Patent Grant
12077550
The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.
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.
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. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
The present disclosure provides transition metal compounds comprising polyfluorinated ligands that exhibit enhanced phosphorescent quantum yield when used in OLEDs, especially in red to near IR emission region and are useful as emitter materials in OLED applications.
In one aspect, the present disclosure provides a compound comprising a first ligand LA of Formula I
wherein two adjacent X1 to X4 are C, at least one of the remaining X1 to X4 is N, and the other of the remaining X1 to X4 is N or CR; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; the two adjacent X1 to X4 that are C are fused to a cyclic ring structure selected from the group consisting of:
wherein the asterisks indicate the two adjacent X1 to X4 that are C; Y is O or S; Z1 to Z16 are each independently C or N; RA, RB, RC, RCC, and RD each independently represent zero, mono, or up to a maximum allowed substitution to its associated ring; each of R, RA, RB, RC, RCC, and RD is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; at least two substituents of RB are selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; at least one substituent of RC or RD is selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof. Formula III-B is fused to Formula I only through X1 and X2 together with X4 being N and with X3 being CR, wherein R is an alkyl, cycloalkyl, or silyl; the ligand LA is coordinated to a metal M through the two indicated dash lines; the metal M can be coordinated to other ligands; the ligand LA can be linked with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and two substituents can be joined or fused to form a ring.
In another aspect, the present disclosure provides a formulation of a compound comprising a first ligand LA of Formula I as described herein.
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound comprising a first ligand LA of Formula I as described herein.
In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising a compound comprising a first ligand LA of Formula I as described herein.
Unless otherwise specified, the below terms used herein are defined as follows:
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
The term “acyl” refers to a substituted carbonyl radical (C(O)—Rs).
The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—Rs or —C(O)—O—Rs) radical.
The term “ether” refers to an —ORs radical.
The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SRs radical.
The term “sulfinyl” refers to a —S(O)—Rs radical.
The term “sulfonyl” refers to a —SO2—Rs radical.
The term “phosphino” refers to a —P(Rs)3 radical, wherein each Rs can be same or different.
The term “silyl” refers to a —Si(Rs)3 radical, wherein each Rs can be same or different.
The term “boryl” refers to a —B(Rs)2 radical or its Lewis adduct —B(Rs)3 radical, wherein Rs can be same or different.
In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred Rs is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted.
The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.
The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.
The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.
The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.
In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.
In yet other instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution). Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents zero or no substitution, R1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.
In one aspect, the present disclosure provides a compound comprising a first ligand LA of Formula I
wherein: two adjacent X1 to X4 are C, at least one of the remaining X1 to X4 is N, and the other of the remaining X1 to X4 is N or CR; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; the two adjacent X1 to X4 that are C are fused to a cyclic ring structure selected from the group consisting of:
wherein the asterisks indicate the two adjacent X1 to X4 that are C; Y is O or S; Z1 to Z16 are each independently C or N; RA, RB, RC, RCC, and RD each independently represents zero, mono, or up to a maximum allowed substitution to its associated ring; each of R, RA, RB, RC, RCC, and RD is independently a hydrogen or a substituent selected from the group consisting of the general substituents as described herein; at least two substituents of RB are selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; at least one substituent of RC or RD is selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; the ligand LA is coordinated to a metal M through the two indicated dash lines; the metal M can be coordinated to other ligands; the ligand LA can be linked with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and two substituents can be joined or fused to form a ring.
In some embodiments, each of R, RA, RB, RC, RCC, and RD can be independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents described herein.
In some embodiments, the maximum number of N within a ring can be 2.
In some embodiments, M can be selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au.
In some embodiments, R can be selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partially or fully fluorinated variants thereof, and combination thereof.
In some embodiments, Z1 to Z16 can each be independently C. In some embodiments, at least one of Z1 to Z16 in each of the structures Formula II, Formula III, Formula III-A, Formula III-B, Formula IV, and Formula IV-A is N. In some embodiments, exactly one of Z1 to Z16 in each respective structure associated with is N, the remaining Z1 to Z16 is C.
In some embodiments, Y is O. In some embodiments, Y is S.
In some embodiments, ring A can be a 6-membered aromatic ring.
In some embodiments, two adjacent RA substituents can be joined together to form a fused 5-membered or 6-membered aromatic ring.
In some embodiments, at least one RA can be selected from the group consisting of alkyl and cycloalkyl.
In some embodiments, when Formula II is present, each Z1 to Z4 can be C and can be substituted by F.
In some embodiments, when Formula III or III-A is present, each Z5 to Z10, or Z6 to Z11, can be C and may be substituted by F.
In some embodiments, when Formula IV or IV-A is present, each Z12 to Z15 can be C and can be substituted by F.
In some embodiments, at least one RB, RC, or RD can be present and can be F.
In some embodiments, at least one RB, RC, or RD can be present and can be CF3.
In some embodiments, M can be further coordinated to a substituted or unsubstituted acetylacetonate ligand.
In some embodiments, the first ligand LA can be selected from the group consisting of LIST 1 shown below:
wherein RE is a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.
In some embodiments, the first ligand LA can have a structure of Formula V
wherein X is C or N; and RA and RC are each independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring; each of RA and RC is independently a hydrogen or a substituent selected from the group consisting of the general substituents described herein; and ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring.
In some embodiments, the first ligand LA can be selected from the group consisting of wherein i is an integer from 1 to 2000, and m is an integer from 1 to 27, wherein LAi-m have the structures LAi-1 through LAi-27 as shown in LIST 2 provided below:
wherein for each i, RE and G in Formula 1 to Formula 27, are defined in LIST 3 shown below:
wherein R1 to R50 have the following structures:
wherein G1 to G40 have the following structures:
In some embodiments, the first ligand LA can have a structure of Formula VI
wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; wherein R is a substituted or unsubstituted alkyl or cycloalkyl group; Z5 to Z10 are each independently C or N; RA, and RCC each independently represents zero, mono, or up to a maximum allowed substitution to its associated ring; each of RA and RCC is independently a hydrogen or a substituent selected from the group consisting of the general substituents described herein; the ligand LA is coordinated to a metal M through the two indicated dash lines; the metal M can be coordinated to other ligands; the ligand LA can be linked with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and two substituents can be joined or fused to form a ring.
In some of the above embodiments, each of RA and RCC can be independently a hydrogen or a substituent selected from the group consisting of the general substituents described herein. In some of the above embodiments, R can be an alkyl or cycloalkyl. In some of the above embodiments, R can be methyl or isopropyl. In some of the above embodiments, ring A can be a 6-membered aromatic ring. In some of the above embodiments, ring A can be benzene, pyridine, pyrimidine, pyrazine, or pyridazine. In some of the above embodiments, one of Z5 to Z10 may be N. In some of the above embodiments, one of Z5 and Z10 can be N. In some of the above embodiments, one of Z6 to Z9 can be N. In some of the above embodiments, two of Z6 to Z9 can be N. In some of the above embodiments, each of Z5 to Z10 can be independently C. In some of the above embodiments, two adjacent RA substituents can be joined to form a fused ring. In some of the above embodiments, two adjacent RA substituents can be joined to form a 6-membered aromatic ring. In some of the above embodiments, one of RA substituents can be D, F, alkyl, cycloalkyl, aryl, heteroaryl, or combinations thereof.
In some of the above embodiments, the first ligand LA can be selected from the group consisting of:
wherein ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; wherein R is a substituted or unsubstituted alkyl or cycloalkyl group; Z5 to Z10 are each independently C or N; RA, and RCC each independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring; each of RA and RCC is independently a hydrogen or a substituent selected from the group consisting of the general substituents described herein; the ligand LA is coordinated to a metal M through the two indicated dash lines; the metal M can be coordinated to other ligands; the ligand LA can be linked with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and two substituents can be joined or fused to form a ring.
In some of the above embodiments, the first ligand LA can selected from the group consisting of LAap-n, wherein p is an integer from 1 to 1280, and n is an integer from 1 to 8, wherein LAap-n have the structures LAap-1 through LAap-8 in LIST 2A shown below:
wherein for each p, RE and GE are defined in LIST 3A provided below:
wherein RE1 to RE32 have the following structures:
wherein GE1 to GE40 have the following structures:
In some embodiments, the compound can have a formula of M(LA)x(LB)y(LC)z, wherein LB and LC are each a bidentate ligand; and wherein x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.
In some embodiments, the compound can have a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)2(LC), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other.
In some embodiments, the compound can have a formula of Pt(LA)(LB); and wherein LA and LB can be same or different.
In some embodiments, LA and LB can be connected to form a tetradentate ligand.
In any of the embodiments of the compounds disclosed herein that include ligands LB or LC, LB and LC can each be independently selected from the group consisting of LIST 4 shown below:
In any of the embodiments of the compounds disclosed herein that include ligands LB or LC, LB and LC can each be independently selected from the group consisting of LIST 5 shown below:
wherein: Ra′, Rb′, and Re′ each independently represents zero, mono, or up to a maximum number of allowed substitutions to its associated ring; each of Ra1, Rb1, Rc1, RN, Ra′, Rb′, and Rc′ is independently hydrogen or a substituent selected from the group consisting of the general substituents described herein; and two adjacent substituents of Ra′, Rb′, and Re′ can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments, the compound can have the formula Ir(LA)3, the formula Ir(LA)(LBk)2, or the formula Ir(LA)2(LCj); wherein LA can be any one of the embodiments of the LA ligands defined herein, wherein k is an integer from 1 to 263 and LBk have the structures as shown in LIST 6 below:
and LCj, can be selected from the group consisting of LCj-I and LCj-II, wherein j is an integer from 1 to 768, wherein LCj-I has a structure based on
and LCj-II has a structure based on
and wherein R1′ and R2′ for each LCj-I and LCj-II are defined as shown in LIST 7 below:
wherein RD1 to RD192 have the following structures:
In some embodiments of the compound having the formula Ir(LA)3, Ir(LA)(LB)2, or the formula Ir(LA)2(LC); LA can be selected from the group consisting of LAi-I to LAi-XXVIII, wherein i is an integer from 1 to 2000, as defined herein; LB can be independently selected from the group consisting of LBk defined herein, where k is an integer from 1 to 263; and LC can be independently selected from the group consisting of LCj-I and LCj-II defined herein, where j is an integer from 1 to 768.
In some embodiments of the compound having the formula Ir(LAa)3, the formula Ir(LAa)(LB)2, or the formula Ir(LAa)2(LC); LAa can be independently selected from the group consisting of LAap-I, to LAap-VIII, wherein p is an integer from 1 to 1280, as defined herein; LB can be independently selected from the group consisting of LBk defined herein, where k is an integer from 1 to 263; and LC can be independently selected from the group consisting of LCj-I and LCj-II defined herein, where j is an integer from 1 to 768.
In some of the above embodiments, LB can be selected from the group consisting of the structures: LB1, LB2, LB18, LB28, LB38, LB108, LB118, LB122, LB124, LB126, LB128, LB130, LB32, LB134, LB136, LB138, LB140, LB142, LB144, LB156, LB58, LB160, LB162, LB164, LB168, LB172, LB175, LB204, LB206, LB214, LB216, LB218, LB220, LB222, LB231, LB233, LB235, LB237, LB240, LB242, LB244, LB246, LB248, LB250, LB252, LB254, LB256, LB258, LB260, LB262, and LB263.
In some of the above embodiments, LB can be selected from the group consisting of LB1, LB2, LB18, LB28, LB38, LB108, LB118, LB122, LB124, LB126, LB128, LB132, LB136, LB138, LB142, LB156, LB162, LB204, LB206, LB214, LB216, LB218, LB220, LB231, LB233, and LB237.
In some of the above embodiments, LC can be selected from the group consisting of only those LCj-I and LCj-II whose corresponding R1 and R2 are defined to be selected from the following structures: RD1, RD3, RD4, RD5, RD9, RD10, RD17, RD18, RD20, RD22, RD37, RD40, RD41, RD42, RD43, RD48, RD49, RD50, RD54, RD55, RD58, RD59, RD78, RD79, RD81, RD87, RD88, RD89, RD93, RD116, RD117, RD118, RD119, RD120, RD133, RD134, RD135, RD136, RD143, RD144, RD145, RD146, RD147, RD149, RD151, RD154, RD155, RD161, RD175, and RD190.
In some of the above embodiments, LC can be selected from the group consisting of only those LCj-I and LCj-II whose corresponding R1 and R2 are defined to be selected from the following structures: RD1, RD3, RD4, RD5, RD9, RD17, RD22, RD43, RD50, RD78, RD116, RD118, RD133, RD134, RD135, RD136, RD143, RD144, RD145, RD146, RD149, RD151, RD154, RD155, and RD190.
In some of the above embodiments, LC can be selected from the group consisting of LIST 11 shown below:
In some embodiments, the compound can be selected from the group consisting of Compound-A-1-1 to Compound-A-2000-27 with the general numbering scheme Compound-A-i-m corresponding to the formula Ir(LAi-m)3; Compound-B-1-1-1 to Compound-B-2000-27-263 with the general numbering scheme Compound-B-i-m-k corresponding to the formula Ir(LAi-m)(LBk)2; Compound-C-1-1-1-I to Compound-C-2000-27-768-I with the general numbering scheme Compound-C-i-m-j-I corresponding to the formula Ir(LAi-m)2(LCj-I); Compound-C-1-1-1-II to Compound-C-2000-27-768-II with the general numbering scheme Compound-C-i-m-j-II corresponding to the formula Ir(LAi-m)2(LCj-II); wherein: i is an integer from 1 to 2000; m is an integer from 1 to 27; k is an integer from 1 to 263; j is an integer from 1 to 768; and wherein LAi-m, LBk, LCj-I, and LCj-II have the structures as described herein.
In some embodiments, the compound can be selected from the group consisting of Compound-Aa-1-1 to Compound-Aa-1280-8 with the general numbering scheme Compound-Aa-p-n corresponding to the formula Ir(LAap-n)3; Compound-Ba-1-1-1 to Compound-Ba-1280-8 with the general numbering scheme Compound-Ba-p-n-k corresponding to the formula Ir(LAap-n)(LBk)2; Compound-Ca-1-1-14 to Compound-Ca-1280-8-768-I with the general numbering scheme Compound-Ca-p-n-j-I corresponding to the formula Ir(LAap-n(LCj-I); Compound-Ca-1-1-1-II to Compound-Ca-1280-8-768-II with the general numbering scheme Compound-Ca-p-n-j-II corresponding to each formula Ir(LAap-n)2(LCj-II); wherein: p is an integer from 1 to 1280; n is an integer from 1 to 8; k is an integer from 1 to 263; j is an integer from 1 to 768; and wherein LAap-n, LBk, LCj-I, and LCj-II have the structures as described herein.
In some embodiments, the compound can be selected from the group consisting of the following LIST 12A:
In some embodiments, the compound can have Formula VII
wherein:
M is Pd or Pt; rings A, B, and C are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring; M1 and M2 are each independently C or N; A1 to A3 are each independently C or N; Y1 and Y2 are each independently selected from the group consisting of a direct bond, O, and S; L1 to L3 are each independently selected from the group consisting of a direct bond, O, S, CR′R″, SiR′R″, BR′, and NR′; m, n, and o are each independently 0 or 1; m+n+o=2 or 3; RB and RC each independently represents zero, mono, or up to a maximum number of allowed substitutions to its associated ring; RB, RC, R′, and R″ are each independently a hydrogen or a substituent selected from the group consisting of the general substituents as described herein; and any two substituents can be joined or fused together to form a ring.
In some embodiments of the compound of Formula VII, ring B and ring C can both be 6-membered aromatic rings. In some embodiments, ring B can be a 5-membered aromatic ring and ring C can be a 6-membered aromatic ring. In some embodiments, L2 can be a direct bond or NR′. In some embodiments, wherein L3 can be O or NR′. In some embodiments, wherein m can be 0. In some embodiments, L′ can be SiRR′.
In some embodiments, M1 can be N and M2 can be C. In some embodiments, M1 can be C and M2 can be N.
In some embodiments, A1, A2, and A3 can each be C. In some embodiments, A1 can be N, A2 can be C, and A3 can be C. In some embodiments, A1 can be N, A2 can be N, and A3 can be C.
In some embodiments, Y1 and Y2 can be direct bonds.
In some embodiments, M can be Pt.
In some embodiments of the compound of Formula VII, the compound can be selected from the group consisting of LIST 12 shown below:
wherein RX is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, the compound can be selected from the group consisting of Compound DL and Compound TK, wherein L is an integer defined by L=11((7500(z−1)+y)−1)+x, K is an integer defined by K=11((7500(y2−1)+y1)−1)+x, wherein y, y1, and y2 are independently an integer from 1 to 7500, x is an integer from 1 to 11, and z is an integer from 1 to 560, wherein each Compound DL has the formula Pt(LDy)(LLx)(LEz), and each Compound TK has the formula Pt(LDy1)(LLx)(LDy2), wherein LDy, LDy1, and LDy2 have the following structures in LIST 13:
wherein R1 to R50 have the following structures:
wherein G1 to G10 have the following structures:
wherein LL1 to LL11 have the structures defined in LIST 14 below:
wherein LE1 to LE560 have the structures in LIST 15 shown below:
and wherein RE1 to RE20 have the following structures:
In another aspect, the present disclosure also provides an OLED device comprising an organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the organic layer can comprise a compound comprising a first ligand LA of
wherein: two adjacent X1 to X4 are C, at least one of the remaining X1 to X4 is N, and the other of the remaining X1 to X4 is N or CR; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; the two adjacent X1 to X4 that are C are fused to a cyclic ring structure selected from the group consisting of:
wherein: the asterisks indicate the two adjacent X1 to X4 that are C; Y is O or S; Z1 to Z16 are each independently C or N; RA, RB, RC, RCC, and RD each independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring; each of R, RA, RB, RC, RCC, and RD is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; at least two substituents of RB are selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; at least one substituent of RC or RD is selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; Formula III-B is fused to Formula I only through X1 and X2 together with X4 being N and with X3 being CR wherein R is an alkyl, cycloalkyl, or silyl; the ligand LA is coordinated to a metal M through the two indicated dash lines; the metal M can be coordinated to other ligands; the ligand LA can be linked with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and two substituents can be joined or fused to form a ring.
In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is 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≡CCnH2n+1, Ar1, Ar1—Ar2, CnH2n—Ar1, or no substitution, wherein n is from 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocathazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
In some embodiments, the host may be selected from the group consisting of:
and combinations thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.
In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the emissive region can comprise a compound comprising a first ligand LA of
wherein two adjacent X1 to X4 are C, at least one of the remaining X1 to X4 is N, and the other of the remaining X1 to X4 is N or CR; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; the two adjacent X1 to X4 that are C are fused to a cyclic ring structure selected from the group consisting of:
wherein: the asterisks indicate the two adjacent X1 to X4 that are C; Y is O or S; Z1 to Z16 are each independently C or N; RA, RB, RC, RCC, and RD each independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring; each of R, RA, RB, RC, RCC, and RD is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; at least two substituents of RB are selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; at least one substituent of RC or RD is selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; Formula IIIB is fused to Formula I only through X1 and X2 together with X4 being N and with X3 being CR wherein R is an alkyl, cycloalkyl, or silyl; the ligand LA is coordinated to a metal M through the two indicated dash lines; the metal M can be coordinated to other ligands; the ligand LA can be linked with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and two substituents can be joined or fused to form a ring.
In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the consumer product comprises an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise a compound comprising a first ligand LA of
wherein: two adjacent X1 to X4 are C, at least one of the remaining X1 to X4 is N, and the other of the remaining X1—X4 is N or CR; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; the two adjacent X1-X4 that are C are fused to a cyclic ring structure selected from the group consisting of:
wherein: the asterisks indicate the two adjacent X1 to X4 that are C; Y is O or S; Z1 to Z16 are each independently C or N; RA, RB, RC, RCC, and RD each independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring; each of R, RA, RB, RC, RCC, and RD is independently a hydrogen or a substituent selected from the group consisting of the general substituents as described above; at least two substituents of RB are selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; at least one substituent of RC or RD is selected from the group consisting of fluorine, an alkyl containing one or more fluorine, cycloalkyl containing one or more fluorine, fully fluorinated alkyl, and fully fluorinated cycloalkyl, and combinations thereof; Formula IIIB is fused to Formula I only through X1 and X2 together with X4 being N and with X3 being CR wherein R is an alkyl, cycloalkyl, or silyl; the ligand LA is coordinated to a metal M through the two indicated dash lines; the metal M can be coordinated to other ligands; the ligand LA can be linked with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and two substituents can be joined or fused to form a ring.
In some embodiments, the consumer product can be one 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, a light therapy device, and a sign.
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.
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.
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”), 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.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
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 some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
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, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.
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) Conductivity Dopants:
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.
b) HIL/HTL:
A hole injecting/transporting material to be used in the present disclosure 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 indolocathazole 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 phosphoric 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.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101-Y102)) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
c) EBL:
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.
d) Hosts:
The light emitting layer of the organic EL device of the present disclosure 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.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, O, or S.
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,
e) Additional Emitters:
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.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
f) HBL:
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.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L101 is another ligand, k′ is an integer from 1 to 3.
g) ETL:
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 one aspect, compound used in ETL contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
h) Charge Generation Layer (CGL)
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.
Synthesis of Materials
Selectfluor (1.58 g, 4.45 mmol/10 min.) was added to a solution of 3-amino-2-naphthoic acid (5 g, 26.7 mmol) in DMF (267 mL), portion-wise, over 1 hour at 0° C. The reaction mixture was gradually warmed up to room temperature and stirred for 16 hrs. The reaction was quenched with H2O (200 mL) and extracted with EtOAc. The combined organic layers were washed with brine (150 mL×3) and dried over MgSO4, filtered, and concentrated in vacuo. The residue was treated with water (125 mL) and stirred for 30 min. The solid was collected by filtration, washed with water (75 mL) and dried on lyophilizer. The product 3-amino-4-fluoro-2-naphthoic acid (3.10 g, 57% yield) recrystallized as solid from MeCN.
A mixture of 3-amino-4-fluoro-2-naphthoic acid (18.0 g, 88 mmol) in formamide (160 ml, 4014 mmol) was heated to get a clear solution. Then, formamide acetate (36.6 g, 352 mmol) was added to the reaction mixture and heated to 160° C. for 22 hours. The reaction mixture was cooled to room temperature and water (400 mL) was added. The reaction mixture was filtered and rinsed with water (50 mL×3) and MeCN (50 mL×2). The residue was suspended in MeCN (100 mL) for 5 hours. The solid was collected by filter and dried on lyophilizer to give 10-fluorobenzo[g]quinazolin-4(1H)-one as an off-white solid (18.0 g, 96% yield).
A 250 mL round-bottom-flask was charged with 10-fluorobenzo[g]quinazolin-4(1H)-one (2.2 g, 10.3 mmol) and PyBroP (14.4 g, 30.8 mmol). The reaction system was vacuumed and backfilled with argon three times, followed by sequential addition of dioxane (44 mL) and triethylamine (8.59 mL, 61.6 mmol). The mixture was heated under argon atmosphere at 70° C. for about 1 hour until the phosphonium intermediate formation was complete on HPLC. At this point, K2CO3 (7.1 g, 51.4 mmol) was added, followed by addition of 2-(4-(tert-butyl)naphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.4 g, 20.5 mmol). The resulting mixture was purged with argon for 30 minutes before adding Pd(PPh3)2Cl2 (0.72 g, 1.03 mmol). The mixture was heated at 100° C. for 1 hour. Then argon-deaerated water (22 mL) was added. The reaction mixture was heated at 100° C. for additional 2 hours. The reaction mixture was cooled to room temperature, then diluted with water (50 mL) and EtOAc (200 mL). The layers were separated. The aqueous layer was extracted with EtOAc (200 mL×2 times). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The residue was loaded on SiO2 and chromatographed on a silica gel column with 0-20% EtOAc/Hex to give 4-(4-(tert-butyl)naphthalen-2-yl)-10-fluorobenzo[g]quinazoline as a bright yellow solid (1.3 g, 33% yield).
IrCl3 (0.98 g) was added to a solution of 4-(4-(tert-butyl)naphthalen-2-yl)-10-fluorobenzo[g]quinazoline (2.012 g, 5.29 mmol). The mixture was degassed by N2 for 20 minutes and then heated up to 130° C. for 16 hours. After the reaction mixture was cooled to room temperature, it was used directly in the next step reaction.
3,7-diethylnonane-4,6-dione (1.63 g, 11.8 mmol), potassium carbonate (2.5 g, 11.8 mmol), and 2-ethoxyethanol (60 mL) were added to the reaction mixture from the previous step. The mixture was degassed by N2 and stirred at room temperature for 15 hours. After the solvent was removed, the residue was purified on silica gel column to give product 0.8 g (29%).
A solution of 3-amino-2-naphthoic acid (20 g, 107 mmol) in DMF (240 mL) was cooled to 0° C., followed by addition of NBS (19.02 g, 107 mmol) in three portions (6.34 g every 15 min). The reaction mixture was allowed to warm to room temperature and stirred for 2 hours. The reaction was quenched by addition of water (720 mL) over 20 mins. The resulting mixture was stirred at room temperature for 30 minutes. The solid was collected by filtration and washed with water (100 mL*2 times) and dried to give a yellow solid (28.1 g, 99% yield).
A mixture of 3-amino-4-bromo-2-naphthoic acid (27 g, 101 mmol) and formamidine acetate (26.4 g, 254 mmol) in formamide (202 mL) was heated at 160° C. for 4 hours. The reaction mixture was cooled to room temperature and poured into water (500 mL). The solid was collected by filtration and washed with water (2*200 mL). The solid was dried on lyophilizer to give 10-bromobenzo[g]quinazolin-4(1H)-one as a light brown crystal (24.8 g, 89% yield).
A 250 mL round-bottom-flask was flushed with argon, and sequentially charged with 10-bromobenzo[g]quinazolin-4(1H)-one (5 g, 18.2 mmol) and POCl3 (100 mL). The reaction mixture was stirred at 100° C. for 1-2 days. The excessive POCl3 was removed by careful distillation under reduced pressure. The residue was cooled to 0° C. Sodium methoxide solution (80 mL, 2M in MeOH, 160 mmol) was slowly added via an additional funnel. The resulting mixture was allowed to warm to room temperature and stirred for 1-2 hrs. The reaction mixture was concentrated in vacuo. The residue was suspended in DCM (1 L) and water (500 mL). The layers were separated and the aqueous layer was extracted with DCM (500 ml*2 times). The combined organic layers were concentrated in vacuo. The residue was suspended in DCM (500 ml) and the solid was removed by filtration. The filtrate was concentrated in vauco. The residue was triturated with MeCN (20 ml) to give 10-bromo-4-methoxybenzo[g]quinazoline as a yellow solid (2.78 g, 53% yield).
A 100 mL round-bottom-flask was flushed with argon, and sequentially charged with 10-bromo-4-methoxybenzo[g]quinazoline (1.53 g, 5.29 mmol), CuI (1.21 g, 6.35 mmol) and DMF (25 mL). Methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (1.35 mL, 10.58 mmoL) was then added and the reaction mixture was heated at 120° C. for 2 hours. More methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (0.2 mL, 1.57 mmoL) was added and the stirring was continued at 120° C. for 1 hour. The reaction mixture was cooled to room temperature. The solid was removed by filtration and the filter cake was washed with EtOAc (100 mL). The filtrate was collected, washed with brine (50 mL*3 times), dried over Na2SO4, filtered and concentrated in vacuo. The residue was loaded on SiO2 and chromatographed on a silica gel column with 0-40% EtOAc/Hex. The fractions containing the desired product were combined and concentrated in vacuo to give 10-bromo-4-methoxybenzo[g]quinazoline as a yellow solid (1.13 g, 77% yield).
A 250 mL round-bottom-flask was flushed with argon, and sequentially charged with 4-methoxy-10-(trifluoromethyl)benzo[g]quinazoline (5.05 g, 18.15 mmol) and pyridine hydrochloride (10.49 g, 91 mmol). The reaction flask was purged with argon and sealed. The reaction mixture was heated at 180° C. for 1 hour. The reaction mixture was cooled to −70° C., followed by addition of DI water (20 mL). The resulting mixture was stirred at room temperature for 1 hour. The solid was collected by filtration, washed with water (10 mL*2 times) and dried on lyophilizer. The crude product was triturated with 20% EtOAc in hexanes (10 mL) to give 10-(trifluoromethyl)benzo[g]quinazolin-4-ol as a pale yellow solid (4.6 g, 90% yield).
A 500 mL round-bottom-flask was charged with 10-(trifluoromethyl)benzo[g]quinazolin-4-ol (5.0 g, 18.92 mmol) and PyBroP (10.59 g, 22.71 mmol). The reaction system was vacuumed and backfilled with argon for three times, followed by sequential addition of 2-MeTHF (200 mL) and N-methylpiperidine (6.9 mL, 56.8 mmol). The mixture was heated at reflux for 2 hours. At this point K2CO3 (5.23 g, 37.8 mmol) was added, followed by addition of Pd(PPh3)2Cl2 (2.66 g, 3.78 mmol) and (4-(tert-butyl)naphthalen-2-3/1)boronic acid (4.75 g, 20.82 mmol). Then argon-deaerated water (10 mL) was added. The mixture was heated at reflux for 4 hours. The reaction mixture was cooled to room temperature. The solid was removed by filtration and the filter cake was washed with acetone. The filtrate was concentrated in vacuo. The residue was loaded on SiO2 and chromatographed on a silica gel column with 0-30% EtOAc/Hex. The fractions containing the desired product were combined and concentrated in vacuo to give a yellow solid (2.8 g, 34% yield).
IrCl3 (0.34 g) was added to a solution of 4-(4-(tert-butyl)naphthalen-2-yl)-10-(trifluoromethyl)benzo[g]quinazoline (0.87 g, 2.02 mmol). The mixture was degassed by N2 for 20 minutes and then heated up to 130° C. for 16 hours. After the reaction mixture was cooled to room temperature, it was used directly in the next step reaction.
3,7-diethylnonane-4,6-dione (0.56 g, 2.56 mmol), potassium carbonate (0.35 g, 2.56 mmol), and 2-ethoxyethanol (60 mL) were added to the reaction mixture from the previous step. The mixture was degassed by N2 and heated at 50° C. for 15 hours. After the solvent was removed, the residue was purified on silica gel column to give product 0.6 g (49%).
A 250 mL flask was flushed with argon, and sequentially charged 10-(trifluoromethyl)benzo[g]quinazolin-4-ol (1.7 g, 6.43 mmol) and PyBroP (3.60 g, 7.72 mmol). The reaction mixture was evacuated and backfilled with argon for 3 times. 2-Me-THF (68.0 mL) was added to the reaction mixture. The resulting solution was bubbled with argon for 5 minutes, followed by addition of 1-methylpiperidine (2.346 ml, 19.30 mmol). The reaction mixture was heated at 85° C. and monitored by LCMS. After 2 hours, the reaction mixture was cooled to room temperature and purged with argon for 10 minutes. Then, K2CO3 (1.779 g, 12.87 mmol) was added, followed by addition of Pd(PPh3)2Cl2 (1.807 g, 2.57 mmol), benzo[b]thiophen-2-ylboronic acid (1.604 g, 9.01 mmol) and water (3.40 mL). The reaction mixture was heated at 85° C. and monitored by LCMS. After 3 hours, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was loaded on SiO2 and chromatographed on a SiO2 column eluting with 0-20% EtOAc/hexane to give 4-(benzo[b]thiophen-2-yl)-10-(trifluoromethyl)benzo[g]quinazoline as a yellow solid (0.860 g, 35% yield).
IrCl3 (0.31 g) was added to a solution of 4-(benzo[b]thiophen-2-yl)-10-(trifluoromethyl)benzo[g]quinazoline (0.70 g, 1.84 mmol. The mixture was degassed by N2 for 20 minutes and then heated up to 130° C. for 16 hours. After the reaction mixture was cooled to room temperature, it was used directly in the next step reaction.
3,7-diethylnonane-4,6-dione (0.52 g, 2.44 mmol), potassium carbonate (0.34 g, 2.44 mmol), and THF (20 mL) were added to the reaction mixture from the previous step. The mixture was degassed by N2 and heated at 50 degree for 15 hours. After the solvent was removed, the residue was purified on silica gel column to give product 0.38 g (37%).
A 1 L flask was flushed with argon, and sequentially charged with 2,3,4,5-tetrafluoro-6-nitrobenzoic acid (20 g, 84 mmol) and IPA (400 mL), followed by addition of Pd/C (10 wt %, 0.98 g, 0.92 mmol). The reaction system was evacuated and backfilled with argon. (This cycle was repeated 3 times.) The reaction mixture was heated at 40° C. for 12 hours under 1 atm of H2. The reaction mixture was bubbled with argon for 20 minutes, then filtered through a short pad of Celite. The filtrate was collected and concentrated. The residue was loaded on SiO2 and chromatographed on a SiO2 column eluting with 0-60% EtOAc/Hexanes to give 2-amino-3,4,5,6-tetrafluorobenzoic acid as a white solid (15.9 g, 91% yield).
A mixture of 2-amino-3,4,5,6-tetrafluorobenzoic acid (32.0 g, 153 mmol) and formamide (30.5 mL, 765 mmol) was heated with Dean-Stark apparatus at 120° C. for 2 days. The reaction mixture was cooled to room temperature and concentrated in vacuo. The residue was loaded on SiO2 and divided into 3 equal portions and chromatographed on a SiO2 column eluting with 0-80% EtOAc/dichloromethane to give 5,6,7,8-tetrafluoroquinazolin-4(1H)-one as a white solid (12.7 g, 38% yield).
A 250 mL round-bottom-flask was charged with 5,6,7,8-tetrafluoroquinazolin-4(1H)-one (5.0 g, 22.92 mmol) and PyBroP (12.82 g, 27.5 mmol). The reaction system was evacuated and backfilled with argon for three times, followed by sequential addition of dioxane (200 mL) and triethylamine (9.59 mL, 68.8 mmol). The mixture was heated under argon atmosphere at room temperature for 1 hour until the phosphonium formation was complete. At this point K2CO3 (6.34 g, 45.8 mmol) was added, followed by addition of Pd(PPh3)2Cl2 (1.61 g, 2.29 mmol) and (4-(tert-butyl)naphthalen-2-yl)boronic acid (5.23 g, 22.92 mmol). Then deaerated water (20 mL) bubbled with argon was added. The mixture was heated at 100° C. for 80 minutes. The reaction mixture was cooled to room temperature, and concentrated in vacuo. The residue was diluted with DCM (50 mL). The solid was removed by filtration. The filtrate was concentrated in vacuo. The residue was loaded on SiO2 and chromatographed on a silica gel column with 0-30% EtOAc/Hex to afford the product.
IrCl3 (0.75 g) was added to 4-(4-(tert-butyl)naphthalen-2-yl)-5,6,7,8-tetrafluoroquinazoline (1.63 g, 4.25 mmol). The mixture was degassed by N2 for 20 minutes and then heated up to 130° C. for 16 hours. After the reaction mixture was cooled to room temperature, it was used directly in the next step reaction.
3,7-diethylnonane-4,6-dione (0.61 g, 2.88 mmol), potassium carbonate (0.40 g, 2.88 mmol), and THF (20 mL) were added to the reaction mixture from the previous step. The mixture was degassed by N2 and heated at 50 degree for 15 hours. After the solvent was removed, the residue was purified on silica gel column to give product 0.6 g (46%).
A 250 mL round-bottom-flask was charged with 5,6,7,8-tetrafluoroquinazolin-4(1H)-one (1.24 g, 5.70 mmol) and PyBroP (3.19 g, 6.84 mmol). The reaction system was vacuumed and backfilled with nitrogen for three times, followed by sequential addition of dioxane (45 mL) and triethylamine (2.38 mL, 17.1 mmol). The mixture was stirred at room temperature for 1 hour until the phosphonium formation was complete. At this point K2CO3 (3.94 g, 28.5 mmol) was added, followed by addition of Pd(PPh3)2Cl2 (0.40 g, 0.57 mmol) and benzo[b]thiophen-2-ylboronic acid (2.03 g, 11.40 mmol). Then deaerated water (4 mL) bubbled with nitrogen was added. The mixture was heated at 100° C. for 1 hour. The reaction mixture was cooled to room temperature, and concentrated in vauco. The residue was diluted with DCM (50 mL). The solid was removed by filtration. The filtrate was concentrated in vacuo. The residue was loaded on SiO2 and chromatographed on a silica gel column with 10% EtOAc/Hep to afford the product 0.75 g (39%).
A solution of 4-(benzo[b]thiophen-2-yl)-5,6,7,8-tetrafluoroquinazoline (0.761 g, 2.276 mmol) in 2-ethoxyethanol and water (v:v=3:1, 28 ml) was degassed under N2 for 20 mins. IrCl3 (0.422 g, 1.138 mmol) was then added to the solution and the reaction was refluxed at 100° C. for 16 hours. The reaction flask was cooled to room temperature, and the product was filtered and washed with MeOH. The resulting solid was dissolved in 1,2-dichlorobenzene (4 mL), followed by adding 2,6-dimethylpyridine (0.20 ml, 1.72 mmol). The mixture was stirred at 130° C. for 16 hours. After the reaction mixture was cooled to room temperature, it was used directly in the next step reaction.
3,7-diethylnonane-4,6-dione (0.365 g, 1.72 mmol), potassium carbonate (0.24 g, 1.72 mmol), and 1,4-dioxane (5 mL) were added to the reaction mixture from the previous step. The mixture was degassed by N2 and heated at 80° C. for 16 hours. After the solvent was removed, the residue was purified on silica gel column to give product 0.63 g (69%).
Device Examples
All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation. The anode electrode was 1,150 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium) followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication, and a moisture getter was incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of HAT-CN as the hole injection layer (HIL); 400 Å of HTM as a hole transporting layer (HTL); 50 Å of EBM as a electron blocking layer (EBL); 400 Å of an emissive layer (EML) containing RH1 as red host and 0.2% of NIR emitter, 50 Å of BM as a blocking layer (BL); and 300 Å of Liq (8-hydroxyquinoline lithium) doped with 35% of ETM as the electron transporting layer (ETL).
The chemical structures of the device materials are shown below:
Upon fabrication, the devices were tested to measure EL and JVL. For this purpose, the samples were energized by the 2 channel Keysight B2902A SMU at a current density of 10 mA/cm2 and measured by the Photo Research PR735 Spectroradiometer. Radiance (W/str/cm2) from 380 nm to 1080 nm, and total integrated photon count were collected. The devices were then placed under a large area silicon photodiode for the JVL sweep. The integrated photon count of the device at 10 mA/cm2 is used to convert the photodiode current to photon count. The voltage is swept from 0 to a voltage equating to 200 mA/cm2. The EQE of the device is calculated using the total integrated photon count. The photoluminescence quantum yield (PLQY) was measured in PMMA film. All results are summarized in Table 2.
The compounds disclosed herein are highly emissive transition metal complexes with fluoro- and/or fluoroalkyl substitution. Table 2 is a summary of performance of electroluminescence device and photoluminescence quantum yield of the inventive OLED examples using the inventive emissive transition metal complexes. As a comparison, the non-fluorinated comparative compound of Ir(L201-21)2Lc17-1 has PL emission at 748 nm. It was unexpectedly found that by just adding one F atom, the emission can shift to redder direction by 9 nm. All inventive examples also exhibit narrow emission spectra with FWHM<70 nm in the near infrared region and high photoluminescence quantum yield. For example, both inventive compounds of Ir(L201-2)2Lc17-1 and Ir(L1501-2)2Lc17-1 having tetrafluoro substitutions on the ligands give high PLQY of 77% and 63% respectively. Organic electroluminescence devices using the inventive compounds exhibit NIR emission with good device performance with EQE as high as 12% for Ir(L201-2)2Lc17-1. It is known that the efficiency of organic electroluminescence device drops significantly as the emission approaches near infrared region with λmax>700 nm, because of the enhanced non-radiative deactivation process from the so called “energy gap law”. As can be seen from Table 2, as the emission wavelength changes from 735 nm to 788 nm, the device efficiency EQE decreases along the same direction. However, the efficiency numbers shown here can be considered as one of the best for each specific wavelength range a person skilled in the art can achieve today.
It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Applications No. 62/869,837 filed on Jul. 2, 2019, and No. 62/913,440 filed on Oct. 10, 2019, the entire contents of which are incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 4769292 | Tang et al. | Sep 1988 | A |
| 5061569 | VanSlyke et al. | Oct 1991 | A |
| 5247190 | Friend et al. | Sep 1993 | A |
| 5703436 | Forrest et al. | Dec 1997 | A |
| 5707745 | Forrest et al. | Jan 1998 | A |
| 5834893 | Bulovic et al. | Nov 1998 | A |
| 5844363 | Gu et al. | Dec 1998 | A |
| 6013982 | Thompson et al. | Jan 2000 | A |
| 6087196 | Sturm et al. | Jul 2000 | A |
| 6091195 | Forrest et al. | Jul 2000 | A |
| 6097147 | Baldo et al. | Aug 2000 | A |
| 6294398 | Kim et al. | Sep 2001 | B1 |
| 6303238 | Thompson et al. | Oct 2001 | B1 |
| 6337102 | Forrest et al. | Jan 2002 | B1 |
| 6468819 | Kim et al. | Oct 2002 | B1 |
| 6528187 | Okada | Mar 2003 | B1 |
| 6687266 | Ma et al. | Feb 2004 | B1 |
| 6835469 | Kwong et al. | Dec 2004 | B2 |
| 6921915 | Takiguchi et al. | Jul 2005 | B2 |
| 7087321 | Kwong et al. | Aug 2006 | B2 |
| 7090928 | Thompson et al. | Aug 2006 | B2 |
| 7154114 | Brooks et al. | Dec 2006 | B2 |
| 7250226 | Tokito et al. | Jul 2007 | B2 |
| 7279704 | Walters et al. | Oct 2007 | B2 |
| 7332232 | Ma et al. | Feb 2008 | B2 |
| 7338722 | Thompson et al. | Mar 2008 | B2 |
| 7393599 | Thompson et al. | Jul 2008 | B2 |
| 7396598 | Takeuchi et al. | Jul 2008 | B2 |
| 7431968 | Shtein et al. | Oct 2008 | B1 |
| 7445855 | Mackenzie et al. | Nov 2008 | B2 |
| 7534505 | Lin et al. | May 2009 | B2 |
| 8920943 | Kamatani et al. | Dec 2014 | B2 |
| 9847497 | Szigethy | Dec 2017 | B2 |
| 20020034656 | Thompson et al. | Mar 2002 | A1 |
| 20020134984 | Igarashi | Sep 2002 | A1 |
| 20020158242 | Son et al. | Oct 2002 | A1 |
| 20030138657 | Li et al. | Jul 2003 | A1 |
| 20030152802 | Tsuboyama et al. | Aug 2003 | A1 |
| 20030162053 | Marks et al. | Aug 2003 | A1 |
| 20030175553 | Thompson et al. | Sep 2003 | A1 |
| 20030230980 | Forrest et al. | Dec 2003 | A1 |
| 20040036077 | Ise | Feb 2004 | A1 |
| 20040137267 | Igarashi et al. | Jul 2004 | A1 |
| 20040137268 | Igarashi et al. | Jul 2004 | A1 |
| 20040174116 | Lu et al. | Sep 2004 | A1 |
| 20050025993 | Thompson et al. | Feb 2005 | A1 |
| 20050112407 | Ogasawara et al. | May 2005 | A1 |
| 20050238919 | Ogasawara | Oct 2005 | A1 |
| 20050244673 | Satoh et al. | Nov 2005 | A1 |
| 20050260441 | Thompson et al. | Nov 2005 | A1 |
| 20050260449 | Walters et al. | Nov 2005 | A1 |
| 20060008670 | Lin et al. | Jan 2006 | A1 |
| 20060202194 | Jeong et al. | Sep 2006 | A1 |
| 20060240279 | Adamovich et al. | Oct 2006 | A1 |
| 20060251923 | Lin et al. | Nov 2006 | A1 |
| 20060263635 | Ise | Nov 2006 | A1 |
| 20060280965 | Kwong et al. | Dec 2006 | A1 |
| 20070190359 | Knowles et al. | Aug 2007 | A1 |
| 20070278938 | Yabunouchi et al. | Dec 2007 | A1 |
| 20080015355 | Schafer et al. | Jan 2008 | A1 |
| 20080018221 | Egen et al. | Jan 2008 | A1 |
| 20080106190 | Yabunouchi et al. | May 2008 | A1 |
| 20080124572 | Mizuki et al. | May 2008 | A1 |
| 20080220265 | Xia et al. | Sep 2008 | A1 |
| 20080297033 | Knowles et al. | Dec 2008 | A1 |
| 20090008605 | Kawamura et al. | Jan 2009 | A1 |
| 20090009065 | Nishimura et al. | Jan 2009 | A1 |
| 20090017330 | Iwakuma et al. | Jan 2009 | A1 |
| 20090030202 | Iwakuma et al. | Jan 2009 | A1 |
| 20090039776 | Yamada et al. | Feb 2009 | A1 |
| 20090045730 | Nishimura et al. | Feb 2009 | A1 |
| 20090045731 | Nishimura et al. | Feb 2009 | A1 |
| 20090078317 | Kim et al. | Mar 2009 | A1 |
| 20090101870 | Prakash et al. | Apr 2009 | A1 |
| 20090108737 | Kwong et al. | Apr 2009 | A1 |
| 20090115316 | Zheng et al. | May 2009 | A1 |
| 20090165846 | Johannes et al. | Jul 2009 | A1 |
| 20090167162 | Lin et al. | Jul 2009 | A1 |
| 20090179554 | Kuma et al. | Jul 2009 | A1 |
| 20090295281 | Shin et al. | Dec 2009 | A1 |
| 20150014659 | Kim et al. | Jan 2015 | A1 |
| 20150236279 | Szigethy | Aug 2015 | A1 |
| 20170352821 | Boudreault | Dec 2017 | A1 |
| 20180277774 | Boudreault | Sep 2018 | A1 |
| Number | Date | Country |
|---|---|---|
| 0650955 | May 1995 | EP |
| 1725079 | Nov 2006 | EP |
| 2034538 | Mar 2009 | EP |
| 200511610 | Jan 2005 | JP |
| 2007123392 | May 2007 | JP |
| 2007254297 | Oct 2007 | JP |
| 2008074939 | Apr 2008 | JP |
| 2013149880 | Aug 2013 | JP |
| 100850886 | Aug 2008 | KR |
| 2009093688 | Sep 2009 | KR |
| 2011077350 | Jul 2011 | KR |
| 0139234 | May 2001 | WO |
| 0202714 | Jan 2002 | WO |
| 02015654 | Feb 2002 | WO |
| 2002044189 | Jun 2002 | WO |
| 03040257 | May 2003 | WO |
| 03060956 | Jul 2003 | WO |
| 2004093207 | Oct 2004 | WO |
| 2004107822 | Dec 2004 | WO |
| 2005014551 | Feb 2005 | WO |
| 2005019373 | Mar 2005 | WO |
| 2005030900 | Apr 2005 | WO |
| 2005089025 | Sep 2005 | WO |
| 2005123873 | Dec 2005 | WO |
| 2006009024 | Jan 2006 | WO |
| 2006056418 | Jun 2006 | WO |
| 2006072002 | Jul 2006 | WO |
| 2006082742 | Aug 2006 | WO |
| 2006098120 | Sep 2006 | WO |
| 2006100298 | Sep 2006 | WO |
| 2006103874 | Oct 2006 | WO |
| 2006114966 | Nov 2006 | WO |
| 2006132173 | Dec 2006 | WO |
| 2007002683 | Jan 2007 | WO |
| 2007004380 | Jan 2007 | WO |
| 2007063754 | Jun 2007 | WO |
| 2007063796 | Jun 2007 | WO |
| 2008056746 | May 2008 | WO |
| 2008101842 | Aug 2008 | WO |
| 2008109824 | Sep 2008 | WO |
| 2008132085 | Nov 2008 | WO |
| 2009000673 | Dec 2008 | WO |
| 2009003898 | Jan 2009 | WO |
| 2009008311 | Jan 2009 | WO |
| 2009018009 | Feb 2009 | WO |
| 2009021126 | Feb 2009 | WO |
| 2009050290 | Apr 2009 | WO |
| 2009062578 | May 2009 | WO |
| 2009063833 | May 2009 | WO |
| 2009066778 | May 2009 | WO |
| 2009066779 | May 2009 | WO |
| 2009086028 | Jul 2009 | WO |
| 2009100991 | Aug 2009 | WO |
| 2011028473 | Mar 2011 | WO |
| Entry |
|---|
| Ahn, So Youn et al., “Color tuning of red phosphorescence: New iridium complexes containing fluorinated 2,3-diphenylquinoxaline ligands”, Thin Solid Films 517 (2009) 4111-4114. |
| Adachi, Chihaya et al., “Organic Electroluminescent Device Having a Hole Conductor as an Emitting Layer,” Appl. Phys. Lett., 55(15): 1489-1491 (1989). |
| Adachi, Chihaya et al., “Nearly 100% Internal Phosphorescence Efficiency in an Organic Light Emitting Device,” J. Appl. Phys., 90(10): 5048-5051 (2001). |
| Adachi, Chihaya et al., “High-Efficiency Red Electrophosphorescence Devices,” Appl. Phys. Lett., 78(11)1622-1624 (2001). |
| Aonuma, Masaki et al., “Material Design of Hole Transport Materials Capable of Thick-Film Formation in Organic Light Emitting Diodes,” Appl. Phys. Lett., 90, Apr. 30, 2007, 183503-1-183503-3. |
| Baldo et al., Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices, Nature, vol. 395, 151-154, (1998). |
| Baldo et al., Very high-efficiency green organic light-emitting devices based on electrophosphorescence, Appl. Phys. Lett., vol. 75, No. 1, 4-6 (1999). |
| Gao, Zhiqiang et al., “Bright-Blue Electroluminescence From a Silyl-Substituted ter-(phenylene-vinylene) derivative,” Appl. Phys. Lett., 74(6): 865-867 (1999). |
| Guo, Tzung-Fang et al., “Highly Efficient Electrophosphorescent Polymer Light-Emitting Devices,” Organic Electronics, 1: 15-20 (2000). |
| Hamada, Yuji et al., “High Luminance in Organic Electroluminescent Devices with Bis(10-hydroxybenzo[h]quinolinato) beryllium as an Emitter, ” Chem. Lett., 905-906 (1993). |
| Holmes, R.J. et al., “Blue Organic Electrophosphorescence Using Exothermic Host-Guest Energy Transfer,” Appl. Phys. Lett., 82(15):2422-2424 (2003). |
| Hu, Nan-Xing et al., “Novel High Tg Hole-Transport Molecules Based on Indolo[3,2-b]carbazoles for Organic Light-Emitting Devices,” Synthetic Metals, 111-112:421-424 (2000). |
| Huang, Jinsong et al., “Highly Efficient Red-Emission Polymer Phosphorescent Light-Emitting Diodes Based on Two Novel Tris(1-phenylisoquinolinato-C2, N)iridium(III) Derivatives,” Adv. Mater., 19:739-743 (2007). |
| Huang, Wei-Sheng et al., “Highly Phosphorescent Bis-Cyclometalated Iridium Complexes Containing Benzoimidazole-Based Ligands,” Chem. Mater., 16(12):2480-2488 (2004). |
| Hung, L.S. et al., “Anode Modification in Organic Light-Emitting Diodes by Low-Frequency Plasma Polymerization of CHF3,” Appl. Phys. Lett., 78(5):673-675 (2001). |
| Ikai, Masamichi et al., “Highly Efficient Phosphorescence From Organic Light-Emitting Devices with an Exciton-Block Layer,” Appl. Phys. Lett., 79(2):156-158 (2001). |
| Ikeda, Hisao et al., “P-185 Low-Drive-Voltage OLEDs with a Buffer Layer Having Molybdenum Oxide,” SID Symposium Digest, 37:923-926 (2006). |
| Inada, Hiroshi and SHIROTA, Yasuhiko, “1,3,5-Tris[4-(diphenylamino)phenyl]benzene and its Methylsubstituted Derivatives as a Novel Class of Amorphous Molecular Materials,” J. Mater. Chem., 3(3):319-320 (1993). |
| Kanno, Hiroshi et al., “Highly Efficient and Stable Red Phosphorescent Organic Light-Emitting Device Using bis[2-(2-benzothiazoyl)phenolato]zinc(II) as host material,” Appl. Phys. Lett., 90:123509-1-123509-3 (2007). |
| Kido, Junji et al., 1,2,4-Triazole Derivative as an Electron Transport Layer in Organic Electroluminescent Devices, Jpn. J. Appl. Phys., 32:L917-L920 (1993). |
| Kuwabara, Yoshiyuki et al., “Thermally Stable Multilayered Organic Electroluminescent Devices Using Novel Starburst Molecules, 4,4′,4″-Tri(N-carbazolyl)triphenylamine (TCTA) and 4,4′,4″-Tris(3-methylphenylphenyl-amino) triphenylamine (m-MTDATA), as Hole-Transport Materials,” Adv. Mater., 6(9):677-679 (1994). |
| Kwong, Raymond C. et al., “High Operational Stability of Electrophosphorescent Devices,” Appl. Phys. Lett., 81(1)162-164 (2002). |
| Lamansky, Sergey et al., “Synthesis and Characterization of Phosphorescent Cyclometalated Iridium Complexes,” Inorg. Chem., 40(7):1704-1711 (2001). |
| Lee, Chang-Lyoul et al., “Polymer Phosphorescent Light-Emitting Devices Doped with Tris(2-phenylpyridine) Iridium as a Triplet Emitter,” Appl. Phys. Lett., 77(15):2280-2282 (2000). |
| Lo, Shih-Chun et al., “Blue Phosphorescence from Iridium(III) Complexes at Room Temperature,” Chem. Mater., 18(21)5119-5129 (2006). |
| Ma, Yuguang et al., “Triplet Luminescent Dinuclear-Gold(I) Complex-Based Light-Emitting Diodes with Low Turn-On voltage,” Appl. Phys. Lett., 74(10):1361-1363 (1999). |
| Mi, Bao-Xiu et al., “Thermally Stable Hole-Transporting Material for Organic Light-Emitting Diode an Isoindole Derivative,” Chem. Mater., 15(16):3148-3151 (2003). |
| Nishida, Jun-ichi et al., “Preparation, Characterization, and Electroluminescence Characteristics of α-Diimine-type Platinum(II) Complexes with Perfluorinated Phenyl Groups as Ligands,” Chem. Lett., 34(4): 592-593 (2005). |
| Niu, Yu-Hua et al., “Highly Efficient Electrophosphorescent Devices with Saturated Red Emission from a Neutral Osmium Complex,” Chem. Mater., 17(13):3532-3536 (2005). |
| Noda, Tetsuya and Shirota, Yasuhiko, “5,5′-Bis(dimesitylboryl)-2,2′-bithiophene and 5,5″-Bis (dimesitylboryl)-2,2′5′,2″-terthiophene as a Novel Family of Electron-Transporting Amorphous Molecular Materials,” J. Am. Chem. Soc., 120 (37):9714-9715 (1998). |
| Okumoto, Kenji et al., “Green Fluorescent Organic Light-Emitting Device with External Quantum Efficiency of Nearly 10%,” Appl. Phys. Lett., 89:063504-1-063504-3 (2006). |
| Palilis, Leonidas C., “High Efficiency Molecular Organic Light-Emitting Diodes Based On Silole Derivatives And Their Exciplexes,” Organic Electronics, 4:113-121 (2003). |
| Paulose, Betty Marie Jennifer S. et al., “First Examples of Alkenyl Pyridines as Organic Ligands for Phosphorescent Iridium Complexes,” Adv. Mater., 16(22):2003-2007 (2004). |
| Ranjan, Sudhir et al., “Realizing Green Phosphorescent Light-Emitting Materials from Rhenium(I) Pyrazolato Diimine Complexes,” Inorg. Chem., 42(4):1248-1255 (2003). |
| Sakamoto, Youichi et al., “Synthesis, Characterization, and Electron-Transport Property of Perfluorinated Phenylene Dendrimers,” J. Am. Chem. Soc., 122(8):1832-1833 (2000). |
| Salbeck, J. et al., “Low Molecular Organic Glasses for Blue Electroluminescence,” Synthetic Metals, 91: 209-215 (1997). |
| Shirota, Yasuhiko et al., “Starburst Molecules Based on pi-Electron Systems as Materials for Organic Electroluminescent Devices,” Journal of Luminescence, 72-74:985-991 (1997). |
| Sotoyama, Wataru et al., “Efficient Organic Light-Emitting Diodes with Phosphorescent Platinum Complexes Containing NΛCΛN-Coordinating Tridentate Ligand,” Appl. Phys. Lett., 86:153505-1-153505-3 (2005). |
| Sun, Yiru and Forrest, Stephen R., “High-Efficiency White Organic Light Emitting Devices with Three Separate Phosphorescent Emission Layers,” Appl. Phys. Lett., 91:263503-1-263503-3 (2007). |
| T. Östergård et al., “Langmuir-Blodgett Light-Emitting Diodes Of Poly(3-Hexylthiophene) Electro-Optical Characteristics Related to Structure,” Synthetic Metals, 88:171-177 (1997). |
| Takizawa, Shin-ya et al., “Phosphorescent Iridium Complexes Based on 2-Phenylimidazo[1,2- α]pyridine Ligands Tuning of Emission Color toward the Blue Region and Application to Polymer Light-Emitting Devices,” Inorg. Chem., 46(10):4308-4319 (2007). |
| Tang, C.W. and VanSlyke, S.A., “Organic Electroluminescent Diodes,” Appl. Phys. Lett., 51(12):913-915 (1987). |
| Tung, Yung-Liang et al., “Organic Light-Emitting Diodes Based on Charge-Neutral Ru II PHosphorescent Emitters,” Adv. Mater., 17(8)1059-1064 (2005). |
| Van Slyke, S. A. et al., “Organic Electroluminescent Devices with Improved Stability,” Appl. Phys. Lett., 69(15):2160-2162 (1996). |
| Wang, Y. et al., “Highly Efficient Electroluminescent Materials Based on Fluorinated Organometallic Iridium Compounds,” Appl. Phys. Lett., 79(4):449-451 (2001). |
| Wong, Keith Man-Chung et al., A Novel Class of Phosphorescent Gold(III) Alkynyl-Based Organic Light-Emitting Devices with Tunable Colour, Chem. Commun., 2906-2908 (2005). |
| Wong, Wai-Yeung, “Multifunctional Iridium Complexes Based on Carbazole Modules as Highly Efficient Electrophosphors,” Angew. Chem. Int. Ed., 45:7800-7803 (2006). |
| Yang, C-H., et al., “Color tuning of iridium complexes for organic light-emitting diodes: The electronegative effect and p-conjugation effect,” Journal of Organometallic Chemistry, vol. 691, pp. 2767-2773 |
| Lee, Y.H., et al., “Theoretical study of a new phosphorescentiridium(III) quinazoline complex,” Thin Solid Films, vol. 515, pp. 5079-5083. |
| Han, H-B., et al., “Efficient orange-red electroluminescence of iridium complexes with 1-(2,6-bis(trifluoromethyl ) pyridin-4-yl)isoquinoline and 4-(2,6-bis (trifluoromethyl)pyridin-4 -yl)quinazoline ligands,” Dalton Trans., vol. 46, p. 14916. |
| Number | Date | Country | |
|---|---|---|---|
| 20210002311 A1 | Jan 2021 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62869837 | Jul 2019 | US | |
| 62913440 | Oct 2019 | US |
