Organic electroluminescent materials and devices
11765970 · 2023-09-19
Assignee
Inventors
Cpc classification
H10K2101/30
ELECTRICITY
H10K85/631
ELECTRICITY
H10K2101/40
ELECTRICITY
H10K85/626
ELECTRICITY
C09K2211/185
CHEMISTRY; METALLURGY
H10K85/6572
ELECTRICITY
H10K85/615
ELECTRICITY
International classification
Abstract
An OLED is disclosed whose emissive layer has a first host and an emitter, where the emitter is a phosphorescent metal complex that is a Pt(II) or Pd(II) complex having a square planar coordinating geometry or has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z, where E.sub.H1T, the T.sub.1 triplet energy of the first host, is higher than E.sub.ET, the T.sub.1 triplet energy of the emitter, where E.sub.ET is at least 2.50 eV, where the LUMO energy of the first host is higher than the HOMO energy of the emitter, where the absolute value of the difference between the HOMO energy of the emitter and the LUMO energy of the first host is ΔE1, where a≤ΔE1−E.sub.ET≤b; and where a≥0.05 eV, and b≤0.60 eV.
Claims
1. An organic light emitting device (OLED), comprising: an anode; a cathode; and an organic emissive layer disposed between the anode and the cathode, the organic emissive layer comprising: a first host having a highest occupied molecular orbital (HOMO) energy, a lowest unoccupied molecular orbital (LUMO) energy, and a T.sub.1 triplet energy, wherein the first host is an electron transporting host; and an emitter having a highest occupied molecular orbital (HOMO) energy, a lowest unoccupied molecular orbital (LUMO) energy, and a T.sub.1 triplet energy, wherein the emitter is a blue emitter; wherein the emitter is a phosphorescent metal complex; wherein E.sub.H1T, the T.sub.1 triplet energy of the first host, is higher than E.sub.ET, the T.sub.1 triplet energy of the emitter; wherein E.sub.ET is at least 2.50 eV; wherein the LUMO energy of the first host is higher than the HOMO energy of the emitter; wherein the absolute value of the difference between the HOMO energy of the emitter and the LUMO energy of the first host is ΔE1; wherein a≤ΔE1−E.sub.ET≤b; wherein a≥0.05 eV, and b≤0.60 eV; wherein the emitter is selected from the group consisting of: ##STR00115## ##STR00116## ##STR00117## wherein L is selected from the group consisting of BR, NR, PR, O, S, CRR′″, SiRR“′, alkyl, cycloalkyl, aryl, and heteroaryl, wherein each R.sup.A to R.sup.F can represent from mono substitution to the possible maximum number of substitutions, or no substitution; wherein R, R′″, R.sup.A to R.sup.F are each independently a hydrogen or a substitution selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; wherein any two R, R′″, R.sup.A to R.sup.F can be fused or joined to form a ring or form a multidentate ligand; and wherein at least one of R, R′″, or R.sup.A to R.sup.F comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other.
2. The OLED of claim 1, wherein R, R′″, and R.sup.A to R.sup.F are each independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, boryl, and combinations thereof.
3. The OLED of claim 1, wherein at least one of R.sup.A to R.sup.F comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other.
4. The OLED of claim 1, wherein the absolute value of the difference between the highest HOMO energy and the lowest LUMO energy among all components in the emissive layer is larger than E.sub.ET by at least a.
5. The OLED of claim 1, wherein the OLED further comprises a second host; wherein E.sub.H2T, the T.sub.1 triplet energy of the second host, is higher than E.sub.ET.
6. The OLED of claim 5, wherein the HOMO energy of the second host is lower than the HOMO energy of the first host, the LUMO energy of the second host is higher than the LUMO energy of the first host.
7. The OLED of claim 5, wherein the HOMO energy of the second host is higher than the HOMO energy of the first host, the LUMO energy of the second host is higher than the LUMO energy of the first host.
8. The OLED of claim 1, wherein the first host comprises at least one chemical group selected from the group consisting of pyridine, pyrimidine, pyrazine, triazine, imidazole, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
9. The OLED of claim 1, wherein the emitter is selected from the group consisting of: ##STR00118##
10. A consumer product comprising an organic light emitting device (OLED) comprising: an anode; a cathode; and an organic emissive layer disposed between the anode and the cathode, the organic emissive layer comprising: a first host having a highest occupied molecular orbital (HOMO) energy, a lowest unoccupied molecular orbital (LUMO) energy, and a T.sub.1 triplet energy, wherein the first host is an electron transporting host; and an emitter having a highest occupied molecular orbital (HOMO) energy, a lowest unoccupied molecular orbital (LUMO) energy, and a T.sub.1 triplet energy, wherein the emitter is a blue emitter; wherein the emitter is a phosphorescent metal complex; wherein E.sub.H1T, the T.sub.1 triplet energy of the first host, is higher than E.sub.ET, the T.sub.1 triplet energy of the emitter; wherein E.sub.ET is at least 2.50 eV; wherein the LUMO energy of the first host is higher than the HOMO energy of the emitter; wherein the absolute value of the difference between the HOMO energy of the emitter and the LUMO energy of the first host is ΔE1; wherein a≤ΔE1−E.sub.ET≤b; wherein a≥0.05 eV, and b≤0.60 eV; wherein the emitter is selected from the group consisting of: ##STR00119## ##STR00120## wherein L is selected from the group consisting of BR, NR, PR, O, S, CRR′″, SiRR′″, alkyl, cycloalkyl, aryl, and heteroaryl, wherein each R.sup.A to R.sup.F can represent from mono substitution to the possible maximum number of substitutions, or no substitution; wherein R, R″′, R.sup.A to R.sup.F are each independently a hydrogen or a substitution selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; wherein any two R, R′″, R.sup.A to R.sup.F can be fused or joined to form a ring or form a multidentate ligand; and wherein at least one of R, R′″, or R.sup.A to R.sup.F comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other.
11. The OLED of claim 5, wherein the second host is a hole transporting host.
12. The OLED of claim 1, wherein at least one R.sup.A comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other.
13. The OLED of claim 1, wherein at least one of R, R′″, or R.sup.A to R.sup.F comprises a chemical group containing at least four 6-membered aromatic rings that are not fused next to each other.
14. The OLED of claim 9, wherein at least one of R, R′″, or R.sup.A to R.sup.F comprises a chemical group containing at least five 6-membered aromatic rings that are not fused next to each other.
15. The OLED of claim 9, wherein at least one of R, R′″, or R.sup.A to R.sup.F comprises a chemical group containing at least six 6-membered aromatic rings that are not fused next to each other.
16. The OLED of claim 1, wherein L is O.
17. The OLED of claim 9, wherein L is O.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(18) 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.
(19) 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.
(20) 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.
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(22) 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 F.sub.4-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.
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(24) The simple layered structure illustrated in
(25) 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
(26) 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 is 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.
(27) Devices fabricated in accordance with embodiments of the present invention 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.
(28) Devices fabricated in accordance with embodiments of the invention 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 invention 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, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, 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 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
(29) 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.
(30) The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
(31) The term “acyl” refers to a substituted carbonyl radical (C(O)—R.sub.s).
(32) The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R.sub.s or —C(O)—O—R.sub.s) radical.
(33) The term “ether” refers to an —OR.sub.s radical.
(34) The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SR.sub.s radical.
(35) The term “sulfinyl” refers to a —S(O)—R.sub.s radical.
(36) The term “sulfonyl” refers to a —SO.sub.2—R.sub.s radical.
(37) The term “phosphino” refers to a —P(R.sub.s).sub.3 radical, wherein each R.sub.s can be same or different.
(38) The term “silyl” refers to a —Si(R.sub.s).sub.3 radical, wherein each R.sub.s can be same or different.
(39) The term “boryl” refers to a —B(R.sub.s).sub.2 radical or its Lewis adduct —B(R.sub.s).sub.3 radical, wherein R.sub.s can be same or different.
(40) In each of the above, R.sub.s 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 R.sub.s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
(41) 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 is optionally substituted.
(42) 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.
(43) 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 is optionally substituted.
(44) 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 is optionally substituted.
(45) The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group is optionally substituted.
(46) 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 is optionally substituted.
(47) 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.
(48) 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.
(49) The term “heteroaryl” refers to and includes both single-ring hetero-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.
(50) 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.
(51) The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted or substituted with one or more general substituents.
(52) In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
(53) In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
(54) In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.
(55) In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
(56) The term “substituted” refers to a substituent other than H that is bonded to the relevant position, e.g., a carbon. For example, where R.sup.1 represents mono-substituted, then one R.sup.1 must be other than H. Similarly, where R.sup.1 represents di-substituted, then two of R.sup.1 must be other than H. Similarly, where R.sup.1 is unsubstituted, R.sup.1 is hydrogen for all available positions. The maximum number of substitutions possible in a structure (for example, a particular ring or fused ring system) will depend on the number of atoms with available valencies.
(57) 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.
(58) 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 fragment 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.
(59) 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.
(60) 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.
(61) 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.
(62) An OLED is disclosed wherein the OLED comprises an anode, a cathode, and an organic emissive layer disposed between the anode and the cathode. The organic emissive layer comprises a first host and an emitter, wherein the emitter is a phosphorescent metal complex. E.sub.H1T, the T.sub.1 triplet energy of the first host, is higher than E.sub.ET, the T.sub.1 triplet energy of the emitter, wherein E.sub.ET is at least 2.50 eV. The LUMO energy level of the first host is higher than the HOMO energy level of the emitter. The absolute value of the difference between the HOMO of the emitter and the LUMO of the first host is represented by ΔE1 and wherein a≤ΔE1−E.sub.ET≤b, where a≥0.05 eV, and b≤0.60 eV. This energy configuration is illustrated in
(63) ##STR00003##
where X.sup.1 to X.sup.11 are each independently selected from the group consisting of carbon and nitrogen; where Y.sup.1 and Y.sup.2 are each independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO.sub.2, CR′R″, SiR′R″, and GeR′R″; where any two substituents selected from the group consisting of R′ and R″ can be fused or joined to form a ring; where each R.sub.a, R.sub.b, R.sub.c, and R.sub.d may represent from mono substitution to the possible maximum number of substitutions, or no substitution; where R′, R″, R.sub.a, R.sub.b, R.sub.c, and R.sub.d are each independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and where any two R.sub.a, R.sub.b, R.sub.c, and R.sub.d can be fused or joined to form a ring or form a multidentate ligand.
(64) In some embodiments, the relationship a≤ΔE1−E.sub.ET≤b is maintained where a is 0.10 eV. In some embodiments a is 0.15 eV. In some embodiments, a is 0.20 eV. In some embodiments, b is 0.50 eV. In some embodiments, b is 0.40 eV. In some embodiments, b is 0.30 eV. In some embodiments, b is 0.25 eV. In some embodiments, E.sub.ET is at least 2.60 eV. In some embodiments, E.sub.ET is at least 2.70 eV. In some embodiments, E.sub.ET is at least 2.75 eV. In some embodiments, E.sub.ET is at least 2.80 eV.
(65) In some embodiments of the OLED, the first host is an e-host.
(66) In some embodiments of the OLED, the absolute value of the difference between the highest HOMO energy and the lowest LUMO energy among all components in the emissive layer is larger than E.sub.ET by at least a.
(67) Referring to
(68) In some embodiments, the difference between the HOMO energy levels of the first host and the second host is from 0.1 to 0.6 eV. As disclosed herein, when energy levels are referred to as being from aa to bb eV, it includes the end values aa and bb. In some embodiments, the difference between the HOMO energy levels between the first host and the second host is from 0.1 to 0.3 eV. In some embodiments, the difference between the HOMO energy levels between the first host and the second host is from 0.1 to 0.2 eV. In some embodiments, the difference between the HOMO energy levels between the first host and the second host is from 0.1 to 0.15 eV. In some embodiments, the difference between the LUMO energy levels between the first host and the second host is from 0.1 to 0.50 eV. In some embodiments, the difference between the LUMO energy levels between the first host and the second host is from 0.1 to 0.35 eV. In some embodiments, the difference between the LUMO energy levels between the first and the second host is from 0.1 to 0.20 eV. In some embodiments, the first host, the second host, and the emitter are the only components in the emissive layer.
(69) In some embodiments, the second host is a hole transporting host.
(70) In some embodiments of the OLED, the OLED has an operating voltage of less than 6.0 V at 10 mA/cm.sup.2. In some embodiments, the OLED has an operating voltage of less than 5.0 V at 10 mA/cm.sup.2. In some embodiments, the OLED has an operating voltage of less than 4.0 V at 10 mA/cm.sup.2.
(71) In some embodiments of the OLED, the first host comprises at least one chemical group selected from the group consisting of pyridine, pyrimidine, pyrazine, triazine, imidazole, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
(72) In some embodiments of the OLED, the emitter is a phosphorescent blue emitter.
(73) In some embodiments of the OLED, the emitter is a PT(II) or Pd(II) complex having a square planar coordinating geometry or has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z; where L.sup.1, L.sup.2 and L.sup.3 can be the same or different; where x is 1, 2, or 3; where y is 0, 1, or 2; where z is 0, 1, or 2; where x+y+z is the oxidation state of the metal M; where L.sup.1, L.sup.2 and L.sup.3 are each independently selected from the group consisting of:
(74) ##STR00004##
where each X.sup.1 to X.sup.11 is independently selected from the group consisting of carbon and nitrogen; where each Y.sup.1 and Y.sup.2 is independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO.sub.2, CR′R″, SiR′R″, and GeR′R″; where any two substituents selected from the group consisting of R′ and R″ are optionally fused or joined to form a ring; where each R.sub.a, R.sub.b, R.sub.c, and R.sub.d may represent from mono substitution to the possible maximum number of substitutions, or no substitution; where R′, R″, R.sub.a, R.sub.b, R.sub.c, and R.sub.d are each independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and wherein any two R.sub.a, R.sub.b, R.sub.c, and R.sub.d can be fused or joined to form a ring or form a multidentate ligand.
(75) In some embodiments of the OLED where the emitter has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z, R′, R″, R.sub.a, R.sub.b, R.sub.c, and R.sub.d are each independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
(76) In some embodiments of the OLED where the emitter has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z, the compound has the formula selected from the group consisting of Ir(L.sup.1)(L.sup.2)(L.sup.3), Ir(L.sup.1).sub.2(L.sup.2), and Ir(L).sub.3; where L, L.sup.2 and L.sup.3 are different from each other, where L.sup.1 is selected from the group consisting of:
(77) ##STR00005## ##STR00006##
(78) In some embodiments of the OLED where the emitter has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z, the compound has the formula of Pt(L.sup.1).sub.2 or Pt(L.sup.1)(L.sup.2). In some embodiments, L.sup.1 is connected to the other L.sup.1 or L.sup.2 to form a tetradentate ligand.
(79) In some embodiments of the OLED, the emitter is a Pt(II) complex comprising a tetradentate ligand.
(80) In some embodiments of the OLED, the emitter is a Pt(II) complex comprising at least one Pt—C bond, and at least one Pt—N bond.
(81) In some embodiments of the OLED where the emitter has the formula of Pt(L.sup.1).sub.2 or Pt(L.sup.1)(L.sup.2), the emitter is selected from the group consisting of:
(82) ##STR00007## ##STR00008## ##STR00009## ##STR00010##
where L is selected from the group consisting of BR, NR, PR, O, S, CRR′″, SiRR′″, alkyl, cycloalkyl, aryl, and heteroaryl, where each R.sup.A to R.sup.N may represent from mono substitution to the possible maximum number of substitutions, or no substitution; where R, R′″, R.sup.A to R.sup.N are each independently a hydrogen or a substitution selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and where any two R, R′″, R.sup.A to R.sup.N are optionally fused or joined to form a ring or form a multidentate ligand. In some embodiments, at least one of R, R′″, R.sup.A to R.sup.N comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other. In some embodiments, at least one of R, R′″, R.sup.A to R.sup.N comprises a chemical group containing at least four 6-membered aromatic rings that are not fused next to each other. In some embodiments, at least one of R, R′″, R.sup.A to R.sup.N comprises a chemical group containing at least five 6-membered aromatic rings that are not fused to each other. In some embodiments, at least one of R, R′″, R.sup.A to R.sup.N comprises a chemical group containing at least six 6-membered aromatic rings that are not fused to each other. In some embodiments, R.sup.A comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other.
(83) In some embodiments of the OLED, the emitter has the formula of M(L.sup.1).sub.2 or M(L.sup.1)(L.sup.2); where M is Ir, Rh, Re, Ru, or Os, and L.sup.1 and L.sup.2 are each a different tridentate ligand.
(84) In some embodiments of the OLED where the emitter has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z, the compound has the formula of M(L.sup.1).sub.2 or M(L.sup.1)(L.sup.2); wherein M is Ir, Rh, Re, Ru, or Os, L.sup.1 and L.sup.2 are each a different tridentate ligand. In some embodiments, L.sup.1, is selected from the group consisting of:
(85) ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042##
(86) A consumer product comprising the OLED of the present disclosure is also disclosed. The OLED comprises an anode, a cathode, and an organic emissive layer disposed between the anode and the cathode. The organic emissive layer comprises a first host and an emitter, wherein the emitter is a phosphorescent metal complex. E.sub.H1T, the T.sub.1 triplet energy of the first host, is higher than E.sub.ET, the T.sub.1 triplet energy of the emitter, wherein E.sub.ET is at least 2.50 eV. The LUMO energy level of the first host is higher than the HOMO energy level of the emitter. The absolute value of the difference between the HOMO of the emitter and the LUMO of the first host is represented by ΔE1 and wherein a≤ΔE1−E.sub.ET≤b, where a≥0.05 eV, and b≤0.60 eV. In this OLED, the emitter is a Pt(II) or Pd(II) complex having a square planar coordinating geometry or has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z; where L.sup.1, L.sup.2 and L.sup.3 can be the same or different; where x is 1, 2, or 3; where y is 0, 1, or 2; where z is 0, 1, or 2; where x+y+z is the oxidation state of the metal M; where L.sup.1, L.sup.2 and L.sup.3 are each independently selected from the group consisting of:
(87) ##STR00043##
where X.sup.1 to X.sup.11 are each independently selected from the group consisting of carbon and nitrogen; where Y.sup.1 and Y.sup.2 are each independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO.sub.2, CR′R″, SiR′R″, and GeR′R″; where any two substituents selected from the group consisting of R′ and R″ can be fused or joined to form a ring; where each R.sub.a, R.sub.b, R.sub.c, and R.sub.d may represent from mono substitution to the possible maximum number of substitutions, or no substitution; where R′, R″, R.sub.a, R.sub.b, R.sub.c, and R.sub.d are each independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof; and where any two R.sub.a, R.sub.b, R.sub.c, and R.sub.d can be fused or joined to form a ring or form a multidentate ligand.
(88) An OLED according to another embodiment is disclosed, comprising: an anode; a cathode; and an organic emissive layer disposed between the anode and the cathode, the organic emissive layer comprising: a first host, a second host; and an emitter; wherein the emitter is a phosphorescent metal complex that is a Pt(II) or Pd(II) complex having a square planar coordinating geometry or has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z described above; wherein E.sub.H1T, the T.sub.1 triplet energy of the first host, is higher than E.sub.ET, the T.sub.1 triplet energy of the emitter; wherein E.sub.ET is at least 2.50 eV; wherein the HOMO energy of the first host is higher than the HOMO energy of the second host; wherein the absolute value of the difference between the HOMO energy of the emitter and the HOMO energy of the first host is ΔE2; wherein ΔE2≤d; wherein d is 1.2 eV; wherein the absolute value of the difference between the LUMO energy of the emitter and the HOMO energy of the first host is represented by ΔE3; wherein the following relationship a≤ΔE3−E.sub.ET≤b is maintained; wherein a≥0.05 eV, and b≤0.60 eV. This energy configuration is shown in
(89) An OLED according to another embodiment is disclosed that comprises: an anode; a cathode; and an organic emissive layer disposed between the anode and the cathode. The organic emissive layer comprises: a first host, a second host, and a third host; and an emitter; wherein the emitter is a phosphorescent metal complex having E.sub.ET, T.sub.1 triplet energy, of at least 2.50 eV; wherein the emitter is a phosphorescent metal complex that is a Pt(II) or Pd(II) complex having a square planar coordinating geometry or has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z described above; wherein the absolute value of the difference between the HOMO of the emitter and the LUMO of the first host is represented by ΔE1; wherein the absolute value of the difference between the HOMO of the emitter and the HOMO of the second host is ΔE4; wherein the following relationship a≤ΔE1−E.sub.ET≤b is maintained wherein a≥0.005 eV, and b≤0.60 eV; wherein ΔE4≤d; wherein d is 1.2 eV; and wherein the absolute energy difference between the HOMO level of the third host and the first emitter is greater than ΔE4. This energy configuration is shown in
(90) In some embodiments, an OLED is disclosed that comprises: an anode; a cathode; and an organic emissive layer disposed between the anode and the cathode. The organic emissive layer comprises: a first host, a second host, and a third host; and an emitter; wherein the emitter is a phosphorescent metal complex having E.sub.ET, T.sub.1 triplet energy, of at least 2.50 eV; wherein the phosphorescent metal complex is a Pt(II) or Pd(II) complex having a square planar coordinating geometry or has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z described above; wherein the absolute value of the difference between the HOMO of the second host and the LUMO of the first host is represented by ΔE5; wherein the absolute value of the difference between the HOMO of the emitter and the HOMO of the second host is ΔE4; wherein the following relationship a≤ΔE5−E.sub.ET≤b is maintained wherein a≥0.005 eV, and b≤0.60 eV; wherein ΔE4≤d; and wherein d is 1.2 eV. This energy configuration is shown in
(91) The following are some examples of host materials that are suitable for use as the first host, the second host, and the third host, depending on the particular emitter compound that is selected.
(92) ##STR00044##
The HOMO, LUMO, and E.sub.ET of Compound 1, Compound 2, Compound 3, Compound 4, and Compound 10, are provided below in Table 1. The oxidation of Compound 1 is outside the window of the solvent of dimethylformamide. This means that the oxidation of Compound 1 is higher than 1.13 V which corresponds to HOMO deeper than −5.93 eV.
(93) TABLE-US-00001 TABLE 1 Material HOMO (eV) LUMO (eV) E.sub.ET (eV) Compound 1 <−5.93 −2.71 2.86 Compound 2 −5.7 −2.47 2.95 Compound 3 −5.73 −2.12 2.95 Compound 4 −5.38 −1.84 2.74 Compound 10 −5.68 −1.99 2.99
(94) The following are some examples of emitter compounds that are suitable for use with the example host compounds.
(95) ##STR00045##
The HOMO, LUMO, and E.sub.ET of Emitter 2, and Emitter 3 are provided below in Table 2.
(96) TABLE-US-00002 TABLE 2 Material HOMO (eV) LUMO (eV) E.sub.ET (eV) Emitter 2 −5.37 −2.18 2.76 Emitter 3 −5.40 −2.22 2.76
(97) The following are some examples of charge transport materials and red sensing compounds.
(98) ##STR00046##
(99) The HOMO, LUMO, and E.sub.ET levels for any given organic compounds can be readily measured and one of ordinary skill in the art would know how to measure these energy values and select the appropriate combination of emitter, first host, second host, and third host compounds that would meet the energy configurations disclosed herein. For example, to measure the energy levels, the inventors performed solution cyclic voltammetry (CV) and differential pulsed voltammetry using a CH Instruments model 6201B potentiostat using anhydrous dimethylformamide solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, and platinum and silver wires were used as the working, counter and reference electrodes, respectively. Electrochemical potentials were referenced to an internal ferrocene-ferrocenium redox couple (Fc/Fc+) by measuring the peak potential differences from differential pulsed voltammetry. The corresponding HOMO and LUMO energies were determined by referencing the cationic and anionic redox potentials to ferrocene (4.8 eV vs. vacuum) according to literature. The T.sub.1 triplet energy of the materials is measured by dissolving the material in 2-methyl tetrahydrofuran and cooling the mixture to 77K to form a frozen glass. The photoluminescence is measured using a Horiba Fluorolog fluorimeter and the T.sub.1 is taken as 1.sup.st emission peak. When the HOMO and LUMO are measured in the solid state with techniques such as Ultraviolet Photoelectron Spectroscopy (UPS) or Inverse Photolectron Spectroscopy (IPES) the actual values are generally different than those measured with CV method. However, the relative difference in the energy levels between different molecules is fairly similar regardless of the measurement technique used. Thus, so long as one compares the relative energy level difference using the same technique, the energy difference should be similar for a given set of molecules being compared.
(100) 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.
(101) 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.
(102) In some embodiments, the compound of the present disclosure is neutrally charged.
(103) An emissive region in an OLED is disclosed. The emissive region comprising a first host and an emitter, wherein the emitter is a phosphorescent metal complex that is a Pt(II) or Pd(II) complex having a square planar coordinating geometry or has the formula of M(L.sup.1).sub.x(L.sup.2).sub.y(L.sup.3).sub.z described above; The T.sub.1 triplet energy of the first host E.sub.H1T is higher than the T.sub.1 triplet energy of the emitter E.sub.ET, wherein E.sub.ET is at least 2.50 eV. The LUMO energy of the first host is higher than the HOMO energy of the emitter. The absolute value of the difference between the HOMO energy of the emitter and the LUMO energy of the first host is represented by ΔE1 and wherein 0.05 eV≤ΔE1−E.sub.ET≤0.60 eV.
(104)
(105) There are a number of requirements for the e-host that increase the performance of blue devices. The two foremost requirements for having the e-host to increase the lifetime of a device are: (1) the addition of e-host does not form an exciplex or charge transfer (CT) state with the emitter; and (2) that the charges are balanced with an exciton profile not pinned at an interface. Exiplex is an electronic state formed between two molecules, one a donor and the other an acceptor, which can subsequently dissociate in a deactivation process. The requirement that the addition of the e-host does not form an exiplex or CT state as the lowest energy state in the device will maintain the blue color of the phosphorescent emitter. The CT state exists between the e-host and the other components when a hole resides on an emitter or a host molecule and an electron resides on the e-host. A rough estimate of the CT state energy is the absolute value of the energy difference between the HOMO level of the emitter and the LUMO level of the e-host, ΔE1. Since the CT state is composed of an electron and a hole that are fairly well separated spatially, the energy difference between the Si singlet and the T.sub.1 triplet state of the CT will be small and ΔE1 is a good approximation of the T.sub.1 triplet state of the CT state. Having any CT state (if formed) that is higher in energy than the T.sub.1 triplet of the emitter is OK for device operation. If the CT state is higher in energy than the emitter's T.sub.1, there are two important aspects for the device. First, the emission spectrum of the device will be that of the emitter and not the CT state. Second, there will be a minimal loss in emitter's photoluminescence quantum yield (PLQY) in the host system. Conversely, if the CT state is the lowest energy state in the emission system, the T.sub.1 triplet of the emitter will be quenched into the CT state and the CT state spectrum will dominate the device's emission spectrum.
(106) For example, Table 3 contains the device structures and data for two different single-component e-hosts for blue phosphorescence emitter (Emitter 2). The terms “device structures” here refers to the material make up of the layers in the device. In the results, we can see that a lower energy CT state is formed when using Compound 1 (Cmp 1) as the host material. This is readily observed by the change in the peak wavelength from 461 nm of Device 2 to the peak of 502 nm in Device 1. This can be seen in the emission spectrum of Device 1 and Device 2 provided in
(107) TABLE-US-00003 TABLE 3 Device structures and data. This table is split into two parts. Device structure EML HIL HTL EBL Host Emitter BL ETL EIL 1931 CIE [100 Å] [250 Å] [50 Å] [300 Å] [10%] [50 Å] [300 Å] [10 Å] x y Device 1 Cmp 5 Cmp 6 Cmp 4 Cmp 1 Emitter 2 Cmp 2 Cmp 7: Cmp 7 0.246 0.507 Cmp 8 35% Device 2 Cmp 5 Cmp 6 Cmp 4 Cmp 2 Emitter 2 Cmp 2 Cmp 7: Cmp 7 0.155 0.282 Cmp 8 35% at 10mA/cm.sup.2 λ max FWHM Voltage LE EQE PE [nm] [nm] [V ] [cd/A] [%] [lm/W] Device 1 502 83 3.6 11 3.7 9 Device 2 461 64 3.5 7 3.7 4.1 HIL = hole injection layer; HTL = hole transport layer; EBL = electron blocking layer; EML = emissive layer; BL = hole blocking layer; ETL = electron transport layer; EIL = electron injection layer; the devices also had a 1000Å Al cathode. All doping percenages are in volume percent.
(108) The experimentally realized CT state formed between Cmp 1 and Emitter 2 can be verified by comparing ΔE to the T.sub.1 triplet energy of Emitter 2. The HOMO level of Emitter 2, as determined by CV, is −5.37 and the LUMO level of Compound 1, as determined by CV, is −2.71. For the combination of Compound 1 and Emitter 2, ΔE is 2.66 eV. For Emitter 2, the 77K emission peak is at 449 nm which corresponds to a triplet energy of 2.76 eV. Thus, we see that the CT state with energy ΔE is lower in energy than the T.sub.1 triplet of Emitter 2. In turn, the device emission is dominated by the CT state, leading to non-blue emission and low external quantum efficiency (EQE).
(109) Compound 2 is the converse example. The LUMO level of Compound 2 is −2.47 eV as determined by CV. The ΔE for Emitter 2 and Compound 2 is 2.90 eV which is greater than the 2.76 eV triplet energy of Emitter 2. This leads to the T.sub.1 triplet energy of Emitter 2 being the lowest energy state in the device, as observed by the emission spectrum of the device matching that of Emitter 2 in PMMA.
(110) In addition to the avoidance of CT state formation, requirement (1), the use of an electron transporting material in a deep blue phosphorescent device requires careful consideration of charge balance, requirement (2). A properly charge balanced device can greatly increase the efficiency and LT of the blue phosphorescent device and spreading the exciton profile over the thickness of the emissive layer can increase lifetime of the device.
(111) In order to evaluate whether a given emissive layer composition spreads the exciton profile over the thickness of the emissive layer requires the ability to probe the location of the exciton population spatially. Inventors used a 20 Å thick sensing layer to probe the location of the exciton population in the emissive layer.
(112)
(113)
(114)
(115) Using the red probe experiment and through varying the composition of the emissive layer we can demonstrate certain compositions that result in either good exciton profiles and/or good charge stability. In doing so we will use the device structure of
(116) Referring to
(117) In addition to having a good exciton profile, blue phosphorescent devices should be stable to different charging current densities (electric field strengths). We can monitor the charge stability of a device by monitoring the R/B ratio as a function of current density of the device.
(118) As an example to how to design a stable blue phosphorescent devices, we can use Emitter 2. Emitter 2 is a blue phosphorescent emitter with a peak wavelength of emission at 460 nm in a device or 452 nm in PMMA and a PLQY of 70% in drop cast PMMA. Using the device structure shown in
(119) TABLE-US-00004 TABLE 4 Device data table. The EML composition is noted. All other layer information is specified in FIG. 10. The lifetime is calculated assuming an acceleration factor of 1.8 at 1K at 10 mA/cm2 nits EML composition 1931 CIE λ max FWHM Voltage LE EQE PE calc* [280-300 Å] x y [nm] [nm] [V] [cd/A][%] x [lm/W] 80% [h] Device 2a Cmp 2:Emitter 2 0.156 0.236 460 53 3.41 4.5 2.7 4.1 15 10% 280Å Device 2b Cmp 3:Emitter 2 0.153 0.218 460 51 4.78 14.5 9.1 9.5 38 10% 280Å Device 2c Cmp 3:Cmp 2: Emitter 2 0.151 0.212 460 50 4.14 11.1 7.1 8.4 60 40:10% 300Å Device 2d Cmp 3:Cmp 2: Cmp 4: 0.155 0.244 460 55 4.04 17.0 9.9 13.2 57 Emitter 2 40:25:10% 300Å
(120) Devices which feature host compounds Cmp 2 and Cmp 3 are single host component devices, where Cmp 2 is an e-host and Cmp 3 is consider a h-host. The device with Cmp 2 does not show any evidence of exiplex emission with Emitter 2 showing that the first requirement for having a stable blue phosphorescent device is satisfied. There are several items to note. First, the efficiency of this device is quite low. Second, the voltage at 10 mA/cm2 is very low which is a positive. Third, the R/B ratio in
(121) In contrast to the single-component e-host device, the single-component h-host has significantly higher EQE. However, this device has a high operating voltage. Additionally, as seen in
(122) This leads to the use of a device with energy levels equivalent to
(123) To combat the good electron transport of the device with Cmp 3: Cmp2 40% we can add an additional h-host. The energetics of the host components are depicted in
(124) The overall conclusions from the red probed devices plus the device results in Table 4 demonstrate managing the composition of the EML can greatly improve device performance. However, the ideal composition can vary by emitter. For example, in Table 5 provided below we show the device performance of Emitter 3 for various EML compositions. The EML composition of each device is noted in the table with the remaining layers per
(125) TABLE-US-00005 TABLE 5 Device data table. The EML composition is noted. All other layer information is specified in FIG. 10. at 1K at 10 mA/cm.sup.2 nits EML composition 1931 CIE λ max FWHM Voltage LE EQE PE calc* [300 Å] x y [nm] [nm] [V] [cd/A] [%] [lm/W] 80%[h] Device 3a Cmp 10:Emitter 3 15% 0.133 0.188 467 29 5.64 12.0 8.9 6.7 8 Device 3b Cmp 10:Cmp 2:Emitter 3 0.132 0.191 467 33 4.03 9.3 6.8 7.3 19 40:10% Device 3c Cmp 10:Cmp 4:Emitter 3 0.129 0.180 468 27 4.07 12.6 9.7 9.7 13 40:10% Device 3d Cmp 10:Cmp 2:Cmp 4: 0.130 0.195 468 33 3.94 19.0 13.8 15.1 58 Emitter 3 40:25:10%
(126) Table 5 highlights the following important information. First, use of Compound 2 in the emissive layer at 40% doping lowers the EQE at 10 mA/cm2 but increase the lifetime and lowers the operating voltage similar to Emitter 2. However, for Emitter 3, the addition of Compound 4 to the emissive layer adds hole transport to the emissive layer which increases EQE, increases lifetime, and decreases operating voltage relative to the single host device. Similar to Emitter 2, Emitter 3 experiences the best EQE, lifetime, and operating voltage when using Compound 10, Compound 2, and Compound 4 in the emissive layer.
(127) The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel.
(128) 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 layer material, disclosed herein.
(129) 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.
(130) Combination with Other Materials
(131) 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.
(132) Conductivity Dopants:
(133) 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.
(134) 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, WO006081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
(135) ##STR00047## ##STR00048##
HIL/HTL:
(136) A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO.sub.x; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
(137) Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to the following general structures:
(138) ##STR00049##
(139) Each of Ar.sup.1 to Ar.sup.9 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, halide, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
(140) In one aspect, Ar.sup.1 to Ar.sup.9 is independently selected from the group consisting of:
(141) ##STR00050##
wherein k is an integer from 1 to 20; X.sup.101 to X.sup.108 is C (including CH) or N; Z.sup.101 is NAr.sup.1, O, or S; Ar.sup.1 has the same group defined above.
(142) Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
(143) ##STR00051##
wherein Met is a metal, which can have an atomic weight greater than 40; (Y.sup.101-Y.sup.102) is a bidentate ligand, Y.sup.101 and Y.sup.102 are independently selected from C, N, O, P, and S; L.sup.01 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.
(144) In one aspect, (Y.sup.101-Y.sup.102) is a 2-phenylpyridine derivative. In another aspect, (Y.sup.101-Y.sup.102) 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.sup.+/Fc couple less than about 0.6 V.
(145) 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,
(146) ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067##
EBL:
(147) 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.
(148) Additional Hosts:
(149) The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting dopant material, and may contain one or more additional host materials 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.
(150) Examples of metal complexes used as host are preferred to have the following general formula:
(151) ##STR00068##
wherein Met is a metal; (Y.sup.103-Y.sup.104) is a bidentate ligand, Y.sup.103 and Y.sup.104 are independently selected from C, N, O, P, and S; L.sup.101 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.
(152) In one aspect, the metal complexes are:
(153) ##STR00069##
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
(154) In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y.sup.103-Y.sup.104) is a carbene ligand.
(155) Examples of other organic compounds used as additional host are selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting 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 group consisting 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. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
(156) In one aspect, host compound contains at least one of the following groups in the molecule:
(157) ##STR00070## ##STR00071##
wherein R.sup.101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, 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. k is an integer from 0 to 20 or 1 to 20. X.sup.101 to X.sup.108 are independently selected from C (including CH) or N. Z.sup.101 and Z.sup.102 are independently selected from NR.sup.101, O, or S.
(158) Non-limiting examples of the additional host materials that may be used in an OLED in combination with the host compound 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.
(159) ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082##
Emitter:
(160) An emitter example is not particularly limited, and any compound may be used as long as the compound is typically used as an emitter material. 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; 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.
(161) 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,
(162) ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102##
HBL:
(163) 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.
(164) In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
(165) In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
(166) ##STR00103##
wherein k is an integer from 1 to 20; L.sup.101 is an another ligand, k′ is an integer from 1 to 3.
ETL:
(167) 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.
(168) In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
(169) ##STR00104##
wherein R.sup.101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, 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. Ar.sup.1 to Ar.sup.3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X.sup.101 to X.sup.108 is selected from C (including CH) or N.
(170) In another aspect, the metal complexes used in ETL include, but are not limited to the following general formula:
(171) ##STR00105##
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L.sup.101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
(172) 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,
(173) ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114##
Charge Generation Layer (CGL)
(174) 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.
(175) 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. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
(176) 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.