Patent Grant
11594691
Organic light emitting devices (OLED) 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 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.
A typical OLED device consists of at least one transparent electrode through which the light emits. For example OLEDs which 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 typically 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, shown in
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.
According to one embodiment, an organic light emitting device (OLED) is provided. The OLED comprises an anode; a cathode; and at least one organic layer disposed between the anode and the cathode; wherein the at least one organic layer includes a phosphorescent/MADF emitter and a fluorescent emitter. In one embodiment, the phosphorescent/MADF emitter is a compound having Formula I or Formula II;
wherein A is an accepting group comprising one or more of the following structures, which can optionally be substituted:
wherein D is a donor group comprising of one or more of the following structures, which can optionally be substituted:
wherein C in Formula I or Formula II comprises one or more of the following structures, which can optionally be substituted:
wherein N in Formula I or II comprises one or more of the following structures, which can optionally be substituted:
wherein each of a0, a1, and a2 independently is present or absent, and if present, comprises a direct bond and/or linking group comprising one or more of the following:
wherein each occurrence of a is independently substituted or unsubstituted N or substituted or unsubstituted C;
wherein b1 and b2 independently is present or absent, and if present, comprises a linking group comprising one or more of the following:
wherein each occurrence of X is independently B, C, N, O, Si, P, S, Ge, As, Se, Sn, Sb, or Te;
wherein Y is O, S, S═O, SO2, Se, N, NR3, PR3, RP═O, CR1R2, C═O, SiR1R2, GeR1R2, BH, P(O)H, PH, NH, CR1H, CH2, SiH2, SiHR1,BH, or BR3,
wherein each of R, R1, R2, and R3 independently is hydrogen, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, deuterium, halogen, hydroxyl, thiol, nitro, cyano, amino, a mono- or di-alkylamino, a mono- or diaryl amino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, nitrile, isonitrile, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramide, mercapto, sulfo, carboxyl, hydrazino, substituted silyl, or polymerizable, or any conjugate or combination thereof,
wherein n is a number that satisfies the valency of Y; and wherein M is platinum, palladium, nickel, manganese, zinc, gold, silver, copper, iridium, rhodium, and/or cobalt.
In one embodiment, the emitting dipole of the fluorescent emitter is horizontally oriented. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.7
The following detailed description of preferred embodiments will be better understood when read in conjunction with the appended drawings. For the purpose of illustration, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the disclosure is not limited to the precise arrangements and instrumentalities of the embodiments shown in the drawings.
It is to be understood that the figures and descriptions herein have been simplified to illustrate elements that are relevant for a clear understanding of the present disclosure, while eliminating, for the purpose of clarity, many other elements found in the art related to phosphorescent organic light emitting devices and the like. Those of ordinary skill in the art may recognize that other elements and/or steps are desirable and/or required in implementing the devices disclosed herein. However, because such elements and steps are well known in the art, a discussion of such elements and steps is not provided herein. The disclosure herein is directed to all such variations and modifications to such elements and methods known to those skilled in the art.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Although any methods, materials and components similar or equivalent to those described herein can be used in the practice or testing of the disclosed devices and compositions, the preferred methods, and materials are described.
As used herein, each of the following terms has the meaning associated with it in this section.
The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element.
“About” as used herein when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations of ±20%, ±10%, ±5%, ±1%, or ±0.1% from the specified value, as such variations are appropriate.
Throughout this disclosure, various aspects can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.
Disclosed are the components to be used to prepare the compositions of the 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 disclosed herein.
As referred to herein, a linking atom or a linking group can connect two groups such as, for example, an N and C group. 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 includes, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, ═O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
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, and heterocyclyl.
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).
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, dodecyl, 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, norbornyl, 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 bond, i.e., C═C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, 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), 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 “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 term “heterocyclyl” 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 “ureido” as used herein refers to a urea group of the formula —NHC(O)NH2 or —NHC(O)NH—.
The term “phosphoramide” as used herein refers to a group of the formula —P(O)(NA1A2)2, where A1 and A2 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “carbamoyl” as used herein refers to an amide group of the formula —CONA1A2, where A1 and A2 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term “sulfamoyl” as used herein refers to a group of the formula —S(O)2NA1A2, where A1 and A2 can be, independently, hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
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)2A′, or —OS(O)2OA1, where A1 is 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)2A′, where A1 is 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 A'S(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, include hydrogen or 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 a 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.
As described herein, compounds of the disclosure 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. 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 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, R is understood to represent five independent substituents, Rn(a), Rn(b), Rn(c), Rn(d), Rn(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.
Phosphorescent/MADF emitters may b used for efficient exciton harvesting while emitting primarily from horizontally aligned and stable fluorescent emitters in order to enhance the device efficiency and device operational lifetime. To achieve this, both phosphorescent/MADF emitters and fluorescent emitters must be present in the EML and energy transfer between the MADF and fluorescent materials is necessary. Two major mechanisms to exciton transport exist, namely the Dexter energy transfer and Forster resonant energy transfer (FRET) mechanisms. The former is a short range transport which consists of consecutive hopping of excitons between neighboring molecules which depends on the orbital overlap between the molecules. The latter 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 necessitates and allowed relaxation transition of the donor molecule and an allowed excitation mechanism of the acceptor molecules, thus, 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 and efficiency of blue phosphorescent OLEDs has remained as a great technical challenge for OLED displays and lighting applications. Thus, alternate solution will be to improve the device efficiency of blue fluorescent OLED with better device stability. As illustrated in
This can be achieved by harvesting the electrogenerated excitons with a phosphorescent material then transferring the energy to a fluorescent emitter through a FRET mechanism. There are at least two methods of creating such a system: 1) a single emissive layer containing both the phosphorescent/MADF emitter and the fluorescent emitter doped into a host matrix and 2) an emissive layer containing alternating fluorescent and phosphorescent/MADF doped layers, which are presented in
The first case,
The second case,
A typical EQE of OLEDs on a standard glass substrate is limited to 20-30% if the emitting dipoles or emitters are randomly oriented (
Compounds
Owing to the potential of phosphorescent tetradentate platinum complexes for harvesting both electro-generated singlet and triplet excitons to achieve 100% internal quantum efficiency, these complexes are good candidates for the emitting materials of OLEDs. In some embodiments, there is an “emitting portion” and an “ancillary portion” in a ligand of platinum complex (e.g., a tetradentate platinum complex). If stabilizing substitution(s), such as conjugated group(s), aryl or heteroaromatic substitution(s) and so on, were introduced into the emitting portion, the “Highest Occupied Molecular Orbital” (HOMO) energy level, the “Lowest Unoccupied Molecular Orbital” (LUMO) energy level, or both may be changed. Accordingly, in some embodiments the energy gap between the HOMO and LUMO can be tuned. Thus, the emission spectra of phosphorescent tetradentate platinum complexes can be modified to lesser or greater extents, such that the emission spectra can become narrower or broader, such that the emission spectra can exhibit a blue shift or a red shift, or a combination thereof.
The emission of the disclosed complexes can be tuned, for example, from the ultraviolet to near-infrared, by, for example, modifying the ligand structure. In another aspect, the disclosed complexes can provide emission over a majority of the visible spectrum. In one embodiment, the disclosed complexes can emit light over a range of from about 400 nm to about 700 nm. In another aspect, the disclosed complexes have improved stability and efficiency over traditional emission complexes. In yet another aspect, the disclosed complexes can be useful as luminescent labels in, for example, bio-applications, anti-cancer agents, emitters in organic light emitting devices (OLED), or a combination thereof. In another aspect, the disclosed complexes can be useful in light emitting devices, such as, for example, compact fluorescent lamps (CFL), light emitting diodes (LED), incandescent lamps, and combinations thereof.
The compounds can also have other known emission mechanisms which are useful in devices.
Disclosed herein are compounds or compound complexes comprising platinum and/or palladium. The terms compound, complex, or combinations thereof, are used interchangeably herein. In one aspect, the compounds disclosed herein have a neutral charge.
The compounds disclosed herein can exhibit desirable properties and have emission spectra, absorption spectra, or both that can be tuned via the selection of appropriate ligands. In another aspect, the present disclosure can exclude any one or more of the compounds, structures, or portions thereof, specifically recited herein.
The compounds disclosed herein are suited for use in a wide variety of optical and electro-optical devices, including, but not limited to, photo-absorbing devices such as solar- and photo-sensitive devices, organic light emitting devices (OLEDs), photo-emitting devices, or devices capable of both photo-absorption and emission and as markers for bio-applications.
As briefly described above, the disclosed compounds are platinum and/or palladium complexes. In one aspect, the compounds disclosed herein can be used as host materials for OLED applications, such as full color displays.
The compounds disclosed herein are useful in a variety of applications. As light emitting materials, the compounds can be useful in organic light emitting devices (OLEDs), luminescent devices and displays, and other light emitting devices.
In another aspect, the compounds can provide improved efficiency, improved operational lifetimes, or both in lighting devices, such as, for example, organic light emitting devices, as compared to conventional materials.
The compounds of the disclosure can be made using a variety of methods, including, but not limited to those recited in the examples provided herein.
Compounds
In one aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with two positive charges selected from Pt (II) or Pd (II);
wherein E1, E2, and E3 independently is a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group wherein a nitrogen atom coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with three positive charges selected from Au (III) or Ag (III);
wherein E1, E2, and E3 independently is a linking group comprising O, NR2, CR2R3, S. AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein N is selected from a substituted or unsubstituted heterocyclic group wherein a nitrogen atom coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with one positive charges selected from Ir (I) or Rh (I),
wherein E1, E2, and E3 independently represent a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein C is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group wherein a nitrogen atom is coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with three positive charges selected from Ir (III), Rh (III), Co (III), Al (III), or Ga (III),
wherein E1, E2, E3, and E4 independently is a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with three positive charges selected from Ir (III), Rh (III), Co (III), Al (III), or Ga (III);
wherein E1, E2, E3, E4, and E5 independently is a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with four positive charges selected from Pd (IV) and Pt (IV);
wherein E1, E2, E3, and E4 independently is a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
where M is a metal cation with four positive charges selected from Pd (IV) and Pt(IV),
wherein E1, E2, E3, E4, and E5 independently is a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with two positive charges selected from Ru (II), or Os (II);
wherein E1, E2, E3, E4, and E5 independently is a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom coordinated to the metal.
In another aspect, the present disclosure relates to compounds having the formula
wherein M is a metal cation with two positive charges selected from Ru (II), or Os (II);
wherein E1, E2, E3, and E4 independently is a linking group comprising O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to a C or N, thereby forming a cyclic structure;
wherein each C independently is selected from a substituted or unsubstituted aromatic ring or heterocyclic group, wherein a carbon atom is coordinated to the metal; and
wherein each N independently is selected from a substituted or unsubstituted heterocyclic group, wherein a nitrogen atom is coordinated to the metal.
In one aspect, the present disclosure relates to compounds having the structure of Formula I or Formula II:
wherein A is an accepting group comprising one or more of the following structures, which can optionally be substituted:
wherein D is a donor group comprising of one or more of the following structures, which can optionally be substituted:
wherein C in Formula I or Formula II comprises one or more of the following structures, which can optionally be substituted:
wherein N in Formula I or II comprises one or more of the following structures, which can optionally be substituted:
wherein each of a0, a1, and a2 independently is present or absent, and if present, comprises a direct bond and/or linking group comprising one or more of the following:
wherein each occurrence of a is independently substituted or unsubstituted N or substituted or unsubstituted C;
wherein b1 and b2 independently is present or absent, and if present, comprises a linking group comprising one or more of the following:
wherein each occurrence of X is independently B, C, N, O, Si, P, S, Ge, As, Se, Sn, Sb, or Te;
wherein Y is O, S, S═O, SO2, Se, N, NR3, PR3, RP═O, CR1R2, C═O, SiR1R2, GeR1R2, BH, P(O)H, PH, NH, CR1H, CH2, SiH2, SiHR1,BH, or BR3,
In one embodiment, a2 is absent in Formula I. In one embodiment, a2 and b2 are absent in Formula I or Formula II.
In one embodiment, X is N.
In one embodiment, A is
a2 is absent, b2 are absent, and D is
In one embodiment, C in Formula I or Formula II is
In one embodiment, N in Formula I or Formula II is substituted or unsubstituted
In one embodiment, the compound having Formula I or Formula II is a compound having Formula III;
wherein M is Ir, Rh, Mn, Ni, Cu, or Ag;
wherein each of R1 and R2 independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of Y1a and Y1b independently is O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure;
wherein each of Y2a, Y2b, Y2c, and Y2d independently is N or CR6a, wherein R6a is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
each of Y3a, Y3b, Y3c, Y3d, Y4a, Y4b, Y4c, and Y4d independently is N, O, S, NR6a, CR6b, or Z(R6c)2, wherein each of R6a and R6b is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; wherein Z is C or Si, and wherein each R6c independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of m and n independently is an integer of 1 or 2; and
wherein each of
independently is partial or full unsaturation of the ring with which it is associated.
In one embodiment, Y2b is C; Y2c, Y3b and Y4b are N. In one embodiment, M is Ir or Rh.
In one embodiment, the compound having Formula I or Formula II is a compound having Formula IV;
wherein M is Pt, Pd and Au;
wherein each of R1 and R2 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of Y1a a and Y1b independently is O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure;
wherein each of Y2a, Y2b, Y2c, and Y2d independently is N or CR6b, wherein R6a is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of Y3a, Y3b, Y3c, Y3d, Y3e, Y3f, Y4a, Y4b, Y4c, and Y4d independently is N, O, S, NR6a, CR6b, or Z(R6c)2, wherein each of R6a and R6b is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; wherein Z is C or Si, and wherein each R6c independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of m is an integer of 1 or 2; and
wherein each of
independently is partial or full unsaturation of the ring with which it is associated.
In one embodiment, Y2b and Y2c is C. In one embodiment, Y3b and Y4b is N. In one embodiment, each of Y1a and Y1b independently is O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O. In one embodiment, each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure. In one embodiment, M is Pt or Pd.
In one embodiment, Y2b, Y2c and Y4b is C. In one embodiment, Y3b is N. In one embodiment, each of Y1a and Y1b independently is O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R1 together form C═O. In one embodiment, each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure. In one embodiment, M is Au.
In one embodiment, the compound having Formula I or Formula II is a compound having Formula V;
wherein M is Pt, Pd, Au, Ag;
wherein each of R1 and R2 independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein one of Y1a and Y1b is B(R2)2 and the other of Y1a and Y1b is O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure;
wherein each of Y2a, Y2b, Y2c, and Y2d independently is N or CR6a, wherein R6a is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of Y3a, Y3b, Y3c, Y3d, Y4a, Y4b, Y4c, and Y4d independently is N, O, S, NR6a, CR6b, or Z(R6c)2, wherein each of R6a and R6b is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; wherein Z is C or Si, and wherein each R6c independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of m and n independently are an integer 1 or 2;
wherein each of
independently is partial or full unsaturation of the ring with which it is associated.
In one embodiment, the compound having Formula I or Formula II is a compound having Formula VI or Formula VIb
wherein M is Pt, Pd, Ir, Rh, or Au;
wherein each of R1 and R2 independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; wherein each of Y1a, Y1b, and Y1c independently is O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure;
wherein each of Y2a, Y2b, Y2c, and Y2d independently is N, NR6a, or CR6b, wherein each of R6a and R6b independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
each of Y3a, Y3b, Y3c, Y3d, Y3e, Y4a, Y4b, Y4c, and Y4d independently is N, O, S, NR6a, CR6b, or Z(R)2, wherein each of R6a and R6b is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; wherein Z is C or Si, and wherein each R6c independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of m and n independently are an integer 1 or 2;
wherein each of
independently is partial or full unsaturation of the ring with which it is associated.
In one embodiment, each of R2 and R3 independently is linked to an adjacent ring structure.
In one embodiment, m is 2. In one embodiment, n is 2. In one embodiment, Y2b and Y2c are CH. In one embodiment, Y3b and Y4b are N. In one embodiment, at least one of Y1b and Y1c is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O. In one embodiment, each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure. In one embodiment, M is Pt or Pd.
In one embodiment, at least of one of Y2a, Y2d, Y3d and Y4d is C. In one embodiment, at least one of Y1b and Y1c is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene. In one embodiment, R2 is covalently linked to at least one of Y2a, Y2d, Y3d and Y4d, thereby forming a cyclic structure. In one embodiment, M is Pt or Pd.
In one embodiment, m is 2. In one embodiment, n is 2. In one embodiment, Y2b is CH. In one embodiment, Y3b, Y2c and Y4b are N. In one embodiment, Y1b is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O. In one embodiment, each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure. In one embodiment, M is Ir or Rh.
In one embodiment, at least of one of Y2a and Y3d is C. In one embodiment, Y1b is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene. In one embodiment, R2 is covalently linked to at least one of Y2a and Y3d, thereby forming a cyclic structure. In one embodiment, M is Ir or Rh.
In one embodiment, m is 2. In one embodiment, n is 2. In one embodiment, Y2b, Y2c and Y4b are CH. In one embodiment, Y3b is N. In one embodiment, Y1b is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O. In one embodiment, each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure. In one embodiment, M is Au.
In one embodiment, at least of one of Y2a and Y3d is C. In one embodiment, Y1b is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene. In one embodiment, R2 is covalently linked to at least one of Y2a and Y3d, thereby forming a cyclic structure. In one embodiment, M is Au.
In one embodiment, the compound having Formula I or Formula II is a compound having Formula VII;
wherein M comprises Ir, Rh, Pt, Os, Zr, Co or Ru;
wherein each of R1 and R2 independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of Y1a, Y1c and Y1d independently is O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof, wherein each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure;
wherein Y1c is present or not present; wherein when Y1e is present, Y1e represents O, NR2, CR2R3, S, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof; wherein each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O, wherein each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure; wherein when Y1e is not present, Y1e represents no bond;
wherein each of Y2a, Y2b Y2c, and Y2d independently is N or CR6a, wherein R6a is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein each of Y3a, Y3b, Y3c, Y3d, Y3e, Y4a, Y4b, Y4c, and Y4d independently is N, O, S, NR6a, CR6b, or Z(R6c)2, wherein each of R6a and R6b is independently hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene; wherein Z is C or Si, and wherein each R6c independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene;
wherein in each of each of Y5a, Y5b, Y5c, Y5d, Y6a, Y6b, Y6c, and Y6d independently is N, O, S, NR6a, or CR;
wherein each of m, n, l and p independently is an integer of 1 or 2;
wherein each of
independently is partial or full unsaturation of the ring with which it is associated.
In one embodiment, in the compound of Formula VII, at least one of m, n, l, and p is 2; Y2b and Y2c are CH. In one embodiment, Y3b and Y4b are N. In one embodiment, at least one of Y1b and Y1c is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene, or R2 and R3 together form C═O. In one embodiment, each of R2 and R3 independently is optionally linked to an adjacent ring structure, thereby forming a cyclic structure. In one embodiment, M is Ir or Rh.
In one embodiment, in the compound of Formula VII, at least of one of Y2a, Y2d, Y3d and Y4d is C. In one embodiment, at least one of Y1c and Y1d is NR2, CR2R3, AsR2, BR2, PR2, P(O)R2, or SiR2R3, or a combination thereof. In one embodiment, each of R2 and R3 independently is hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, arylalkene. In one embodiment, R2 is covalently linked to at least one of Y2a, Y2d, Y3d and Y4d, thereby forming a cyclic structure. In one embodiment, M is Ir or Rh.
In one embodiment, in the compound of Formula VII, each of R2 and R3 independently is linked to an adjacent ring structure.
In one embodiment, the phosphorescent/MADF emitter is PtNON;
Exemplary fluorescent emitters include, but are not limited to:
1. Aromatic Hydrocarbons and their Derivatives
2. Arylethylene, Arylacetylene and their Derivatives
3. Heterocyclic Compounds and their Derivatives
4. Other Fluorescent Luminophors
wherein each of R1l, R2l, R3l, R4l, R5l, R6l, R7l and R8l independently represents hydrogen, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, deuterium, halogen, hydroxyl, thiol, nitro, cyano, amino, a mono- or di-alkylamino, a mono- or diarylamino, alkoxy, aryloxy, haloalkyl, aralkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramide, mercapto, sulfo, carboxyl, hydrazino, substituted silyl, polymeric, or any conjugate or combination thereof.
wherein each of Ya, Yb, Yc, Yd, Ye, Yf, Yg, Yh, Yi, Yj, Yk, Y1, Ym, Yn, Yo and Yp independently represents C, N or B; and
wherein each of Ua, Ub and Uc independently represents CH2, CR1R2, C═O, CH2, SiR1R2, GeH2, GeR1R2, NH, NR3, PH, PR3, R3P═O, AsR3, R3As═O, O, S, S═O, SO2, Se, Se═O, SeO2, BH, BR3, R3Bi═O, BiH, or BiR3; wherein each of R1, R2, and R3 independently are hydrogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, nitro hydroxyl, halogen, thio, alkoxy, haloalkyl, arylalkane, or arylalkene.
In one embodiment, the fluorescent emitter is a thermally active delayed fluorescent (TADF) emitter. Exemplary TADF emitters include, but are not limited to, DABNA-1 and DABNA-2.
Hosts:
In one embodiment, the devices of the present disclosure may include a host material In one embodiment, the host material comprises a carbazole-based host material. Suitable carbazole based host materials include, but are not limited to, compounds having one to three carbazole skeletons, such as compounds of Formulas 1-3:
In Formulas 1-3, each of R1-R9 independently represents hydrogen, halogen, hydroxyl, nitro, cyanide, thiol, or optionally substituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkane, cycloalkane, heterocyclyl, amino, alkoxy, haloalkyl, arylalkane, or arylalkene.
Further non-limiting examples of suitable carbazole-based host materials include (9,9′,9″-triphenyl-9H,9′H,9″H-3,3′:6′3″-tercarbazole) (tris-PCz), (4,4-di(9H-carbazol-9-yl) biphenyl) (CBP), (3,3-di(9H-carbazol-9-yl) biphenyl) (mCBP), meta-di(carbazolyl) phenyl (mCP) shown below.
Additional carbazole-based hosts include, but are not limited to, mCPy (2,6-bis(N-carbazolyl)pyridine), TCP (1,3,5-tris(carbazol-9-yl)benzene), TCTA (4,4′,4″-tris(carbazol-9-yl)triphenylamine), TPBi (1,3,5-tris(1-phenyl-1-H-benzimidazol-2-yl)benzene), pCBP (4,4′-bis(carbazol-9-yl)biphenyl), CDBP (4,4′-bis(9-carbazolyl)-2,2′-dimethylbiphenyl), DMFL-CBP (4,4′-bis(carbazol-9-yl)-9,9-dimethylfluorene), FL-4CBP (4,4′-bis(carbazol-9-yl)-9,9-bis(9-phenyl-9H-carbazole)fluorene), FL-2CBP (9,9-bis(4-carbazol-9-yl)phenyl)fluorene, also abbreviated as CPF), DPFL-CBP (4,4′-bis(carbazol-9-yl)-9,9-ditolylfluorene), FL-2CBP (9,9-bis(9-phenyl-9H-carbazole)fluorene), Spiro-CBP (2,2′,7,7′-tetrakis(carbazol-9-yl)-9,9′-spirobifluorene). In one embodiment, a single host is used. In one embodiment, a mixture of two or more hosts is used. In one embodiment, the mixture of hosts may comprise between 0.01% and 99.99% of at least one host and between 0.01% and 99.99% of a second host.
Compositions and Devices
Also disclosed herein are devices comprising one or more compound and/or compositions disclosed herein.
In one aspect, the device is an electro-optical device. Electro-optical devices include, but are not limited to, photo-absorbing devices such as solar- and photo-sensitive devices, organic light emitting devices (OLEDs), photo-emitting devices, or devices capable of both photo-absorption and emission and as markers for bio-applications. For example, the device can be an OLED.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art. Such devices are disclosed herein which comprise one or more of the compounds or compositions disclosed herein.
OLEDs can be produced by methods known to those skilled in the art. In general, the OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates include, for example, glass, inorganic materials such as ITO or IZO or polymer films. For the vapor deposition, customary techniques may be used, such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and others.
In an alternative process, the organic layers may be coated from solutions or dispersions in suitable solvents, in which case coating techniques known to those skilled in the art are employed. Suitable coating techniques are, for example, spin-coating, the casting method, the Langmuir-Blodgett (“LB”) method, the inkjet printing method, dip-coating, letterpress printing, screen printing, doctor blade printing, slit-coating, roller printing, reverse roller printing, offset lithography printing, flexographic printing, web printing, spray coating, coating by a brush or pad printing, and the like. Among the processes mentioned, in addition to the aforementioned vapor deposition, preference is given to spin-coating, the inkjet printing method and the casting method since they are particularly simple and inexpensive to perform. In the case that layers of the OLED are obtained by the spin-coating method, the casting method or the inkjet printing method, the coating can be obtained using a solution prepared by dissolving the composition in a concentration of 0.0001 to 90% by weight in a suitable organic solvent such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethyl sulfoxide, water and mixtures thereof.
According to one aspect of the present disclosure, an OLED is provided. The OLED includes an anode, a cathode, and at least one organic layer disposed between the anode and the cathode. The at least one organic layer may include a host and a phosphorescent dopant and/or a fluorescent dopant The organic layer can include a compound of Formula I or Formula II, and its variations as described herein.
In various aspects, any of the one or more layers depicted in
Light processing material 108 may include one or more compounds of the present disclosure optionally together with a host material. The host material can be any suitable host material known in the art. The emission color of an OLED is determined by the emission energy (optical energy gap) of the light processing material 108, which can be tuned by tuning the electronic structure of the emitting compounds, the host material, or both. Both the hole-transporting material in the HTL layer 106 and the electron-transporting material(s) in the ETL layer 110 may include any suitable hole-transporter known in the art.
Compounds described herein may exhibit phosphorescence. Phosphorescent OLEDs (i.e., OLEDs with phosphorescent emitters) typically have higher device efficiencies than other OLEDs, such as fluorescent OLEDs. Light emitting devices based on electrophosphorescent emitters are described in more detail in WO2000/070655 to Baldo et al., which is incorporated herein by this reference for its teaching of OLEDs, and in particular phosphorescent OLEDs.
An exemplary OLED is represented in
Another exemplary OLED is represented in
In some embodiments, the emissive layer includes n emitter layers including the fluorescent emitter and/or a host, and m donor layers including the MADF/phosphorescent emitter and/or a host, where n and m are integers≥1. In some implementations, n=m, n=m+1, or m=n+1. In one embodiment, each emitter layer is adjacent to at least one donor layer. In one embodiment, each emitter layer and each donor layer further comprise a host. In one embodiment, each host can be the same or different.
In device 500, the thickness and location of the layers must be tuned to ensure that exciton formation primarily occurs in the region that is doped with the MADF 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.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In one embodiment, the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, and a sign.
In some embodiments of the emissive region, the emissive region further comprises a host, wherein the host comprises at least one selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
The organic layer(s) can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1—Ar2, and CnH2n—Ar1, or the host has no substitutions. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound. For example, a Zn containing inorganic material e.g. ZnS. In some embodiments, the host comprises at least one selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
In some embodiments, the emitting dipole of the fluorescent emitter is horizontally oriented. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.1. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.2. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.3. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.4. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.5. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.6. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.7. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.8. In one embodiment, the ratio of organic dipoles in at least one organic layer is greater than 0.9.
In one embodiment, the ratio of organic dipoles in at least one organic layer is between about 0.5 and about 0.9. In one embodiment, the ratio of organic dipoles in at least one organic layer is between about 0.6 and about 0.9. In one embodiment, the ratio of organic dipoles in at least one organic layer is between about 0.7 and about 0.8. In one embodiment, the ratio of organic dipoles in at least one organic layer is about 0.75. In one embodiment, the ratio of organic dipoles in at least one organic layer is about 0.8.
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
A hole injecting/transporting material is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
The light emitting layer of the organic EL device preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.
The following experimental examples are provided for purposes of illustration only, and are not intended to be limiting unless otherwise specified. Thus, the disclosure should in no way be construed as being limited to the following examples, but rather, should be construed to encompass any and all variations which become evident as a result of the teaching provided herein.
Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize the composite materials disclosed herein and practice the claimed methods. The following working examples therefore, specifically point out the preferred embodiments of the present disclosure, and are not to be construed as limiting in any way the remainder of the disclosure.
To demonstrate the utility of this disclosure, devices were made for each general structure shown in
The second system of selected materials for the demonstration of this disclosure is the use of a t-butyl-perylene based fluorescent emitter (FLB1) and the phosphorescent platinum emitter PtNON. These materials are selected due to the high PLQY for each and favorable overlap between the PtNON emission spectrum, with emission onset as low as 430 nm, and the absoption spectrum of FLB1. 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 fact that there is very little stokes shift in the FLB1 emitter will result in an emission primarily from the fluorescent emitter that is remarkably bluer than that of the phosphorescent emitter alone. Further materials optimization of a narrow blue emitters may further enhance this effect.
Devices were made for each general structure shown in
As shown in
To circumvent any potential tradeoff between high FRET efficiency and efficiency losses from direct exciton formation on FLB1 molecules, the second strategy (
The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this disclosure refers to specific embodiments, it is apparent that other embodiments and variations of this disclosure may be devised by others skilled in the art without departing from the true spirit and scope of the disclosure. The appended claims are intended to be construed to include all such embodiments and equivalent variations.
The present application claims priority to U.S. Provisional Application No. 62/796,704, filed Jan. 25, 2019, which is incorporated by reference herein in its entirety.
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| 9698359 | Li | Jul 2017 | B2 |
| 9711739 | Li | Jul 2017 | B2 |
| 9711741 | Li | Jul 2017 | B2 |
| 9711742 | Li | Jul 2017 | B2 |
| 9735397 | Riegel | Aug 2017 | B2 |
| 9755163 | Li | Sep 2017 | B2 |
| 9818959 | Li | Nov 2017 | B2 |
| 9865825 | Li | Jan 2018 | B2 |
| 9879039 | Li | Jan 2018 | B2 |
| 9882150 | Li | Jan 2018 | B2 |
| 9899614 | Li | Feb 2018 | B2 |
| 9920242 | Li | Mar 2018 | B2 |
| 9923155 | Li | Mar 2018 | B2 |
| 9941479 | Li | Apr 2018 | B2 |
| 9947881 | Li | Apr 2018 | B2 |
| 9985224 | Li | May 2018 | B2 |
| 10020455 | Li | Jul 2018 | B2 |
| 10033003 | Li | Jul 2018 | B2 |
| 10056564 | Li | Aug 2018 | B2 |
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| 10177323 | Li | Jan 2019 | B2 |
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| 20010019782 | Igarashi | Sep 2001 | A1 |
| 20020068190 | Tsuboyama | Jun 2002 | A1 |
| 20030062519 | Yamazaki | Apr 2003 | A1 |
| 20030180574 | Huang | Sep 2003 | A1 |
| 20030186077 | Chen | Oct 2003 | A1 |
| 20040230061 | Seo | Nov 2004 | A1 |
| 20050037232 | Tyan | Feb 2005 | A1 |
| 20050139810 | Kuehl | Jun 2005 | A1 |
| 20050170207 | Ma | Aug 2005 | A1 |
| 20050260446 | Mackenzie | Nov 2005 | A1 |
| 20060024522 | Thompson | Feb 2006 | A1 |
| 20060032528 | Wang | Feb 2006 | A1 |
| 20060066228 | Antoniadis | Mar 2006 | A1 |
| 20060073359 | Ise | Apr 2006 | A1 |
| 20060094875 | Itoh | May 2006 | A1 |
| 20060127696 | Stossel | Jun 2006 | A1 |
| 20060182992 | Nii | Aug 2006 | A1 |
| 20060202197 | Nakayama | Sep 2006 | A1 |
| 20060210831 | Sano | Sep 2006 | A1 |
| 20060255721 | Igarashi | Nov 2006 | A1 |
| 20060263635 | Ise | Nov 2006 | A1 |
| 20060286406 | Igarashi | Dec 2006 | A1 |
| 20070057630 | Nishita | Mar 2007 | A1 |
| 20070059551 | Yamazaki | Mar 2007 | A1 |
| 20070082284 | Stoessel | Apr 2007 | A1 |
| 20070103060 | Itoh | May 2007 | A1 |
| 20070160905 | Morishita | Jul 2007 | A1 |
| 20070252140 | Limmert | Nov 2007 | A1 |
| 20080001530 | Ise | Jan 2008 | A1 |
| 20080036373 | Itoh | Feb 2008 | A1 |
| 20080054799 | Satou | Mar 2008 | A1 |
| 20080079358 | Satou | Apr 2008 | A1 |
| 20080102310 | Thompson | May 2008 | A1 |
| 20080111476 | Choi | May 2008 | A1 |
| 20080241518 | Satou | Oct 2008 | A1 |
| 20080241589 | Fukunaga | Oct 2008 | A1 |
| 20080269491 | Jabbour | Oct 2008 | A1 |
| 20080315187 | Bazan | Dec 2008 | A1 |
| 20090026936 | Satou | Jan 2009 | A1 |
| 20090026939 | Kinoshita | Jan 2009 | A1 |
| 20090032989 | Karim | Feb 2009 | A1 |
| 20090039768 | Igarashi | Feb 2009 | A1 |
| 20090079340 | Kinoshita | Mar 2009 | A1 |
| 20090126796 | Yang | May 2009 | A1 |
| 20090128008 | Ise | May 2009 | A1 |
| 20090136779 | Cheng | May 2009 | A1 |
| 20090153045 | Kinoshita | Jun 2009 | A1 |
| 20090167167 | Aoyama | Jul 2009 | A1 |
| 20090205713 | Mitra | Aug 2009 | A1 |
| 20090218561 | Kitamura | Sep 2009 | A1 |
| 20090261721 | Murakami | Oct 2009 | A1 |
| 20090267500 | Kinoshita | Oct 2009 | A1 |
| 20100000606 | Thompson | Jan 2010 | A1 |
| 20100013386 | Thompson | Jan 2010 | A1 |
| 20100043876 | Tuttle | Feb 2010 | A1 |
| 20100093119 | Shimizu | Apr 2010 | A1 |
| 20100127246 | Nakayama | May 2010 | A1 |
| 20100141127 | Xia | Jun 2010 | A1 |
| 20100147386 | Benson-Smith | Jun 2010 | A1 |
| 20100171111 | Takada | Jul 2010 | A1 |
| 20100171418 | Kinoshita | Jul 2010 | A1 |
| 20100200051 | Triani | Aug 2010 | A1 |
| 20100204467 | Lamarque | Aug 2010 | A1 |
| 20100270540 | Chung | Oct 2010 | A1 |
| 20100288362 | Hatwar | Nov 2010 | A1 |
| 20100297522 | Creeth | Nov 2010 | A1 |
| 20100307594 | Zhu | Dec 2010 | A1 |
| 20110028723 | Li | Feb 2011 | A1 |
| 20110049496 | Fukuzaki | Mar 2011 | A1 |
| 20110062858 | Yersin | Mar 2011 | A1 |
| 20110132440 | Sivarajan | Jun 2011 | A1 |
| 20110217544 | Young | Sep 2011 | A1 |
| 20110227058 | Masui | Sep 2011 | A1 |
| 20110301351 | Li | Dec 2011 | A1 |
| 20120024383 | Kaiho | Feb 2012 | A1 |
| 20120025588 | Humbert | Feb 2012 | A1 |
| 20120039323 | Hirano | Feb 2012 | A1 |
| 20120095232 | Li | Apr 2012 | A1 |
| 20120108806 | Li | May 2012 | A1 |
| 20120146012 | Limmert | Jun 2012 | A1 |
| 20120181528 | Takada | Jul 2012 | A1 |
| 20120199823 | Molt | Aug 2012 | A1 |
| 20120202997 | Parham | Aug 2012 | A1 |
| 20120204960 | Kato | Aug 2012 | A1 |
| 20120215001 | Li | Aug 2012 | A1 |
| 20120223634 | Xia | Sep 2012 | A1 |
| 20120264938 | Li | Oct 2012 | A1 |
| 20120273736 | James | Nov 2012 | A1 |
| 20120302753 | Li | Nov 2012 | A1 |
| 20130048963 | Beers | Feb 2013 | A1 |
| 20130082245 | Kottas | Apr 2013 | A1 |
| 20130137870 | Li | May 2013 | A1 |
| 20130168656 | Tsai | Jul 2013 | A1 |
| 20130172561 | Tsai | Jul 2013 | A1 |
| 20130200340 | Otsu | Aug 2013 | A1 |
| 20130203996 | Li | Aug 2013 | A1 |
| 20130237706 | Li | Sep 2013 | A1 |
| 20130341600 | Lin | Dec 2013 | A1 |
| 20140014922 | Lin | Jan 2014 | A1 |
| 20140014931 | Riegel | Jan 2014 | A1 |
| 20140027733 | Zeng | Jan 2014 | A1 |
| 20140042475 | Park | Feb 2014 | A1 |
| 20140066628 | Li | Mar 2014 | A1 |
| 20140073798 | Li | Mar 2014 | A1 |
| 20140084261 | Brooks | Mar 2014 | A1 |
| 20140114072 | Li | Apr 2014 | A1 |
| 20140147996 | Vogt | May 2014 | A1 |
| 20140148594 | Li | May 2014 | A1 |
| 20140191206 | Cho | Jul 2014 | A1 |
| 20140203248 | Zhou | Jul 2014 | A1 |
| 20140249310 | Li | Sep 2014 | A1 |
| 20140326960 | Kim | Nov 2014 | A1 |
| 20140330019 | Li | Nov 2014 | A1 |
| 20140364605 | Li | Dec 2014 | A1 |
| 20150008419 | Li | Jan 2015 | A1 |
| 20150018558 | Li | Jan 2015 | A1 |
| 20150028323 | Xia | Jan 2015 | A1 |
| 20150060804 | Kanitz | Mar 2015 | A1 |
| 20150069334 | Xia | Mar 2015 | A1 |
| 20150105556 | Li | Apr 2015 | A1 |
| 20150123047 | Maltenberger | May 2015 | A1 |
| 20150162552 | Li | Jun 2015 | A1 |
| 20150194616 | Li | Jul 2015 | A1 |
| 20150207086 | Li | Jul 2015 | A1 |
| 20150228914 | Li | Aug 2015 | A1 |
| 20150274762 | Li | Oct 2015 | A1 |
| 20150287938 | Li | Oct 2015 | A1 |
| 20150311456 | Li | Oct 2015 | A1 |
| 20150318500 | Li | Nov 2015 | A1 |
| 20150349279 | Li | Dec 2015 | A1 |
| 20150380666 | Szigethy | Dec 2015 | A1 |
| 20160028028 | Li | Jan 2016 | A1 |
| 20160028029 | Li | Jan 2016 | A1 |
| 20160043331 | Li | Feb 2016 | A1 |
| 20160072082 | Brooks | Mar 2016 | A1 |
| 20160133861 | Li | May 2016 | A1 |
| 20160133862 | Li | May 2016 | A1 |
| 20160181529 | Tsai | Jun 2016 | A1 |
| 20160194344 | Li | Jul 2016 | A1 |
| 20160197285 | Zeng | Jul 2016 | A1 |
| 20160197291 | Li | Jul 2016 | A1 |
| 20160285015 | Li | Sep 2016 | A1 |
| 20160359120 | Li | Dec 2016 | A1 |
| 20160359125 | Li | Dec 2016 | A1 |
| 20170005278 | Li | Jan 2017 | A1 |
| 20170012224 | Li | Jan 2017 | A1 |
| 20170040555 | Li | Feb 2017 | A1 |
| 20170047533 | Li | Feb 2017 | A1 |
| 20170066792 | Li | Mar 2017 | A1 |
| 20170069855 | Li | Mar 2017 | A1 |
| 20170077420 | Li | Mar 2017 | A1 |
| 20170125708 | Li | May 2017 | A1 |
| 20170267923 | Li | Sep 2017 | A1 |
| 20170271611 | Li | Sep 2017 | A1 |
| 20170301871 | Li | Oct 2017 | A1 |
| 20170305881 | Li | Oct 2017 | A1 |
| 20170309943 | Angell | Oct 2017 | A1 |
| 20170331056 | Li | Nov 2017 | A1 |
| 20170342098 | Li | Nov 2017 | A1 |
| 20170373260 | Li | Dec 2017 | A1 |
| 20180006246 | Li | Jan 2018 | A1 |
| 20180013096 | Hamada | Jan 2018 | A1 |
| 20180052366 | Hao | Feb 2018 | A1 |
| 20180053904 | Li | Feb 2018 | A1 |
| 20180130960 | Li | May 2018 | A1 |
| 20180138428 | Li | May 2018 | A1 |
| 20180148464 | Li | May 2018 | A1 |
| 20180159051 | Li | Jun 2018 | A1 |
| 20180166655 | Li | Jun 2018 | A1 |
| 20180175329 | Li | Jun 2018 | A1 |
| 20180194790 | Li | Jul 2018 | A1 |
| 20180219161 | Li | Aug 2018 | A1 |
| 20180226592 | Li | Aug 2018 | A1 |
| 20180226593 | Li | Aug 2018 | A1 |
| 20180277777 | Li | Sep 2018 | A1 |
| 20180301641 | Li | Oct 2018 | A1 |
| 20180312750 | Li | Nov 2018 | A1 |
| 20180331307 | Li | Nov 2018 | A1 |
| 20180334459 | Li | Nov 2018 | A1 |
| 20180337345 | Li | Nov 2018 | A1 |
| 20180337349 | Li | Nov 2018 | A1 |
| 20180337350 | Li | Nov 2018 | A1 |
| 20180353771 | Kim | Dec 2018 | A1 |
| 20190013485 | Li | Jan 2019 | A1 |
| 20190058137 | Ko | Feb 2019 | A1 |
| 20190067602 | Li | Feb 2019 | A1 |
| 20190109288 | Li | Apr 2019 | A1 |
| 20190119312 | Chen | Apr 2019 | A1 |
| 20190157352 | Li | May 2019 | A1 |
| 20190194536 | Li | Jun 2019 | A1 |
| 20190259963 | Li | Aug 2019 | A1 |
| 20190276485 | Li | Sep 2019 | A1 |
| 20190312217 | Li | Oct 2019 | A1 |
| 20190367546 | Li | Dec 2019 | A1 |
| 20190389893 | Li | Dec 2019 | A1 |
| 20200006678 | Li | Jan 2020 | A1 |
| 20200071330 | Li | Mar 2020 | A1 |
| 20200075868 | Li | Mar 2020 | A1 |
| 20200119288 | Li | Apr 2020 | A1 |
| 20200119289 | Lin | Apr 2020 | A1 |
| 20200140471 | Chen | May 2020 | A1 |
| 20200152891 | Li | May 2020 | A1 |
| 20200239505 | Li | Jul 2020 | A1 |
| 20200243776 | Li | Jul 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 1680366 | Oct 2005 | CN |
| 1777663 | May 2006 | CN |
| 1894267 | Jan 2007 | CN |
| 1894269 | Jan 2007 | CN |
| 101142223 | Mar 2008 | CN |
| 101667626 | Mar 2010 | CN |
| 102449108 | May 2012 | CN |
| 102892860 | Jan 2013 | CN |
| 102971396 | Mar 2013 | CN |
| 103102372 | May 2013 | CN |
| 104232076 | Dec 2014 | CN |
| 104377231 | Feb 2015 | CN |
| 104576934 | Apr 2015 | CN |
| 104693243 | Jun 2015 | CN |
| 105367605 | Mar 2016 | CN |
| 105418591 | Mar 2016 | CN |
| 106783922 | May 2017 | CN |
| 1617493 | Jan 2006 | EP |
| 1808052 | Jul 2007 | EP |
| 1874893 | Jan 2008 | EP |
| 1874894 | Jan 2008 | EP |
| 1919928 | May 2008 | EP |
| 1968131 | Sep 2008 | EP |
| 2020694 | Feb 2009 | EP |
| 2036907 | Mar 2009 | EP |
| 2096690 | Sep 2009 | EP |
| 2112213 | Oct 2009 | EP |
| 2417217 | Feb 2012 | EP |
| 2684932 | Jan 2014 | EP |
| 2711999 | Mar 2014 | EP |
| 3032293 | Jun 2016 | EP |
| 2002010505 | Jan 2002 | JP |
| 2002105055 | Apr 2002 | JP |
| 2003342284 | Dec 2003 | JP |
| 2005031073 | Feb 2005 | JP |
| 2005267557 | Sep 2005 | JP |
| 2005310733 | Nov 2005 | JP |
| 2006047240 | Feb 2006 | JP |
| 2006232784 | Sep 2006 | JP |
| 2006242080 | Sep 2006 | JP |
| 2006242081 | Sep 2006 | JP |
| 2006256999 | Sep 2006 | JP |
| 2006257238 | Sep 2006 | JP |
| 2006261623 | Sep 2006 | JP |
| 2006290988 | Oct 2006 | JP |
| 2006313796 | Nov 2006 | JP |
| 2006332622 | Dec 2006 | JP |
| 2006351638 | Dec 2006 | JP |
| 2007019462 | Jan 2007 | JP |
| 2007031678 | Feb 2007 | JP |
| 2007042875 | Feb 2007 | JP |
| 2007051243 | Mar 2007 | JP |
| 2007053132 | Mar 2007 | JP |
| 2007066581 | Mar 2007 | JP |
| 2007073620 | Mar 2007 | JP |
| 2007073845 | Mar 2007 | JP |
| 2007073900 | Mar 2007 | JP |
| 2007080593 | Mar 2007 | JP |
| 2007080677 | Mar 2007 | JP |
| 2007088105 | Apr 2007 | JP |
| 2007088164 | Apr 2007 | JP |
| 2007096259 | Apr 2007 | JP |
| 2007099765 | Apr 2007 | JP |
| 2007110067 | Apr 2007 | JP |
| 2007110102 | Apr 2007 | JP |
| 2007519614 | Jul 2007 | JP |
| 2007258550 | Oct 2007 | JP |
| 2007324309 | Dec 2007 | JP |
| 2008010353 | Jan 2008 | JP |
| 2008091860 | Apr 2008 | JP |
| 2008103535 | May 2008 | JP |
| 2008108617 | May 2008 | JP |
| 2008109085 | May 2008 | JP |
| 2008109103 | May 2008 | JP |
| 2008116343 | May 2008 | JP |
| 2008117545 | May 2008 | JP |
| 2008160087 | Jul 2008 | JP |
| 2008198801 | Aug 2008 | JP |
| 2008270729 | Nov 2008 | JP |
| 2008270736 | Nov 2008 | JP |
| 2008310220 | Dec 2008 | JP |
| 2009016184 | Jan 2009 | JP |
| 2009016579 | Jan 2009 | JP |
| 2009032977 | Feb 2009 | JP |
| 2009032988 | Feb 2009 | JP |
| 2009059997 | Mar 2009 | JP |
| 2009076509 | Apr 2009 | JP |
| 2009161524 | Jul 2009 | JP |
| 2009247171 | Oct 2009 | JP |
| 2009266943 | Nov 2009 | JP |
| 2009267171 | Nov 2009 | JP |
| 2009267244 | Nov 2009 | JP |
| 2009272339 | Nov 2009 | JP |
| 2009283891 | Dec 2009 | JP |
| 2010135689 | Jun 2010 | JP |
| 2010171205 | Aug 2010 | JP |
| 2011071452 | Apr 2011 | JP |
| 2012079895 | Apr 2012 | JP |
| 2012079898 | Apr 2012 | JP |
| 5604505 | Sep 2012 | JP |
| 2012522843 | Sep 2012 | JP |
| 2012207231 | Oct 2012 | JP |
| 2012222255 | Nov 2012 | JP |
| 2012231135 | Nov 2012 | JP |
| 2013023500 | Feb 2013 | JP |
| 2013048256 | Mar 2013 | JP |
| 2013053149 | Mar 2013 | JP |
| 2013525436 | Jun 2013 | JP |
| 2014019701 | Feb 2014 | JP |
| 2014058504 | Apr 2014 | JP |
| 2014520096 | Aug 2014 | JP |
| 2012709899 | Nov 2014 | JP |
| 2014221807 | Nov 2014 | JP |
| 2014239225 | Dec 2014 | JP |
| 2015081257 | Apr 2015 | JP |
| 20060011537 | Feb 2006 | KR |
| 20060015371 | Feb 2006 | KR |
| 20060115371 | Nov 2006 | KR |
| 20070061830 | Jun 2007 | KR |
| 20070112465 | Nov 2007 | KR |
| 20130043460 | Apr 2013 | KR |
| 101338250 | Dec 2013 | KR |
| 20140052501 | May 2014 | KR |
| 200701835 | Jan 2007 | TW |
| 201249851 | Dec 2012 | TW |
| 201307365 | Feb 2013 | TW |
| 201710277 | Mar 2017 | TW |
| 0070655 | Nov 2000 | WO |
| 2000070655 | Nov 2000 | WO |
| 2004003108 | Jan 2004 | WO |
| 2004070655 | Aug 2004 | WO |
| 2004085450 | Oct 2004 | WO |
| 2004108857 | Dec 2004 | WO |
| 2005042444 | May 2005 | WO |
| 2005042550 | May 2005 | WO |
| 2005113704 | Dec 2005 | WO |
| 2006033440 | Mar 2006 | WO |
| 2006067074 | Jun 2006 | WO |
| 2006081780 | Aug 2006 | WO |
| 2006098505 | Sep 2006 | WO |
| 2006113106 | Oct 2006 | WO |
| 2006115299 | Nov 2006 | WO |
| 2006115301 | Nov 2006 | WO |
| 2007034985 | Mar 2007 | WO |
| 2007069498 | Jun 2007 | WO |
| 2008054578 | May 2008 | WO |
| 2008066192 | Jun 2008 | WO |
| 2008066195 | Jun 2008 | WO |
| 2008066196 | Jun 2008 | WO |
| 2008101842 | Aug 2008 | WO |
| 2008117889 | Oct 2008 | WO |
| 2008123540 | Oct 2008 | WO |
| 2008131932 | Nov 2008 | WO |
| 2009003455 | Jan 2009 | WO |
| 2009008277 | Jan 2009 | WO |
| 2009011327 | Jan 2009 | WO |
| 2009017211 | Feb 2009 | WO |
| 2009023667 | Feb 2009 | WO |
| 2009086209 | Jul 2009 | WO |
| 2009111299 | Sep 2009 | WO |
| 2010007098 | Jan 2010 | WO |
| 2010056669 | May 2010 | WO |
| 2010093176 | Aug 2010 | WO |
| 2010105141 | Sep 2010 | WO |
| 2010118026 | Oct 2010 | WO |
| 2011064335 | Jun 2011 | WO |
| 2011070989 | Jun 2011 | WO |
| 2011089163 | Jul 2011 | WO |
| 2011137429 | Nov 2011 | WO |
| 2011137431 | Nov 2011 | WO |
| 2012074909 | Jun 2012 | WO |
| 2012112853 | Aug 2012 | WO |
| 2012116231 | Aug 2012 | WO |
| 2012142387 | Oct 2012 | WO |
| 2012162488 | Nov 2012 | WO |
| 2012163471 | Dec 2012 | WO |
| 2013130483 | Sep 2013 | WO |
| 2014009310 | Jan 2014 | WO |
| 2014016611 | Jan 2014 | WO |
| 2014031977 | Feb 2014 | WO |
| 2014047616 | Mar 2014 | WO |
| 2014109814 | Jul 2014 | WO |
| 2014208271 | Dec 2014 | WO |
| 2015027060 | Feb 2015 | WO |
| 2015131158 | Sep 2015 | WO |
| 2016025921 | Feb 2016 | WO |
| 2016029137 | Feb 2016 | WO |
| 2016029186 | Feb 2016 | WO |
| 2016197019 | Dec 2016 | WO |
| 2017117935 | Jul 2017 | WO |
| 2018071697 | Apr 2018 | WO |
| 2018140765 | Aug 2018 | WO |
| 2019079505 | Apr 2019 | WO |
| 2019079508 | Apr 2019 | WO |
| 2019079509 | Apr 2019 | WO |
| 2019236541 | Dec 2019 | WO |
| 2020018476 | Jan 2020 | WO |
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| Number | Date | Country | |
|---|---|---|---|
| 20200243776 A1 | Jul 2020 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62796704 | Jan 2019 | US |
