Organic light-emitting diodes with fluorescent and phosphorescent emitters

Abstract

A light emitting device includes a first electrode, a hole transporting layer in contact with the first electrode, a second electrode, an electron transporting layer in contact with the second electrode; and an emissive layer between the hole transporting layer and the electron transporting layer. The emissive layer includes a phosphorescent emitter, a fluorescent emitter, and a host, and the phosphorescent emitter harvests electrogenerated excitons and transfers energy to the fluorescent emitter.

Description

TECHNICAL FIELD

This disclosure relates to organic light emitting diodes (OLEDs), and more particularly to OLEDs with emissive layers including phosphorescent and fluorescent emitters.

BACKGROUND

Organic light emitting devices (OLEDs) are typically multilayer devices which upon an applied voltage are capable emitting light from the radiative relaxation of an excited state located on an organic material. OLEDs have found widespread application as an alternative to liquid crystal displays (LCDs) for handheld devices or flat panel displays. Furthermore, OLEDs have shown promise as next generation solid state white lighting, use in medical devices, and as infrared emitters for communication applications. The use of organic materials presents a number of unique benefits including: compatibility with flexible substrates, capabilities for large scale production, and simplified tuning of the emission properties through molecular modification.

FIG. 1 depicts a cross-sectional view of an OLED 100. OLED 100 includes substrate 102, anode 104, hole-transporting material(s) (HTL) 106, light processing material (EML) 108, electron-transporting material(s) (ETL) 110, and a metal cathode layer 112. Anode 104 may be indium tin oxide (ITO). Light processing material 108 may be an emissive material (EML) including an emitter and a host. A typical OLED device includes at least one transparent electrode through which light is emitted. For example, OLEDs that emit through the bottom substrate typically contain a transparent conductive oxide material, such as indium tin oxide, as an anode, while at the cathode a reflective metal is typically used. Alternatively, devices may emit from the top through a thin metal layer as the cathode while having an either opaque or transparent anode layer. In this way it is possible to have dual emission from both top and bottom if such a device is so desired and furthermore it is possible for these OLEDs to be transparent. Sandwiched between the electrodes is typically a multilayer organic stack. A multilayer organic stack typically includes a single layer of hole-transporting materials (HTL), a single layer of emissive materials (EML) including emitters and hosts, a single layer of electron-transporting materials (ETL) and a layer of metal cathode, as depicted in FIG. 1.

For each of the transport layers, care must be taken to optimize the separate process of facilitating charge injection, having efficient charge transport, and confining the charges and excitons in a specified emissive region (typically the emissive layer). Such a process can be achieved through either a single material or through a multilayer stack which may separate the injection, transport, charge confining, and exciton confining tasks. The emissive layer may be composed of a single emissive material, a single emissive material dispersed in a host matrix material, multiple emissive materials dispersed in a host matrix, or any number of emissive materials dispersed in multiple host materials. The host materials are typically chosen carefully to not quench the excited state of the emitter as well as to provide appropriate distribution of charges and excitons within the emissive layer. The emission color of the OLED is determined by the emission energy (optical energy gap) of emitters.

Light is generated in OLEDs through the formation of excited states from separately injected electrons and holes to form an exciton, located on the organic material. Due to the uncorrelated nature of the injected charges, excitons with total spin of 0 and 1 are possible. Spin 0 excitons are denoted singlets, while spin 1 excitons are denoted triplets, reflecting their respective degeneracies. Due to the selection rules for radiative transitions, the symmetry of the excited state and the ground state must be the same. Since the ground state of most molecules are antisymmetric, radiative relaxation of the symmetric triplet excited state is typically disallowed. As such, emission from the triplet state, called phosphorescence, is very slow and the transition probability is very low. However emission from the singlet state, called fluorescence, can be very rapid and consequently very efficient. Nevertheless, statistically there is only 1 singlet exciton for every 3 triplet excitons formed. There are very few fluorescent emitters which exhibit emission from the triplet state at room temperature, so 75% of the generated excitons are wasted in most fluorescent emitters. However, emission from the triplet state can be facilitated through spin orbit coupling which incorporates a heavy metal atom in order to perturb the triplet state and add in some singlet character to and achieve a higher probability of radiative relaxation.

Some efficient emitters include heavy metals such as Ir, Pt, Pd, Au, Os, Rh, and Ru, which can emit efficiently across the visible spectrum. Thus, due to their typically high efficiencies, phosphorescent OLEDs (i.e. OLEDs with phosphorescent materials as emitters) have been a mainstay in OLED development. Recently, reports of OLEDs with electron to photon conversion efficiencies near 100% across the visible spectrum have been demonstrated. However, there remains a deficit of efficient phosphorescent emissive materials that also demonstrate long operational stability in a device setting, particularly in the blue region. Fluorescent OLEDs (i.e., OLEDs with fluorescent materials as emitters), on the other hand, have found widespread use in devices with long operational lifetime. Furthermore, fluorescent emitters typically do not contain precious metals and are not affected by triplet-triplet annihilation which degrades device performance at high current densities.

SUMMARY

In a general aspect, a light emitting device includes a first electrode, a hole transporting layer in contact with the first electrode, a second electrode, an electron transporting layer in contact with the second electrode; and an emissive layer between the hole transporting layer and the electron transporting layer. The emissive layer includes a phosphorescent emitter, a fluorescent emitter, and a host, and the phosphorescent emitter harvests electrogenerated excitons and transfers energy to the fluorescent emitter.

Certain implementations may include one or more of the following features. In some cases, the emissive layer is a single layer including the host, the phosphorescent emitter, and the fluorescent emitter. The phosphorescent emitter may include a luminophore with a six-membered chelation ring. In certain cases, the emissive layer includes n emitter layers including the host and the fluorescent emitter, and m donor layers including the host and the phosphorescent emitter, where n and m are integers≥1. n and m may be equal. In some cases, n=m+1 or m=n+1. Each emitter layer may be adjacent to at least one donor layer.

Light emitting devices described herein may be fluorescent organic light emitting devices. The disclosed light emitting devices generally redistribute the excited states to primarily reside on known stable fluorescent emitters to achieve high device operational stability but maintain the high efficiency characteristic of phosphorescent OLEDs.

Thus, particular embodiments have been described. Variations, modifications, and enhancements of the described embodiments and other embodiments can be made based on what is described and illustrated. In addition, one or more features of one or more embodiments may be combined. The details of one or more implementations and various features and aspects are set forth in the accompanying drawings, the description, and the claims below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a cross-sectional view of an exemplary organic light emitting device (OLED).

FIG. 2 depicts an energy transfer process inside an emissive layer of the phosphorescent OLEDs described herein.

FIG. 3 depicts a cross-sectional view of an OLED that includes a phosphorescent emitter and a fluorescent emitter.

FIG. 4 depicts a cross-sectional view of an OLED that includes alternating fluorescent and phosphorescent doped layers.

FIGS. 5A-5C show external quantum efficiency versus luminance, current-voltage characteristics, and electroluminescent spectra, respectively, of three devices doped with PtNON and TBPe. FIG. 5D depicts a cross-sectional view of the structure of the devices corresponding to the data in FIGS. 5A-5C.

FIGS. 6A-6C show external quantum efficiency versus luminance, current-voltage characteristics, and electroluminescent spectra, respectively, of a device that includes alternating doped layers including PtNON or TBPe. FIG. 6D depicts a cross-sectional view of the device corresponding to the data in FIGS. 6A-6C.

FIG. 7 shows electroluminescent spectra of devices doped with PtNON and with PtNON and TBPe.

FIG. 8 shows operational lifetimes of devices doped with PtNON and with PtNON and TBPe.

FIGS. 9A and 9B show current-voltage characteristics and external quantum efficiency versus luminance, respectively, of a device doped with PtNON and TBPe.

FIGS. 10A-10D show electroluminescent spectra, current-density voltage characteristics, external quantum efficiency versus luminance, and operational lifetimes, respectively, of four devices doped with PtNON and TBPe.

FIGS. 11A-11D show electroluminescent spectra, current-density voltage characteristics, external quantum efficiency versus luminance, and operational lifetimes, respectively, of four devices doped with PtNON and TBPe.

DETAILED DESCRIPTION

The present disclosure can be understood more readily by reference to the following detailed description and the Examples included therein.

Before the present compounds, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of compounds of the present disclosure, example methods and materials are now described.

As used in the specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a component” includes mixtures of two or more components.

As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

Disclosed are the components to be used to prepare the compositions of this disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions disclosed herein. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods described herein.

As referred to herein, a linking atom or group connects two atoms such as, for example, an N atom and a C atom. A linking atom or group is in one aspect disclosed as L¹, L², L³, etc. herein. The linking atom can optionally, if valency permits, have other chemical moieties attached. For example, in one aspect, an oxygen would not have any other chemical groups attached as the valency is satisfied once it is bonded to two groups (e.g., N and/or C groups). In another aspect, when carbon is the linking atom, two additional chemical moieties can be attached to the carbon. Suitable chemical moieties include amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl moieties. The term “cyclic structure” or the like terms used herein refer to any cyclic chemical structure which includes, but is not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, the heteroatoms, such as nitrogen, can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the terms “substitution” or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. It is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

In defining various terms, “A¹”, “A²”, “A³”, “A⁴” and “A⁵” are used herein as generic symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents.

The term “alkyl” as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dode cyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol, as described herein. A “lower alkyl” group is an alkyl group containing from one to six (e.g., from one to four) carbon atoms.

Throughout the specification “alkyl” is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group. For example, the term “halogenated alkyl” or “haloalkyl” specifically refers to an alkyl group that is substituted with one or more halide, e.g., fluorine, chlorine, bromine, or iodine. The term “alkoxyalkyl” specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below. The term “alkylamino” specifically refers to an alkyl group that is substituted with one or more amino groups, as described below, and the like. When “alkyl” is used in one instance and a specific term such as “alkylalcohol” is used in another, it is not meant to imply that the term “alkyl” does not also refer to specific terms such as “alkylalcohol” and the like.

This practice is also used for other groups described herein. That is, while a term such as “cycloalkyl” refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moieties can, in addition, be specifically identified herein; for example, a particular substituted cycloalkyl can be referred to as, e.g., an “alkylcycloalkyl.” Similarly, a substituted alkoxy can be specifically referred to as, e.g., a “halogenated alkoxy,” a particular substituted alkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, the practice of using a general term, such as “cycloalkyl,” and a specific term, such as “alkylcycloalkyl,” is not meant to imply that the general term does not also include the specific term.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbomyl, and the like. The term “heterocycloalkyl” is a type of cycloalkyl group as defined above, and is included within the meaning of the term “cycloalkyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl group and heterocycloalkyl group can be substituted or unsubstituted. The cycloalkyl group and heterocycloalkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “polyalkylene group” as used herein is a group having two or more CH₂ groups linked to one another. The polyalkylene group can be represented by the formula —(CH₂)_a—, where “a” is an integer of from 2 to 500.

The terms “alkoxy” and “alkoxyl” as used herein to refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, an “alkoxy” group can be defined as —OA¹ where A¹ is alkyl or cycloalkyl as defined above. “Alkoxy” also includes polymers of alkoxy groups as just described; that is, an alkoxy can be a polyether such as —OA¹-OA² or -OA¹-(OA²)_a-OA³, where “a” is an integer of from 1 to 200 and A¹, A², and A³ are alkyl and/or cycloalkyl groups.

The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (A¹A²)C═C(A³A⁴) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C═C. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms and containing at least one carbon-carbon double bound, i.e., C═C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbomenyl, and the like. The term “heterocycloalkenyl” is a type of cycloalkenyl group as defined above, and is included within the meaning of the term “cycloalkenyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group and heterocycloalkenyl group can be substituted or unsubstituted. The cycloalkenyl group and heterocycloalkenyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24 carbon atoms with a structural formula containing at least one carbon-carbon triple bond. The alkynyl group can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol, as described herein.

The term “cycloalkynyl” as used herein is a non-aromatic carbon-based ring composed of at least seven carbon atoms and containing at least one carbon-carbon triple bound. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term “heterocycloalkynyl” is a type of cycloalkenyl group as defined above, and is included within the meaning of the term “cycloalkynyl,” where at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkynyl group and heterocycloalkynyl group can be substituted or unsubstituted. The cycloalkynyl group and heterocycloalkynyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein.

The term “aryl” as used herein is a group that contains any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term “aryl” also includes “heteroaryl,” which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term “non-heteroaryl,” which is also included in the term “aryl,” defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described herein. The term “biaryl” is a specific type of aryl group and is included in the definition of “aryl.” Biaryl refers to two aryl groups that are bound together via a fused ring structure, as in naphthalene, or are attached via one or more carbon-carbon bonds, as in biphenyl.

The term “aldehyde” as used herein is represented by the formula —C(O)H. Throughout this specification “C(O)” is a short hand notation for a carbonyl group, i.e., C═O.

The terms “amine” or “amino” as used herein are represented by the formula —NA¹A², where A¹ and A² can be, independently, hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “alkylamino” as used herein is represented by the formula —NH(-alkyl) where alkyl is a described herein. Representative examples include, but are not limited to, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, (sec-butyl)amino group, (tert-butyl)amino group, pentylamino group, isopentylamino group, (tert-pentyl)amino group, hexylamino group, and the like.

The term “dialkylamino” as used herein is represented by the formula —N(-alkyl)₂ where alkyl is a described herein. Representative examples include, but are not limited to, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, di(sec-butyl)amino group, di(tert-butyl)amino group, dipentylamino group, diisopentylamino group, di(tert-pentyl)amino group, dihexylamino group, N-ethyl-N-methylamino group, N-methyl-N-propylamino group, N-ethyl-N-propylamino group and the like.

The term “carboxylic acid” as used herein is represented by the formula —C(O)OH.

The term “ester” as used herein is represented by the formula —OC(O)A¹ or —C(O)OA¹, where A¹ can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term “polyester” as used herein is represented by the formula -(A¹O(O)C-A²-C(O)O)_a— or -(A¹O(O)C-A²-OC(O))_a, where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and “a” is an integer from 1 to 500. “Polyester” is as the term used to describe a group that is produced by the reaction between a compound having at least two carboxylic acid groups with a compound having at least two hydroxyl groups.

The term “ether” as used herein is represented by the formula A¹OA², where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein. The term “polyether” as used herein is represented by the formula -(A¹O-A²O)_a—, where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and “a” is an integer of from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

The term “polymeric” includes polyalkylene, polyether, polyester, and other groups with repeating units, such as, but not limited to —(CH₂O)_n—CH₃, —(CH₂CH₂O)_n—CH₃, —[CH₂CH(CH₃)]_n—CH₃, —[CH₂CH(COOCH₃)]_n—CH₃, —[CH₂CH(COO CH₂CH₃)]_n—CH₃, and —[CH₂CH(COO^tBu)]_n—CH₃, where n is an integer (e.g., n>1 or n>2).

The term “halide” as used herein refers to the halogens fluorine, chlorine, bromine, and iodine.

The term “heterocyclyl,” as used herein refers to single and multi-cyclic non-aromatic ring systems and “heteroaryl as used herein refers to single and multi-cyclic aromatic ring systems: in which at least one of the ring members is other than carbon. The terms includes azetidine, dioxane, furan, imidazole, isothiazole, isoxazole, morpholine, oxazole, oxazole, including, 1,2,3-oxadiazole, 1,2,5-oxadiazole and 1,3,4-oxadiazole, piperazine, piperidine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrazine, including 1,2,4,5-tetrazine, tetrazole, including 1,2,3,4-tetrazole and 1,2,4,5-tetrazole, thiadiazole, including, 1,2,3-thiadiazole, 1,2,5-thiadiazole, and 1,3,4-thiadiazole, thiazole, thiophene, triazine, including 1,3,5-triazine and 1,2,4-triazine, triazole, including, 1,2,3-triazole, 1,3,4-triazole, and the like.

The term “hydroxyl” as used herein is represented by the formula —OH.

The term “ketone” as used herein is represented by the formula A¹C(O)A², where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “azide” as used herein is represented by the formula —N₃.

The term “nitro” as used herein is represented by the formula —NO₂.

The term “nitrile” as used herein is represented by the formula —CN.

The term “silyl” as used herein is represented by the formula —SiA¹A²A³, where A¹, A², and A³ can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “sulfo-oxo” as used herein is represented by the formulas —S(O)A¹, —S(O)₂A¹, —OS(O)₂A¹, or —OS(O)₂OA¹, where A¹ can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout this specification “S(O)” is a short hand notation for S═O. The term “sulfonyl” is used herein to refer to the sulfo-oxo group represented by the formula —S(O)₂A¹, where A¹ can be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term “sulfone” as used herein is represented by the formula A¹S(O)₂A², where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term “sulfoxide” as used herein is represented by the formula A¹S(O)A², where A¹ and A² can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term “thiol” as used herein is represented by the formula —SH.

“R,” “R¹,” “R²,” “R³,” “Rⁿ,” where n is an integer, as used herein can, independently, possess one or more of the groups listed above. For example, if R¹ is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halide, and the like. Depending upon the groups that are selected, a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase “an alkyl group comprising an amino group,” the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.

Compounds described herein may contain “optionally substituted” moieties. In general, the term “substituted,” whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this disclosure are preferably those that result in the formation of stable or chemically feasible compounds. In is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

In some aspects, a structure of a compound can be represented by a formula:

which is understood to be equivalent to a formula:

wherein n is typically an integer. That is, Rⁿ is understood to represent up to five independent non-hydrogen substituents, R^n(a), R^n(b), R^n(c), R^n(d), R^n(e). By “independent substituents,” it is meant that each R substituent can be independently defined. For example, if in one instance Rⁿ(a) is halogen, then Rⁿ(b) is not necessarily halogen in that instance.

Several references to R, R¹, R², R³, R⁴, R⁵, R⁶, etc. are made in chemical structures and moieties disclosed and described herein. Any description of R, R¹, R², R³, R⁴, R⁵, R⁶, etc. in the specification is applicable to any structure or moiety reciting R, R¹, R², R³, R⁴, R⁵, R⁶, etc. respectively.

OLEDs described herein use phosphorescent platinum complexes as efficient exciton harvesters while emitting primarily from stable fluorescent emitters in order to enhance the device operational lifetime. To achieve this, both phosphorescent platinum complexes and fluorescent emitters must be present in the EML, and energy transfer between the phosphorescent and fluorescent materials is necessary. Two major mechanisms to exciton transport exist, namely the Dexter energy transfer and Forster resonant energy transfer (FRET) mechanisms. Dexter energy transfer is a short range transport which consists of consecutive hopping of excitons between neighboring molecules and depends on the orbital overlap between the molecules. FRET is a long range transport process in which dipole coupling between an excited donor molecule (D) and a ground state acceptor molecule (A) leads to a long range non-radiative transfer. This process depends on the overlap between the emission profile of D and the absorption of A. This transfer mechanism requires an allowed relaxation transition of the donor molecule and an allowed excitation mechanism of the acceptor molecules. As such, FRET typically occurs between singlet excitons. However, if the phosphorescent emission process of the donor molecule is efficient, transfer between the triplet of the donor molecule and the singlet of the acceptor molecule is also possible.

The stability of blue phosphorescent OLEDs has remained as a great technical challenge for OLED displays and lighting applications. If triplet emitters are less stable than singlet emitters with the same emission energy, the relocation of exciton from triplet emitters to known stable blue singlet emitters may improve the device operational stability. Thus, a process may occur, such as that depicted in FIG. 2, in which excitons are formed on a phosphorescent emitter, which can then transfer via FRET to a fluorescent donor material and emit with high efficiency. Such a process may maintain the efficient (e.g., 100% utilization) of electrogenerated excitons while emitting primarily from the fluorescent emitter to achieve high stability and avoid triplet-triplet annihilation. As an added benefit, the color quality of EL spectra of devices may also improve if the emission originates solely from the narrow band fluorescent emitters.

If triplet emitters are less stable than singlet emitters with the same emission energy, the relocation of exciton from triplet emitters to known stable blue singlet emitters may improve the device operational stability. This may be achieved by harvesting the electrogenerated excitons with a phosphorescent material, then transferring the energy to a fluorescent emitter through a FRET mechanism. This process may be achieved by OLEDs with different designs, including: 1) a single emissive layer containing both the phosphorescent emitter and the fluorescent emitter doped into a host matrix, as depicted in FIG. 3; and 2) an emissive layer containing alternating fluorescent and phosphorescent doped layers, as depicted in FIG. 4. In both cases, there are constraints on the suitable materials. First, the emission spectrum of the phosphorescent emitter must have spectral overlap with the absorption spectrum of the fluorescent emitter in order for the FRET process to occur. Additionally, the photoluminescent quantum yield of the phosphorescent material must be high enough to ensure that the dipole relaxation in the FRET process can occur with high efficiency. Similarly, the photoluminescent quantum yield of the fluorescent emitter must be high enough to ensure efficient emission.

The first case, depicted in FIG. 3, includes OLED device 300. Device 300 includes substrate 302, anode 304, HTL 306, emissive layer 308, ETL 310, and metal cathode 312. The anode may be ITO. Emissive layer 308 typically includes a phosphorescent sensitizer (emitter) and a fluorescent emitter dispersed within a host matrix. When both the phosphorescent and fluorescent materials exist within the same layer, care must be taken to avoid direct formation of excitons on the fluorescent emitter (which can only harvest singlet excitons) to ensure that most or all (e.g., 100%) of the electrogenerated excitons are utilized. On the other hand, the concentration of the fluorescent emitter must be high enough for there to close proximity between the phosphorescent material and the fluorescent emitter so that rapid transfer from the phosphorescent emitter to the fluorescent emitter can be achieved and direct phosphorescent emission or triplet-triplet annihilation can be avoided.

The second case, depicted in FIG. 4, includes OLED device 400. Device 400 includes substrate 402, anode 404, HTL 406, phosphorescent sensitizer (emitter) layer 408, fluorescent emitter layer 410, phosphorescent sensitizer (emitter) layer 412, ETL 414, and metal cathode 416. Anode 404 may be ITO. Phosphorescent and fluorescent emitter layers 408, 410, and 412 form the emissive layer (EML). In FIG. 4, a space is depicted between layers 408 and 410 for clarity. Fluorescent emitter layer 410 and phosphorescent emitter layer 412 alternate and may be present in pairs (e.g., n pairs, where n is an integer such as 1, 2, 3, or the like).

In some implementations, the emissive layer includes n emitter layers including the host and the fluorescent emitter, and m donor layers including the host and the phosphorescent emitter, where n and m are integers ≥1. In certain implementations, n=m. In other implementations, n=m+1 or m=n+1. Each emitter layer may be adjacent to at least one donor layer.

In device 400, the thickness and location of the layers is typically tuned to ensure that exciton formation primarily occurs in the region that is doped with the phosphorescent material. Furthermore, the region that contains the fluorescent doped layer should be close enough to the exciton formation zone so that the fluorescent emitters are within the distance for FRET to occur.

Emitters described herein include six-membered emitters. As used herein, a “six-membered emitter” refers to an emitter with a luminophore (i.e., a portion of the emitter responsible for its luminescent properties) including a six-membered chelation ring. In one example, a six-membered phosphorescent emitter has a luminophore including a six-membered chelation ring.

Phosphorescent emitters for devices described herein include six-membered phosphorescent emitters of General Formula I:

wherein:

M is Pt, Pd, Ir, Rh, or Au;

each R¹ and R² is independently hydrogen, halogen, hydroxyl, thiol, nitro, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl;

each of Y¹, Y^1b, and Y^1c is independently O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to an adjacent ring structure, thereby forming a cyclic structure;

each of Y^2a, Y^2b, Y^2c, and Y^2d is independently N, NR⁵, or CR⁶, wherein each R⁵ and R⁶ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl;

each of Y^3a, Y^3b, Y^3c, Y^3d, Y^4a, Y^4b, Y^4c, and Y^4d is independently N, O, S, NR⁷, CR⁸, wherein each R⁷ and R⁸ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, aminoalkoxy, haloalkyl, arylalkyl, or arylalkenyl; or Z(R⁹)₂, wherein Z is C or Si, and wherein each R⁹ is independently hydrogen, halogen, hydroxyl, thiol, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl;

each of m and n is independently 1 or 2; and

each

independently represents partial or full unsaturation of the ring with which it is associated.

Other phosphorescent emitters include General Formula I, wherein:

M is Pt or Pd;

m is 2;

n is 2;

at least one of Y^1a and Y^1c is independently NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴;

Y^2b and Y^2c are C; and

Y^3b and Y^4b are N.

Other phosphorescent emitters include General Formula I, wherein:

M is Ir or Rh;

m is 2;

n is 2;

Y^1a is NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴;

Y^2b is C; and

Y^3b, Y^2c and Y^4b are N.

Other phosphorescent emitters include General Formula I, wherein:

M is Au;

m is 2;

n is 2;

Y^1b is NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴;

Y^2b, Y^2c and Y^4b are C; and

Y^3b is N.

Other phosphorescent emitters include General Formula I, wherein each of R³ and R⁴ is independently linked to an adjacent ring structure.

Other phosphorescent emitters include General Formula I, wherein:

M is Pt or Pd;

at least one of Y^1b and Y^1c is independently NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein R³ is covalently linked to at least one of Y^2a, Y^2d, Y^3d, and Y^4d, thereby forming a cyclic structure; and

at least of one of Y^2a, Y^2d, Y^3d and Y^4d is C.

Other phosphorescent emitters include General Formula I, wherein:

M is Ir or Rh;

• • Y^1b is NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein R³ is covalently linked to at least one of Y^2a and Y^3d, thereby forming a cyclic structure; and

at least of one of Y^2a and Y^3d is C.

Other phosphorescent emitters include General Formula I, wherein:

M is Au;

at least of one of Y^2a and Y^3d is C; and

Y^1b is NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein R³ is covalently linked to at least one of Y^2a and Y^3d, thereby forming a cyclic structure.

Other phosphorescent emitters include General Formula II,

wherein:

M is Ir, Rh, Pt, Os, or Ru;

each of R¹ and R² is independently hydrogen, halogen, hydroxyl, nitro, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl;

each of Y^1a, Y^1b, Y^1c, Y^1d, and Y^1e is independently O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to an adjacent ring structure, thereby forming a cyclic structure;

each of Y^2a, Y^2b, Y^2c, and Y^2d is independently N, NR⁵, or CR⁶, wherein each of R⁵ and R⁶ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl;

each of Y^3a, Y^3b, Y^3c, Y^3d, Y^4a, Y^4b, Y^4c, and Y^4d is independently N, O, S, NR⁷, CR⁸, wherein each of R⁷ and R⁸ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl; or Z(R⁹)₂, wherein Z is C or Si, and wherein each R⁹ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, or arylalkenyl;

in each of each of Y^5a, Y^5b, Y^5c, Y^5d, Y^6a, Y^6b, Y^6c, and Y^6d is independently N, O, S, NR⁷, or CR⁸;

each of m and n is independently 1 or 2; and

each

independently represents partial or full unsaturation of the ring with which it is associated.

Other phosphorescent emitters include General Formula II, wherein:

M is Ir or Rh;

m is 2;

Y^2b and Y^2c are C;

Y^3b and Y^4b are N; and

at least one of Y^1b and Y^1c is NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴.

Other phosphorescent emitters include General Formula II, wherein each of R² and R³ is independently linked to an adjacent ring structure.

Other phosphorescent emitters include General Formula II, wherein:

M is Ir or Rh;

• • at least of one of Y^2a, Y^2d, Y^3d and Y^4d is C; and

at least one of Y^1b and Y^1c is NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein R³ is covalently linked to at least one of Y^2a, Y^2d, Y^3d and Y^4d, thereby forming a cyclic structure.

Other phosphorescent emitters include compounds of General Formula III:

wherein:

M is a metal cation with two positive charges selected from Pt (II) and Pd (II);

each E¹, E², and E³ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group wherein a nitrogen atom coordinated to M.

Other phosphorescent emitters include compounds of General Formula IV:

wherein:

M is a metal cation with three positive charges selected from Au (III) and Ag (III);

each E¹, E², and E³ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

N represents a substituted or unsubstituted heterocyclic group wherein a nitrogen atom is coordinated to M.

Other phosphorescent emitters include compounds of General Formula V:

wherein:

M is a metal cation with one positive charge selected from Ir (I) and Rh (I);

each E¹, E², and E³ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

C represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group wherein a nitrogen atom is coordinated to M.

Other phosphorescent emitters include compounds of General Formula VI:

wherein:

M is a metal cation with three positive charges selected from Ir (III), Rh (III), Co (III), Al (III), and Ga (III);

each of E¹, E², E³, and E⁴ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to the metal.

Other phosphorescent emitters include compounds of General Formulas VII and VIII:

wherein:

M is a metal cation with three positive charges selected from Ir (III), Rh (III), Co (III), Al (III), or Ga (III);

each of E¹, E², E³, E⁴, and E⁵ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, hydroxyl, halogen, thiol, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R² and R³ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to M.

Other phosphorescent emitters include compounds of General Formula IX:

wherein:

M is a metal cation with four positive charges selected from Pd (IV) and Pt (IV);

each of E¹, E², E³, and E⁴ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to M.

Other phosphorescent emitters include compounds of General Formula X:

wherein:

M is a metal cation with four positive charges selected from Pd (IV) and Pt(IV);

each of E¹, E², E³, E⁴, and E⁵ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom is coordinated to M.

Other phosphorescent emitters include compounds of General Formula XI:

wherein:

M is a metal cation with two positive charges selected from Ru (II) and Os (II);

each of E¹, E², E³, E⁴, and E⁵ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom is coordinated to M.

Other phosphorescent emitters include compounds of General Formula XII:

wherein:

M is a metal cation with two positive charges selected from Ru (II) and Os (II);

each of E¹, E², E³, and E⁴ independently represents O, NR³, CR³R⁴, S, AsR³, BR³, PR³, P(O)R³, or SiR³R⁴, wherein each of R³ and R⁴ is independently hydrogen, halogen, hydroxyl, thiol, or substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclic group, amino, alkoxy, haloalkyl, arylalkyl, arylalkenyl, or R³ and R⁴ together form C═O, wherein each of R³ and R⁴ is independently optionally linked to a C or N, thereby forming a cyclic structure;

each C independently represents a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to M; and

each N independently represents a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom is coordinated to M.

Phosphorescent emitters are also disclosed in US 2015/0207086, entitled “METAL COMPOUNDS AND METHODS AND USES THEREOF,” which is incorporated by reference herein.

As described herein, fluorescent emitters include:

1. Aromatic Hydrocarbons and their Derivatives

2. Aryletheylene, Arylacetylene and their Derivatives

3. Heterocyclic Compounds and their Derivatives

4. Other Fluorescent Luminophors

wherein:

each of R^1l, R^2l, R^3l, R^4l, R^5l, R^6l, R^7l and R^8l is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, or any conjugate or combination thereof, and

each of Y^a, Y^b, Y^c, Y^d, Y^e, Y^f, Y^g, Y^h, Yⁱ, Y^j, Y^k, Y^l, Y^m, Yⁿ, Y^o and Y^p is independently C, N or B; and

each of U^a, U^b and U^c is independently CH₂, CRR, C═O, SiRR, GeH₂, GeRR, NH, NR, PH, PR, RP═O, AsR, RAs═O, O, S, S═O, SO₂, Se, Se═O, SeO₂, BH, BR, RBi═O, BiH, or BiR, wherein each R is independently is independently hydrogen, deuterium, halogen, hydroxyl, thiol, nitro, cyano, nitrile, isonitrile, sulfinyl, mercapto, sulfo, carboxyl, hydrazino; substituted or unsubstituted: aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, ureido, phosphoramide, silyl, polymeric, or any conjugate or combination thereof.

EXAMPLES

Device Fabrication:

TAPC (di-[4-(N,N-di-toylyl-amino)-phyenyl]cyclohexane), TrisPCz (9,9′,9″-triphenyl-9H,9′H,9″H-3,3′:6′3″-tercarbazole), 26mCPy (2,6-bis(N-carbazolyl) pyridine), DPPS (diphenyl-bis[4-(pyridin-3-yl)phenyl]silane), BmPyPB (1,3-bis[3, 5-di(pyridin-3-yl)phenyl]benzene), and BPyTP (2,7-di(2,2′-bipyridin-5-yl)triphenylene) were all synthesized by methods known in the art. HATCN (1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile), NPD (N,N′-diphyenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4″-diamine), BAlq bis(2-methyl-8-quinolinolato)(biphenyl-4-olato)aluminum, mCBT (9,9′-(2,8-dibenzothiophenediyl)bis-9H-carbazole), mCBP (3,3-di(9H-carbazol-9-yl)biphenyl), and TBPe (2,5,8,11-tetra-tert-butylperylene) were obtained from commercial suppliers. Prior to use all materials were purified via thermal gradient sublimation under high vacuum (10⁻⁵-10⁻⁶ Torr). Devices were deposited on pre-patterned ITO substrates cleaned by sonication in deionized water, acetone, and isopropanol. The devices were fabricated by vacuum thermal evaporation at a pressure of less than 10⁻⁷ Torr. Organic layers were deposited at rates of 0.5 to 1.5 Å/s, and the Al cathode was deposited through a shadow mask without breaking vacuum, defining device areas of 0.04 cm². The current-voltage-luminance characteristics were measured using a Keithley 2400 SourceMeter in conjunction with a Newport 818 Si Photodiode. Electroluminescent spectra were measured with an Horiba Jobin Yvon FluoroLog-3 spectrometer at a driving current of 1 mA/cm².

Devices A-C.

TBPe, a t-butyl-perylene based fluorescent emitter, and PtNON, a phosphorescent platinum emitter, both shown below, were used in this example. These materials were selected due to the high photoluminescence quantum yield (PLQY) for each and favorable overlap between the PtNON emission spectrum, with emission onset as low as 430 nm, and the absorption spectrum of TBPe. Furthermore, the advantage of the emission onset of PtNON at a much higher energy than the room temperature peak emission wavelength (˜500 nm) and the small stokes shift in the TBPe emitters will result in an emission primarily from the fluorescent emitter that is bluer than that of the phosphorescent emitter alone.

OLEDs were fabricated with each general structure depicted FIGS. 3 and 4. For the first case (FIG. 3) devices were fabricated in the structure ITO/HATCN (10 nm)/NPD (40 nm)/TAPC (10 nm)/26mCPy:10% PtNON:x % TBPe (25 nm)/DPPS (10 nm)/BmPyPB (40 nm)/LiF/Al, where HATCN is 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile, NPD is N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4″-diamine, TAPC is di-[4-(N,N-di-tolyl-amino)-phenyl]cyclohexane, 26mCPy is 2,6-bis(N-carbazolyl) pyridine, DPPS is diphenyl-bis[4-(pyridin-3-yl)phenyl]silane, and BmPyPB is 1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene.

FIGS. 5A-5C show external efficiency vs. luminance, current-voltage characteristics, and electroluminescent spectra, respectively, for PtNON Devices A-C having the general structure depicted in FIG. 5D (ITO/HATCN/NPD/TAPc/EML/DPPS/BmPyPB/LiF/Al), where the EML for Devices A-C were (1) 10% PtNON:26mCPy; (2) 10% PtNON:1% TBPe:26mCPy; and (3) 10% PtNON:2% TBPe:26mCPy, respectively.

Plots 500, 502, and 504 in FIG. 5A show external quantum efficiency (EQE) versus luminance for Devices A-C, respectively. The moderate EQE of 10-15% indicate that a large portion of the electrogenerated excitons are being harvested (assuming a 100% electron to photon conversion efficiency corresponds to an EQE of 20-30% due to outcoupling losses). Plots 510, 512, and 514 in FIG. 5B show current voltage characteristics of Devices A-C, respectively. Plots 520, 522, and 524 in FIG. 5C show electroluminescent spectra of Devices A-C, respectively. The emission from Devices B and C originated nearly exclusively from the fluorescent emitter. When considering these results, it is understood that excitons are being formed on the phosphorescent PtNON molecules, as evidenced by the high efficiencies, which then transfer to the fluorescent TBPe emitter via FRET as evidenced by the nearly exclusive fluorescent emission. It also appears that precise control of TBPe concentration is important since the device efficiencies vary with the change of fluorescent emitter concentration. This may be due at least in part to the direct formation of excitons on the fluorescent dopant, possibly due to charge trapping as suggested by the change in current-voltage characteristics, although other mechanisms for losses may exist.

Device 530 in FIG. 5D is a cross-sectional view of the general structure of Devices A-C (in particular, Device B). Device 530 includes substrate 532, anode 534, and layers 536, 538, and 540, of HATCN, NPD, and TAPC, respectively, emissive layer 542, layers 544, 546, and 548 of DPPS, BmPyPB, and LiF, respectively, and cathode 550.

Device D.

FIGS. 6A-6C show external efficiency vs. brightness, current-voltage characteristics, and electroluminescent spectra, respectively, for Device D having the general structure ITO/HATCN/NPD/TAPc/EML/DPPS/BmPyPB/LiF/Al as depicted in FIG. 6D, where the alternative EMLs for Device D are (1) 10% PtNON:26mCPy and (2) 2% TBPe:26mCPy. The general structure depicted in FIG. 6D was used to circumvent the potential tradeoff between high FRET efficiency and efficiency losses from direct exciton formation on TBPe molecules. Device D was fabricated with the structure ITO/HATCN (10 nm)/NPD (40 nm)/TAPC (10 nm)/26mCPy: 10% PtNON (4 nm)/26mCPy:2% TBPe (2 nm)/26mCPy:10% PtNON (4 nm)/26mCPy:2% TBPe (2 nm)/26mCPy: 10% PtNON (4 nm)/DPPS (10 nm)/BmPyPB (40 nm)/LiF/Al, with alternating phosphorescent and fluorescent doped layers.

Plot 600 in FIG. 6A shows external quantum efficiency versus luminance for Device D. Plot 610 in FIG. 6B shows current density versus voltage for Device D. Plots 620 and 622 show electroluminescent spectra for Device D and a 10% PtNON reference device, respectively. As shown in FIGS. 6A-6C, Device D exhibited an efficiency of over 20% while still exhibiting emission primarily originating from the fluorescent emitter, thereby demonstrating the capability to manipulate the emission spectrum and emit nearly exclusively from fluorescent emitters while maintaining a high efficiency.

As depicted in FIG. 6D, Device 630 includes substrate 632, anode 634, layers 636, 638, and 640 of HATCN, NPD, and TAPC, respectively, layers 642, 646, and 650 of 26mCPy:10% PtNON 642, layers 644 and 648 of 26mCPy:2% TBPe 644, layers 652, 654, and 656 of DPPS, BmPyPB, and LiF, respectively, and cathode 658. This order was selected with the recombination zone located on the PtNON doped layer so that the majority of the excitons are formed on the PtNON molecules, thereby allowing harvest of 100% of the electrogenerated excitons. The layer thicknesses were also kept low so that there was a sufficiently small distance between the phosphorescent material and the fluorescent emitters to allow rapid FRET to occur.

Devices 1-2.

PtNON can be used to harvest triplet excitons with and subsequently transfer the energy to a fluorescent emitter with high emission energy. Devices 1 and 2 were fabricated with the structure ITO/HATCN (10 nm)/NPD (40 nm)/6% PtNON:mCBP/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm) and ITO/HATCN (10 nm)/NPD (40 nm)/6% PtNON:1% TBPe:mCBP (25 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm), respectively, where Device 1 has an EML of 6% PtNON:mCBP and Device 2 has an EML of 6% PtNON: 1% TBPe:mCBP (25 nm), where TBPe is 1% 2,5,8,11-tetra-tert-butylperylene (TBPe), a known efficient fluorescent blue emitter. Plots 700 and 702 in FIG. 7 show electroluminescent spectra of Devices 1 and 2, respectively. As shown in plot 702, the electroluminescent spectrum of Device 2 takes on the narrow blue emission character of the fluorescent emitter rather than the broad emission characteristics of PtNON, indicating effective energy transfer to the fluorescent dopant. The emission peak of Device 2 shifts to 464 nm, yielding blue emission with CIE coordinates of (0.15, 0.21). This shift in color between Devices 1 and 2 achieved while maintaining similar efficiencies.

The operational lifetime of Device 2 was also measured at an accelerated constant driving current of 20 mA/cm². Plots 800 and 802 in FIG. 8 shows relative luminance versus operational time for Devices 1 and 2, respectively. As shown in plot 802, LT₇₀ of Device 2 is 85 h at L₀=2257 cd/m², corresponding to nearly 17,000 h at 100 cd/m².

Plot 900 in FIG. 9A shows current density voltage characteristics of Device 2. Plot 910 in FIG. 9B shows a peak EQE of 9.8% for Device 2, and an EQE of 8.2% at 1000 cd/m². The similar efficiencies of Devices 1 and 2 suggest that PtNON is still effectively harvesting the triplet excitons then transferring the energy to the TBPe molecules. Such a strategy highlights the compatibility of the high triplet energy of PtNON with a deep blue fluorescent emitter such as TBPe.

Devices 3-6.

Devices 3-6 were fabricated with the following structures:

Device 3: ITO/HATCN (10 nm)/NPD (40 nm)/6% PtNON:1% TBPe:mCBP (25 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm);

Device 4: ITO/HATCN (10 nm)/NPD (40 nm)/6% PtNON:1% TBPe:mCBP (25 nm)/1% TBPe:mCBP (2.5 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm);

Device 5: ITO/HATCN (10 nm)/NPD (40 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON: 1% TBPe:mCBP (25 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm);

Device 6: ITO/HATCN (10 nm)/NPD (40 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:1% TBPe:mCBP (25 nm)/1% TBPe:mCBP (2.5 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm).

Plots 1000, 1002, 1004, and 1006 in FIG. 10A are electroluminescent spectra of Devices 3-6, respectively. Plots 1010, 1012, 1014, and 1016 in FIG. 10B show current density voltage characteristics for Devices 3-6, respectively. Plots 1020, 1022, 1024, and 1026 in FIG. 10C show EQE versus luminance for Devices 3-6, respectively. Plots 1030, 1032, 1034, and 1036 in FIG. 10D show electroluminescent intensity versus operational time at a constant driving current of 20 mA/cm² for Devices 3-6, respectively.

Devices 7-10.

Devices 7-10 were fabricated with the following structures:

Device 7: ITO/HATCN (10 nm)/NPD (40 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm);

Device 8: ITO/HATCN (10 nm)/NPD (40 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm);

Device 9: ITO/HATCN (10 nm)/NPD (40 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm);

Device 10: ITO/HATCN (10 nm)/NPD (40 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/6% PtNON:mCBP (5 nm)/1% TBPe:mCBP (2.5 nm)/mCBT (10 nm)/BpyTP (40 nm)/LiF (1 nm)/Al (100 nm).

Plots 1100, 1102, 1104, and 1106 in FIG. 10A show electroluminescent spectra of Devices 7-10, respectively. Plots 1110, 1112, 1114, and 1116 in FIG. 10B show current density voltage characteristics for Devices 7-10, respectively. Plots 1120, 1122, 1124, and 1126 in FIG. 10C show EQE versus luminance for Devices 7-10, respectively. Plots 1130, 1132, 1134, and 1136 in FIG. 10D show electroluminescent intensity versus operational time at a constant driving current of 20 mA/cm² for Devices 7-10, respectively.

Table 1 lists device performance of Devices 1-10.

TABLE 1
Device performance of PtNON with TBPe.
	EQE (%)		Lifetime (hours)
Device	Dopant	CIE	Peak	100 cd/m2	1000 cd/m2	Lo (cd/m2)	L = L0	L = 1000 cd/m2	L = 100 cd/m2
1	PtNON	(0.17,	10.7	10.5	9.1	3145	89	624	31286
		0.32)
2	PtNON +	(0.15,	9.8	9.7	8.2	2257	85	340	16999
	TBPe	0.21)
3	PtNON +		9.3	9.0	7.5	1987	88	282	14171
	TBPe
4	PtNON +		9.5	9.1	7.6	2009	87	284	14275
	TBPe
5	PtNON +		9.3	9.1	7.5	2180	88	331	16590
	TBPe
6	PtNON +		9.7	9.0	7.1	1935	89	273	13700
	TBPe
7	PtNON +		7.0	7.0	5.9	2413	94	420	21060
	TBPe
8	PtNON +		8.2	7.9	6.5	2585	95	477	23928
	TBPe
9	PtNON +		8.6	8.2	7.8	2581	58	290	14570
	TBPe
10	PtNON +		11.8	10.9	8.5	2532	62	300	15075
	TBPe

Further modifications and alternative embodiments of various aspects will be apparent to those skilled in the art in view of this description. Accordingly, this description is to be construed as illustrative only. It is to be understood that the forms shown and described herein are to be taken as examples of embodiments. Elements and materials may be substituted for those illustrated and described herein, parts and processes may be reversed, and certain features may be utilized independently, all as would be apparent to one skilled in the art after having the benefit of this description. Changes may be made in the elements described herein without departing from the spirit and scope as described in the following claims.

Claims

1. A light emitting device comprising: a first electrode;a hole transporting layer in contact with the first electrode;a second electrode;an electron transporting layer in contact with the second electrode; andan emissive layer between the hole transporting layer and the electron transporting layer, the emissive layer comprising: a phosphorescent emitter, a fluorescent emitter, and a host; wherein the emissive layer comprises:n emitter layers comprising the host and the fluorescent emitter, andm donor layers comprising the host and the phosphorescent emitter, wherein n and m are integers≥2,wherein the emitter layers do not comprise the phosphorescent emitter;wherein the donor layers do not comprise the fluorescent emitter;wherein the phosphorescent emitter is capable of harvesting electrogenerated excitons and transferring energy to the fluorescent emitter; andwherein the phosphorescent emitter comprises a compound of General Formula I:

2. A light emitting device comprising: a first electrode;a hole transporting layer in contact with the first electrode;a second electrode;an electron transporting layer in contact with the second electrode; andan emissive layer between the hole transporting layer and the electron transporting layer, the emissive layer comprising: a phosphorescent emitter, a fluorescent emitter, and a host; wherein the emissive layer comprises:n emitter layers comprising the host and the fluorescent emitter, andm donor layers comprising the host and the phosphorescent emitter,wherein n and m are integers≥1, and n=m+1, or m=n+1, and thefluorescent emitter layers and phosphorescent emitter layers alternate;wherein the emitter layers do not comprise the phosphorescent emitter;wherein the donor layers do not comprise the fluorescent emitter;wherein the phosphorescent emitter is capable of harvesting electrogenerated excitons and transferring energy to the fluorescent emitter; andwherein the phosphorescent emitter comprises a compound of General Formula I:

3. The light emitting device of claim 1, wherein n and m are equal.

4. The light emitting device of claim 1, wherein each emitter layer is adjacent to at least one donor layer.

5. The light emitting device of claim 1, wherein n=m+1, or m=n+1.

6. The light emitting device of claim 1, wherein the light emitting device is a fluorescent organic light emitting device.

7. The light emitting device of claim 1, wherein: M is Pt or Pd;m in General Formula I is 2;n in General Formula I is 2;at least one of Y1a and Y1c is independently NR3, CR3R4, S, AsR3, BR3, PR3, P(O)R3, or SiR3R4;Y2b and Y2c are C; andY3b and Y4b are N.

8. The light emitting device of claim 1, wherein: M is Ir or Rh;m in General Formula I is 2;n in General Formula I is 2;Y1a is NR3, CR3R4, S, AsR3, BR3, PR3, P(O)R3, or SiR3R4;Y2b is C; andY3b, Y2c and Y4b are N.

9. The light emitting device of claim 1, wherein: M is Au;m in General Formula I is 2;n in General Formula I is 2;Y1b is NR3, CR3R4, S, AsR3, BR3, PR3, P(O)R3, or SiR3R4;Y2b, Y2c and Y4b are C; andY3b is N.

10. The light emitting device of claim 1, wherein each of R3 and R4 is independently linked to an adjacent ring structure.

11. The light emitting device of claim 1, wherein: M is Pt or Pd;at least one of Y1b and Y1c is independently NR3, CR3R4, S, AsR3, BR3, PR3, P(O)R3, or SiR3R4, wherein R3 is covalently linked to at least one of Y2a, Y2d, Y3d, and Y4d, thereby forming a cyclic structure; andat least of one of Y2a, Y2d, Y3d and Y4d is C.

12. The light emitting device of claim 1, wherein: M is Ir or Rh;Y1b is NR3, CR3R4, S, AsR3, BR3, PR3, P(O)R3, or SiR3R4, wherein R3 is covalently linked to at least one of Y2a and Y3d, thereby forming a cyclic structure; and

13. The light emitting device of claim 1, wherein: M is Au;at least of one of Y2a and Y3d is C; and

14. The light emitting device of claim 1, wherein the fluorescent emitter comprises one of the following compounds: