example version 1400 of the device 600, which may encompass the device shown in cross-sectional view in FIG. 7, but with additional deposition steps that are described herein.


The device 1400 may show an NIC 110 selectively deposited over the exposed layer surface 11 of the underlying layer, in the figure, the second electrode 640, within a first portion 101 of the device 1400, corresponding substantially to the lateral aspect 710 of emissive region(s) 1210 corresponding to (sub-) pixel(s) 1810/134x and not within a second portion 102 of the device 1400, corresponding substantially to the lateral aspect(s) 720 of non-emissive region(s) 1220 surrounding the first portion 101.


In some non-limiting examples, the NIC 110 may be selectively deposited using a shadow mask 215.


The NIC 110 may provide, within the first portion 101, an exposed layer surface 11 with a relatively low initial sticking probability S0 against deposition of a deposited material 331 to be thereafter deposited as a deposited layer 130 to form an auxiliary electrode 1150.


After selective deposition of the NIC 110, the deposited material 331 may be deposited over the device 1400 but may remain substantially only within the second portion 102, which may be substantially devoid of NIC 110, to form the auxiliary electrode 1150.


In some non-limiting examples, the deposited material 331 may be deposited using an open mask and/or a mask-free deposition process.


The auxiliary electrode 1150 may be electrically coupled with the second electrode 640 to reduce a sheet resistance R of the second electrode 640, including, as shown, by lying above and in physical contact with the second electrode 640 across the second portion that may be substantially devoid of NIC 110.


In some non-limiting examples, the deposited layer 130 may comprise substantially the same material as the second electrode 640, to ensure a high initial sticking probability S0 against deposition of the deposited material 331 in the second portion 102.


In some non-limiting examples, the second electrode 640 may comprise substantially pure Mg, and/or an alloy of Mg and another metal, including without limitation, Ag. In some non-limiting examples, an Mg:Ag alloy composition may range from about 1:9-by volume. In some non-limiting examples, the second electrode 640 may comprise metal oxides, including without limitation, ternary metal oxides, such as, without limitation, ITO, and/or IZO, and/or a combination of metals, and/or metal oxides.


In some non-limiting examples, the deposited layer 130 used to form the auxiliary electrode 1150 may comprise substantially pure Mg.


Turning now to FIG. 15, there may be shown an example version 1500 of the device 600, which may encompass the device shown in cross-sectional view in FIG. 7, but with additional deposition steps that are described herein.


The device 1500 may show an NIC 110 selectively deposited over the exposed layer surface 11 of the underlying layer, in the figure, the second electrode 640, within a first portion 101 of the device 1500, corresponding substantially to a part of the lateral aspect 710 of emissive region(s) 1210 corresponding to (sub-) pixel(s) 1810/134x, and not within a second portion 102. In the figure, the first portion 101 may extend partially along the extent of an inclined part of the PDLs 740 defining the emissive region(s) 1210.


In some non-limiting examples, the NIC 110 may be selectively deposited using a shadow mask 215.


The NIC 110 may provide, within the first portion 101, an exposed layer surface 11 with a relatively low initial sticking probability S0 against deposition of a deposited material 331 to be thereafter deposited as a deposited layer 130 to form an auxiliary electrode 1150.


After selective deposition of the NIC 110, the deposited material 331 may be deposited over the device 1500 but may remain substantially only within the second portion 102, which may be substantially devoid of NIC 110, to form the auxiliary electrode 1150.


As such, in the device 1500, the auxiliary electrode 1150 may extend partly across the inclined part of the PDLs 740 defining the emissive region(s) 1210.


In some non-limiting examples, the deposited layer 130 may be deposited using an open mask and/or a mask-free deposition process.


The auxiliary electrode 1150 may be electrically coupled with the second electrode 640 to reduce a sheet resistance R of the second electrode 640, including, as shown, by lying above and in physical contact with the second electrode 640 across the second portion 102 that may be substantially devoid of NIC 110.


In some non-limiting examples, the material of which the second electrode 640 may be comprised, may not have a high initial sticking probability S0 against deposition of the deposited material 331.



FIG. 16 may illustrate such a scenario, in which there may be shown an example version 1600 of the device 600, which may encompass the device shown in cross-sectional view in FIG. 7, but with additional deposition steps that are described herein.


The device 1600 may show an NPC 520 deposited over the exposed layer surface 11 of the underlying material, in the figure, the second electrode 640.


In some non-limiting examples, the NPC 520 may be deposited using an open mask and/or a mask-free deposition process.


Thereafter, an NIC 110 may be deposited selectively deposited over the exposed layer surface 11 of the underlying material, in the figure, the NPC 520, within a first portion 101 of the device 1600, corresponding substantially to a part of the lateral aspect 710 of emissive region(s) 1210 corresponding to (sub-) pixel(s) 1810/134x, and not within a second portion 102 of the device 1600, corresponding substantially to the lateral aspect(s) 720 of non-emissive region(s) 1220 surrounding the first portion 101.


In some non-limiting examples, the NIC 110 may be selectively deposited using a shadow mask 215.


The NIC 110 may provide, within the first portion 101, an exposed layer surface 11 with a relatively low initial sticking probability S0 against deposition of a deposited material 331 to be thereafter deposited as a deposited layer 130 to form an auxiliary electrode 1150.


After selective deposition of the NIC 110, the deposited material 331 may be deposited over the device 1600 but may remain substantially only within the second portion 102, which may be substantially devoid of NIC 110, to form the auxiliary electrode 1150.


In some non-limiting examples, the deposited layer 130 may be deposited using an open mask and/or a mask-free deposition process.


The auxiliary electrode 1150 may be electrically coupled with the second electrode 640 to reduce a sheet resistance thereof. While, as shown, the auxiliary electrode 1150 may not be lying above and in physical contact with the second electrode 640, those having ordinary skill in the relevant art will nevertheless appreciate that the auxiliary electrode 1150 may be electrically coupled with the second electrode 640 by several well-understood mechanisms. By way of non-limiting example, the presence of a relatively thin film (in some non-limiting examples, of up to about 50 nm) of an NIC 110 may still allow a current to pass therethrough, thus allowing a sheet resistance R of the second electrode 640 to be reduced.


Turning now to FIG. 17, there may be shown an example version 1700 of the device 600, which may encompass the device shown in cross-sectional view in FIG. 7, but with additional deposition steps that are described herein.


The device 1700 may show an NIC 110 deposited over the exposed layer surface 11 of the underlying material, in the figure, the second electrode 640.


In some non-limiting examples, the NIC 110 may be deposited using an open mask and/or a mask-free deposition process.


The NIC 110 may provide an exposed layer surface 11 with a relatively low initial sticking probability S0 against deposition of a deposited material 331 to be thereafter deposited as a deposited layer 130 to form an auxiliary electrode 1150.


After deposition of the NIC 110, an NPC 520 may be selectively deposited over the exposed layer surface 11 of the underlying layer, in the figure, the NIC 110, corresponding substantially to a part of the lateral aspect 720 of non-emissive region(s) 1220, and surrounding a second portion 102 of the device 2800, corresponding substantially to the lateral aspect(s) 710 of emissive region(s) 1210 corresponding to (sub-) pixel(s) 1810/134x.


In some non-limiting examples, the NPC 520 may be selectively deposited using a shadow mask 215.


The NPC 520 may provide, within the first portion 101, an exposed layer surface 11 with a relatively high initial sticking probability S0 against deposition of a deposited material 331 to be thereafter deposited as a deposited layer 130 to form an auxiliary electrode 1150.


After selective deposition of the NPC 520, the deposited material 331 may be deposited over the device 1700 but may remain substantially where the NIC 110 has been overlaid with the NPC 520, to form the auxiliary electrode 1150.


In some non-limiting examples, the deposited layer 130 may be deposited using an open mask and/or a mask-free deposition process.


The auxiliary electrode 1150 may be electrically coupled with the second electrode 640 to reduce a sheet resistance R of the second electrode 640.


Transparent OLED

Because the OLED device 600 may emit photons through either, or both, of the first electrode 620 (in the case of a bottom-emission, and/or a double-sided emission device), as well as the substrate 10, and/or the second electrode 640 (in the case of a top-emission, and/or double-sided emission device), there may be an aim to make either, or both of, the first electrode 620, and/or the second electrode 640 substantially photon- (or light)-transmissive (“transmissive”), in some non-limiting examples, at least across a substantial part of the lateral aspect 710 of the emissive region(s) 1210 of the device 600. In the present disclosure, such a transmissive element, including without limitation, an electrode 620, 640, a material from which such element may be formed, and/or property thereof, may comprise an element, material, and/or property thereof that is substantially transmissive (“transparent”), and/or, in some non-limiting examples, partially transmissive (“semi-transparent”), in some non-limiting examples, in at least one wavelength range.


A variety of mechanisms may be adopted to impart transmissive properties to the device 600, at least across a substantial part of the lateral aspect 710 of the emissive region(s) 1210 thereof.


In some non-limiting examples, including without limitation, where the device 600 is a bottom-emission device, and/or a double-sided emission device, the TFT structure(s) 701 of the driving circuit associated with an emissive region 1210 of a (sub-) pixel 1810/134x, which may at least partially reduce the transmissivity of the surrounding substrate 10, may be located within the lateral aspect 720 of the surrounding non-emissive region(s) 1220 to avoid impacting the transmissive properties of the substrate 10 within the lateral aspect 710 of the emissive region 1210.


In some non-limiting examples, where the device 600 is a double-sided emission device, in respect of the lateral aspect 710 of an emissive region 1210 of a (sub-) pixel 1810/134x, a first one of the electrode 620, 640 may be made substantially transmissive, including without limitation, by at least one of the mechanisms disclosed herein, in respect of the lateral aspect 710 of neighbouring, and/or adjacent (sub-) pixel(s) 1810/134x, a second one of the electrodes 620, 640 may be made substantially transmissive, including without limitation, by at least one of the mechanisms disclosed herein. Thus, the lateral aspect 710 of a first emissive region 1210 of a (sub-) pixel 1810/134x may be made substantially top-emitting while the lateral aspect 710 of a second emissive region 1210 of a neighbouring (sub-) pixel 1810/134x may be made substantially bottom-emitting, such that a subset of the (sub-) pixel(s) 1810/134x may be substantially top-emitting and a subset of the (sub-) pixel(s) 1810/134x may be substantially bottom-emitting, in an alternating (sub-) pixel 1810/134x sequence, while only a single electrode 620, 640 of each (sub-) pixel 1810/134x may be made substantially transmissive.


In some non-limiting examples, a mechanism to make an electrode 620, 640, in the case of a bottom-emission device, and/or a double-sided emission device, the first electrode 620, and/or in the case of a top-emission device, and/or a double-sided emission device, the second electrode 640, transmissive, may be to form such electrode 620, 640 of a transmissive thin film.


In some non-limiting examples, an electrically conductive deposited layer 130, in a thin film, including without limitation, those formed by a depositing a thin conductive film layer of a metal, including without limitation, Ag, Al, and/or by depositing a thin layer of a metallic alloy, including without limitation, an Mg:Ag alloy, and/or a Yb:Ag alloy, may exhibit transmissive characteristics. In some non-limiting examples, the alloy may comprise a composition ranging from between about 1:9-9:1 by volume. In some non-limiting examples, the electrode 620, 640 may be formed of a plurality of thin conductive film layers of any combination of deposited layers 130, any at least one of which may be comprised of TCOs, thin metal films, thin metallic alloy films, and/or any combination of any of these.


In some non-limiting examples, especially in the case of such thin conductive films, a relatively thin layer thickness may be up to substantially a few tens of nm to contribute to enhanced transmissive qualities but also favorable optical properties (including without limitation, reduced microcavity effects) for use in an OLED device 600.


In some non-limiting examples, a reduction in the thickness of an electrode 620, 640 to promote transmissive qualities may be accompanied by an increase in the sheet resistance of the electrode 620, 640.


In some non-limiting examples, a device 600 having at least one electrode 620, 640 with a high sheet resistance creates a large current resistance (IR) drop when coupled with the power source 605, in operation. In some non-limiting examples, such an IR drop may be compensated for, to some extent, by increasing a level of the power source 605. However, in some non-limiting examples, increasing the level of the power source 605 to compensate for the IR drop due to high sheet resistance, for at least one (sub-) pixel 1810/134x may call for increasing the level of a voltage to be supplied to other components to maintain effective operation of the device 600.


In some non-limiting examples, to reduce power supply demands for a device 600 without significantly impacting an ability to make an electrode 620, 640 substantially transmissive (by employing at least one thin film layer of any combination of TCOs, thin metal films, and/or thin metallic alloy films), an auxiliary electrode 1150 may be formed on the device 600 to allow current to be carried more effectively to various emissive region(s) of the device 600, while at the same time, reducing the sheet resistance and its associated IR drop of the transmissive electrode 620, 640.


In some non-limiting examples, a sheet resistance specification, for a common electrode 620, 640 of a display device 600, may vary according to several parameters, including without limitation, a (panel) size of the device 600, and/or a tolerance for voltage variation across the device 600. In some non-limiting examples, the sheet resistance specification may increase (that is, a lower sheet resistance R is specified) as the panel size increases. In some non-limiting examples, the sheet resistance specification may increase as the tolerance for voltage variation decreases.


In some non-limiting examples, a sheet resistance specification may be used to derive an example thickness of an auxiliary electrode 1150 to comply with such specification for various panel sizes.


By way of non-limiting example, for a top-emission device, the second electrode 640 may be made transmissive. On the other hand, in some non-limiting examples, such auxiliary electrode 1150 may not be substantially transmissive but may be electrically coupled with the second electrode 640, including without limitation, by deposition of a conductive deposited layer 130 therebetween, to reduce an effective sheet resistance of the second electrode 640.


In some non-limiting examples, such auxiliary electrode 1150 may be positioned, and/or shaped in either, or both of, a lateral aspect, and/or cross-sectional aspect to not interfere with the emission of photons from the lateral aspect 710 of the emissive region 1210 of a (sub-) pixel 1810/134x.


In some non-limiting examples, a mechanism to make the first electrode 620, and/or the second electrode 640, may be to form such electrode 620, 640 in a pattern across at least a part of the lateral aspect 710 of the emissive region(s) 1210 thereof, and/or in some non-limiting examples, across at least a part of the lateral aspect 720 of the non-emissive region(s) 1220 surrounding them. In some non-limiting examples, such mechanism may be employed to form the auxiliary electrode 1150 in a position, and/or shape in either, or both of, a lateral aspect, and/or cross-sectional aspect to not interfere with the emission of photons from the lateral aspect 710 of the emissive region 1210 of a (sub-) pixel 1810/134x, as discussed above.


In some non-limiting examples, the device 600 may be configured such that it may be substantially devoid of a conductive oxide material in an optical path of photons emitted by the device 600. By way of non-limiting example, in the lateral aspect 710 of at least one emissive region 1210 corresponding to a (sub-) pixel 1810/134x, at least one of the layers, and/or coatings deposited after the at least one semiconducting layer 630, including without limitation, the second electrode 640, the NIC 110, and/or any other layers, and/or coatings deposited thereon, may be substantially devoid of any conductive oxide material. In some non-limiting examples, being substantially devoid of any conductive oxide material may reduce absorption, and/or reflection of light emitted by the device 600. By way of non-limiting example, conductive oxide materials, including without limitation, ITO, and/or IZO, may absorb light in at least the B(lue) region of the visible spectrum, which may, in generally, reduce efficiency, and/or performance of the device 600.


In some non-limiting examples, a combination of these, and/or other mechanisms may be employed.


Additionally, in some non-limiting examples, in addition to rendering at least one of the first electrode 620, the second electrode 640, and/or the auxiliary electrode 1150, substantially transmissive across at least across a substantial part of the lateral aspect 710 of the emissive region 1210 corresponding to the (sub-) pixel(s) 1810/134x of the device 600, to allow photons to be emitted substantially across the lateral aspect 710 thereof, there may be an aim to make at least one of the lateral aspect(s) 720 of the surrounding non-emissive region(s) 1220 of the device 600 substantially transmissive in both the bottom and top directions, to render the device 600 substantially transmissive relative to light incident on an external surface thereof, such that a substantial part of such externally-incident light may be transmitted through the device 600, in addition to the emission (in a top-emission, bottom-emission, and/or double-sided emission) of photons generated internally within the device 600 as disclosed herein.


Turning now to FIG. 18A, there may be shown an example plan view of a transmissive (transparent) version, shown generally at 1800, of the device 600. In some non-limiting examples, the device 600 may be an AMOLED device having a plurality of pixels or pixel regions 1810 and a plurality of transmissive regions 1820. In some non-limiting examples, at least one auxiliary electrode 1150 may be deposited on an exposed layer surface 11 of an underlying material between the pixel region(s) 1810, and/or the transmissive region(s) 1820.


In some non-limiting examples, each pixel region 1810 may comprise a plurality of emissive regions 1210 each corresponding to a sub-pixel 134x. In some non-limiting examples, the sub-pixels 134x may correspond to, respectively, R(ed) sub-pixels 1341, G(reen) sub-pixels 1342, and/or B(lue) sub-pixels 1343.


In some non-limiting examples, each transmissive region 1820 may be substantially transparent and allows light to pass through the entirety of a cross-sectional aspect thereof.


Turning now to FIG. 18B, there may be shown an example cross-sectional view of a version 1800 of the device 600, taken along line 18B-18B in FIG. 18A. In the figure, the device 1800 may be shown as comprising a substrate 10, a TFT insulating layer 709 and a first electrode 620 formed on a surface of the TFT insulating layer 709. The substrate 10 may comprise the base substrate 612 (not shown for purposes of simplicity of illustration), and/or at least one TFT structure 701, corresponding to, and for driving, each sub-pixel 134x positioned substantially thereunder and electrically coupled with the first electrode 620 thereof. PDL(s) 740 may be formed in non-emissive regions 1220 over the substrate 10, to define emissive region(s) 1210 also corresponding to each sub-pixel 134x, over the first electrode 620 corresponding thereto. The PDL(s) 740 may cover edges of the first electrode 620.


In some non-limiting examples, at least one semiconducting layer 630 may be deposited over exposed region(s) of the first electrode 620 and, in some non-limiting examples, at least parts of the surrounding PDLs 740.


In some non-limiting examples, a second electrode 640 may be deposited over the at least one semiconducting layer(s) 630, including over the pixel region 1810 to form the sub-pixel(s) 134x thereof and, in some non-limiting examples, at least partially over the surrounding PDLs 740 in the transmissive region 1820.


In some non-limiting examples, an NIC 110 may be selectively deposited over first portion(s) 301 of the device 1800, comprising both the pixel region 1810 and the transmissive region 1820 but not the region of the second electrode 640 corresponding to the auxiliary electrode 1150 comprising second portion(s) 302 thereof.


In some non-limiting examples, the entire exposed layer surface 11 of the device 1800 may then be exposed to a vapor flux 332 of the deposited material 331, which in some non-limiting examples may be Mg. The deposited layer 130 may be selectively deposited over second portion(s) of the second electrode 640 that may be substantially devoid of the NIC 110 to form an auxiliary electrode 1150 that may be electrically coupled with and in some non-limiting examples, in physical contact with uncoated parts of the second electrode 640.


At the same time, the transmissive region 1820 of the device 1800 may remain substantially devoid of any materials that may substantially affect the transmission of light therethrough. In particular, as shown in the figure, the TFT structure 701 and the first electrode 620 may be positioned, in a cross-sectional aspect, below the sub-pixel 134x corresponding thereto, and together with the auxiliary electrode 1150, may lie beyond the transmissive region 1820. As a result, these components may not attenuate or impede light from being transmitted through the transmissive region 1820. In some non-limiting examples, such arrangement may allow a viewer viewing the device 1800 from a typical viewing distance to see through the device 1800, in some non-limiting examples, when all the (sub-) pixel(s) 1810/134x may not be emitting, thus creating a transparent device 1800.


While not shown in the figure, in some non-limiting examples, the device 1800 may further comprise an NPC 520 disposed between the auxiliary electrode 1150 and the second electrode 640. In some non-limiting examples, the NPC 520 may also be disposed between the NIC 110 and the second electrode 640.


In some non-limiting examples, the NIC 110 may be formed concurrently with the at least one semiconducting layer(s) 630. By way of non-limiting example, at least one material used to form the NIC 110 may also be used to form the at least one semiconducting layer(s) 630. In such non-limiting example, several stages for fabricating the device 1800 may be reduced.


Those having ordinary skill in the relevant art will appreciate that in some non-limiting examples, various other layers, and/or coatings, including without limitation those forming the at least one semiconducting layer(s) 630, and/or the second electrode 640, may cover a part of the transmissive region 1820, especially if such layers, and/or coatings are substantially transparent. In some non-limiting examples, the PDL(s) 740 may have a reduced thickness, including without limitation, by forming a well therein, which in some non-limiting examples may be similar to the well defined for emissive region(s) 1210, to further facilitate light transmission through the transmissive region 1820.


Those having ordinary skill in the relevant art will appreciate that (sub-) pixel(s) 1810/134x arrangements other than the arrangement shown in FIGS. 18A and 18B may, in some non-limiting examples, be employed.


Those having ordinary skill in the relevant art will appreciate that arrangements of the auxiliary electrode(s) 1150 other than the arrangement shown in FIGS. 18A and 18B may, in some non-limiting examples, be employed. By way of non-limiting example, the auxiliary electrode(s) 1150 may be disposed between the pixel region 1810 and the transmissive region 1820. By way of non-limiting example, the auxiliary electrode(s) 1150 may be disposed between sub-pixel(s) 134x within a pixel region 1810.


Turning now to FIG. 19A, there may be shown an example plan view of a transparent version, shown generally at 1900, of the device 600. In some non-limiting examples, the device 1900 may be an AMOLED device having a plurality of pixel regions 1810 and a plurality of transmissive regions 1820. The device 1900 may differ from device 1800 in that no auxiliary electrode(s) 1150 lie between the pixel region(s) 1810, and/or the transmissive region(s) 1820.


In some non-limiting examples, each pixel region 1810 may comprise a plurality of emissive regions 1210, each corresponding to a sub-pixel 134x. In some non-limiting examples, the sub-pixels 134x may correspond to, respectively, R(ed) sub-pixels 1341, G(reen) sub-pixels 1342, and/or B(lue) sub-pixels 1343.


In some non-limiting examples, each transmissive region 1820 may be substantially transparent and may allow light to pass through the entirety of a cross-sectional aspect thereof.


Turning now to FIG. 19B, there may be shown an example cross-sectional view of the device 1900, taken along line 19-19 in FIG. 19A. In the figure, the device 1900 may be shown as comprising a substrate 10, a TFT insulating layer 709 and a first electrode 620 formed on a surface of the TFT insulating layer 709. The substrate 10 may comprise the base substrate 612 (not shown for purposes of simplicity of illustration), and/or at least one TFT structure 701 corresponding to, and for driving, each sub-pixel 134x positioned substantially thereunder and electrically coupled with the first electrode 620 thereof. PDL(s) 740 may be formed in non-emissive regions 1220 over the substrate 10, to define emissive region(s) 1210 also corresponding to each sub-pixel 134x, over the first electrode 620 corresponding thereto. The PDL(s) 740 cover edges of the first electrode 620.


In some non-limiting examples, at least one semiconducting layer 630 may be deposited over exposed region(s) of the first electrode 620 and, in some non-limiting examples, at least parts of the surrounding PDLs 740.


In some non-limiting examples, a first deposited layer 130a may be deposited over the at least one semiconducting layer(s) 630, including over the pixel region 1810 to form the sub-pixel(s) 134x thereof and over the surrounding PDLs 740 in the transmissive region 1820. In some non-limiting examples, the thickness of the first deposited layer 130a may be relatively thin such that the presence of the first deposited layer 130a across the transmissive region 1820 does not substantially attenuate transmission of light therethrough. In some non-limiting examples, the first deposited layer 130a may be deposited using an open mask and/or mask-free deposition process.


In some non-limiting examples, an NIC 110 may be selectively deposited over first portions of the device 1900, comprising the transmissive region 1820.


In some non-limiting examples, the entire exposed layer surface 11 of the device 1900 may then be exposed to a vapor flux 332 of the deposited material 331, which in some non-limiting examples may be Mg, to selectively deposit a second deposited layer 130b, over second portion(s) 302 of the first deposited layer 130a that may be substantially devoid of the NIC 110, in some examples, the pixel region 1810, such that the second deposited layer 130b may be electrically coupled with and in some non-limiting examples, in physical contact with uncoated parts of the first deposited layer 130a, to form the second electrode 640.


In some non-limiting examples, a thickness of the first deposited layer 130a may be less than a thickness of the second deposited layer 130b. In this way, relatively high transmittance may be maintained in the transmissive region 1820, over which only the first deposited layer 130a may extend. In some non-limiting examples, a thickness of the first deposited layer 130a may be less than about: 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, 8 nm, and/or 5 nm. In some non-limiting examples, a thickness of the second deposited layer 130b may be less than about: 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, or 8 nm.


Thus, in some non-limiting examples, a thickness of the second electrode 640 may be less than about 40 nm, and/or in some non-limiting examples, between about: 5-30 nm, 10-25 nm, or 15-25 nm.


In some non-limiting examples, the thickness of the first deposited layer 130a may exceed the thickness of the second deposited layer 130b. In some non-limiting examples, the thickness of the first deposited layer 130a and the thickness of the second deposited layer 130b may be substantially the same.


In some non-limiting examples, at least one deposited material 331 used to form the first deposited layer 130a may be substantially the same as at least one deposited material 331 used to form the second deposited layer 130b. In some non-limiting examples, such at least one deposited material 331 may be substantially as described herein in respect of the first electrode 620, the second electrode 640, the auxiliary electrode 1150, and/or a deposited layer 130 thereof.


In some non-limiting examples, the transmissive region 1820 of the device 3100 may remain substantially devoid of any materials that may substantially inhibit the transmission of light therethrough. In particular, as shown in the figure, the TFT structure, and/or the first electrode 620 may be positioned, in a cross-sectional aspect below the sub-pixel 134x corresponding thereto and beyond the transmissive region 1820. As a result, these components may not attenuate or impede light from being transmitted through the transmissive region 1820. In some non-limiting examples, such arrangement may allow a viewer viewing the device 1900 from a typical viewing distance to see through the device 3100, in some non-limiting examples, when the (sub-) pixel(s) 1810/134x are not emitting, thus creating a transparent AMOLED device 1900.


While not shown in the figure, in some non-limiting examples, the device 1900 may further comprise an NPC 520 disposed between the second deposited layer 130b and the first deposited layer 130a. In some non-limiting examples, the NPC 520 may also be disposed between the NIC 110 and the first deposited layer 130a.


In some non-limiting examples, the NIC 110 may be formed concurrently with the at least one semiconducting layer(s) 630. By way of non-limiting example, at least one material used to form the NIC 110 may also be used to form the at least one semiconducting layer(s) 630. In such non-limiting example, several stages for fabricating the device 1900 may be reduced.


Those having ordinary skill in the relevant art will appreciate that in some non-limiting examples, various other layers, and/or coatings, including without limitation those forming the at least one semiconducting layer(s) 630, and/or the first deposited layer 130a, may cover a part of the transmissive region 1820, especially if such layers, and/or coatings are substantially transparent. In some non-limiting examples, the PDL(s) 740 may have a reduced thickness, including without limitation, by forming a well therein, which in some non-limiting examples may be similar to the well defined for emissive region(s) 1210, to further facilitate light transmission through the transmissive region 1820.


Those having ordinary skill in the relevant art will appreciate that (sub-) pixel(s) 1810/134x arrangements other than the arrangement shown in FIGS. 19A and 19B may, in some non-limiting examples, be employed.


Turning now to FIG. 19C, there may be shown an example cross-sectional view of a different version 1910 of the device 600, taken along the same line 19-19 in FIG. 19A. In the figure, the device 1910 may be shown as comprising a substrate 10, a TFT insulating layer 709 and a first electrode 620 formed on a surface of the TFT insulating layer 709. The substrate 10 may comprise the base substrate 612 (not shown for purposes of simplicity of illustration), and/or at least one TFT structure 701 corresponding to and for driving each sub-pixel 134x positioned substantially thereunder and electrically coupled with the first electrode 620 thereof. PDL(s) 740 may be formed in non-emissive regions 1220 over the substrate 10, to define emissive region(s) 1210 also corresponding to each sub-pixel 134x, over the first electrode 620 corresponding thereto. The PDL(s) 740 may cover edges of the first electrode 620.


In some non-limiting examples, at least one semiconducting layer 630 may be deposited over exposed region(s) of the first electrode 620 and, in some non-limiting examples, at least parts of the surrounding PDLs 740.


In some non-limiting examples, an NIC 110 may be selectively deposited over first portions 101 of the device 1910, comprising the transmissive region 1820.


In some non-limiting examples, a deposited layer 130 may be deposited over the at least one semiconducting layer(s) 630, including over the pixel region 1810 to form the sub-pixel(s) 134x thereof but not over the surrounding PDLs 740 in the transmissive region 1820. In some non-limiting examples, the first deposited layer 130a may be deposited using an open mask and/or mask-free deposition process. In some non-limiting examples, such deposition may be effected by exposing the entire exposed layer surface 11 of the device 1910 to a vapor flux 332 of the deposited material 331, which in some non-limiting examples may be Mg, to selectively deposit the deposited layer 130 over second portions 102 of the at least one semiconducting layer(s) 630 that are substantially devoid of the NIC 110, in some examples, the pixel region 1810, such that the deposited layer 130 may be deposited on the at least one semiconducting layer(s) 630 to form the second electrode 640.


In some non-limiting examples, the transmissive region 1820 of the device 1910 may remain substantially devoid of any materials that may substantially affect the transmission of light therethrough. In particular, as shown in the figure, the TFT structure 701, and/or the first electrode 620 may be positioned, in a cross-sectional aspect below the sub-pixel 134x corresponding thereto and beyond the transmissive region 1820. As a result, these components may not attenuate or impede light from being transmitted through the transmissive region 1820. In some non-limiting examples, such arrangement may allow a viewer viewing the device 1910 from a typical viewing distance to see through the device 3110, in some non-limiting examples, when the (sub-) pixel(s) 1810/134x are not emitting, thus creating a transparent AMOLED device 3110.


By providing a transmissive region 1820 that may be free, and/or substantially devoid of any deposited layer 130, the transmittance in such region may, in some non-limiting examples, be favorably enhanced, by way of non-limiting example, by comparison to the device 1900 of FIG. 19B.


While not shown in the figure, in some non-limiting examples, the device 1910 may further comprise an NPC 520 disposed between the deposited layer 130 and the at least one semiconducting layer(s) 630. In some non-limiting examples, the NPC 520 may also be disposed between the NIC 110 and the PDL(s) 740.


In some non-limiting examples, the NIC 110 may be formed concurrently with the at least one semiconducting layer(s) 630. By way of non-limiting example, at least one material used to form the NIC 110 may also be used to form the at least one semiconducting layer(s) 630. In such non-limiting example, several stages for fabricating the device 3110 may be reduced.


Those having ordinary skill in the relevant art will appreciate that in some non-limiting examples, various other layers, and/or coatings, including without limitation those forming the at least one semiconducting layer(s) 630, and/or the deposited layer 130, may cover a part of the transmissive region 1820, especially if such layers, and/or coatings are substantially transparent. In some non-limiting examples, the PDL(s) 740 may have a reduced thickness, including without limitation, by forming a well therein, which in some non-limiting examples may be similar to the well defined for emissive region(s) 1210, to further facilitate light transmission through the transmissive region 1820.


Those having ordinary skill in the relevant art will appreciate that (sub-) pixel(s) 1810/134x arrangements other than the arrangement shown in FIGS. 19A and 19C may, in some non-limiting examples, be employed.


Selective Deposition to Modulate Electrode Thickness over Emissive Region(s)


As discussed above, modulating the thickness of an electrode 620, 640, 1150 in and across a lateral aspect 710 of emissive region(s) 1210 of a (sub-) pixel 1810/134x may impact the microcavity effect observable. In some non-limiting examples, selective deposition of at least one deposited layer 130 through deposition of at least one patterning coating 210, such as an NIC 110, and/or an NPC 520, in the lateral aspects 710 of emissive region(s) 1210 corresponding to different sub-pixel(s) 134x in a pixel region 1810 may allow the optical microcavity effect in each emissive region 1210 to be controlled, and/or modulated to optimize desirable optical microcavity effects on a sub-pixel 134x basis, including without limitation, an emission spectrum, a luminous intensity, and/or an angular dependence of a brightness, and/or a color shift of emitted light.


Such effects may be controlled by independently modulating a thickness and/or several the deposited layer(s) 130, disposed in each emissive region 1210 of the sub-pixel(s) 134x. By way of non-limiting example, the thickness of a second electrode 640 disposed over a B(lue) sub-pixel 1343 may be less than the thickness of second electrode 640 disposed over a G(reen) sub-pixel 1342, and the thickness of the second electrode 640 disposed over a G(reen) sub-pixel 1342 may be less than the thickness of a second electrode 640 disposed over a R(ed) sub-pixel 1341.


In some non-limiting examples, such effects may be controlled to an even greater extent by independently modulating the thickness and/or a number of the deposited layers 130, but also of the patterning coating 210, including without limitation, an NIC 110 and/or an NPC 520, deposited in part(s) of each emissive region 1210 of the sub-pixel(s) 134x.


As shown by way of non-limiting example in FIG. 20, there may be deposited layer(s) 330 of varying thickness selectively deposited for emissive region(s) 1210 corresponding to sub-pixel(s) 134x, in some non-limiting examples, in a version 2000 of an OLED display device 600, having different emission spectra. In some non-limiting examples, a first emissive region 1210a may correspond to a sub-pixel 134x configured to emit light of a first wavelength, and/or emission spectrum, and/or in some non-limiting examples, a second emissive region 1210b may correspond to a sub-pixel 134x configured to emit light of a second wavelength, and/or emission spectrum. In some non-limiting examples, a device 600 may comprise a third emissive region 1210c that may correspond to a sub-pixel 134x configured to emit light of a third wavelength, and/or emission spectrum.


In some non-limiting examples, the first wavelength may be less than, greater than, and/or equal to at least one of the second wavelength, and/or the third wavelength. In some non-limiting examples, the second wavelength may be less than, greater than, and/or equal to at least one of the first wavelength, and/or the third wavelength. In some non-limiting examples, the third wavelength may be less than, greater than, and/or equal to at least one of the first wavelength, and/or the second wavelength.


In some non-limiting examples, the device 2000 may also comprise at least one additional emissive region 1210 (not shown) that may in some non-limiting examples be configured to emit light having a wavelength, and/or emission spectrum that is substantially identical to at least one of the first emissive region 1210a, the second emissive region 1210b, and/or the third emissive region 1210c.


In some non-limiting examples, the NIC 110 may be selectively deposited using a shadow mask 215 that may also have been used to deposit the at least one semiconducting layer 630 of the first emissive region 1210a. In some non-limiting examples, such shared use of a shadow mask 215 may allow the optical microcavity effect(s) to be tuned for each sub-pixel 134x in a cost-effective manner.


The device 2000 may be shown as comprising a substrate 10, a TFT insulating layer 709 and a plurality of first electrodes 620a-620c, formed on an exposed layer surface 11 of the TFT insulating layer 709.


The substrate 10 may comprise the base substrate 612 (not shown for purposes of simplicity of illustration), and/or at least one TFT structure 701a-701c corresponding to, and for driving, a corresponding emissive region 1210a-2210c, each having a corresponding sub-pixel 134x, positioned substantially thereunder and electrically coupled with its associated first electrode 620a-620c. PDL(s) 740a-740d may be formed over the substrate 10, to define emissive region(s) 1210a-1210c. The PDL(s) 740a-740d may cover edges of their respective first electrodes 620a-620c.


In some non-limiting examples, at least one semiconducting layer 630a-630c may be deposited over exposed region(s) of their respective first electrodes 620a-620c and, in some non-limiting examples, at least parts of the surrounding PDLs 740a-740d.


In some non-limiting examples, a first deposited layer 130a may be deposited over the at least one semiconducting layer(s) 630a-630c. In some non-limiting examples, the first deposited layer 130a may be deposited using an open mask and/or mask-free deposition process. In some non-limiting examples, such deposition may be effected by exposing the entire exposed layer surface 11 of the device 2000 to a vapor flux 332 of deposited material 331, which in some non-limiting examples may be Mg, to deposit the first deposited layer 130a over the at least one semiconducting layer(s) 630a-1030c to form a first layer of the second electrode 640a (not shown), which in some non-limiting examples may be a common electrode, at least for the first emissive region 1210a. Such common electrode may have a first thickness tc1 in the first emissive region 1210a. The first thickness tc1 may correspond to a thickness of the first deposited layer 130a.


In some non-limiting examples, a first NIC 110a may be selectively deposited over first portions 101 of the device 3300, comprising the first emissive region 1210a.


In some non-limiting examples, a second deposited layer 130b may be deposited over the device 3300. In some non-limiting examples, the second deposited layer 130b may be deposited using an open mask and/or mask-free deposition process. In some non-limiting examples, such deposition may be effected by exposing the entire exposed layer surface 11 of the device 3300 to a vapor flux 332 of deposited material 331, which in some non-limiting examples may be Mg, to deposit the second deposited layer 130b over the first deposited layer 130a that may be substantially devoid of the first NIC 110a, in some examples, the second and third emissive regions 1210b, 1210c, and/or at least part(s) of the non-emissive region(s) 1220 in which the PDLs 740a-740d lie, such that the second deposited layer 130b may be deposited on the second portion(s) 302 of the first deposited layer 130a that are substantially devoid of the first NIC 110a to form a second layer of the second electrode 640b (not shown), which in some non-limiting examples, may be a common electrode, at least for the second emissive region 1210b. Such common electrode may have a second thickness tc2 in the second emissive region 1210b. The second thickness tc2 may correspond to a combined thickness of the first deposited layer 130a and of the second deposited layer 130b and may in some non-limiting examples exceed the first thickness tc1.


In some non-limiting examples, a second NIC 110b may be selectively deposited over further first portions 101 of the device 2000, comprising the second emissive region 1210b.


In some non-limiting examples, a third deposited layer 130c may be deposited over the device 2000. In some non-limiting examples, the third deposited layer 130c may be deposited using an open mask and/or mask-free deposition process. In some non-limiting examples, such deposition may be effected by exposing the entire exposed layer surface 11 of the device 3300 to a vapor flux 332 of deposited material 331, which in some non-limiting examples may be Mg, to deposit the third deposited layer 130c over the second deposited layer 130b that may be substantially devoid of either the first NIC 110a or the second NIC 110b, in some examples, the third emissive region 1210c, and/or at least part(s) of the non-emissive region 1220 in which the PDLs 740a-740d lie, such that the third deposited layer 130c may be deposited on the further second portion(s) 102 of the second deposited layer 130b that are substantially devoid of the second NIC 110b to form a third layer of the second electrode 640c (not shown), which in some non-limiting examples, may be a common electrode, at least for the third emissive region 1210c. Such common electrode may have a third thickness tc3 in the third emissive region 1210c. The third thickness tc3 may correspond to a combined thickness of the first deposited layer 130a, the second deposited layer 130b and the third deposited layer 130c and may in some non-limiting examples exceed either, or both of, the first thickness tc1 and the second thickness tc2.


In some non-limiting examples, a third NIC 110c may be selectively deposited over additional first portions 101 of the device 3300, comprising the third emissive region 1210b.


In some non-limiting examples, at least one auxiliary electrode 1150 may be disposed in the non-emissive region(s) 1220 of the device 2000 between neighbouring emissive regions 1210a-1210c thereof and in some non-limiting examples, over the PDLs 740a-740d. In some non-limiting examples, the deposited layer 130 used to deposit the at least one auxiliary electrode 1150 may be deposited using an open mask and/or mask-free deposition process. In some non-limiting examples, such deposition may be effected by exposing the entire exposed layer surface 11 of the device 3300 to a vapor flux 332 of deposited material 331, which in some non-limiting examples may be Mg, to deposit the deposited layer 130 over the exposed parts of the first deposited layer 130a, the second deposited layer 130b and the third deposited layer 130c that may be substantially devoid of any of the first NIC 110a the second NIC 110b, and/or the third NIC 110c, such that the deposited layer 130 is deposited on an additional second portion 102 comprising the exposed part(s) of the first deposited layer 130a, the second deposited layer 130b, and/or the third deposited layer 130c that may be substantially devoid of any of the first NIC 110a, the second NIC 110b, and/or the third NIC 110c to form the at least one auxiliary electrode 1150. Each of the at least one auxiliary electrodes 1150 may be electrically coupled with a respective one of the second electrodes 640a-1040c. In some non-limiting examples, each of the at least one auxiliary electrode 1150 may be in physical contact with such second electrode 640a-1040c.


In some non-limiting examples, the first emissive region 1210a, the second emissive region 1210b and the third emissive region 1210c may be substantially devoid of a closed coating 140 of the deposited material 331 used to form the at least one auxiliary electrode 1150.


In some non-limiting examples, at least one of the first deposited layer 130a, the second deposited layer 130b, and/or the third deposited layer 130c may be transmissive, and/or substantially transparent in at least a part of the visible wavelength range of the electromagnetic spectrum. Thus, the second deposited layer 130b, and/or the third deposited layer 130a (and/or any additional deposited layer(s) 330) may be disposed on top of the first deposited layer 130a to form a multi-coating electrode 620, 640, 1150 that may also be transmissive, and/or substantially transparent in at least a part of the visible wavelength range of the electromagnetic spectrum. In some non-limiting examples, the transmittance of any at least one of the first deposited layer 130a, the second deposited layer 130b, the third deposited layer 130c, any additional deposited layer(s) 330, and/or the multi-coating electrode 620, 640, 1150 may exceed about: 30%, 40% 45%, 50%, 60%, 70%, 75%, or 80% in at least a part of the visible spectrum.


In some non-limiting examples, a thickness of the first deposited layer 130a, the second deposited layer 130b, and/or the third deposited layer 130c may be made relatively thin to maintain a relatively high transmittance. In some non-limiting examples, a thickness of the first deposited layer 130a may be between about: 5-30 nm, 8-25 nm, or 10-20 nm. In some non-limiting examples, a thickness of the second deposited layer 130b may be between about: 1-25 nm, 1-20 nm, 1-15 nm, 1-10 nm, or 3-6 nm. In some non-limiting examples, a thickness of the third deposited layer 130c may be between about: 1-25 nm, 1-20 nm, 1-15 nm, 1-10 nm, or 3-6 nm. In some non-limiting examples, a thickness of a multi-coating electrode formed by a combination of the first deposited layer 130a, the second deposited layer 130b, the third deposited layer 130c, and/or any additional deposited layer(s) 330 may be between about: 6-35 nm, 10-30 nm, 10-25 nm, or 12-18 nm.


In some non-limiting examples, a thickness of the at least one auxiliary electrode 1150 may exceed a thickness of the first deposited layer 130a, the second deposited layer 130b, the third deposited layer 130c, and/or a common electrode. In some non-limiting examples, the thickness of the at least one auxiliary electrode 1150 may exceed about: 50 nm, 80 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 700 nm, 800 nm, 1 μm, 1.2 μm, 1.5 μm, 2 μm, 2.5 μm, or 3 μm.


In some non-limiting examples, the at least one auxiliary electrode 1150 may be substantially non-transparent, and/or opaque. However, since the at least one auxiliary electrode 1150 may be in some non-limiting examples provided in a non-emissive region 1220 of the device 3300, the at least one auxiliary electrode 1150 may not cause or contribute to significant optical interference. In some non-limiting examples, the transmittance of the at least one auxiliary electrode 1150 may be less than about: 50%, 70%, 80%, 85%, 90%, or 95% in at least a part of the visible spectrum.


In some non-limiting examples, the at least one auxiliary electrode 1150 may absorb light in at least a part of the visible spectrum.


In some non-limiting examples, a thickness of the first NIC 110a, the second NIC 110b, and/or the third NIC 110c disposed in the first emissive region 1210a, the second emissive region 1210b, and/or the third emissive region 1210c respectively, may be varied according to a colour, and/or emission spectrum of light emitted by each emissive region 1210a-2210c. In some non-limiting examples, the first NIC 110a may have a first NIC thickness tn1, the second NIC 110b may have a second NIC thickness tn2, and/or the third NIC 110c may have a third NIC thickness tn3. In some non-limiting examples, the first NIC thickness tn1, the second NIC thickness tn2, and/or the third NIC thickness tn3, may be substantially the same. In some non-limiting examples, the first NIC thickness tn1, the second NIC thickness tn2, and/or the third NIC thickness 673, may be different from one another.


In some non-limiting examples, the device 2000 may also comprise any number of emissive regions 1210a-1210c, and/or (sub-) pixel(s) 1810/134x thereof. In some non-limiting examples, a device may comprise a plurality of pixels 1810, wherein each pixel 1810 comprises two, three or more sub-pixel(s) 134x.


Those having ordinary skill in the relevant art will appreciate that the specific arrangement of (sub-) pixel(s) 1810/134x may be varied depending on the device design. In some non-limiting examples, the sub-pixel(s) 134x may be arranged according to known arrangement schemes, including without limitation, RGB side-by-side, diamond, and/or PenTile®.


Conductive Coating for Electrically Coupling an Electrode to an Auxiliary Electrode

Turning to FIG. 21, there may be shown a cross-sectional view of an example version 2100 of the device 600. The device 2100 may comprise in a lateral aspect, an emissive region 1210 and an adjacent non-emissive region 1220.


In some non-limiting examples, the emissive region 1210 may correspond to a sub-pixel 134x of the device 2100. The emissive region 1210 may have a substrate 10, a first electrode 620, a second electrode 640 and at least one semiconducting layer 630 arranged therebetween.


The first electrode 620 may be disposed on an exposed layer surface 11 of the substrate 10. The substrate 10 may comprise a TFT structure 701, that may be electrically coupled with the first electrode 620. The edges, and/or perimeter of the first electrode 620 may generally be covered by at least one PDL 740.


The non-emissive region 1220 may have an auxiliary electrode 1150 and a first part of the non-emissive region 1220 may have a projecting structure 2160 arranged to project over and overlap a lateral aspect of the auxiliary electrode 1150. The projecting structure 2160 may extend laterally to provide a sheltered region 2165. By way of non-limiting example, the projecting structure 2160 may be recessed at, and/or near the auxiliary electrode 1150 on at least one side to provide the sheltered region 2165. As shown, the sheltered region 2165 may in some non-limiting examples, correspond to a region on a surface of the PDL 740 that may overlap with a lateral projection of the projecting structure 2160. The non-emissive region 1220 may further comprise a deposited layer 130 disposed in the sheltered region 2165. The deposited layer 130 may electrically couple the auxiliary electrode 1150 with the second electrode 640.


An NIC 110a may be disposed in the emissive region 1210 over the exposed layer surface 11 of the second electrode 640. In some non-limiting examples, an exposed layer surface 11 of the projecting structure 2160 may be coated with a residual thin conductive film from deposition of a thin conductive film to form a second electrode 640. In some non-limiting examples, an exposed layer surface 11 of the residual thin conductive film may be coated with a residual NIC 110b from deposition of the NIC 110.


However, because of the lateral projection of the projecting structure 2160 over the sheltered region 2165, the sheltered region 2165 may be substantially devoid of NIC 110. Thus, when a deposited layer 130 may be deposited on the device 3400 after deposition of the NIC 110, the deposited layer 130 may be deposited on, and/or migrate to the sheltered region 2165 to couple the auxiliary electrode 1150 to the second electrode 640.


Those having ordinary skill in the relevant art will appreciate that a non-limiting example has been shown in FIG. 21 and that various modifications may be apparent. By way of non-limiting example, the projecting structure 2160 may provide a sheltered region 2165 along at least two of its sides. In some non-limiting examples, the projecting structure 2160 may be omitted and the auxiliary electrode 1150 may comprise a recessed portion that may define the sheltered region 2165. In some non-limiting examples, the auxiliary electrode 1150 and the deposited layer 130 may be disposed directly on a surface of the substrate 10, instead of the PDL 740.


Selective Deposition of Optical Coating

In some non-limiting examples, a device (not shown), which in some non-limiting examples may be an opto-electronic device, may comprise a substrate 10, an NIC 110 and an optical coating. The NIC 110 may cover a first lateral portion 101 of the substrate 10. The optical coating may cover a second lateral portion 102 of the substrate. At least a part of the NIC 110 may be substantially devoid of a closed coating 140 of the optical coating.


In some non-limiting examples, the optical coating may be used to modulate optical properties of light being transmitted, emitted, and/or absorbed by the device, including without limitation, plasmon modes. By way of non-limiting example, the optical coating may be used as an optical filter, index-matching coating, optical out-coupling coating, scattering layer, diffraction grating, and/or parts thereof.


In some non-limiting examples, the optical coating may be used to modulate at least one optical microcavity effect in the device by, without limitation, tuning the total optical path length, and/or the refractive index n thereof. At least one optical property of the device may be affected by modulating at least one optical microcavity effect including without limitation, the output light, including without limitation, an angular dependence of a brightness, and/or a color shift thereof. In some non-limiting examples, the optical coating may be a non-electrical component, that is, the optical coating may not be configured to conduct, and/or transmit electrical current during normal device operations.


In some non-limiting examples, the optical coating may be formed of any deposited material 331, and/or may employ any mechanism of depositing a deposited layer 130 as described herein.


Partition and Recess

Turning to FIG. 22, there may be shown a cross-sectional view of an example version 2200 of the device 600. The device 2200 may comprise a substrate 10 having an exposed layer surface 11. The substrate 10 may comprise at least one TFT structure 701. By way of non-limiting example, the at least one TFT structure 701 may be formed by depositing and patterning a series of thin films when fabricating the substrate 10, in some non-limiting examples, as described herein.


The device 2200 may comprise, in a lateral aspect, an emissive region 1210 having an associated lateral aspect 710 and at least one adjacent non-emissive region 1220, each having an associated lateral aspect 720. The exposed layer surface 11 of the substrate 10 in the emissive region 1210 may be provided with a first electrode 620, that may be electrically coupled with the at least one TFT structure. A PDL 740 may be provided on the exposed layer surface 11, such that the PDL 740 covers the exposed layer surface 11 as well as at least one edge, and/or perimeter of the first electrode 620. The PDL 740 may, in some non-limiting examples, be provided in the lateral aspect 720 of the non-emissive region 1220. The PDL 740 may define a valley-shaped configuration that may provide an opening that generally may correspond to the lateral aspect 710 of the emissive region 1210 through which a layer surface of the first electrode 620 may be exposed. In some non-limiting examples, the device 2200 may comprise a plurality of such openings defined by the PDLs 400, each of which may correspond to a (sub-) pixel 1810/134x region of the device 2200.


As shown, in some non-limiting examples, a partition 2221 may be provided on the exposed layer surface 11 in the lateral aspect 720 of a non-emissive region 1220 and, as described herein, may define a sheltered region 2165, such as a recess 2222. In some non-limiting examples, the recess 2222 may be formed by an edge of a lower section of the partition 2221 being recessed, staggered, and/or offset with respect to an edge of an upper section of the partition 2221 that may overlap, and/or project beyond the recess 2222.


In some non-limiting examples, the lateral aspect 710 of the emissive region 1210 may comprise at least one semiconducting layer 630 disposed over the first electrode 620, a second electrode 640, disposed over the at least one semiconducting layer 630, and an NIC 110 disposed over the second electrode 640. In some non-limiting examples, the at least one semiconducting layer 630, the second electrode 640 and the NIC 110 may extend laterally to cover at least the lateral aspect 720 of a part of at least one adjacent non-emissive region 1220. In some non-limiting examples, as shown, the at least one semiconducting layer 630, the second electrode 640 and the NIC 110 may be disposed on at least a part of at least one PDL 740 and at least a part of the partition 2221. Thus, as shown, the lateral aspect 710 of the emissive region 1210, the lateral aspect 720 of a part of at least one adjacent non-emissive region 1220 and a part of at least one PDL 740 and at least a part of the partition 2221, together may make up a first portion 101, in which the second electrode 640 may lie between the NIC 110 and the at least one semiconducting layer 630.


An auxiliary electrode 1150 may be disposed proximate to, and/or within the recess 2222 and a deposited layer 130 may be arranged to electrically couple the auxiliary electrode 1150 with the second electrode 640. Thus as shown, the recess 2222 may comprise a second portion 102, in which the deposited layer 130 is disposed on the exposed layer surface 11.


In some non-limiting examples, in depositing the deposited layer 130, at least a part of the evaporated flux 332 of the deposited material 331 may be directed at a non-normal angle relative to a lateral plane of the exposed layer surface 11. By way of non-limiting example, at least a part of the evaporated flux 332 may be incident on the device 2100 at an angle of incidence that is, relative to such lateral plane of the exposed layer surface 11, less than about: 90°, 85°, 80°, 75°, 70°, 60°, or 50°. By directing an evaporated flux of a deposited material 331, including at least a part thereof incident at a non-normal angle, at least one exposed layer surface 11 of, and/or in the recess 2222 may be exposed to such evaporated flux.


In some non-limiting examples, a likelihood of such evaporated flux 332 being precluded from being incident onto at least one exposed layer surface 11 of, and/or in the recess 2222 due to the presence of the partition 2221, may be reduced since at least a part of such evaporated flux 332 may be flowed at a non-normal angle of incidence.


In some non-limiting examples, at least a part of such evaporated flux 332 be non-collimated. In some non-limiting examples, at least a part of such evaporated flux 332 may be generated by an evaporation source that is a point source, a linear source, and/or a surface source.


In some non-limiting examples, the device 2200 may be displaced during deposition of the deposited layer 130. By way of non-limiting example, the device 2200, and/or the substrate 10 thereof, and/or any layer(s) deposited thereon, may be subjected to a displacement that is angular, in a lateral aspect, and/or in an aspect substantially parallel to the cross-sectional aspect.


In some non-limiting examples, the device 2200 may be rotated about an axis that substantially normal to the lateral plane of the exposed layer surface 11 while being subjected to the evaporated flux 332.


In some non-limiting examples, at least a part of such evaporated flux 332 may be directed toward the exposed layer surface 11 of the device 2200 in a direction that is substantially normal to the lateral plane of the surface.


Without wishing to be bound by a particular theory, it may be postulated that the deposited material 331 may nevertheless be deposited within the recess 2222 due to lateral migration, and/or desorption of adatoms adsorbed onto the surface of the NIC 110.


In some non-limiting examples, it may be postulated that any adatoms adsorbed onto the exposed layer surface 11 of the NIC 110 may tend to migrate, and/or desorb from such surface due to unfavorable thermodynamic properties of the surface for forming a stable nucleus. In some non-limiting examples, it may be postulated that at least some of the adatoms migrating, and/or desorbing off such surface may be re-deposited onto the surfaces in the recess 2222 to form the deposited layer 130.


In some non-limiting examples, the deposited layer 130 may be formed such that the deposited layer 130 may be electrically coupled with both the auxiliary electrode 1150 and the second electrode 640. In some non-limiting examples, the deposited layer 130 may be in physical contact with at least one of the auxiliary electrode 1150, and/or the second electrode 640. In some non-limiting examples, an intermediate layer may be present between the deposited layer 130 and at least one of the auxiliary electrode 1150, and/or the second electrode 640. However, in such example, such intermediate layer may not substantially preclude the deposited layer 130 from being electrically coupled with the at least one of the auxiliary electrode 1150, and/or the second electrode 640. In some non-limiting examples, such intermediate layer may be relatively thin and be such as to permit electrical coupling therethrough. In some non-limiting examples, a sheet resistance R of the deposited layer 130 may be no more than a sheet resistance of the second electrode 640.


As shown in FIG. 22, the recess 2222 may be substantially devoid of the second electrode 640. In some non-limiting examples, during the deposition of the second electrode 640, the recess 2222 may be masked, by the partition 2221, such that the evaporated flux 332 of the deposited material 331 for forming the second electrode 640 may be substantially precluded form being incident on at least one exposed layer surface 11 of, and/or in the recess 2222. In some non-limiting examples, at least a part of the evaporated flux 332 of the deposited material 331 for forming the second electrode 640 may be incident on at least one exposed layer surface 11 of, and/or in the recess 2222, such that the second electrode 640 may extend to cover at least a part of the recess 2222.


In some non-limiting examples, the auxiliary electrode 1150, the deposited layer 130, and/or the partition 2221 may be selectively provided in certain region(s) of a display panel. In some non-limiting examples, any of these features may be provided at, and/or proximate to, at least one edges of such display panel for electrically coupling at least one element of the frontplane 610, including without limitation, the second electrode 640, to at least one element of the backplane 1015. In some non-limiting examples, providing such features at, and/or proximate to, such edges may facilitate supplying and distributing electrical current to the second electrode 640 from an auxiliary electrode 1150 located at, and/or proximate to, such edges. In some non-limiting examples, such configuration may facilitate reducing a bezel size of the display panel.


In some non-limiting examples, the auxiliary electrode 1150, the deposited layer 130, and/or the partition 2221 may be omitted from certain regions(s) of such display panel. In some non-limiting examples, such features may be omitted from parts of the display panel, including without limitation, where a relatively high pixel density may be provided, other than at, and/or proximate to, at least one edge thereof.


Aperture in Non-Emissive Region

Turning now to FIG. 23A, there may be shown a cross-sectional view of an example version 2300a of the device 600. The device 2300a may differ from the device 2200 in that a pair of partitions 2221 in the non-emissive region 1220 may be disposed in a facing arrangement to define a sheltered region 2165, such as an aperture 2322, therebetween. As shown, in some non-limiting examples, at least one of the partitions 2221 may function as a PDL 740 that covers at least an edge of the first electrode 620 and that defines at least one emissive region 1210. In some non-limiting examples, at least one of the partitions 2221 may be provided separately from a PDL 740.


A sheltered region 2165, such as the recess 2222, may be defined by at least one of the partitions 2221. In some non-limiting examples, the recess 2222 may be provided in a part of the aperture 2322 proximal to the substrate 10. In some non-limiting examples, the aperture 2322 may be substantially elliptical when viewed in plan view. In some non-limiting examples, the recess 2222 may be substantially annular when viewed in plan view and surround the aperture 2322.


In some non-limiting examples, the recess 2222 may be substantially devoid of materials for forming each of the layers of a device stack 2310, and/or of a residual device stack 2311.


In these figures, a device stack 2310 may be shown comprising the at least one semiconducting layer 630, the second electrode 640 and the NIC 110 deposited on an upper section of the partition 2221.


In these figures, a residual device stack 2311 may be shown comprising the at least one semiconducting layer 630, the second electrode 640 and the NIC 110 deposited on the substrate 10 beyond the partition 2221 and recess 2222. From comparison with FIG. 22, it may be seen that the residual device stack 2311 may, in some non-limiting examples, correspond to the semiconductor layer 630, second electrode 640 and the NIC 110 as it approaches the recess 2222 at, and/or proximate to, a lip of the partition. In some non-limiting examples, the residual device stack 2311 may be formed when an open mask and/or mask-free deposition process is used to deposit various materials of the device stack 2310.


In some non-limiting examples, the residual device stack 2311 may be disposed within the aperture 2322. In some non-limiting examples, evaporated materials for forming each of the layers of the device stack 2310 may be deposited within the aperture 2322 to form the residual device stack 2311 therein.


In some non-limiting examples, the auxiliary electrode 1150 may be arranged such that at least a part thereof is disposed within the recess 2222. As shown, in some non-limiting examples, the auxiliary electrode 1150 may be arranged within the aperture 2322, such that the residual device stack 2311 is deposited onto a surface of the auxiliary electrode 1150.


A deposited layer 130 may be disposed within the aperture 2322 for electrically coupling the second electrode 640 with the auxiliary electrode 1150. By way of non-limiting example, at least a part of the deposited layer 130 may be disposed within the recess 2222.


Turning now to FIG. 23B, there may be shown a cross-sectional view of a further example of the device 2300b. As shown, the auxiliary electrode 1150 may be arranged to form at least a part of a side 2326. As such, the auxiliary electrode 1150 may be substantially annular, when viewed in plan view, and may surround the aperture 2322. As shown, in some non-limiting examples, the residual device stack 2311 may be deposited onto an exposed layer surface 11 of the substrate 10.


In some non-limiting examples, the partition 2222 may comprise, and/or is formed by, an NPC 520. By way of non-limiting examples, the auxiliary electrode 1150 may act as an NPC 520.


In some non-limiting examples, the NPC 520 may be provided by the second electrode 640, and/or a portion, layer, and/or material thereof. In some non-limiting examples, the second electrode 640 may extend laterally to cover the exposed layer surface 11 arranged in the sheltered region 2165. In some non-limiting examples, the second electrode 640 may comprise a lower layer thereof and a second layer thereof, wherein the second layer thereof may be deposited on the lower layer thereof. In some non-limiting examples, the lower layer of the second electrode 640 may comprise an oxide such as, without limitation, ITO, IZO, or ZnO. In some non-limiting examples, the upper layer of the second electrode 640 may comprise a metal such as, without limitation, at least one of Ag, Mg, Mg:Ag, Yb/Ag, other alkali metals, and/or other alkali earth metals.


In some non-limiting examples, the lower layer of the second electrode 640 may extend laterally to cover a surface of the sheltered region 2165, such that it forms the NPC 520. In some non-limiting examples, at least one surface defining the sheltered region 2165 may be treated to form the NPC 520. In some non-limiting examples, such NPC 520 may be formed by chemical, and/or physical treatment, including without limitation, subjecting the surface(s) of the sheltered region 2165 to a plasma, UV, and/or UV-ozone treatment.


Without wishing to be bound to any particular theory, it may be postulated that such treatment may chemically, and/or physically alter such surface(s) to modify at least one property thereof. By way of non-limiting example, such treatment of the surface(s) may increase a concentration of C—O, and/or C—OH bonds on such surface(s), may increase a roughness of such surface(s), and/or may increase a concentration of certain species, and/or functional groups, including without limitation, halogens, nitrogen-containing functional groups, and/or oxygen-containing functional groups to thereafter act as an NPC 520.


Removal of Selective Coating

In some non-limiting examples, the NIC 110 may be removed after deposition of the deposited layer 130, such that at least a part of a previously exposed layer surface 11 of an underlying material covered by the NIC 110 may become exposed once again. In some non-limiting examples, the NIC 110 may be selectively removed by etching, and/or dissolving the NIC 110, and/or by employing plasma, and/or solvent processing techniques that do not substantially affect or erode the deposited layer 130.


Turning now to FIG. 24A, there may be shown an example cross-sectional view of an example version 2400 of the device 600, at a deposition stage 2400a, in which an NIC 110 may have been selectively deposited on a first portion 101 of an exposed layer surface 11 of an underlying material. In the figure, the underlying material may be the substrate 10.


In FIG. 24B, the device 2400 may be shown at a deposition stage 2400b, in which a deposited layer 130 may be deposited on the exposed layer surface 11 of the underlying material, that is, on both the exposed layer surface 11 of NIC 110 where the NIC 110 may have been deposited during the stage 2400a, as well as the exposed layer surface 11 of the substrate 10 where that NIC 110 may not have been deposited during the stage 2400a. Because of the nucleation-inhibiting properties of the first portion 101 where the NIC 110 may have been disposed, the deposited layer 130 disposed thereon may tend to not remain, resulting in a pattern of selective deposition of the deposited layer 130, that may correspond to a second portion 102, leaving the first portion 101 substantially devoid of the deposited layer 130.


In FIG. 24C, the device 2400 may be shown at a deposition stage 2400c, in which the NIC 110 may have been removed from the first portion 101 of the exposed layer surface 11 of the substrate 10, such that the deposited layer 130 deposited during the stage 2400b may remain on the substrate 10 and regions of the substrate 10 on which the NIC 110 may have been deposited during the stage 2400a may now be exposed or uncovered.


In some non-limiting examples, the removal of the NIC 110 in the stage 2400c may be effected by exposing the device 2400 to a solvent, and/or a plasma that reacts with, and/or etches away the NIC 110 without substantially impacting the deposited layer 130.


Thin Film Formation

The formation of thin films during vapor deposition on an exposed layer surface 11 of an underlying layer may involve processes of nucleation and growth.


During initial stages of film formation, a sufficient number of vapor monomers 332 (which in some non-limiting examples may be molecules, and/or atoms of a deposited material 331 in vapor form 332) may typically condense from a vapor phase to form initial nuclei on the exposed layer surface 11 presented of an underlying layer. As vapor monomers 332 may impinge on such surface, a characteristic size S1, and/or deposited density of these initial nuclei may increase to form small particle structures 441. Non-limiting examples of a dimension to which such characteristic size S1 refers may include a height, width, length, and/or diameter of such particle structure 441.


After reaching a saturation island density, adjacent particle structures 441 may typically start to coalesce, increasing an average characteristic size S1 of such particle structures 441, while decreasing a deposited density thereof.


With continued vapor deposition of monomers 332, coalescence of adjacent particle structures 441 may continue until a substantially closed coating 140 may eventually be deposited on an exposed layer surface 11 of an underlying layer. The behaviour, including optical effects caused thereby, of such closed coatings 340 may be generally relatively uniform, consistent, and unsurprising.


There may be at least three basic growth modes for the formation of thin films, in some non-limiting examples, culminating in a closed coating 140: 1) island (Volmer-Weber), 2) layer-by-layer (Frank-van der Merwe), and 3) Stranski-Krastanov.


Island growth may typically occur when stale clusters of monomers 332 nucleate on an exposed layer surface 11 and grow to form discrete islands. This growth mode may occur when the interaction between the monomers 332 is stronger than that between the monomers and the surface.


The nucleation rate may describe how many nuclei of a given size (where the free energy does not push a cluster of such nuclei to either grow or shrink) (“critical nuclei”) on a surface per unit time. During initial stages of film formation, it may be unlikely that nuclei will grow from direct impingement of monomers 332 on the surface, since the deposited density of nuclei is low, and thus the nuclei may cover a relatively small fraction of the surface (e.g., there are large gaps/spaces between neighboring nuclei). Therefore, the rate at which critical nuclei may grow may typically depend on the rate at which adatoms (e.g., adsorbed monomers 332) on the surface migrate and attach to nearby nuclei.


An example of an energy profile of an adatom adsorbed onto an exposed layer surface 11 of an underlying material is illustrated in FIG. 25. Specifically, FIG. 25 may illustrate example qualitative energy profiles corresponding to: an adatom escaping from a local low energy site (2510); diffusion of the adatom on the exposed layer surface 11 (2520); and desorption of the adatom (2530).


In 2510, the local low energy site may be any site on the exposed layer surface 11 of an underlying layer, onto which an adatom will be at a lower energy. Typically, the nucleation site may comprise a defect, and/or an anomaly on the exposed layer surface 11, including without limitation, a ledge, a step edge, a chemical impurity, a bonding site, and/or a kink (“heterogeneity”).


Sites of substrate heterogeneity may increase an energy involved to desorb the adatom from the surface Edes 2531, leading to a higher deposited density of nuclei observed at such sites. Also, impurities or contamination on a surface may also increase Edes 2531, leading to a higher deposited density of nuclei. For vapor deposition processes, conducted under high vacuum conditions, the type and deposited density of contaminants on a surface may be affected by a vacuum pressure and a composition of residual gases that make up that pressure.


Once the adatom is trapped at the local low energy site, there may typically, in some non-limiting examples, be an energy barrier before surface diffusion takes place. Such energy barrier may be represented as ΔE 2511 in FIG. 25. In some non-limiting examples, if the energy barrier ΔE 2511 to escape the local low energy site is sufficiently large, the site may act as a nucleation site.


In 2520, the adatom may diffuse on the exposed layer surface 11. By way of non-limiting example, in the case of localized absorbates, adatoms may tend to oscillate near a minimum of the surface potential and migrate to various neighboring sites until the adatom is either desorbed, and/or is incorporated into growing islands 441 formed by a cluster of adatoms, and/or a growing film. In FIG. 25, the activation energy associated with surface diffusion of adatoms may be represented as Es 2511.


In 2530, the activation energy associated with desorption of the adatom from the surface may be represented as Edes 2531. Those having ordinary skill in the relevant art will appreciate that any adatoms that are not desorbed may remain on the exposed layer surface 11. By way of non-limiting example, such adatoms may diffuse on the exposed layer surface 11, become part of a cluster of adatoms that form islands 441 on the exposed layer surface 11, and/or be incorporated as part of a growing film, and/or coating.


After adsorption of an adatom on a surface, the adatom may either desorb from the surface, or may migrate some distance on the surface before either desorbing, interacting with other adatoms to form a small cluster, or attaching to a growing nucleus. An average amount of time that an adatom may remain on the surface after initial adsorption may be given by:










τ
s

=


1
v



exp

(


E
des

kT

)






(
TF1
)







In the above equation:


v is a vibrational frequency of the adatom on the surface,


k is the Botzmann constant, and


T is temperature.


From this equation it may be noted that the lower the value of Edes 2531, the easier it may be for the adatom to desorb from the surface, and hence the shorter the time the adatom may remain on the surface. A mean distance an adatom can diffuse may be given by,









X
=


a
0



exp

(



E
des

-

E
s



2

kT


)






(
TF2
)







where:


α0 is a lattice constant.


For low values of Edes 2531, and/or high values of Es 2521, the adatom may diffuse a shorter distance before desorbing, and hence may be less likely to attach to growing nuclei or interact with another adatom or cluster of adatoms.


During initial stages of formation of a deposited layer of particle structures 441, adsorbed adatoms may interact to form particle structures 441, with a critical concentration of particle structures 441 per unit area being given by,











N
i


n
0


=





"\[LeftBracketingBar]"



N
1


n
0




"\[RightBracketingBar]"


i



exp

(


E
i

kT

)






(

TF

3

)







where:


Ei is an energy involved to dissociate a critical cluster containing I adatoms into separate adatoms,


n0 is a total deposited density of adsorption sites, and


N1 is a monomer deposited density given by:






N
1
={dot over (R)}τ
s  (TF4)


where:


{dot over (R)} is a vapor impingement rate.


Typically, I may depend on a crystal structure of a material being deposited and may determine a critical size of particle structures 441 to form a stable nucleus.


A critical monomer supply rate for growing particle structures 441 may be given by the rate of vapor impingement and an average area over which an adatom can diffuse before desorbing:











R
.



X
2


=


α
0
2



exp

(



E
des

-

E
s


kT

)






(
TF5
)







The critical nucleation rate may thus be given by the combination of the above equations:











N
.

i

=


R
.



α
0
2





n
0

(


R
.


vn
0


)

i



exp

(




(

i
+
1

)



E
des


-

E
s

+

E
i


kT

)






(
TF6
)







From the above equation, it may be noted that the critical nucleation rate may be suppressed for surfaces that have a low desorption energy for adsorbed adatoms, a high activation energy for diffusion of an adatom, are at high temperatures, and/or are subjected to vapor impingement rates.


Under high vacuum conditions, a flux 332 of molecules that may impinge on a surface (per cm2-sec) may be given by:









ϕ
=

3.513
×

10
22



P
MT






(
TF7
)







where:


P is pressure, and


M is molecular weight.


Therefore, a higher partial pressure of a reactive gas, such as H2O, may lead to a higher deposited density of contamination on a surface during vapor deposition, leading to an increase in Edes 2531 and hence a higher deposited density of nuclei.


In the present disclosure, “nucleation-inhibiting” may refer to a coating, material, and/or a layer thereof, that may have a surface that exhibits an initial sticking probability S0 against deposition of a deposited material 331 thereon, that may be close to 0, including without limitation, less than about 0.3, such that the deposition of the deposited material 331 on such surface may be inhibited.


In the present disclosure, “nucleation-promoting” may refer to a coating, material, and/or a layer thereof, that has a surface that exhibits an initial sticking probability S0 against deposition of a deposited material 331 thereon, that may be close to 1, including without limitation, greater than about 0.7, such that the deposition of the deposited material 331 on such surface may be facilitated.


Without wishing to be bound by a particular theory, it may be postulated that the shapes and sizes of such nuclei and the subsequent growth of such nuclei into islands 441 and thereafter into a thin film may depend upon various factors, including without limitation, interfacial tensions between the vapor, the surface, and/or the condensed film nuclei.


One measure of a nucleation-inhibiting, and/or nucleation-promoting property of a surface may be the initial sticking probability S0 of the surface against the deposition of a given deposited material 331.


In some non-limiting examples, the sticking probability S may be given by:









S
=


N
ads


N
total






(
TF8
)







where:


Nads is a number of adatoms that remain on an exposed layer surface 11 (that is, are incorporated into a film), and


Ntotal is a total number of impinging monomers on the surface.


A sticking probability S equal to 1 may indicate that all monomers 332 that impinge on the surface are adsorbed and subsequently incorporated into a growing film. A sticking probability S equal to 0 may indicate that all monomers 332 that impinge on the surface are desorbed and subsequently no film may be formed on the surface.


A sticking probability S of a deposited material 331 on various surfaces may be evaluated using various techniques of measuring the sticking probability S, including without limitation, a dual quartz crystal microbalance (QCM) technique as described by Walker et al., J. Phys. Chem. C 2007, 111, 765 (2006).


As the deposited density of a deposited material 331 may increase (e.g., increasing average film thickness d), a sticking probability S may change.


An initial sticking probability S0 may therefore be specified as a sticking probability S of a surface prior to the formation of any significant number of critical nuclei. One measure of an initial sticking probability S0 may involve a sticking probability S of a surface against the deposition of a deposited material 331 during an initial stage of deposition thereof, where an average film thickness d of the deposited material 331 across the surface is at or below a threshold value. In the description of some non-limiting examples a threshold value for an initial sticking probability S0 may be specified as, by way of non-limiting example, 1 nm. An average sticking probability S may then be given by:







S=S

0(1−Anuc)+Snuc(Anuc)  (TF9)


where:


Snuc is a sticking probability S of an area covered by particle structures 441, and


Anuc is a percentage of an area of a substrate surface covered by particle structures


By way of non-limiting example, a low initial sticking probability S0 may increase with increasing average film thickness d. This may be understood based on a difference in sticking probability S between an area of an exposed layer surface 11 with no particle structures 441, by way of non-limiting example, a bare substrate 10, and an area with a high deposited density. By way of non-limiting example, a monomer 332 that may impinge on a surface of a particle structure 441 may have a sticking probability S that may approach 1.


Based on the energy profiles 2510, 2520, 2530 shown in FIG. 25, it may be postulated that materials that exhibit relatively low activation energy for desorption (Edes 2531), and/or relatively high activation energy for surface diffusion (Es 2521), may be deposited as an NIC 110, and may be suitable for use in various applications.


Without wishing to be bound by a particular theory, it may be postulated that, in some non-limiting examples, the relationship between various interfacial tensions present during nucleation and growth may be dictated according to Young's equation in capillarity theory:





γsvfsvf cos θ  (TF10)


where:


γsv corresponds to the interfacial tension between the substrate 10 and vapor 332,


γfs corresponds to the interfacial tension between the deposited material 331 and the substrate 10,)


γvf corresponds to the interfacial tension between the vapor 332 and the film, and Bis the film nucleus contact angle.



FIG. 26 may illustrate the relationship between the various parameters represented in this equation.


On the basis of Young's equation, it may be derived that, for island growth, the film nucleus contact angle θ may exceed 0 and therefore: γsvfsvf.


For layer growth, where the deposited material 331 may “wet” the substrate 10, the nucleus contact angle θ may be equal to 0, and therefore: γsv=yfsvf. For Stranski-Krastanov (S-K) growth, where the strain energy per unit area of the film overgrowth may be large with respect to the interfacial tension between the vapor 332 and the deposited material 331: γsvfsvf.


Without wishing to be bound by any particular theory, it may be postulated that the nucleation and growth mode of a deposited material 331 at an interface between the NIC 110 and the exposed layer surface 11 of the substrate 10, may follow the island growth model, where θ>0.


Particularly in cases where the NIC 110 may exhibit a relatively low initial sticking probability S0 (in some non-limiting examples, under the conditions identified in the dual QCM technique described by Walker et. al) against deposition of the deposited material 331, there may be a relatively high thin film contact angle θ of the deposited material 331.


On the contrary, when a deposited material 331 may be selectively deposited on an exposed layer surface 11 without the use of a patterning coating 210, by way of non-limiting example, by employing a shadow mask 215, the nucleation and growth mode of such deposited material 331 may differ. In particular, it has been observed that a coating formed using a shadow mask 215 patterning process may, at least in some non-limiting examples, exhibit relatively low thin film contact angle θ of less than about 10°.


It has now been found, somewhat surprisingly, that in some non-limiting examples, a nucleation-inhibiting coating 310 (and/or the NIC material of which it is comprised) may exhibit a relatively low critical surface tension.


Those having ordinary skill in the relevant art will appreciate that a “surface energy” of a coating, layer, and/or a material constituting such coating, and/or layer, may generally correspond to a critical surface tension of the coating, layer, and/or material. According to some models of surface energy, the critical surface tension of a surface may correspond substantially to the surface energy of such surface.


Generally, a material with a low surface energy may exhibit low intermolecular forces. Generally, a material with low intermolecular forces may readily crystallize or undergo other phase transformation at a lower temperature in comparison to another material with high intermolecular forces. In at least some applications, a material that may readily crystallize or undergo other phase transformations at relatively low temperatures may be detrimental to the long-term performance, stability, reliability, and/or lifetime of the device.


Without wishing to be bound by a particular theory, it may be postulated that certain low energy surfaces may exhibit relatively low initial sticking probabilities S0 and may thus be suitable for forming the NIC 110.


Without wishing to be bound by any particular theory, it may be postulated that, especially for low surface energy surfaces, the critical surface tension may be positively correlated with the surface energy. By way of non-limiting example, a surface exhibiting a relatively low critical surface tension may also exhibit a relatively low surface energy, and a surface exhibiting a relatively high critical surface tension may also exhibit a relatively high surface energy.


In reference to Young's equation described above, a lower surface energy may result in a greater contact angle θ, while also lowering the γsv, thus enhancing the likelihood of such surface having low wettability and low initial sticking probability S0 with respect to the deposited material 331.


The critical surface tension values, in various non-limiting examples, herein may correspond to such values measured at around normal temperature and pressure (NTP), which in some non-limiting examples, may correspond to a temperature of 20° C., and an absolute pressure of 1 atm. In some non-limiting examples, the critical surface tension of a surface may be determined according to the Zisman method, as further detailed in Zisman, W. A., “Advances in Chemistry” 43 (1964), p. 1-51.


In some non-limiting examples, the exposed layer surface 11 of the NIC 110 may exhibit a critical surface tension of less than about: 20 dynes/cm, 19 dynes/cm, 18 dynes/cm, 17 dynes/cm, 16 dynes/cm, 15 dynes/cm, 13 dynes/cm, 12 dynes/cm, or 11 dynes/cm.


In some non-limiting examples, the exposed layer surface 11 of the NIC 110 may exhibit a critical surface tension of greater than about: 6 dynes/cm, 7 dynes/cm, 8 dynes/cm, 9 dynes/cm, and 10 dynes/cm.


Those having ordinary skill in the relevant art will appreciate that various methods and theories for determining the surface energy of a solid may be known. By way of non-limiting example, the surface energy may be calculated, and/or derived based on a series of measurements of contact angle θ, in which various liquids are brought into contact with a surface of a solid to measure the contact angle θ between the liquid-vapor interface and the surface. In some non-limiting examples, the surface energy of a solid surface may be equal to the surface tension of a liquid with the highest surface tension that completely wets the surface. By way of non-limiting example, a Zisman plot may be used to determine the highest surface tension value that would result in a contact angle θ of 0° with the surface. According to some theories of surface energy, various types of interactions between solid surfaces and liquids may be considered in determining the surface energy of the solid. By way of non-limiting example, according to some theories, including without limitation, the Owens/Wendt theory, and/or Fowkes' theory, the surface energy may comprise a dispersive component and a non-dispersive or “polar” component.


Without wishing to be bound by a particular theory, it may be postulated that, in some non-limiting examples, the contact angle θ of a coating of deposited material 331 may be determined, based at least partially on the properties (including, without limitation, initial sticking probability S0) of the NIC 110 onto which the deposited material 331 is deposited. Accordingly, NIC materials 511 that allow selective deposition of deposited materials 531 exhibiting relatively high contact angles θ may provide some benefit.


Those having ordinary skill in the relevant art will appreciate that various methods may be used to measure a contact angle θ, including without limitation, the static, and/or dynamic sessile drop method and the pendant drop method.


In some non-limiting examples, the activation energy for desorption (Edes 2531) (in some non-limiting examples, at a temperature T of about 300K) may be less than about: 2 times, 1.5 times, 1.3 times, 1.2 times, 1.0 times, 0.8 times, or 0.5 times, the thermal energy (kBT). In some non-limiting examples, the activation energy for surface diffusion (Es 2521) (in some non-limiting examples, at a temperature T of about 300K) may exceed about: 1.0 times, 1.5 times, 1.8 times, 2 times, 3 times, 5 times, 7 times, or 10 times the thermal energy (kBT).


Without wishing to be bound by a particular theory, it may be postulated that, during thin film nucleation and growth of a deposited material 331 at, and/or near an interface between the exposed layer surface 11 of the underlying layer and the NIC 110, a relatively high contact angle θ between the edge of the deposited material 331 and the underlying layer may be observed due to the inhibition of nucleation of the solid surface of the deposited material 331 by the NIC 110. Such nucleation inhibiting property may be driven by minimization of surface energy between the underlying layer, thin film vapor and the NIC 110.


One measure of a nucleation-inhibiting, and/or nucleation-promoting property of a surface may be an initial deposition rate of a given (electrically conductive) deposited material 331, on the surface, relative to an initial deposition rate of the same deposited material 331 on a reference surface, where both surfaces are subjected to, and/or exposed to an evaporation flux of the deposited material 331.


EXAMPLES

As used in the examples herein, a reference to a layer thickness of a material refers to an amount of the material deposited on a target surface (and/or target region(s) and/or portion(s) thereof of the surface in the case of selective deposition), which corresponds to an amount of the material to cover the target surface with a uniformly thick layer of the material having the referenced layer thickness. By way of example, depositing a layer thickness of 10 nm indicates that an amount of the material deposited on the surface corresponds to an amount of the material to form a uniformly thick layer of the material that is 10 nm thick. It will be appreciated that, by way of non-limiting example, due to possible stacking and/or clustering of molecules and/or atoms, an actual thickness of the deposited material may be non-uniform. By way of non-limiting example, depositing a layer thickness of 10 nm may yield some portions of the deposited material having an actual thickness greater than 10 nm, and/or other portions of the deposited material having an actual thickness less than 10 nm. A certain layer thickness of a material deposited on a surface can correspond to an average thickness of the deposited material across the surface.


Example I

Example materials, the molecular structures of which are identified in the table below, were synthesized and used to form the NIC 810 in the present example.


















Molecular
R Group



Material
Structure Formula
Formula









Example Material A
Formula (C-2)
(F-40)



Example Material B
Formula (C-2)
(F-34)










In the above table, the molecular structure of each material may be derived by substituting each R of the Molecular Structure Formula with the corresponding R Group Formula described in the present application. Unless otherwise indicated, all R groups in a given formula are selected to be identical to one another.


In addition to the above example materials, the following comparative example materials were also used in the present example: capping layer material (Comparative Example Material A); 8-hydroxyquinolinolato-lithium (Comparative Example Material B); and 9-(naphthalen-1-yl)-10-4-trifluoromethylphenylanthracene (Comparative Example Material C).


A series of samples were fabricated by depositing, in vacuo, approximately 50 nm thick layer of the above example materials and comparative example materials over glass substrates. The refractive index, n, and the extinction coefficient, k, of the coating formed by each material was determined using an ellipsometer. The refractive index and extinction coefficient determined at a wavelength of 589 nm is summarized in the table below for each material.

















Material
n
k









Comparative Example Material A
1.774
0



Comparative Example Material B
1.633
0



Comparative Example Material C
1.625
0



Example Material A
1.299
0



Example Material B
1.290
0










As can be seen from the above table, Example Material A and Example Material B both exhibit a relatively low refractive index of about 1.299 and 1.29, respectively, at the measured wavelength. On the other hand, Comparative Example Materials A, B, and C all exhibit substantially higher refractive indices of greater than about 1.6 at the measured wavelength.


Additional samples were fabricated by similarly depositing each of the above example materials and comparative example materials, in vacuo, to form a coating over a glass substrate. The surfaces of the coatings formed by the materials were then subjected to an open mask deposition of Ag or Mg:Ag. More specifically, in the case of Ag deposition, each sample was subjected to an Ag vapor flux having an average deposition rate of about 1 Å/s until a reference thickness of about 15 nm was reached. In the case of Mg:Ag deposition, each sample was subjected to a coevaporated vapor flux containing Mg and Ag having an average deposition rate of about 0.1 Å/s for Mg and 0.9 Å/s for Ag, for a combined deposition rate of 1 Å/s, until a reference thickness of about 15 nm for Mg:Ag coating having a Mg:Ag composition ratio of 1:9 by volume was reached.


Once the samples were fabricated, optical transmission measurements were taken to determine the relative amount of metal, for example Ag or Mg:Ag, deposited on the surface of the nucleation inhibiting coating. As will be appreciated, samples having relatively little to no metal present thereon are substantially transparent, while samples with metal deposited thereon, particularly as a closed film, generally exhibits a substantially lower light transmittance. Accordingly, the relative performance of various example materials and comparative example materials as an NIC 810 may be assessed by measuring the light transmission through the samples, which directly correlates to the amount or thickness of metallic coating deposited thereon from the Ag or Mg:Ag deposition process. Based on the optical transmission measurements, it was found that samples fabricated with Example Materials A and B exhibited a high degree of light transmission of over 90% in the visible spectrum, while those fabricated with Comparative Example Materials A, B, and C all exhibited poor optical transmission of less than about 50% in the visible spectrum. This indicates that Comparative Examples Materials A, B, and C may not be suitable for use in forming the NIC 810 in applications in which the electrode coating includes Ag. Furthermore, Example Materials A and B, both of which exhibit substantially lower refractive index of 1.3 or less, were found to be suitable for use in forming the NIC 810 in applications in which the electrode coating includes Ag.


As used in this and other examples described herein, a reference layer thickness refers to a layer thickness of a metallic coating that is deposited on a reference surface exhibiting a high initial sticking probability S0 (e.g., a surface with an initial sticking probability S0 of about and/or close to 1.0). Specifically, for these examples, the reference surface was a surface of a quartz crystal positioned inside a deposition chamber for monitoring a deposition rate and the reference layer thickness. In other words, the reference layer thickness does not indicate an actual thickness of the metallic coating deposited on a target surface (i.e., a surface of the NIC 810). Rather, the reference layer thickness refers to the layer thickness of the metallic coating that would be deposited on the reference surface upon subjecting the target surface and reference surface to identical vapor flux of the metallic material for the same deposition period (i.e. the surface of the quartz crystal). As would be appreciated, in the event that the target surface and reference surface are not subjected to identical vapor flux simultaneously during deposition, an appropriate tooling factor may be used to determine and monitor the reference thickness.


Example II

Example materials, the molecular structures of which are identified in the table below, were synthesized and used to form the NIC 810 in the present example.


















Molecular
R Group



Material
Structure Formula
Formula









Example Material C
Formula (C-2)
(F-35)



Example Material D
Formula (C-2)
(F-32)










In the above table, the molecular structure of each material may be derived by substituting each R of the Molecular Structure Formula with the corresponding R Group Formula described in the present application. Unless otherwise indicated, all R groups in a given formula are selected to be identical to one another.


The above Example Materials C and D were each deposited, in vacuo, over a substrate surface in order to measure the critical surface tension of the NIC 810 formed by such materials. Specifically, a contact angle goniometer was used to measure the contact angle of various solvents on the surfaces of the NIC 810 formed by each material, then the Zisman method was used to calculate the critical surface tension of the surfaces based on the contact angle measurements. The measurements were conducted at a temperature of about 25° C. in air.

















Critical Surface



Material
Tension (dynes/cm)









Example Material C
7.8-9.1



Example Material D
6.5-7.6










Based on the above, it can be seen that both Example Materials C and D exhibit relatively low critical surface tension of less than about 10 dynes/cm. As described above, it has been postulated that coatings formed by materials exhibiting relatively low critical surface tension may be particularly suitable for use in providing the NIC 810.


To determine the suitability of these example materials for providing the NIC 810, additional samples were fabricated by similarly depositing each of the above example materials, in vacuo, to form a coating over a glass substrate. The surfaces of the coatings formed by the materials were then subjected to an open mask deposition of Ag or Mg:Ag. More specifically, in the case of Ag deposition, each sample was subjected to an Ag vapor flux having an average deposition rate of about 1 Å/s until a reference thickness of about 15 nm was reached. In the case of Mg:Ag deposition, each sample was subjected to a coevaporated vapor flux containing Mg and Ag having an average deposition rate of about 0.1 Å/s for Mg and 0.9 Å/s for Ag, for a combined deposition rate of 1 Å/s, until a reference thickness of about 15 nm for Mg:Ag coating having a Mg:Ag composition ratio of 1:9 by volume was reached.


Once the samples were fabricated, optical transmission measurements were taken to determine the relative amount of metal, for example Ag or Mg:Ag, deposited on the surface of the nucleation inhibiting coating. Based on the optical transmission measurements, it was found that samples fabricated with Example Materials C and D exhibited a high degree of light transmission of over 90% in the visible spectrum, indicating that Examples Materials C and D may be useful in forming the NIC 810 for applications in which the electrode coating includes Ag.


Example III

A series of samples were fabricated to analyze the features of the discontinuous coating 1050 formed on the surface of the NIC 810, following exposure of such surface to Ag vapor flux.


Each sample was fabricated by depositing, in vacuo, an approximately 30 nm thick coating of an organic semiconducting material, also referred to herein as an organic coating, over a silicon substrate. The surface of the organic coating was then coated by depositing the Example Material A to form the NIC 810 thereon. The surface of the NIC 810 was then subjected to a vapor flux of Ag until a reference thickness of 20 nm was reached. Following the exposure of the surface of the NIC 810 to the Ag vapor flux, the formation of discontinuous coating 1050 in the form of discrete islands of Ag on the surface of the NIC 810 was observed. The structure of the samples fabricated according to the present example are summarized in the table below.
















Sample Name
Sample Structure









Sample III-1
Si/organic coating (30 nm)/Example




Material A (10 nm)/discontinuous coating



Sample III-2
Si/organic coating (30 nm)/Example




Material A (25 nm)/discontinuous coating



Sample III-3
Si/organic coating (30 nm)/Example




Material A (50 nm)/discontinuous coating










The features of the discontinuous coating 1050 formed on the surface of each sample were characterized by scanning electron microscopy (SEM) to measure the size of the discrete Ag islands deposited on the surface of the NIC 810 in each sample. Specifically, the average diameter of each discrete Ag island or feature was calculated by measuring the surface area occupied by each island or feature when the surface of the NIC 810 is viewed in plan view, and calculating the average diameter upon fitting the area occupied by each island or feature with a circle having an equivalent area. The distribution of average diameter obtained from analyses of Samples III-1, III-2, and III-3 are shown in FIGS. 27A, 27B, and 27C, respectively. For each sample, images obtained at two different magnifications which are identified by the size of the scale bar at each magnification were analyzed.


Additionally, glass samples having substantially identical configuration of NIC 810 and discontinuous coating 1050 were prepared and analyzed in order to determine the effects of the discontinuous coating 1050 on light transmittance through the sample. The median, mean, and mode of the discrete Ag islands, the percentage of the surface of the NIC 810 covered by the discrete Ag islands when viewed in planar view, as well as the light transmittance measured through each corresponding glass sample and expressed as a percentage of light transmission through a reference sample in which no discontinuous coating is present, are summarized in the table below.


















Median
Mean
Mode
Surface
Transmittance


Sample
(nm)
(nm)
(nm)
coverage (%)
(%)




















Sample III-1,
10.1
10.3
10.0-11.0
18.7
91


500 nm scale







Sample III-1,
7.84
8.01
8.0-9.0
12.0



200 nm scale







Sample III-2,
8.78
9.01
8.0-9.0
11.3
99


500 nm scale







Sample III-2,
8.38
8.00
8.0-9.0,
10.0



200 nm scale


10.0-11.0




Sample III-3,
9.25
9.46
 9.0-10.0
13.8
100


500 nm scale







Sample III-3,
9.54
9.42
 9.0-10.0
14.2



200 nm scale









As can be seen from the table above, the median size of the discrete Ag islands varied from about 8.4 nm to about 10.1 nm, the mean size varied from about 8 nm to about 10.3 nm, and the mode varied from about 8 nm to about 11 nm. The corresponding surface coverage of the discrete Ag islands on the NIC 810 surface ranged from about 10% to about 19%, and the transmittance was above 90% for all samples.


For the purpose of the above analysis, small Ag islands or features below a threshold area of less than about 10 nm2 for 500 nm scale, and less than about 2.5 nm2 for 200 nm scale were disregarded due to resolution of the images.


Definitions

In some non-limiting examples, the electro-luminescent device may be an organic light-emitting diode (OLED) device. In some non-limiting examples, the electro-luminescent device may be part of an electronic device. By way of non-limiting example, the electro-luminescent device may be an OLED lighting panel or module, and/or an OLED display or module of a computing device, such as a smartphone, a tablet, a laptop, an e-reader, and/or of some other electronic device such as a monitor, and/or a television set.


In some non-limiting examples, the opto-electronic device may be an organic photo-voltaic (OPV) device that converts photons into electricity. In some non-limiting examples, the opto-electronic device may be an electro-luminescent quantum dot (QD) device.


In the present disclosure, unless specifically indicated to the contrary, reference will be made to OLED devices, with the understanding that such disclosure could, in some examples, equally be made applicable to other opto-electronic devices, including without limitation, an OPV, and/or QD device, in a manner apparent to those having ordinary skill in the relevant art.


The structure of such devices may be described from each of two aspects, namely from a cross-sectional aspect, and/or from a lateral (plan view) aspect.


In the present disclosure, a directional convention may be followed, extending substantially normally to the lateral aspect described above, in which the substrate may be the “bottom” of the device, and the layers may be disposed on “top” of the substrate. Following such convention, the second electrode may be at the top of the device shown, even if (as may be the case in some examples, including without limitation, during a manufacturing process, in which at least one layers may be introduced by means of a vapor deposition process), the substrate may be physically inverted, such that the top surface, in which one of the layers, such as, without limitation, the first electrode, may be disposed, may be physically below the substrate, to allow the deposition material (not shown) to move upward and be deposited upon the top surface thereof as a thin film.


In the context of introducing the cross-sectional aspect herein, the components of such devices may be shown in substantially planar lateral strata. Those having ordinary skill in the relevant art will appreciate that such substantially planar representation may be for purposes of illustration only, and that across a lateral extent of such a device, there may be localized substantially planar strata of different thicknesses and dimension, including, in some non-limiting examples, the substantially complete absence of a layer, and/or layer(s) separated by non-planar transition regions (including lateral gaps and even discontinuities). Thus, while for illustrative purposes, the device may be shown below in its cross-sectional aspect as a substantially stratified structure, in the plan view aspect discussed below, such device may illustrate a diverse topography to define features, each of which may substantially exhibit the stratified profile discussed in the cross-sectional aspect.


In the present disclosure, the terms “layer” and “strata” may be used interchangeably to refer to similar concepts.


The thickness of each layer shown in the figures may be illustrative only and not necessarily representative of a thickness relative to another layer.


For purposes of simplicity of description, in the present disclosure, a combination of a plurality of elements in a single layer may be denoted by a colon “:”, while a plurality of (combination(s) of) elements comprising a plurality of layers in a multi-layer coating may be denoted by separating two such layers by a slash “/”. In some non-limiting examples, the layer after the slash may be deposited after, and/or on the layer preceding the slash.


For purposes of illustration, an exposed layer surface of an underlying material, onto which a coating, layer, and/or material may be deposited, may be understood to be a surface of such underlying material that may be presented for deposition of the coating, layer, and/or material thereon, at the time of deposition.


Those having ordinary skill in the relevant art will appreciate that when a component, a layer, a region, and/or a portion thereof, is referred to as being “formed”, “disposed”, and/or “deposited” on, and/or over another underlying material, component, layer, region, and/or portion, such formation, disposition, and/or deposition may be directly, and/or indirectly on an exposed layer surface (at the time of such formation, disposition, and/or deposition) of such underlying material, component, layer, region, and/or portion, with the potential of intervening material(s), component(s), layer(s), region(s), and/or portion(s) therebetween.


In the present disclosure, the terms “overlap”, and/or “overlapping” may refer generally to plurality layers, and/or structures arranged to intersect a cross-sectional axis extending substantially normally away from a surface onto which such layers, and/or structures may be disposed.


While the present disclosure discusses thin film formation, in reference to at least one layer or coating, in terms of vapor deposition, those having ordinary skill in the relevant art will appreciate that, in some non-limiting examples, various components of the device may be selectively deposited using a wide variety of techniques, including without limitation, evaporation (including without limitation, thermal evaporation, and/or electron beam evaporation), photolithography, printing (including without limitation, ink jet, and/or vapor jet printing, reel-to-reel printing, and/or micro-contact transfer printing), PVD (including without limitation, sputtering), chemical vapor deposition (CVD) (including without limitation, plasma-enhanced CVD (PECVD), and/or organic vapor phase deposition (OVPD)), laser annealing, laser-induced thermal imaging (LITI) patterning, atomic-layer deposition (ALD), coating (including without limitation, spin-coating, di coating, line coating, and/or spray coating), and/or combinations thereof (collectively “deposition process”).


Some processes may be used in combination with a shadow mask, which may, in some non-limiting examples, may be an open mask, and/or fine metal mask (FMM), during deposition of any of various layers, and/or coatings to achieve various patterns by masking, and/or precluding deposition of a deposited material on certain parts of a surface of an underlying material exposed thereto.


In the present disclosure, the terms “evaporation”, and/or “sublimation” may be used interchangeably to refer generally to deposition processes in which a source material is converted into a vapor, including without limitation, by heating, to be deposited onto a target surface in, without limitation, a solid state. As will be understood, an evaporation deposition process may be a type of PVD process where at least one source materials are evaporated, and/or sublimed under a low pressure (including without limitation, a vacuum) environment to form vapor monomers and deposited on a target surface through de-sublimation of the at least one evaporated source materials. A variety of different evaporation sources may be used for heating a source material, and, as such, it will be appreciated by those having ordinary skill in the relevant art, that the source material may be heated in various ways. By way of non-limiting example, the source material may be heated by an electric filament, electron beam, inductive heating, and/or by resistive heating. In some non-limiting examples, the source material may be loaded into a heated crucible, a heated boat, a Knudsen cell (which may be an effusion evaporator source), and/or any other type of evaporation source.


In some non-limiting examples, a deposition source material may be a mixture. In some non-limiting examples, at least one component of a mixture of a deposition source material may be not be deposited during the deposition process (or, in some non-limiting examples, be deposited in a relatively small amount compared to other components of such mixture).


In the present disclosure, a reference to a layer thickness, a film thickness, and/or an average layer, and/or film thickness, of a material, irrespective of the mechanism of deposition thereof, may refer to an amount of the material deposited on a target exposed layer surface, which corresponds to an amount of the material to cover the target surface with a uniformly thick layer of the material having the referenced layer thickness. By way of non-limiting example, depositing a layer thickness of 10 nm of material may indicate that an amount of the material deposited on the surface may correspond to an amount of the material to form a uniformly thick layer of the material that may be 10 nm thick. It will be appreciated that, having regard to the mechanism by which thin films are formed discussed above, by way of non-limiting example, due to possible stacking or clustering of monomers, an actual thickness of the deposited material may be non-uniform. By way of non-limiting example, depositing a layer thickness of 10 nm may yield some parts of the deposited material 331 having an actual thickness greater than 10 nm, or other parts of the deposited material 331 having an actual thickness less than 10 nm. A certain layer thickness of a material deposited on a surface may thus correspond, in some non-limiting examples, to an average thickness of the deposited material across the target surface.


In the present disclosure, a reference to a reference layer thickness may refer to a layer thickness of the deposited material, also referred to herein as the deposited material (such as Mg), that may be deposited on a reference surface exhibiting a high initial sticking probability or initial sticking coefficient S0 (that is, a surface having an initial sticking probability S0 that is about, and/or close to 1.0). The reference layer thickness may not indicate an actual thickness of the deposited material deposited on a target surface (such as, without limitation, a surface of an NIC). Rather, the reference layer thickness may refer to a layer thickness of the deposited material that would be deposited on a reference surface, in some non-limiting examples a surface of a quartz crystal positioned inside a deposition chamber for monitoring a deposition rate and the reference layer thickness, upon subjecting the target surface and the reference surface to identical vapor flux of the deposited material for the same deposition period. Those having ordinary skill in the relevant art will appreciate that in the event that the target surface and the reference surface are not subjected to identical vapor flux simultaneously during deposition, an appropriate tooling factor may be used to determine, and/or to monitor the reference layer thickness.


In the present disclosure, a reference deposition rate may refer to a rate at which a layer of the deposited material would grow on the reference surface, if it were identically positioned and configured within a deposition chamber as the sample surface.


In the present disclosure, a reference to depositing a number X of monolayers of material may refer to depositing an amount of the material to cover a given area of an exposed layer surface with X single layer(s) of constituent monomers of the material, such as, without limitation, in a closed coating.


In the present disclosure, a reference to depositing a fraction 1/X monolayer of a material may refer to depositing an amount of the material to cover a fraction 0.X of a given area of an exposed layer surface with a single layer of constituent monomers of the material. Those having ordinary skill in the relevant art will appreciate that due to, by way of non-limiting example, possible stacking, and/or clustering of monomers, an actual local thickness of a deposited material across a given area of a surface may be non-uniform. By way of non-limiting example, depositing 1 monolayer of a material may result in some local regions of the given area of the surface being uncovered by the material, while other local regions of the given area of the surface may have multiple atomic, and/or molecular layers deposited thereon.


In the present disclosure a target surface (and/or target region(s) thereof) may be considered to be “substantially devoid of”, “substantially free of”, and/or “substantially uncovered by” a material if there may be a substantial absence of the material on the target surface as determined by any suitable determination mechanism.


In the present disclosure, the terms “sticking probability” and “sticking coefficient” may be used interchangeably.


In the present disclosure, the term “nucleation” may reference a nucleation stage of a thin film formation process, in which monomers in a vapor phase condense onto a surface to form nuclei.


In the present disclosure, in some non-limiting examples, as the context dictates, the terms “patterning coating” and “patterning material” may be used interchangeably to refer to similar concepts, and references to an patterning coating herein, in the context of being selectively deposited to pattern a deposited layer 130 may, in some non-limiting examples, be applicable to a NIC material in the context of selective deposition thereof to pattern a deposited material, and/or an electrode coating material.


Similarly, in some non-limiting examples, as the context dictates, the term “patterning coating” and “patterning material” may be used interchangeably to refer to similar concepts, and reference to an NPC herein, in the context of being selectively deposited to pattern a deposited layer may, in some non-limiting examples, be applicable to an NPC material in the context of selective deposition thereof to pattern an electrode coating.


While a patterning material may be either nucleation-inhibiting or nucleation-promoting, in the present disclosure, unless the context dictates otherwise, a reference herein to a patterning material is intended to be a reference to an NIC.


In some non-limiting examples, reference to a patterning material may signify a coating having a specific composition as described herein.


In the present disclosure, the terms “deposited layer” and “electrode coating” may be used interchangeably to refer to similar concepts and references to a deposited layer herein, in the context of being patterned by selective deposition of an NIC, and/or an NPC may, in some non-limiting examples, be applicable to an electrode coating in the context of being patterned by selective deposition of a patterning material. In some non-limiting examples, reference to an electrode coating may signify a coating having a specific composition as described herein. Similarly, in the present disclosure, the terms “deposited material”, “deposited material” and “electrode coating material” may be used interchangeably to refer to similar concepts and references to a deposited material herein.


In the present disclosure, it will be appreciated by those having ordinary skill in the relevant art that an organic material, may comprise, without limitation, a wide variety of organic molecules, and/or organic polymers. Further, it will be appreciated by those having ordinary skill in the relevant art that organic materials that are doped with various inorganic substances, including without limitation, elements, and/or inorganic compounds, may still be considered organic materials. Still further, it will be appreciated by those having ordinary skill in the relevant art that various organic materials may be used, and that the processes described herein are generally applicable to an entire range of such organic materials. Still further, it will be appreciated by those having ordinary skill in the relevant art that organic materials that contain metals, and/or other organic elements, may still be considered as organic materials. Still further, it will be appreciated by those having ordinary skill in the relevant art that various organic materials may be molecules, oligomers, and/or polymers.


In the present disclosure, a semiconductor material may be described as a material that generally exhibits a band gap. In some non-limiting examples, the band gap may be formed between a highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO) of the semiconductor material. Semiconductor materials thus generally exhibit electrical conductivity that is less than that of a conductive material (including without limitation, a metal), but that is greater than that of an insulating material (including without limitation, a glass). In some non-limiting examples, the semiconductor material may comprise an organic semiconductor material. In some non-limiting examples, the semiconductor material may comprise an inorganic semiconductor material.


As used herein, an oligomer may generally refer to a material which includes at least two monomer units or monomers. As would be appreciated by a person skilled in the art, an oligomer may differ from a polymer in at least one aspect, including but not limited to: (1) the number of monomer units contained therein; (2) the molecular weight; and (3) other materials properties, and/or characteristics. By way of non-limiting example, further description of polymers and oligomers may be found in Naka K. (2014) Monomers, Oligomers, Polymers, and Macromolecules (Overview), and in Kobayashi S., Müllen K. (eds.) Encyclopedia of Polymeric Nanomaterials, Springer, Berlin, Heidelberg.


An oligomer or a polymer may generally include monomer units that may be chemically bonded together to form a molecule. Such monomer units may be substantially identical to one another such that the molecule is primarily formed by repeating monomer units, or the molecule may include plurality different monomer units. Additionally, the molecule may include at least one terminal units, which may be different from the monomer units of the molecule. An oligomer or a polymer may be linear, branched, cyclic, cyclo-linear, and/or cross-linked. An oligomer or a polymer may include plurality different monomer units which are arranged in a repeating pattern, and/or in alternating blocks of different monomer units.


In the present disclosure, the term “semiconducting layer(s)” may be used interchangeably with “organic layer(s)” since the layers in an OLED device may in some non-limiting examples, may comprise organic semiconducting materials.


In the present disclosure, an inorganic substance may refer to a substance that primarily includes an inorganic material. In the present disclosure, an inorganic material may comprise any material that is not considered to be an organic material, including without limitation, metals, glasses, and/or minerals.


In the present disclosure, the terms “photon” and “light” may be used interchangeably to refer to similar concepts. In the present disclosure, photons may have a wavelength that lies in the visible spectrum, in the infrared (IR) region (IR spectrum), near IR region (NIR spectrum), ultraviolet (UV) region (UV spectrum), and/or UVA region (UVA spectrum) (which may correspond to a wavelength range between about 315-400 nm) thereof.


In the present disclosure, the term “visible spectrum” as used herein, generally refers to at least one wavelength in the visible part of the EM spectrum.


In the present disclosure, the term “emission spectrum” as used herein, generally refers to an electroluminescence spectrum of light emitted by an opto-electronic device. By way of non-limiting example, an emission spectrum may be detected using an optical instrument, such as, by way of non-limiting example, a spectrophotometer, which may measure an intensity of EM radiation across a wavelength range.


In the present disclosure, the term “onset wavelength” λonset, onset, as used herein, may generally refer to a lowest wavelength at which an emission is detected within an emission spectrum.


In the present disclosure, the term “peak wavelength” λmax, as used herein, may generally refer to a wavelength at which a maximum luminous intensity is detected within an emission spectrum.


In some non-limiting examples, the onset wavelength λonset may be less than the peak wavelength λmax. In some non-limiting examples, the onset wavelength λonset may correspond to a wavelength at which a luminous intensity is no more than about: 10%, 5%, 3%, 1%, 0.5%, 0.1%, or 0.01%, of the luminous intensity at the peak wavelength λmax.


As would be appreciated by those having ordinary skill in the relevant art, such visible part may correspond to any wavelength between about 380-740 nm. In general, electro-luminescent devices may be configured to emit, and/or transmit light having wavelengths in a range of between about 425-725 nm, and more specifically, in some non-limiting examples, light having peak emission wavelengths λe max of 456 nm, 528 nm, and 624 nm, corresponding to B(lue), G(reen), and R(ed) sub-pixels, respectively. Accordingly, in the context of such electro-luminescent devices, the visible part may refer to any wavelength between about 425-725 nm, or between about 456-624 nm. Photons having a wavelength in the visible spectrum may, in some non-limiting examples, also be referred to as “visible light” herein.


In some non-limiting examples, an emission spectrum that lies in the R(ed) part of the visible spectrum may be characterized by a peak wavelength λmax that may lie in a wavelength range of about 410-640 nm and in some non-limiting examples, may be substantially about 620 nm.


In some non-limiting examples, an emission spectrum that lies in the G(reen) part of the visible spectrum may be characterized by a peak wavelength λmax that may lie in a wavelength range of about 510-340 nm and in some non-limiting examples, may be substantially about 530 nm.


In some non-limiting examples, an emission spectrum that lies in the B(lue) part of the visible spectrum may be characterized by a peak wavelength λmax that may lie in a wavelength range of about 450-4941 nm and in some non-limiting examples, may be substantially about 455 nm.


In the present disclosure, the term “IR signal” as used herein, may generally refer to EM radiation having a wavelength in an IR subset (IR spectrum) of the EM spectrum. An IR signal may, in some non-limiting examples, have a wavelength corresponding to a near-infrared (NIR) subset (NIR spectrum) thereof. By way of non-limiting examples, an NIR signal may have a wavelength of between about: 750-1400 nm, 750-1300 nm, 800-1300 nm, 800-1200 nm, 850-1300 nm, or 900-1300 nm.


In the present disclosure, the term “absorption spectrum”, as used herein, may generally refer to a wavelength (sub-)range of the EM spectrum over which absorption may be concentrated.


In the present disclosure, the terms “absorption edge”, “absorption discontinuity”, and/or “absorption limit” as used herein, may generally refer to a sharp discontinuity in the absorption spectrum of a substance. In some non-limiting examples, an absorption edge may tend to occur at wavelengths where the energy of an absorbed photon may correspond to an electronic transition, and/or ionization potential.


In the present disclosure, the term “extinction coefficient” as used herein, may generally refer to the degree to which an EM coefficient is attenuated when propagating through a material. In some non-limiting examples, the extinction coefficient may be understood to correspond to the imaginary component k of a complex refractive index N In some non-limiting examples, the extinction coefficient k of a material may be measured by a variety of methods, including without limitation, by ellipsometry.


In the present disclosure, the terms “refractive index”, and/or “index”, as used herein to describe a medium, may refer to a value calculated from a ratio of the speed of light in such medium relative to the speed of light in a vacuum. In the present disclosure, particularly when used to describe the properties of substantially transparent materials, including without limitation, thin film layers, and/or coatings, the terms may correspond to the real part, n, in the expression N═n+ik, in which N may represent the complex refractive index and k may represent the extinction coefficient.


As would be appreciated by those having ordinary skill in the relevant art, substantially transparent materials, including without limitation, thin film layers, and/or coatings, may generally exhibit a relatively low k value in the visible spectrum, and therefore the imaginary component of the expression may have a negligible contribution to the complex refractive index, N On the other hand, light-transmissive electrodes formed, for example, by a metallic thin film, may exhibit a relatively low n value and a relatively high k value in the visible spectrum. Accordingly, the complex refractive index, N of such thin films may be dictated primarily by its imaginary component k


In the present disclosure, unless the context dictates otherwise, reference without specificity to a refractive index may be intended to be a reference to the real part 17 of the complex refractive index N


In some non-limiting examples, there may be a generally positive correlation between refractive index n and transmittance, or in other words, a generally negative correlation between refractive index n and absorption. In some non-limiting examples, the absorption edge of a substance may correspond to a wavelength at which the extinction coefficient k approaches 0.


It will be appreciated that the refractive index n, and/or extinction coefficient k values described herein may correspond to such value(s) measured at a wavelength in the visible range of the EM spectrum. In some non-limiting examples, the refractive index n, and/or extinction coefficient k value may correspond to the value measured at wavelength(s) of about 456 nm which may correspond to the peak emission wavelength of a B(lue) subpixel, about 528 nm which may correspond to the peak emission wavelength of a G(reen) subpixel, and/or about 624 nm which may correspond to the peak emission wavelength of a R(ed) subpixel. In some non-limiting examples, the refractive index n, and/or extinction coefficient k value described herein may correspond to the value measured at a wavelength of about 589 nm, which may approximately correspond to the Fraunhofer D-line.


In the present disclosure, the concept of a pixel may be discussed on conjunction with the concept of at least one sub-pixel thereof. For simplicity of description only, such composite concept may be referenced herein as a “(sub-) pixel” and such term may be understood to suggest either, or both of, a pixel, and/or at least one sub-pixel thereof, unless the context dictates otherwise.


In some nonlimiting examples, one measure of an amount of a material on a surface may be a percentage coverage of the surface by such material. In some non-limiting examples, surface coverage may be assessed using a variety of imaging techniques, including without limitation, TEM, AFM, and/or SEM.


In the present disclosure, the terms “particle”, “island” and “cluster” may be used interchangeably to refer to similar concepts.


In the present disclosure, for purposes of simplicity of description, the terms “coating film”, “closed coating”, and/or “closed coating”, as used herein, may refer to a thin film structure, and/or coating of a deposited material used for a deposited layer, in which a relevant part of a surface may be substantially coated thereby, such that such surface may be not substantially exposed by or through the coating film deposited thereon.


In the present disclosure, unless the context dictates otherwise, reference without specificity to a thin film may be intended to be a reference to a substantially closed coating.


In some non-limiting examples, a closed coating, in some non-limiting examples, of a deposited layer, and/or a deposited material, may be disposed to cover a portion of an underlying surface, such that, within such part, less than about: 40%, 30%, 25%, 20%, 15%, 10%, 5%, 3%, 011% of the underlying surface therewithin may be exposed by, or through, the closed coating.


Those having ordinary skill in the relevant art will appreciate that a closed coating may be patterned using various techniques and processes, including without limitation, those described herein, to deliberately leave a part of the exposed layer surface of the underlying surface to be exposed after deposition of the closed coating. In the present disclosure, such patterned films may nevertheless be considered to constitute a closed coating, if, by way of non-limiting example, the thin film, and/or coating that is deposited, within the context of such patterning, and between such deliberately exposed parts of the exposed layer surface of the underlying surface, itself substantially comprises a closed coating.


Those having ordinary skill in the relevant art will appreciate that, due to inherent variability in the deposition process, and in some non-limiting examples, to the existence of impurities in either, or both of, the deposited materials, in some non-limiting examples, the deposited material, and the exposed layer surface of the underlying material, deposition of a thin film, using various techniques and processes, including without limitation, those described herein, may nevertheless result in the formation of small apertures, including without limitation, pin-holes, tears, and/or cracks, therein. In the present disclosure, such thin films may nevertheless be considered to constitute a closed coating, if, by way of non-limiting example, the thin film, and/or coating that is deposited substantially comprises a closed coating and meets any specified percentage coverage criterion set out, despite the presence of such apertures.


In the present disclosure, for purposes of simplicity of description, the term “discontinuous layer” as used herein, may refer to a thin film structure, and/or coating of a material used for a deposited layer, in which a relevant part of a surface coated thereby, may be neither substantially devoid of such material, or forms a closed coating thereof. In some non-limiting examples, a discontinuous layer of a deposited material may manifest as a plurality of discrete islands disposed on such surface.


In the present disclosure, for purposes of simplicity of description, the result of deposition of vapor monomers onto an exposed layer surface of an underlying material, that has not (yet) reached a stage where a closed coating has been formed, may be referred to as a “intermediate stage layer”. In some non-limiting examples, such an intermediate stage layer may reflect that the deposition process has not been completed, in which such an intermediate stage layer may be considered as an interim stage of formation of a closed coating. In some non-limiting examples, an intermediate stage layer may be the result of a completed deposition process, and thus constitute a final stage of formation in and of itself.


In some non-limiting examples, an intermediate stage layer may more closely resemble a thin film than a discontinuous layer but may have apertures, and/or gaps in the surface coverage, including without limitation, at least one dendritic projection, and/or at least one dendritic recess. In some non-limiting examples, such an intermediate stage layer may comprise a fraction 1/X of a single monolayer of the deposited material 331 such that it does not form a closed coating.


In the present disclosure, for purposes of simplicity of description, the term “dendritic”, with respect to a coating, including without limitation, the deposited layer, may refer to feature(s) that resemble a branched structure when viewed in a lateral aspect. In some non-limiting examples, the deposited layer may comprise a dendritic projection, and/or a dendritic recess. In some non-limiting examples, a dendritic projection may correspond to a part of the deposited layer that exhibits a branched structure comprising a plurality of short projections that are physically connected and extend substantially outwardly. In some non-limiting examples, a dendritic recess may correspond to a branched structure of gaps, openings, and/or uncovered parts of the deposited layer that are physically connected and extend substantially outwardly. In some non-limiting examples, a dendritic recess may correspond to, including without limitation, a mirror image, and/or inverse pattern, to the pattern of a dendritic projection. In some non-limiting examples, a dendritic projection, and/or a dendritic recess may have a configuration that exhibits, and/or mimics a fractal pattern, a mesh, a web, and/or an interdigitated structure.


In some non-limiting examples, sheet resistance R may be a property of a component, layer, and/or part that may alter a characteristic of an electric current passing through such component, layer, and/or part. In some non-limiting examples, a sheet resistance of a coating may generally correspond to a characteristic sheet resistance of the coating, measured, and/or determined in isolation from other components, layers, and/or parts of the device.


In the present disclosure, a deposited density may refer to a distribution, within a region, which in some non-limiting examples may comprise an area, and/or a volume, of a deposited material therein. Those having ordinary skill in the relevant art will appreciate that such deposited density may be unrelated to a density of mass or material within a particle structure itself that may comprise such deposited material. In the present disclosure, unless the context dictates otherwise, reference to a deposited density, and/or to a density, may be intended to be a reference to a distribution of such deposited material, including without limitation, as at least one particle, within an area.


In some non-limiting examples, a bond dissociation energy of a metal may correspond to a standard-state enthalpy change measured at 298 K from the breaking of a bond of a diatomic molecule formed by two identical atoms of the metal. Bond dissociation energies may, by way of non-limiting example, be determined based on known literature including without limitation, Luo, Yu-Ran, “Bond Dissociation Energies” (2010).


Without wishing to be bound by a particular theory, it is postulated that providing an NPC 520 may facilitate deposition of the deposited layer onto certain surfaces.


Non-limiting examples of suitable materials for forming an NPC may comprise without limitation, at least one of metals, including without limitation, alkali metals, alkaline earth metals, transition metals, and/or post-transition metals, metal fluorides, metal oxides, and/or fullerene.


Non-limiting examples of such materials may comprise Ca, Ag, Mg, Yb, ITO, IZO, ZnO, ytterbium fluoride (YbF3), magnesium fluoride (MgF2), and/or cesium fluoride (CsF).


In the present disclosure, the term “fullerene” may refer generally to a material including carbon molecules. Non-limiting examples of fullerene molecules include carbon cage molecules, including without limitation, a three-dimensional skeleton that includes multiple carbon atoms that form a closed shell, and which may be, without limitation, spherical, and/or semi-spherical in shape. In some non-limiting examples, a fullerene molecule may be designated as Cn, where n may be an integer corresponding to several carbon atoms included in a carbon skeleton of the fullerene molecule. Non-limiting examples of fullerene molecules include a, where n may be in the range of 50 to 250, such as, without limitation, C60, C70, C72, C74, C76, C78, C80, C82, and C84. Additional non-limiting examples of fullerene molecules include carbon molecules in a tube, and/or a cylindrical shape, including without limitation, single-walled carbon nanotubes, and/or multi-walled carbon nanotubes.


Based on findings and experimental observations, it may be postulated that nucleation promoting materials, including without limitation, fullerenes, metals, including without limitation, Ag, and/or Yb, and/or metal oxides, including without limitation, ITO, and/or IZO, as discussed further herein, may act as nucleation sites for the deposition of a deposited layer, including without limitation Mg.


In some non-limiting examples, suitable materials for use to form an NPC 520, may include those exhibiting or characterized as having an initial sticking probability S0 for a material of a deposited layer of at least about: 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 0.93, 0.95, 0.98, or 0.99.


By way of non-limiting example, in scenarios where Mg is deposited using without limitation, an evaporation process on a fullerene-treated surface, in some non-limiting examples, the fullerene molecules may act as nucleation sites that may promote formation of stable nuclei for Mg deposition.


In some non-limiting examples, less than a monolayer of an NPC 520, including without limitation, fullerene, may be provided on the treated surface to act as nucleation sites for deposition of Mg.


In some non-limiting examples, treating a surface by depositing several monolayers of an NPC 520 thereon may result in a higher number of nucleation sites and accordingly, a higher initial sticking probability S0.


Those having ordinary skill in the relevant art will appreciate than an amount of material, including without limitation, fullerene, deposited on a surface, may be more, or less than one monolayer. By way of non-limiting example, such surface may be treated by depositing: 0.1, 1, 10, or more monolayers of a nucleation promoting material, and/or a nucleation inhibiting material.


In some non-limiting examples, a thickness of the NPC 520 deposited on an exposed layer surface of underlying material(s) may be between about: 1-5 nm, or 1-3 nm.


Where features or aspects of the present disclosure may be described in terms of Markush groups, it will be appreciated by those having ordinary skill in the relevant art that the present disclosure may also be thereby described in terms of any individual member of sub-group of members of such Markush group.


Terminology

References in the singular form may include the plural and vice versa, unless otherwise noted.


As used herein, relational terms, such as “first” and “second”, and numbering devices such as “a”, “b” and the like, may be used solely to distinguish one entity or element from another entity or element, without necessarily requiring or implying any physical or logical relationship or order between such entities or elements.


The terms “including” and “comprising” may be used expansively and in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to”. The terms “example” and “exemplary” may be used simply to identify instances for illustrative purposes and should not be interpreted as limiting the scope of the invention to the stated instances. In particular, the term “exemplary” should not be interpreted to denote or confer any laudatory, beneficial, or other quality to the expression with which it is used, whether in terms of design, performance or otherwise.


Further, the term “critical”, especially when used in the expressions “critical nuclei”, “critical nucleation rate”, “critical concentration”, “critical cluster”, “critical monomer”, “critical particle structure size”, and/or “critical surface tension” may be a term familiar to those having ordinary skill in the relevant art, including as relating to or being in a state in which a measurement or point at which some quality, property or phenomenon undergoes a definite change. As such, the term “critical” should not be interpreted to denote or confer any significance or importance to the expression with which it is used, whether in terms of design, performance, or otherwise.


The terms “couple” and “communicate” in any form may be intended to mean either a direct connection or indirect connection through some interface, device, intermediate component, or connection, whether optically, electrically, mechanically, chemically, or otherwise.


The terms “on” or “over” when used in reference to a first component relative to another component, and/or “covering” or which “covers” another component, may encompass situations where the first component is direct on (including without limitation, in physical contact with) the other component, as well as cases where at least one intervening component is positioned between the first component and the other component.


Directional terms such as “upward”, “downward”, “left” and “right” may be used to refer to directions in the drawings to which reference is made unless otherwise stated. Similarly, words such as “inward” and “outward” may be used to refer to directions toward and away from, respectively, the geometric center of the device, area or volume or designated parts thereof. Moreover, all dimensions described herein may be intended solely to be by way of example of purposes of illustrating certain embodiments and may not be intended to limit the scope of the disclosure to any embodiments that may depart from such dimensions as may be specified.


As used herein, the terms “substantially”, “substantial”, “approximately”, and/or “about” may be used to denote and account for small variations. When used in conjunction with an event or circumstance, such terms may refer to instances in which the event or circumstance occurs precisely, as well as instances in which the event or circumstance occurs to a close approximation. By way of non-limiting example, when used in conjunction with a numerical value, such terms may refer to a range of variation of no more than about ±10% of such numerical value, such as no more than: ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.1%, or ±0.05%.


As used herein, the phrase “consisting substantially of” may be understood to include those elements specifically recited and any additional elements that do not materially affect the basic and novel characteristics of the described technology, while the phrase “consisting of” without the use of any modifier, may exclude any element not specifically recited.


As will be understood by those having ordinary skill in the relevant art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein may also encompass any and all possible sub-ranges, and/or combinations of sub-ranges thereof. Any listed range may be easily recognized as sufficiently describing, and/or enabling the same range being broken down at least into equal fractions thereof, including without limitation, halves, thirds, quarters, fifths, tenths etc. As a non-limiting example, each range discussed herein may be readily be broken down into a lower third, middle third, and/or upper third, etc.


As will also be understood by those having ordinary skill in the relevant art, all language, and/or terminology such as “up to”, “at least”, “greater than”, “less than”, and the like, may include, and/or refer the recited range(s) and may also refer to ranges that may be subsequently broken down into sub-ranges as discussed herein.


As will be understood by those having ordinary skill in the relevant art, a range may include each individual member of the recited range.


General

The purpose of the Abstract is to enable the relevant patent office or the public generally, and specifically, persons of ordinary skill in the art who are not familiar with patent or legal terms or phraseology, to quickly determine from a cursory inspection, the nature of the technical disclosure. The Abstract is neither intended to define the scope of this disclosure, nor is it intended to be limiting as to the scope of this disclosure in any way.


The structure, manufacture and use of the presently disclosed examples have been discussed above. The specific examples discussed are merely illustrative of specific ways to make and use the concepts disclosed herein, and do not limit the scope of the present disclosure. Rather, the general principles set forth herein are merely illustrative of the scope of the present disclosure.


It should be appreciated that the present disclosure, which is described by the claims and not by the implementation details provided, and which can be modified by varying, omitting, adding or replacing, and/or in the absence of any element(s), and/or limitation(s) with alternatives, and/or equivalent functional elements, whether or not specifically disclosed herein, will be apparent to those having ordinary skill in the relevant art, may be made to the examples disclosed herein, and may provide many applicable inventive concepts that may be embodied in a wide variety of specific contexts, without straying from the present disclosure.


In particular, features, techniques, systems, sub-systems and methods described and illustrated in at least one of the above-described examples, whether or not described an illustrated as discrete or separate, may be combined or integrated in another system without departing from the scope of the present disclosure, to create alternative examples comprised of a combination or sub-combination of features that may not be explicitly described above, or certain features may be omitted, or not implemented.


Features suitable for such combinations and sub-combinations would be readily apparent to persons skilled in the art upon review of the present application as a whole. Other examples of changes, substitutions, and alterations are easily ascertainable and could be made without departing from the spirit and scope disclosed herein.


All statements herein reciting principles, aspects, and examples of the disclosure, as well as specific examples thereof, are intended to encompass both structural and functional equivalents thereof and to cover and embrace all suitable changes in technology. Additionally, it is intended that such equivalents include both currently known equivalents as well as equivalents developed in the future, i.e., any elements developed that perform the same function, regardless of structure.


CLAUSES

The present disclosure includes, without limitation, the following clauses:


1. An opto-electronic device comprising a compound that is a fluorine-containing phosphazene compound.


2. The device according to clause 1, wherein the compound comprises a chain moiety, the chain moiety comprising a backbone and a fluorine (F) atom attached thereto.


3. The device according to clause 2, wherein the backbone is a carbon-containing backbone.


4. The device according to clause 2 or 3, wherein the chain moiety comprises an intermediate moiety.


5. The device according to clause 4, wherein the intermediate moiety comprises at least one of: oxygen (O), an ether, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubsituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted heteroarylene, and an unsubstituted heteroarylene.


6. The device according to clause 4 or 5, wherein the intermediate moiety comprises a fluorine (F) atom.


7. The device according to any one of clauses 4 through 6, wherein the intermediate moiety comprises a fluoroalkylene unit.


8. The device according to any one of clauses 4 through 7, wherein the intermediate moiety comprises a CF2 unit.


9. The device according to any one of clauses 4 through 8, wherein the intermediate moiety comprises a CHF unit.


10. The device according to any one of clauses 4 through 9, wherein the intermediate moiety comprises a CH2 unit.


11. The device according to any one of clauses 4 through 10, wherein the intermediate moiety comprises saturated bonds.


12. The device according to any one of clauses 4 through 11, wherein the intermediate moiety comprises at least one of: oxygen (O), an ether, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, and an unsubstituted fluoroalkylene.


13. The device according to any one of clauses 4 through 12, wherein the intermediate moiety is a saturated moiety.


14. The device according to any one of clauses 4 through 13, wherein the intermediate moiety contains up to 15 carbon atoms.


15. The device according to any one of clauses 4 through 14, wherein the intermediate moiety is represented by the formula:




embedded image


wherein:


X is each independently hydrogen (H), deutero (D), fluorine (F), or CF3;


a is an integer between 0 and 6;


bis an integer between 0 and 12; and


a sum of a and b is no more than 15.


16. The device according to any one of clauses 2 through 15, wherein the chain moiety comprises a terminal moiety bonded to the intermediate moiety, the terminal moiety being arranged at a terminal portion of the chain moiety.


17. The device according to clause 16, wherein the terminal moiety comprises a fluorine (F) atom.


18. The device according to clause 16 or 17, wherein the terminal moiety comprises at least one of: a branched alkyl, an unbranched alkyl, a branched fluoroalkyl, an unbranched fluoroalkyl, a fluorine-substituted cycloheteroalkyl, a branched fluoroalkoxy; an unbranched fluoroalkoxy, a fluoroaryl, a polyfluorosulfanyl, and a fluorocycloalkyl.


19. The device according to any one of clauses 16 through 18, wherein the terminal moiety comprises fluorine (F) and hydrogen (H).


20. The device according to any one of clauses 16 through 19, wherein the terminal moiety comprises a CF2H unit.


21. The device according to any one of clauses 16 through 20, wherein the terminal moiety is represented by at least one of Formula: (EC-1), (EC-2), (EC-3), (EC-4), (EC-5), (EC-6), and (EC-7):




embedded image


22. The device according to any one of clauses 2 through 21, wherein the compound comprises a core moiety attached to the chain moiety.


23. The device according to clause 22, wherein the chain moiety comprises a linker moiety adapted to attach the chain moiety to the core moiety.


24. The device according to clause 23, wherein the linker moiety comprises at least one of: oxygen (O), nitrogen (N), sulfur (S), a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubsituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted arylene, an unsubstituted arylene, a substituted heteroarylene, and an unsubstituted heteroarylene.


25. The device according to clause 23 or 24, wherein the linker moiety comprises at least one of: oxygen (O), nitrogen (N), sulfur (S), a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, and an unsubsituted fluoroalkylene.


26. The device according to any one of clauses 23 through 25, wherein the linker moiety is represented by at least one of Formula: (EA-1), (EA-2), (EA-3), (EA-4), (EA-5), and (EA-6):




embedded image


wherein:


RH is selected from at least one of: hydrogen (H), deutero (D), CF3, a branched alkyl, an unbranched alkyl, a branched fluoroalkyl, an unbranched fluoroalkyl, a fluorine-substituted cycloheteroalkyl, a branched fluoroalkoxy, an unbranched fluoroalkoxy, a fluoroaryl, a polyfluorosulfanyl, and a fluorocycloalkyl.


27. The device according to any one of clauses 22 through 26, wherein the core moiety comprises a phosphazene unit.


28. The device according to clause 27, wherein the chain moiety is attached to the phosphorus (P) atom of the phosphazene unit.


29. The device according to any one of clauses 22 through 28, wherein the core moiety comprises a cyclophosphazene.


30. The device according to clause 29, wherein the cyclophosphazene is provided by a plurality of phosphazene units.


31. The device according to clause 29 or 30, wherein the cyclophosphazene is provided by a number of phosphazene units selected from 3 and 4.


32. The device according to any one of clauses 2 through 31, wherein the chain moiety comprises a branching moiety attached to at least three moieties selected from: an intermediate moiety, a terminal moiety, and a linker moiety.


33. The device according to clause 32, wherein the branching moiety comprises at least one of: nitrogen (N), an amine, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubstituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted cycloheteroalkylene, an unsubstituted cycloheteroalkylene, a substituted arylene, an unsubstituted arylene, a substituted heteroarylene, and an unsubstituted heteroarylene.


34. The device according to clause 32 or 33, wherein the branching moiety comprises at least one of: nitrogen (N), an amine, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, and an unsubstituted fluoroalkylene.


35. The device according to any one of clauses 1 through 34, wherein the compound does not substantially absorb light at a wavelength in a visible portion of an electromagnetic spectrum.


36. The device according to any one of clauses 1 through 35, wherein the compound does not substantially exhibit photoluminescence at a wavelength in a visible portion of an electromagnetic spectrum.


37. The device according to any one of clauses 1 through 36, wherein the compound has an optical gap that exceeds at least one of about: 3.4 eV, 3.5 eV, 4.1 eV, 5 eV, and 6.2 eV.


38. The device according to any one of clauses 1 through 37, wherein the compound has a melting temperature that exceeds about 100° C.


39. The device according to any one of clauses 1 through 38, wherein the compound has a sublimation temperature that exceeds about 100° C.


40. The device according to any one of clauses 1 through 39, wherein the compound has a characteristic surface energy that is less than at least one of about: 25 dynes/cm, 21 dynes/cm, 20 dynes/cm, 19 dynes/cm, 18 dynes/cm, 17 dynes/cm, 16 dynes/cm, 15 dynes/cm, 14 dynes/cm, 13 dynes/cm, 12 dynes/cm, 11 dynes/cm, and 10 dynes/cm.


41. The device according to any one of clauses 1 through 40, wherein the compound has a refractive index of no more than at least one of about: 1.5, 1.45, 1.4, 1.35, 1.3, and 1.25.


42. The device according to any one of clauses 1 through 41, further comprising first and second electrodes, and an active region comprising at least one semiconducting layer and bounded, in a transverse aspect, by the electrodes and confined, in a lateral aspect, to an emissive region defined by the electrodes, wherein the active region is substantially devoid of the compound.


43. The device according to clause 42, further comprising: a patterning coating comprising the compound, the patterning coating being disposed on a first layer surface of an underlying layer in a first portion of a lateral aspect thereof; and a deposited layer comprised of a deposited material, disposed on a second layer surface; wherein the first portion is substantially devoid of a closed coating of the deposited material.


44. The device according to clause 43, wherein the first portion excludes a lateral aspect of the emissive region.


45. The device according to clause 43 or 44, wherein the second electrode comprises at least a part of the deposited layer as a layer thereof.


46. The device according to clause 43, wherein the first portion includes a lateral aspect of the emissive region.


47. The device according to clause 46, further comprising an auxiliary electrode comprising the deposited layer as a layer thereof.


48. The device according to any one of clauses 43 through 45, further comprising a conductor electrically coupled with the second electrode.


49. An opto-electronic device comprising a compound, the compound comprising a terminal moiety comprising a CF2H unit.


50. The device according to clause 49, wherein the compound comprises a chain moiety, wherein the terminal moiety is arranged at a terminal portion of the chain moiety.


51. The device according to clause 49 or 50, wherein the chain moiety comprises a backbone and a fluorine (F) atom attached thereto.


52. The device according to clause 51, wherein the backbone is a carbon-containing backbone.


53. The device according to any one of clauses 50 through 52, wherein the chain moiety comprises an intermediate moiety attached to the terminal moiety.


54. The device according to clause 53, wherein the intermediate moiety comprises at least one of: oxygen (O), an ether, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubsituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted heteroarylene, and an unsubstituted heteroarylene.


55. The device according to 53 or 54, wherein the intermediate moiety comprises a fluorine (F) atom.


56. The device according to any one of clauses 53 through 55, wherein the intermediate moiety comprises a CF2 unit.


57. The device according to any one of clauses 53 through 56, wherein the intermediate moiety comprises a CH2 unit.


58. The device according to any one of clauses 53 through 57, wherein the intermediate moiety comprises a fluoroalkylene unit.


59. The device according to any one of clauses 57 through 58, wherein the compound comprises a core moiety attached to the chain moiety.


60. The device according to clause 59, wherein the chain moiety comprises a linker moiety adapted to attach the chain moiety to the core moiety.


61. The device according to clause 60, wherein the linker moiety comprises at least one of: oxygen (O), nitrogen (N), sulfur (S), a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubsituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted arylene, an unsubstituted arylene, a substituted heteroarylene, and an unsubstituted heteroarylene.


62. The device according to any one of clauses 59 through 61, wherein the core moiety comprises a phosphazene unit.


63. The device according to clause 62, wherein the chain moiety is attached to the phosphorus (P) atom of the phosphazene unit.


64. The device according to any one of clauses 59 through 63, wherein the core moiety comprises a cyclophosphazene.


65. The device according to clause 64, wherein the cyclophosphazene is provided by a plurality of phosphazene units.


66. The device according to clause 64 or 65, wherein the cyclophosphazene is provided by a number of phosphazene units selected from 3 and 4.


67. The device according to any one of clauses 59 through 66, wherein the chain moiety is selected such that an equivalent precursor form of the chain moiety, derived by cleaving a bond between the linker moiety and the core moiety and attaching a hydrogen (H) atom to the cleaved linker moiety, has a melting temperature that exceeds about 60° C.


68. The device according to any one of clauses 57 through 67, wherein the chain moiety comprises a branching moiety attached to at least three moieties selected from: an intermediate moiety, a terminal moiety, and a linker moiety.


69. The device according to clause 68, wherein the branching moiety comprises at least one of: nitrogen (N), an amine, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubstituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted cycloheteroalkylene, an unsubstituted cycloheteroalkylene, a substituted arylene, an unsubstituted arylene, a substituted heteroarylene, and an unsubstituted heteroarylene.


70. The device according to any one of clauses 49 through 69, wherein the compound does not substantially absorb light at a wavelength in a visible portion of an electromagnetic spectrum.


71. The device according to any one of clauses 49 through 70, wherein the compound does not substantially exhibit photoluminescence at a wavelength in a visible portion of an electromagnetic spectrum.


72. The device according to any one of clauses 49 through 71, wherein the compound has an optical gap that exceeds at least one of about: 3.4 eV, 3.5 eV, 4.1 eV, 5 eV, and 6.2 eV.


73. The device according to any one of clauses 49 through 72, wherein the compound has a melting temperature that exceeds about 100° C.


74. The device according to any one of clauses 49 through 73, wherein the compound has a sublimation temperature that exceeds about 100° C.


75. The device according to any one of clauses 49 through 74, wherein the compound has a characteristic surface energy that is less than at least one of about: 25 dynes/cm, 21 dynes/cm, 20 dynes/cm, 19 dynes/cm, 18 dynes/cm, 17 dynes/cm, 16 dynes/cm, 15 dynes/cm, 14 dynes/cm, 13 dynes/cm, 12 dynes/cm, 11 dynes/cm, and 10 dynes/cm.


76. The device according to any one of clauses 49 through 75, wherein the compound has a refractive index of no more than at least one of about: 1.5, 1.45, 1.4, 1.35, 1.3, and 1.25.


77. The device according to any one of clauses 50 through 76, wherein the compound comprises a plurality of the chain moieties.


78. The device according to clause 77, wherein a first one of the plurality of chain moieties is independently selected from an other one of the plurality of chain moieties.


79. The device according to clause 77 or 78, wherein each of the plurality of chain moieties is identical.


80. The device according to any one of clauses 77 through 79, wherein a sum of the molar mass of the plurality of chain moieties exceeds about 90% of the molar mass of the compound.


81. The device according to any one of clauses 77 through 80, wherein a sum of the molar mass of the plurality of chain moieties exceeds about 10 times the molar mass of the core moiety.


82. The device according to any one of clauses 50 through 81, wherein the chain moiety is devoid of a continuous perfluorinated unit longer than at least one of: 8, 7, and 6 carbon (C) atoms.


83. The device according to any one of clauses 49 through 82, further comprising first and second electrodes, and an active region comprising at least one semiconducting layer and bounded in a transverse aspect by the electrodes and confined, in a lateral aspect, to an emissive region defined by the electrodes, wherein the active region is substantially devoid of the compound.


84. The device according to clause 83, further comprising: a patterning coating comprising the compound, the patterning coating being disposed on a first layer surface of an underlying layer in a first portion of a lateral aspect thereof; and a deposited layer comprised of a deposited material, disposed on a second layer surface; wherein the first portion is substantially devoid of a closed coating of the deposited material.


85. The device according to clause 84, wherein the first portion excludes a lateral aspect of the emissive region.


86. The device according to clause 84 or 85, wherein the second electrode comprises at least a part of the deposited layer as a layer thereof.


87. The device according to clause 84, wherein the first portion includes a lateral aspect of the emissive region.


88. The device according to clause 87, further comprising an auxiliary electrode comprising the deposited layer as a layer thereof.


89. The device according to any one of clauses 86 through 88, further comprising a conductor electrically coupled with the second electrode.


90. A phosphazene derivative compound comprising first and second chain moieties, each comprising a backbone and a fluorine (F) atom attached thereto, wherein the first chain moiety is different from the second chain moiety.


91. The compound according to clause 90, wherein the molar mass of each chain moiety of the first and second chain moieties is about 200 g/mol to about 900 g/mol.


92. The compound according to clause 91, wherein a difference between the molar mass of the first chain moiety and the molar mass of the second chain moiety is less than about: 500 g/mol.


93. The compound according to any one of clauses 90 through 92, wherein a quotient (P/V) of a parachor (P) by a molar volume (V) of each chain moiety of the first and second chain moieties is less than at least one of about: 3, 2.5, 2, 1.8, 1.6, and 1.5.


94. The compound according to any one of clauses 90 through 93, further comprising a phosphazene unit, wherein each of the first chain moiety and the second chain moiety are attached to a phosphorus (P) atom of the phosphazene unit.


95. The compound according to clause 94, wherein the first chain moiety and the second chain moiety are attached to a common phosphorus (P) atom.


96. The compound according to any one of clauses 94 through 95, wherein at least one of the first and second chain moieties comprises at least one of a CF2 unit, a CH2 unit, and a fluoroalkylene unit.


97. The compound of any one of clauses 90 through 96, wherein the number of carbon (C) atoms contained in the first chain moiety differs from the number of carbon atoms contained in the second chain moiety by about 1 to 8 C atoms, 1 to 6 C atoms, 2 to 6 C atoms, 2 to 4 C atoms, 2 to 3 C atoms, or 1 to 3 C atoms.


98. The compound of any one of clauses 90 through 97, wherein the number of fluorine (F) atoms contained in the first chain moiety differs from the number of fluorine atoms contained in the second chain moiety by about 1 to 16 F atoms, 1 to 12 F atoms, 2 to 12 F atoms, 4 to 12 F atoms, 4 to 8 F atoms, 4 to 6 F atoms, or 2 to 6 F atoms.


99. The compound of any one of clauses 90 through 98, wherein the compound is represented by the formula:




embedded image


wherein:


A represents an integer between 3 and 5;


R1 represents the first chain moiety;


B represents an integer between 1 and 9;


R2 represents the second chain moiety;


C represents an integer of 1 to 9; and


the sum of B and C is no more than twice the value of A.


100. The compound of any one of clauses 90 through 99, wherein the first chain moiety is represented by the formula:





*—O—(CH2)t(CF2)uZ


wherein:


t represents an integer between 1 and 3;


u represents an integer between 5 and 12; and


Z represents hydrogen (H), deutero (D), or fluorine (F).


101. The compound of any one of clauses 90 through 100, wherein the second chain moiety is represented by the formula:





*—O—(CH2)v(CF2)wZ


wherein:


v represents an integer between 1 and 3;


w represents an integer between 5 and 12; and


Z represents hydrogen (H), deutero (D), or fluorine (F).


102. The compound of any one of clauses 90 through 101, wherein the compound is represented by Formula (X):




embedded image


wherein:


t and v each represent an integer between 1 and 3;


u and w each represent an integer between 5 and 12;


y represents an integer between 2 and 6; and


Z individually represents hydrogen (H), deutero (D), or fluorine (F).


103. The compound of clause 102, wherein the values of u and w are different.


104. The compound of clause 102 or 103, wherein t and v are both 1.


105. The compound of any one of clauses 102 through 104, wherein y is 3 or 4.


106. The compound of any one of clauses 102 through 105, wherein u is 8.


107. The compound of any one of clauses 102 through 106, wherein w is 10.


108. A compound comprising a moiety according to Formula (PX-1):




embedded image


wherein:


R1 and R2 each independently represents at least one of: a substituted alkyl, an unsubsituted alkyl, a substituted alkoxy, an unsubstituted alkoxy, and a chain moiety comprising a backbone and a fluorine (F) atom attached thereto; and


R1 and R2 are different.


The device according to at least one clause herein wherein the NIC comprises an NIC material.


The device according to at least one clause herein wherein the NIC comprises the compound of any one of clauses 90 to 108.


The device according to at least one clause herein, wherein an initial sticking probability against deposition of the deposited material of the NIC is less than an initial sticking probability against deposition of the deposited material of the exposed layer surface.


The device according to at least one clause herein, wherein the NIC is substantially devoid of a closed coating of the deposited material.


The device according to at least one clause herein, wherein at least one of the NIC and the NIC material has an initial sticking probability against deposition of the deposited material that is less than at least one of about: 0.9, 0.3, 0.2, 0.15, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0.008, 0.005, 0.003, 0.001, 0.0008, 0.0005, 0.0003, and 0.0001.


The device according to at least one clause herein, wherein at least one of the NIC and the NIC material has an initial sticking probability against deposition of at least one of silver (Ag) and magnesium (Mg) that is less than at least one of about: 0.9, 0.3, 0.2, 0.15, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0.008, 0.005, 0.003, 0.001, 0.0008, 0.0005, 0.0003, and 0.0001.


The device according to at least one clause herein, wherein at least one of the NIC and the NIC material has an initial sticking probability against deposition of the deposited material of at least one of between about: 0.15-0.0001, 0.1-0.0003, 0.08-0.0005, 0.08-0.0008, 0.05-0.001, 0.03-0.0001, 0.03-0.0003, 0.03-0.0005, 0.03-0.0008, 0.03-0.001, 0.03-0.005, 0.03-0.008, 0.03-0.01, 0.02-0.0001, 0.02-0.0003, 0.02-0.0005, 0.02-0.0008, 0.02-0.001, 0.02-0.005, 0.02-0.008, 0.02-0.01, 0.01-0.0001, 0.01-0.0003, 0.01-0.0005, 0.01-0.0008, 0.01-0.001, 0.01-0.005, 0.01-0.008, 0.008-0.0001, 0.008-0.0003, 0.008-0.0005, 0.008-0.0008, 0.008-0.001, 0.008-0.005, 0.005-0.0001, 0.005-0.0003, 0.005-0.0005, 0.005-0.0008, and 0.005-0.001.


The device according to at least one clause herein, wherein at least one of the NIC and the NIC material has an initial sticking probability against deposition of at least one of the deposited material that is less than a threshold value that is at least one of about: 0.3, 0.2, 0.18, 0.15, 0.13, 0.1, 0.08, 0.05, 0.03, 0.02, 0.01, 0.008, 0.005, 0.003, and 0.001.


The device according to at least one clause herein, wherein at least one of the NIC and the NIC material has an initial sticking probability against the deposition of at least one of: Ag, Mg, ytterbium (Yb), cadmium (Cd), and zinc (Zn), that is less than the threshold value.


The device according to at least one clause herein, wherein the threshold value has a first threshold value against the deposition of a first deposited material and a second threshold value against the deposition of a second deposited material.


The device according to at least one clause herein, wherein the first deposited material is Ag and the second deposited material is Mg.


The device according to at least one clause herein, wherein the first deposited material is Ag and the second deposited material is Yb.


The device according to at least one clause herein, wherein the first deposited material is Yb and the second deposited material is Mg.


The device according to at least one clause herein, wherein the first threshold value exceeds the second threshold value.


The device according to at least one clause herein, wherein at least one of the NIC and the NIC material has an extinction coefficient that is less than about 0.01 for photons at a wavelength that exceeds at least one of about: 600 nm, 500 nm, 460 nm, 420 nm, and 410 nm.


The device according to at least one clause herein, wherein the NIC has at least one nucleation site for the deposited material.


The device according to at least one clause herein, wherein the NIC is supplemented with a seed material that acts as a nucleation site for the deposited material.


The device according to at least one clause herein, wherein the seed material comprises at least one of: a nucleation promoting coating (NPC) material, an organic material, a polycyclic aromatic compound, and a material comprising a non-metallic element selected from at least one of oxygen (O), sulfur (S), nitrogen (N), and carbon (C).


The device according to at least one clause herein, wherein the NIC acts as an optical coating.


The device according to at least one clause herein, wherein the NIC modifies at least one of a property and a characteristic of EM radiation emitted by the device.


The device according to at least one clause herein, wherein the NIC comprises a crystalline material.


The device according to at least one clause herein, wherein the NIC is deposited as a non-crystalline material and becomes crystallized after deposition.


The device according to at least one clause herein, wherein the deposited layer comprises a deposited material.


The device according to at least one clause herein, wherein the deposited material comprises an element selected from at least one of: potassium (K), sodium (Na), lithium (Li), barium (Ba), cesium (Cs), ytterbium (Yb), silver (Ag), gold (Au), copper (Cu), aluminum (Al), magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), and yttrium (Y).


The device according to at least one clause herein, wherein the deposited material comprises a pure metal.


The device according to at least one clause herein, wherein the deposited material is selected from at least one of pure Ag and substantially pure Ag.


The device according to at least one clause herein, wherein the substantially pure Ag has a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, and 99.9995%.


The device according to at least one clause herein, wherein the deposited material is selected from at least one of pure Mg and substantially pure Mg.


The device according to at least one clause herein, wherein the substantially pure Mg has a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, or 99.9995%.


The device according to at least one clause herein, wherein the deposited material comprises an alloy.


The device according to at least one clause herein, wherein the deposited material comprises at least one of: an Ag-containing alloy, an Mg-containing alloy, and an AgMg-containing alloy.


The device according to at least one clause herein, wherein the AgMg-containing alloy has an alloy composition that ranges from 1:10 (Ag:Mg) to about 10:1 by volume.


The device according to at least one clause herein, wherein the deposited material comprises at least one metal other than Ag.


The device according to at least one clause herein, wherein the deposited material comprises an alloy of Ag with at least one metal.


The device according to at least one clause herein, wherein the at least one metal is selected from at least one of Mg and Yb.


The device according to at least one clause herein, wherein the alloy is a binary alloy having a composition between about 5-95 vol. % Ag.


The device according to at least one clause herein, wherein the alloy comprises a Yb:Ag alloy having a composition between about 1:20-10:1 by volume.


The device according to at least one clause herein, wherein the deposited material comprises an Mg:Yb alloy.


The device according to at least one clause herein, wherein the deposited material comprises an Ag:Mg:Yb alloy.


The device according to at least one clause herein, wherein the deposited layer comprises at least one additional element.


The device according to at least one clause herein, wherein the at least one additional element is a non-metallic element.


The device according to at least one clause herein, wherein the non-metallic element is selected from at least one of O, S, N, and C.


The device according to at least one clause herein, wherein a concentration of the non-metallic element is less than about: 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, and 0.0000001%.


The device according to at least one clause herein, wherein the deposited layer has a composition in which a combined amount of O and C is less than about: 10%, 5%, 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, and 0.0000001%.


The device according to at least one clause herein, wherein the non-metallic element acts as a nucleation site for the deposited material on the NIC.


The device according to at least one clause herein, wherein the deposited material and the underlying layer comprise a common metal.


The device according to at least one clause herein, the deposited layer comprises a plurality of layers of the deposited material.


The device according to at least one clause herein, a deposited material of a first one of the plurality of layers is different from a deposited material of a second one of the plurality of layers.


The device according to at least one clause herein, wherein the deposited layer comprises a multilayer coating.


The device according to at least one clause herein, wherein the multilayer coating is at least one of: Yb/Ag, Yb/Mg, Yb/Mg:Ag, Yb/Yb:Ag, Yb/Ag/Mg, and Yb/Mg/Ag.


The device according to at least one clause herein, wherein the deposited material comprises a metal having a bond dissociation energy of no more than about: 300 kJ/mol, 200 kJ/mol, 165 kJ/mol, 150 kJ/mol, 100 kJ/mol, 50 kJ/mol, and 20 kJ/mol.


The device according to at least one clause herein, wherein the deposited material comprises a metal having an electronegativity of no more than about: 1.4, 1.3, and 1.2.


The device according to at least one clause herein, wherein a sheet resistance of the deposited layer is no more than about: 10Ω/□, 5Ω/□, 1Ω/□, 0.5Ω/□, 0.2Ω/□, and 0.1Ω/□.


The device according to at least one clause herein, wherein the deposited layer is disposed in a pattern defined by at least one region therein that is substantially devoid of a closed coating thereof.


The device according to at least one clause herein, wherein the at least one region separates the deposited layer into a plurality of discrete fragments thereof.


The device according to at least one clause herein, wherein at least two discrete fragments are electrically coupled.


The device according to at least one clause herein, wherein the NIC has a boundary defined by an NIC edge.


The device according to at least one clause herein, wherein the NIC comprises at least one NIC transition region and an NIC non-transition part.


The device according to at least one clause herein, wherein the at least one NIC transition region transitions from a maximum thickness to a reduced thickness.


The device according to at least one clause herein, wherein the at least one NIC transition region extends between the NIC non-transition part and the NIC edge.


The device according to at least one clause herein, wherein the NIC has an average film thickness in the NIC non-transition part that is in a range of at least one of between about: 1-100 nm, 2-50 nm, 3-30 nm, 4-20 nm, 5-15 nm, 5-10 nm, and 1-10 nm.


The device according to at least one clause herein, wherein a thickness of the NIC in the NIC non-transition part is within at least one of about: 95%, and 90% of the average film thickness of the NIC.


The device according to at least one clause herein, wherein the average film thickness is less than at least one of about: 80 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, 15 nm, and 10 nm.


The device according to at least one clause herein, wherein the average film thickness exceeds at least one of about: 3 nm, 5 nm, and 8 nm.


The device according to at least one clause herein, wherein the average film thickness is less than about 10 nm.


The device according to at least one clause herein, wherein the NIC has an NIC thickness that decreases from a maximum to a minimum within the NIC transition region.


The device according to at least one clause herein, wherein the maximum is proximate to a boundary between the NIC transition region and the NIC non-transition part.


The device according to at least one clause herein, wherein the maximum is a percentage of the average film thickness that is at least one of about: 100%, 95%, and


The device according to at least one clause herein, wherein the minimum is proximate to the NIC edge.


The device according to at least one clause herein, wherein the minimum is in a range of between about: 0-0.1 nm.


The device according to at least one clause herein, wherein a profile of the NIC thickness is at least one of sloped, tapered, and defined by a gradient.


The device according to at least one clause herein, wherein the tapered profile follows at least one of a linear, non-linear, parabolic, and exponential decaying profile.


The device according to at least one clause herein, wherein a non-transition width along a lateral axis of the NIC non-transition region exceeds a transition width along the axis of the NIC transition part.


The device according to at least one clause herein, wherein a quotient of the non-transition width by the transition width is at least one of at least about: 5, 10, 20, 50, 100, 500, 1,000, 1,500, 5,000, 10,000, 50,000, or 100,000.


The device according to at least one clause herein, wherein at least one of the non-transition width and the transition width exceeds an average film thickness of the underlying layer.


The device according to at least one clause herein, wherein at least one of the non-transition width and the transition width exceeds the average film thickness of the NIC.


The device according to at least one clause herein, wherein the average film thickness of the underlying layer exceeds the average film thickness of the NIC.


The device according to at least one clause herein, wherein the deposited layer has a boundary defined by a deposited layer edge.


The device according to at least one clause herein, wherein the deposited layer comprises at least one deposited layer transition region and a deposited layer non-transition part.


The device according to at least one clause herein, wherein the at least one deposited layer transition region transitions from a maximum thickness to a reduced thickness.


The device according to at least one clause herein, wherein the at least one deposited layer transition region extends between the deposited layer non-transition part and the deposited layer edge.


The device according to at least one clause herein, wherein the deposited layer has an average film thickness in the deposited layer non-transition part that is in a range of at least one of between about: 1-500 nm, 5-200 nm, 5-40 nm, 10-30 nm, and 10-100 nm.


The device according to at least one clause herein, wherein the average film thickness exceeds at least one of about: 10 nm, 50 nm, and 100 nm.


The device according to at least one clause herein, wherein the average film thickness of is substantially constant thereacross.


The device according to at least one clause herein, wherein the average film thickness exceeds an average film thickness of the underlying layer.


The device according to at least one clause herein, wherein a quotient of the average film thickness of the deposited layer by the average film thickness of the underlying layer is at least one of at least about: 1.5, 2, 5, 10, 20, 50, and 100.


The device according to at least one clause herein, wherein the quotient is in a range of at least one of between about: 0.1-10, and 0.2-40.


The device according to at least one clause herein, wherein the average film thickness of the deposited layer exceeds an average film thickness of the NIC.


The device according to at least one clause herein, wherein a quotient of the average film thickness of the deposited layer by the average film thickness of the NIC is at least one of at least about: 1.5, 2, 5, 10, 20, 50, and 100.


The device according to at least one clause herein, wherein the quotient is in a range of at least one of between about: 0.2-10, and 0.5-40.


The device according to at least one clause herein, wherein a deposited layer non-transition width along a lateral axis of the deposited layer non-transition region exceeds an NIC non-transition width along the axis of the NIC non-transition region.


The device according to at least one clause herein, wherein a quotient of the NIC non-transition width by the deposited layer non-transition width is at least one of between about: 0.1-10, 0.2-5, 0.3-3, and 0.4-2.


The device according to at least one clause herein, wherein a quotient of the deposited layer non-transition width by the NIC non-transition width is at least one of at least: 1, 2, 3, and 4.


The device according to at least one clause herein, wherein the deposited layer non-transition width exceeds the average film thickness of the deposited layer.


The device according to at least one clause herein, wherein a quotient of the deposited layer non-transition width by the average film thickness is at least one of at least about: 10, 50, 100, and 500.


The device according to at least one clause herein, wherein the quotient is less than about 100,000.


The device according to at least one clause herein, wherein the deposited layer has a deposited layer thickness that decreases from a maximum to a minimum within the deposited layer transition region.


The device according to at least one clause herein, wherein the maximum is proximate to a boundary between the deposited layer transition region and the deposited layer non-transition part.


The device according to at least one clause herein, wherein the maximum is the average film thickness.


The device according to at least one clause herein, wherein the minimum is proximate to the deposited layer edge.


The device according to at least one clause herein, wherein the minimum is in a range of between about: 0-0.1 nm.


The device according to at least one clause herein, wherein the minimum is the average film thickness.


The device according to at least one clause herein, wherein a profile of the deposited layer thickness is at least one of sloped, tapered, and defined by a gradient.


The device according to at least one clause herein, wherein the tapered profile follows at least one of a linear, non-linear, parabolic, and exponential decaying profile.


The device according to at least one clause herein, wherein the deposited layer comprises a discontinuous layer in at least a part of the deposited layer transition region.


The device according to at least one clause herein, wherein the deposited layer overlaps the NIC in an overlap portion.


The device according to at least one clause herein, wherein the NIC overlaps the deposited layer in an overlap portion.


The device according to at least one clause herein, further comprising at least one particle structure disposed on an exposed layer surface of an underlying layer.


The device according to at least one clause herein, wherein the underlying layer is the NIC.


The device according to at least one clause herein, wherein the at least one particle structure comprises a particle structure material.


The device according to at least one clause herein, wherein the particle structure material is the same as the deposited material.


The device according to at least one clause herein, wherein at least two of the particle structure material, the deposited material, and a material of which the underlying layer is comprised, comprises a common metal.


The device according to at least one clause herein, wherein the particle structure material comprises an element selected from at least one of: potassium (K), sodium (Na), lithium (Li), barium (Ba), cesium (Cs), ytterbium (Yb), silver (Ag), gold (Au), copper (Cu), aluminum (Al), magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), and yttrium (Y).


The device according to at least one clause herein, wherein the particle structure material comprises a pure metal.


The device according to at least one clause herein, wherein the particle structure material is selected from at least one of pure Ag and substantially pure Ag.


The device according to at least one clause herein, wherein the substantially pure Ag has a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, and 99.9995%.


The device according to at least one clause herein, wherein the particle structure material is selected from at least one of pure Mg and substantially pure Mg.


The device according to at least one clause herein, wherein the substantially pure Mg has a purity of at least about: 95%, 99%, 99.9%, 99.99%, 99.999%, or 99.9995%.


The device according to at least one clause herein, wherein the particle structure material comprises an alloy.


The device according to at least one clause herein, wherein the particle structure material comprises at least one of: an Ag-containing alloy, an Mg-containing alloy, and an AgMg-containing alloy.


The device according to at least one clause herein, wherein the AgMg-containing alloy has an alloy composition that ranges from 1:10 (Ag:Mg) to about 10:1 by volume.


The device according to at least one clause herein, wherein the particle structure material comprises at least one metal other than Ag.


The device according to at least one clause herein, wherein the particle structure material comprises an alloy of Ag with at least one metal.


The device according to at least one clause herein, wherein the at least one metal is selected from at least one of Mg and Yb.


The device according to at least one clause herein, wherein the alloy is a binary alloy having a composition between about 5-95 vol. % Ag.


The device according to at least one clause herein, wherein the alloy comprises a Yb:Ag alloy having a composition between about 1:20-10:1 by volume.


The device according to at least one clause herein, wherein the particle structure material comprises an Mg:Yb alloy.


The device according to at least one clause herein, wherein the particle structure material comprises an Ag:Mg:Yb alloy.


The device according to at least one clause herein, wherein the at least one particle structure comprises at least one additional element.


The device according to at least one clause herein, wherein the at least one additional element is a non-metallic element.


The device according to at least one clause herein, wherein the non-metallic element is selected from at least one of O, S, N, and C.


The device according to at least one clause herein, wherein a concentration of the non-metallic element is less than about: 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, and 0.0000001%.


The device according to at least one clause herein, wherein the at least one particle structure has a composition in which a combined amount of O and C is less than about: 10%, 5%, 1%, 0.1%, 0.01%, 0.001%, 0.0001%, 0.00001%, 0.000001%, and 0.0000001%.


The device according to at least one clause herein, wherein the at least one particle is disposed at an interface between the NIC and at least one covering layer in the device.


The device according to at least one clause herein, wherein the at least one particle is in physical contact with an exposed layer surface of the NIC.


The device according to at least one clause herein, wherein the at least one particle structure affects at least one optical property of the device.


The device according to at least one clause herein, wherein the at least one optical property is controlled by selection of at least one property of the at least one particle structure selected from at least one of: a characteristic size, a size distribution, a shape, a surface coverage, a configuration, a deposited density, and a dispersity.


The device according to at least one clause herein, wherein the at least one property of the at least one particle structure is controlled by selection of at least one of: at least one characteristic of the NIC material, an average film thickness of the NIC, at least one heterogeneity in the NIC, and a deposition environment for the NIC, selected from at least one of a temperature, pressure, duration, deposition rate, and deposition process.


The device according to at least one clause herein, wherein the at least one property of the at least one particle structure is controlled by selection of at least one of: at least one characteristic of the particle structure material, an extent to which the NIC is exposed to deposition of the particle structure material, a thickness of the discontinuous layer, and a deposition environment for the particle structure material, selected from at least one of a temperature, pressure, duration, deposition rate, and deposition process.


The device according to at least one clause herein, wherein the at least one particle structures are disconnected from one another.


The device according to at least one clause herein, wherein the at least one particle structure forms a discontinuous layer.


The device according to at least one clause herein, wherein the discontinuous layer is disposed in a pattern defined by at least one region therein that is substantially devoid of the at least one particle structure.


The device according to at least one clause herein, wherein a characteristic of the discontinuous layer is determined by an assessment according to at least one criterion selected from at least one of: a characteristic size, size distribution, shape, configuration, surface coverage, deposited distribution, dispersity, presence of aggregation instances, and extent of such aggregation instances.


The device according to at least one clause herein, wherein the assessment is performed by determining at least one attribute of the discontinuous layer by an applied imaging technique selected from at least one of: electron microscopy, atomic force microscopy, and scanning electron microscopy.


The device according to at least one clause herein, wherein the assessment is performed across an extent defined by at least one observation window.


The device according to at least one clause herein, wherein the at least one observation window is located at at least one of: a perimeter, interior location, and grid coordinate of the lateral aspect.


The device according to at least one clause herein, wherein the observation window corresponds to a field of view of the applied imaging technique.


The device according to at least one clause herein, wherein the observation window corresponds to a magnification level selected from at least one of: 2.00 μm, 1.00 μm, 500 nm, and 200 nm.


The device according to at least one clause herein, wherein the assessment incorporates at least one of: manual counting, curve fitting, polygon fitting, shape fitting, and an estimation technique.


The device according to at least one clause herein, wherein the assessment incorporates a manipulation selected from at least one of: an average, median, mode, maximum, minimum, probabilistic, statistical, and data calculation.


The device according to at least one clause herein, wherein the characteristic size is determined from at least one of: a mass, volume, diameter, perimeter, major axis, and minor axis of the at least one particle structure.


The device according to at least one clause herein, wherein the dispersity is determined from:







D
=



S
s

_



S
n

_






where
:







S
s

_

=








i
=
1

n



S
i
2









i
=
1

n



S
i




,



S
n

_

=








i
=
1

n



S
i


n


,





n is the number of particles 60 in a sample area,


Si is the (area) size of the ith particle 60,



S
n is the number average of the particle (area) sizes; and



S
s is the (area) size average of the particle (area) sizes.


Accordingly, the specification and the examples disclosed therein are to be considered illustrative only, with a true scope of the disclosure being disclosed by the following numbered claims:

Claims
  • 1. An opto-electronic device comprising a compound that is a fluorine-containing phosphazene compound, wherein the fluorine-containing phosphazene compound is an oligomeric phosphazene compound containing less than about 20 phosphazene units.
  • 2. The device according to claim 1, wherein the compound comprises a chain moiety, the chain moiety comprising a backbone and a fluorine (F) atom attached thereto.
  • 3. The device according to claim 2, wherein the backbone is a carbon-containing backbone.
  • 4. The device according to claim 2, wherein the chain moiety comprises an intermediate moiety.
  • 5. The device according to claim 4, wherein the intermediate moiety comprises at least one of: oxygen (O), an ether, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubsituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted heteroarylene, and an unsubstituted heteroarylene.
  • 6. The device according to claim 4, wherein the intermediate moiety comprises a fluorine (F) atom.
  • 7. The device according to claim 4, wherein the intermediate moiety comprises a fluoroalkylene unit.
  • 8. The device according to claim 4, wherein the intermediate moiety comprises a CF2 unit.
  • 9. The device according to claim 4, wherein the intermediate moiety comprises a CHF unit.
  • 10. The device according to claim 4, wherein the intermediate moiety comprises a CH2 unit.
  • 11. The device according to claim 4, wherein the intermediate moiety comprises saturated bonds.
  • 12. The device according to claim 4, wherein the intermediate moiety comprises at least one of: oxygen (O), an ether, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, and an unsubstituted fluoroalkylene.
  • 13. The device according to claim 4, wherein the intermediate moiety is a saturated moiety.
  • 14. The device according to claim 4, wherein the intermediate moiety contains up to 15 carbon atoms.
  • 15. The device according to claim 4, wherein the intermediate moiety is represented by the formula:
  • 16. The device according to claim 2, wherein the chain moiety comprises a terminal moiety bonded to the intermediate moiety, the terminal moiety being arranged at a terminal portion of the chain moiety.
  • 17. The device according to claim 16, wherein the terminal moiety comprises a fluorine (F) atom.
  • 18. The device according to claim 16, wherein the terminal moiety comprises at least one of: a branched alkyl, an unbranched alkyl, a branched fluoroalkyl, an unbranched fluoroalkyl, a fluorine-substituted cycloheteroalkyl, a branched fluoroalkoxy; an unbranched fluoroalkoxy, a fluoroaryl, a polyfluorosulfanyl, and a fluorocycloalkyl.
  • 19. The device according to claim 16, wherein the terminal moiety comprises fluorine (F) and hydrogen (H).
  • 20. The device according to claim 16, wherein the terminal moiety comprises a CF2H unit.
  • 21. The device according to claim 16, wherein the terminal moiety is represented by at least one of Formula: (EC-1), (EC-2), (EC-3), (EC-4), (EC-5), (EC-6), and (EC-7):
  • 22. The device according to claim 2, wherein the compound comprises a core moiety attached to the chain moiety.
  • 23. The device according to claim 22, wherein the chain moiety comprises a linker moiety adapted to attach the chain moiety to the core moiety.
  • 24. The device according to claim 23, wherein the linker moiety comprises at least one of: oxygen (O), nitrogen (N), sulfur (S), a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubsituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted arylene, an unsubstituted arylene, a substituted heteroarylene, and an unsubstituted heteroarylene.
  • 25. The device according to claim 23, wherein the linker moiety comprises at least one of: oxygen (O), nitrogen (N), sulfur (S), a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, and an unsubsituted fluoroalkylene.
  • 26. The device according to claim 23, wherein the linker moiety is represented by at least one of Formula: (EA-1), (EA-2), (EA-3), (EA-4), (EA-5), and (EA-6):
  • 27. The device according to claim 22, wherein the core moiety comprises a phosphazene unit.
  • 28. The device according to claim 27, wherein the chain moiety is attached to the phosphorus (P) atom of the phosphazene unit.
  • 29. The device according to claim 22, wherein the core moiety comprises a cyclophosphazene.
  • 30. The device according to claim 29, wherein the cyclophosphazene is provided by a plurality of phosphazene units.
  • 31. The device according to claim 29, wherein the cyclophosphazene is provided by a number of phosphazene units selected from 3 to 7.
  • 32. The device according to claim 2, wherein the chain moiety comprises a branching moiety attached to at least three moieties selected from: an intermediate moiety, a terminal moiety, and a linker moiety.
  • 33. The device according to claim 32, wherein the branching moiety comprises at least one of: nitrogen (N), an amine, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, an unsubstituted fluoroalkylene, a substituted cycloalkylene, an unsubstituted cycloalkylene, a substituted cycloheteroalkylene, an unsubstituted cycloheteroalkylene, a substituted arylene, an unsubstituted arylene, a substituted heteroarylene, and an unsubstituted heteroarylene.
  • 34. The device according to claim 32, wherein the branching moiety comprises at least one of: nitrogen (N), an amine, a substituted alkylene, an unsubstituted alkylene, a substituted fluoroalkylene, and an unsubstituted fluoroalkylene.
  • 35. The device according to claim 1, wherein the compound does not substantially absorb light at a wavelength in a visible portion of an electromagnetic spectrum.
  • 36. The device according to claim 1, wherein the compound does not substantially exhibit photoluminescence at a wavelength in a visible portion of an electromagnetic spectrum.
  • 37. The device according to claim 1, wherein the compound has an optical gap that exceeds at least one of about: 3.4 eV, 3.5 eV, 4.1 eV, 5 eV, and 6.2 eV.
  • 38. The device according to claim 1, wherein the compound has a melting temperature that exceeds about 100° C.
  • 39. The device according to claim 1, wherein the compound has a sublimation temperature that exceeds about 100° C.
  • 40. The device according to claim 1, wherein the compound has a characteristic surface energy that is less than at least one of about: 25 dynes/cm, 21 dynes/cm, 20 dynes/cm, 19 dynes/cm, 18 dynes/cm, 17 dynes/cm, 16 dynes/cm, 15 dynes/cm, 14 dynes/cm, 13 dynes/cm, 12 dynes/cm, 11 dynes/cm, and 10 dynes/cm.
  • 41. The device according to claim 1, wherein the compound has a refractive index of no more than at least one of about: 1.5, 1.45, 1.4, 1.35, 1.3, and 1.25.
  • 42. The device according to claim 1, further comprising first and second electrodes, and an active region comprising at least one semiconducting layer and bounded, in a transverse aspect, by the electrodes and confined, in a lateral aspect, to an emissive region defined by the electrodes, wherein the active region is substantially devoid of the compound.
  • 43. The device according to claim 42, further comprising: a patterning coating comprising the compound, the patterning coating being disposed on a first layer surface of an underlying layer in a first portion of a lateral aspect thereof; anda deposited layer comprised of a deposited material, disposed on a second layer surface;wherein the first portion is substantially devoid of a closed coating of the deposited material.
  • 44. The device according to claim 43, wherein the first portion excludes a lateral aspect of the emissive region.
  • 45. The device according to claim 43, wherein the second electrode comprises at least a part of the deposited layer as a layer thereof.
  • 46. The device according to claim 43, wherein the first portion includes a lateral aspect of the emissive region.
  • 47. The device according to claim 46, further comprising an auxiliary electrode comprising the deposited layer as a layer thereof.
  • 48. The device according to claim 43, further comprising a conductor electrically coupled with the second electrode.
  • 49. An opto-electronic device comprising a compound, the compound comprising a terminal moiety comprising a CF2H unit.
  • 50. A phosphazene derivative compound comprising first and second chain moieties, each comprising a backbone and a fluorine (F) atom attached thereto, wherein the first chain moiety is different from the second chain moiety, and wherein the phosphazene derivative compound is an oligomeric phosphazene compound containing less than about 20 phosphazene units.
  • 51. A compound comprising a moiety according to Formula (PX-1):
RELATED APPLICATIONS

The present application claims the benefit of priority to: U.S. Provisional Patent Application No. 63/038,632 filed 12 Jun. 2020, U.S. Provisional Patent Application No. 63/047,778 filed 2 Jul. 2020, U.S. Provisional Patent Application No. 63/066,667 filed 17 Aug. 2020, U.S. Provisional Patent Application No. 63/067,789 filed 19 Aug. 2020, U.S. Provisional Patent Application No. 63/106,243 filed 27 Oct. 2020, U.S. Provisional Patent Application No. 63/107,393 filed 29 Oct. 2020, U.S. Provisional Patent Application No. 63/153,834 filed 25 Feb. 2021, U.S. Provisional Patent Application No. 63/163,453 filed 19 Mar. 2021, U.S. Provisional Patent Application No. 63/181,100 filed 28 Apr. 2021, U.S. Provisional Patent Application No. 63/122,421 filed 7 Dec. 2020, and U.S. Provisional Patent Application No. 63/141,857 filed 26 Jan. 2021, the contents of each of which are incorporated herein by reference in their entirety.

PCT Information
Filing Document Filing Date Country Kind
PCT/IB2021/055232 6/14/2021 WO
Provisional Applications (11)
Number Date Country
63038632 Jun 2020 US
63047778 Jul 2020 US
63066667 Aug 2020 US
63067789 Aug 2020 US
63106243 Oct 2020 US
63107393 Oct 2020 US
63122421 Dec 2020 US
63141857 Jan 2021 US
63153834 Feb 2021 US
63163453 Mar 2021 US
63181100 Apr 2021 US