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WO2025132194A1 - Nouveaux matériaux pour dispositifs électroluminescents organiques - Google Patents

Nouveaux matériaux pour dispositifs électroluminescents organiques Download PDF

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WO2025132194A1
WO2025132194A1 PCT/EP2024/086537 EP2024086537W WO2025132194A1 WO 2025132194 A1 WO2025132194 A1 WO 2025132194A1 EP 2024086537 W EP2024086537 W EP 2024086537W WO 2025132194 A1 WO2025132194 A1 WO 2025132194A1
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atoms
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aromatic
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Philipp Stoessel
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to novel compounds (materials) and organic electronic devices such as OLEDs (organic light-emitting diodes) that contain these compounds, for example as electron-transport materials and/or matrix materials, optionally in combination with another matrix material. Furthermore, the present invention relates to mixtures and formulations containing these novel compounds.
  • organic electroluminescent devices e.g., OLEDs or OLECs - organic light-emitting electrochemical cells
  • organic semiconductors are used as organic functional materials
  • organometallic complexes that exhibit phosphorescence are increasingly being used as emitting materials (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6).
  • organometallic compounds for quantum mechanical reasons, up to four times the energy and power efficiency is possible using organometallic compounds as phosphorescence emitters.
  • there is still room for improvement in both OLEDs that exhibit singlet emission and OLEDs that exhibit triplet emission particularly with regard to efficiency, operating voltage, and lifetime.
  • organic electroluminescent devices are not only determined by the emitters used.
  • the other materials used such as host and matrix materials, hole-blocking materials, electron-transport materials, hole-transport materials, and electron- or exciton-blocking materials, are also of particular importance. Improvements to these materials can lead to significant improvements in electroluminescent devices.
  • heteroaromatic compounds are used in particular as electron-transport materials and as matrix materials for phosphorescent compounds.
  • matrix material is typically used when referring to a host material for phosphorescent emitters. This use of the term “matrix material” is also used for the present invention.
  • improvement in these compounds for example for use as matrix materials, particularly in terms of lifetime, but also in terms of efficiency and operating voltage of the device.
  • the object of the present invention is therefore to provide compounds which are suitable for use in an organic electroluminescent device and which, when used in this device, lead to good device properties, as well as to provide the corresponding organic electroluminescent device.
  • the object of the present invention is to provide compounds which lead to a long lifetime, good efficiency, and low operating voltage in a phosphorescent or fluorescent, in particular phosphorescent, OLED.
  • the properties of the matrix materials in particular have a significant influence on the lifetime and efficiency of the organic electroluminescent device.
  • the compounds should lead to devices with excellent color purity, particularly when used as electron transport materials, matrix materials or hole transport materials in organic electroluminescent devices.
  • R x is, on each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl chain having 1 to 40 C atoms, preferably 1 to 20 C atoms, more preferably 1 to 10 C atoms, a branched or cyclic alkyl chain having 3 to 40 C atoms, preferably 3 to 20 C atoms, more preferably 3 to 10 C atoms, where in the alkyl chains one or more H atoms may be replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably 5 to 24 aromatic ring atoms, more preferably 5 to 18 aromatic ring atoms, each of which may be substituted by one or more radicals R 6 ; two R x may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R 6 ;
  • Y 1 represents an electron-transporting group Q 1 , which may be substituted by one or more radicals R 7 , or a hole-transporting group H 1 , which may be substituted by one or more radicals R 8
  • L is a single bond, or an aromatic or heteroaromatic ring system with 5 - 40 aromatic ring atoms, which may be substituted by one or more radicals R 9 ;
  • Y is an electron-transporting group Q which may be substituted by one or more radicals R 3 , or a hole-transporting group H which may be substituted by one or more radicals R 10 ;
  • Ar, Ar 1 is at each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 - 40 aromatic ring atoms, each of which may be substituted by one or more radicals R 5 ;
  • R 5 , R 9 is, identically or differently, H, D, F, CN, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms in which one or more H atoms may be replaced by D, F, Cl, I, Br or CN or a straight-chain or branched alkyl chain having 1 - 4 C atoms, and the following compounds are excluded:
  • the symbol “D” or “D-atom” stands for deuterium.
  • An aryl group within the meaning of this invention contains 6 to 40 ring atoms, preferably C atoms.
  • a heteroaryl group within the meaning of this invention contains 5 to 40 ring atoms, where the ring atoms comprise C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5.
  • the heteroatoms are preferably selected from N, O and/or S.
  • An aryl group or heteroaryl group is understood to be either a simple aromatic cycle, i.e.
  • phenyl derived from benzene, or a simple heteroaromatic cycle, for example derived from pyridine, pyrimidine or thiophene, or a fused aryl or heteroaryl group, for example derived from naphthalene, anthracene, phenanthrene, quinoline or isoquinoline.
  • An aryl group with 6 to 30 C atoms is therefore preferably phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, dibenzoanthracenyl, chrysenyl or perylenyl, whereby the attachment of the aryl group as a substituent is not restricted.
  • An aromatic ring system within the meaning of this invention contains 6 to 40 C atoms in the ring system, wherein the ring system also comprises the aryl groups described above.
  • a heteroaromatic ring system within the meaning of this invention contains 5 to 40 ring atoms and at least one heteroatom.
  • a preferred heteroaromatic ring system has 9 to 40 ring atoms and at least one heteroatom.
  • the heteroaromatic ring system also includes heteroaryl groups, as described above.
  • the heteroatoms in the heteroaromatic ring system are preferably selected from N, O, and/or S.
  • An aromatic or heteroaromatic ring system within the meaning of this invention is understood to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryl or heteroaryl groups can also be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as a C or O atom or a carbonyl group.
  • a non-aromatic unit preferably less than 10% of the atoms other than H
  • systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, 9,9-diarylfluorene, diaryl ethers, stilbene, etc.
  • aromatic or heteroaromatic ring systems within the meaning of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group.
  • systems in which two or more Aryl or heteroaryl groups are directly bonded to one another such as biphenyl, terphenyl, quaterphenyl or bipyridine, are also included in the definition of the aromatic or heteroaromatic ring system.
  • An aromatic or heteroaromatic ring system with 5 - 40 ring atoms which can be linked to the aromatic or heteroaromatic ring via any position, is understood to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene
  • 4,5-diazapyrene, 4,5,9, 10-tetraazaperylene pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1 ,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole,
  • a straight-chain alkyl group having 1 to 40 C atoms preferably 1 to 20 C atoms, more preferably 1 to 10 C atoms
  • a branched or cyclic alkyl group having 3 to 40 C atoms preferably having 3 to 20 C atoms, more preferably having 3 to 10 C atoms, for example the radicals methyl, ethyl, n-propyl,
  • cyclic alkyl group includes a monocyclic compound, 1,1-Diethyl-n-dec-1-yl-, 1,1-Diethyl-n-dodec-1-yl-, 1,1-Diethyl-n-tetradec-1-yl-, 1,1-Diethyln-n-hexadec-1-yl-, 1, 1-Diethyl-n-octadec-1-yl-, 1-(n-propyl)-cyclohex-1-yl-, 1-(n-butyl)-cyclohex-1-yl-, l-(n-hexyl)-cyclohex-1-yl-, 1-(n-Octyl)-cyclohex-1-yl- and 1-(n-Decyl)-cyclohex-1-yl- understood.
  • cyclic alkyl group includes a monocyclic alkyl group, 1,1-Diethyl-n-oct-1-y
  • a straight-chain alkyl group having 1-20 C atoms, preferably having 1-10 C atoms, or a branched alkyl group having 3-20 C atoms, preferably having 3-10 C atoms, in which one or more non-adjacent CH2 groups can be replaced by O or S, and in which at least one H atom can be replaced by D, F or CN, is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, thiomethyl, 1-thioethyl, 1-thio-i-propyl, 1-thio-n-propoyl, 1-thio-i-butyl, 1-thio-n-butyl or 1-thio-t-butyl.
  • adjacent carbon atoms are carbon atoms that are directly linked to one another.
  • adjacent radicals in the definition of radicals means that these radicals are bonded to the same carbon atom or to adjacent carbon atoms.
  • two or more residues can form a ring system refers to the formation of an aliphatic, aromatic, or heteroaromatic ring system.
  • the two residues are linked by a chemical bond with the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:
  • R represents an aromatic or heteroaromatic ring system having 5 to 25 aromatic ring atoms, it is on each occurrence, identically or differently, phenyl, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, quaterphenyl, in particular ortho-, meta-, para- or branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, triphenylenyl, phenanthrenyl, pyridyl, pyrimidinyl, triazinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-Carbazolyl, , Quinazolinyl, Quinaxolinyl,
  • Y in formula (I) is a hole-transporting group H
  • said hole-transporting group is a carbazole, biscarbazole, tricarbazole, indenocarbazole, indolocarbazole, benzimidazobenzimidazole or a diarylamine, which may be substituted by one or more radicals R 10 .
  • the hole-transporting group H can be chosen from the following formulas (H-1) to
  • (H-39) can be selected: Formula (H-4) Formula (H-5)
  • Ar 2 , Ar 3 and Ar 4 are an aromatic or heteroaromatic
  • Ring system with 5 to 40 aromatic ring atoms which may be independently substituted by one or more radicals R 10 , where the The radical R 10 has the meaning given above.
  • Ar 2 , Ar 3 and Ar 4 identical or different, are an aromatic or heteroaromatic ring system having 5-25 aromatic ring atoms, more preferably having 5 to 18 aromatic ring atoms, even more preferably having 5 to 13 aromatic ring atoms, each of which may be substituted by one or more radicals R 10 .
  • aromatic or heteroaromatic ring systems mentioned can be selected, for example, from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, in particular branched terphenyl, quaterphenyl, in particular phenyl, ortho-, meta- or para-biphenyl, 1-, 2-, 3- or 4-fluorenyl, in particular 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, 1-, 2-, 3- or 4-carbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and/or triphenylenyl.
  • the compounds of the invention can be prepared by synthetic steps known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc.
  • the compounds are shown with a small number of substituents to simplify the structures. This does not exclude the presence of any other substituents in the processes.
  • the processes shown for synthesizing the compounds of the invention are to be understood as examples. The skilled person can develop alternative synthetic routes within the scope of their general technical knowledge.
  • Suitable and preferred solvents are for example toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1 ,2,4,5-Tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, Cyclohexanol, Cyclohexanone, Cyclohexylbenzene, Decalin, Dodecy
  • Particularly suitable fully deuterated solvents are benzene-d6 and toluene-d8.
  • a particularly preferred deuterium source is a combination of D2O and toluene-d8.
  • the reaction is preferably carried out with heating, more preferably with heating to temperatures between 100 °C and 200 °C. Furthermore, the reaction is preferably carried out under pressure.
  • Suitable further matrix materials for combination with compounds of formula (I), as previously described or preferably described are the compounds described in W02019/229011 A1, Table 3, pages 137 to 203, which may also be partially or fully deuterated.
  • suitable further matrix materials for combination with compounds of formula (I) or preferred compounds of formula (Ia), as previously described or preferably described, are the compounds described in KR20230034896 A, on pages 42 to 47, compounds [2-1] to [2-110], or on pages 49 to 51, compounds [3-1] to [3-26].
  • the following Table 3 lists suitable further matrix materials which may also be partially or fully deuterated.
  • the concentration of the host material of formula (I), as described above or preferably described, in the mixture according to the invention or in the light-emitting layer of the device according to the invention is usually in the range from 5 wt.% to 90 wt.%, preferably in the range from 10 wt.% to 85 wt.%, more preferably in the range from 20 wt.% to 85 wt.%, even more preferably in the range from 30 wt.% to 80 wt.%, very particularly preferably in the range from 20 wt.% to 60 wt.% and most preferably in the range from 30 wt.% to 50 wt.%, based on the total mixture or based on the total composition of the light-emitting layer.
  • the present invention also relates to an organic electroluminescent device as described above or preferably described, wherein the light-emitting layer contains, in addition to the above-mentioned host materials of the formula (I) and at least one above-mentioned further matrix material, at least one phosphorescent emitter.
  • phosphorescent emitters typically encompasses compounds in which light emission occurs through a spin-forbidden transition from an excited state with higher spin multiplicity, i.e., a spin state > 1, for example, through a transition from a triplet state or a state with an even higher spin quantum number, such as a quintet state. Preferably, this refers to a transition from a triplet state.
  • Particularly suitable phosphorescent emitters are compounds which, upon suitable excitation, emit light, preferably in the visible range, and which also contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal with this atomic number.
  • Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, Osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are used, especially compounds containing iridium or platinum.
  • all luminescent compounds containing the above-mentioned metals are considered phosphorescent emitters.
  • Preferred phosphorescent emitters according to the present invention Formula (3a), where the symbols and indices for this formula (3a) have the meaning: n+q is 3, n is 1 or 2, q is 2 or 1 ,
  • R x is, identically or differently at each occurrence, H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 7 C atoms which may be partially or fully substituted with deuterium or an aromatic or heteroaromatic ring system having 5 to 60 ring atoms which may be partially or fully substituted with deuterium.
  • a further subject matter of the invention is accordingly an organic electroluminescent device as described above or preferably described, characterized in that the light-emitting layer contains, in addition to the host materials 1 and 2, at least one phosphorescent emitter which corresponds to the formula (3a), as described above.
  • n is preferably 1 and q is preferably 2.
  • one X is preferably selected from N and the other Xs are CR or all Xs, identically or differently on each occurrence, are CR.
  • at least one R is preferably different from H.
  • two Rs are preferably different from H and have one of the meanings otherwise previously given for the emitters of formula (3a).
  • Preferred phosphorescent emitters according to the present invention correspond to formulas (1), (2), (3), (4) or (5),
  • Ri is H or D
  • R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.
  • Preferred phosphorescent emitters according to the present invention correspond to formulas (6), (7) or (8),
  • Ri is H or D
  • R2 is H, D, F, CN or a branched or linear alkyl group having 1 to 10 C atoms or a partially or fully deuterated branched or linear alkyl group having 1 to 10 C atoms or a cycloalkyl group having 4 to 10 C atoms, which may be partially or fully substituted with deuterium.
  • Preferred examples of phosphorescent emitters are described in WO2019/007867 on pages 120 to 126 in Table 5 and on pages 127 to 129 in Table 6. The emitters are incorporated into the description by this reference. Particularly preferred examples of phosphorescent emitters are listed in Table 4 below.
  • the light-emitting layer in the organic electroluminescent device according to the invention containing at least one phosphorescent emitter is preferably an infrared-emitting, yellow, orange, red, green, blue or ultraviolet-emitting layer, particularly preferably a yellow or green-emitting layer and very particularly preferably a green-emitting layer.
  • a yellow-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 540 to 570 nm.
  • An orange-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 570 to 600 nm.
  • a red-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 600 to 750 nm.
  • a green-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 490 to 540 nm.
  • a blue-emitting layer is understood to be a layer whose photoluminescence maximum lies in the range from 440 to 490 nm. The photoluminescence maximum of the layer is determined by measuring the photoluminescence spectrum of the layer with a layer thickness of 50 nm at room temperature.
  • the photoluminescence spectrum of the layer is recorded, for example, using a commercially available photoluminescence spectrometer.
  • the photoluminescence spectrum of the selected emitter is usually measured in an oxygen-free solution ( 10'5 molar). The measurement is carried out at room temperature. Any solvent in which the selected emitter dissolves at the specified concentration is suitable. Particularly suitable solvents are usually toluene or 2-methyl-THF, but also dichloromethane. The measurement is carried out using a commercially available photoluminescence spectrometer.
  • Preferred phosphorescent emitters are therefore yellow emitters, preferably of formula (3a), formulas (1) to (8) or from Table 6, whose triplet energy T-
  • Preferred phosphorescent emitters are therefore green emitters, preferably of formula (3a), formulas (1) to (8) or from Table 6, whose triplet energy T-
  • Particularly preferred phosphorescent emitters are accordingly green emitters, preferably of formula (3a), formulas (1) to (8) or from Table 6, as described above, whose triplet energy T-
  • the mixture contains no further components, i.e., functional materials, in addition to the constituents of the host material of formula (I) and the further matrix material, as described above or preferably described.
  • these are material mixtures that are used as such to produce the light-emitting layer.
  • These mixtures are also referred to as premix systems, which are used as the sole material source during the vapor deposition of the host materials for the light-emitting layer and which have a constant mixing ratio during vapor deposition. This allows the vapor deposition of a layer with a uniform distribution of the components to be achieved in a simple and rapid manner, without the need for precise control of a large number of material sources.
  • the mixture contains, in addition to the constituents of the host material of formula (I) and the further matrix material, as described above or preferably described, a phosphorescent emitter as described above. With a suitable mixing ratio during vapor deposition, this mixture can also be used as the sole material source.
  • the components or constituents of the light-emitting layer of the device according to the invention can thus be processed by vapor deposition or from solution.
  • the material combination of the host materials, as described above or preferably described, optionally with the phosphorescent emitter, as described above or preferably described, is provided for this purpose in a formulation containing at least one solvent. Suitable formulations have been described previously.
  • the light-emitting layer in the device according to the invention according to the preferred embodiments and the emitting compound preferably contains between 99.9 and 1 vol.%, more preferably between 99 and 10 vol.%, particularly preferably between 98 and 60 vol.%, very particularly preferably between 97 and 80 vol.% of matrix material comprising at least one compound of the formula (I), preferably of the formula (Ia) and at least one compound of a further matrix material, based on the total composition of Emitter and matrix material.
  • the light-emitting layer in the device according to the invention preferably contains between 0.1 and 99 vol. %, more preferably between 1 and 90 vol. %, particularly preferably between 2 and 40 vol. %, most preferably between 3 and 20 vol.
  • the emitter based on the total composition of the light-emitting layer consisting of emitter and matrix material. If the compounds are processed from solution, the corresponding amounts in wt. % are preferably used instead of the above-specified amounts in vol. %.
  • the organic electroluminescent device according to the invention is preferably characterized in that one or more layers are coated using the OVPD (Organic Vapor Phase Deposition) process or by means of carrier gas sublimation.
  • the materials are applied at a pressure between 10'5 mbar and 1 bar.
  • OVJP Organic Vapor Jet Printing
  • the materials are applied directly through a nozzle and thus structured (e.g., M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).
  • the organic electroluminescent device according to the invention is preferably characterized in that one or more organic layers containing the composition according to the invention are applied from solution, such as by spin coating, or by any printing method, such as screen printing, flexographic printing, nozzle printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (ink-jet printing).
  • LITI Light Induced Thermal Imaging, thermal transfer printing
  • ink-jet printing ink-jet printing
  • Solution processing has the advantage that, for example, the light-emitting layer can be applied very easily and cost-effectively. This technique is particularly suitable for the mass production of organic electroluminescent devices.
  • the organic layer according to the invention preferably the light-emitting layer
  • the materials used can each be placed in a material source and then evaporated from the various material sources ("co-evaporation”).
  • the various materials can be premixed ("premixed", premix systems) and the mixture placed in a single material source, from which it is then evaporated (“premix evaporation”). This allows for the vapor deposition of the light-emitting layer with a uniform distribution of the components in a simple and rapid manner, without the need for precise control of a large number of material sources.
  • a method for producing the organic electroluminescent device according to the invention as described above or preferably described, characterized in that the organic layer, preferably the light-emitting layer, the electron transport layer and/or hole blocking layer, is applied by vapor deposition, in particular with a sublimation process and/or with an OVPD (Organic Vapor Phase Deposition) process and/or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.
  • vapor deposition in particular with a sublimation process and/or with an OVPD (Organic Vapor Phase Deposition) process and/or with the aid of carrier gas sublimation, or from solution, in particular by spin coating or with a printing process.
  • OVPD Organic Vapor Phase Deposition
  • a process for producing the organic electroluminescent device according to the invention as described above or preferably described, characterized in that the light-emitting layer of the organic layer is applied by gas phase deposition, wherein the at least one compound of formula (I), in particular of formula (Ia), together with the further materials which form the light-emitting layer, are deposited successively or simultaneously from at least two material sources from the gas phase.
  • a method for producing the device according to the invention characterized in that the light-emitting layer of the organic layer is applied by vapor deposition, wherein the at least one compound of formula (I), in particular of formula (Ia) together with at least one further matrix material as a premix, is deposited from the vapor phase successively or simultaneously with the light-emitting materials selected from the group of phosphorescent emitters, fluorescent emitters and/or emitters which exhibit TADF (thermally activated delayed fluorescence).
  • TADF thermalally activated delayed fluorescence
  • Electronic devices in particular organic electroluminescent devices comprising compounds of formula (I) or the preferred embodiments described above and below, in particular as matrix material or as electron-conducting materials, exhibit a very long lifetime. These compounds, in particular, result in low roll-off, i.e., a low drop in the power efficiency of the device at high luminance levels. 2. Electronic devices, in particular organic electroluminescent devices containing compounds of formula (I) or the preferred embodiments described above and below as electron-conducting materials and/or matrix materials, exhibit excellent efficiency. Compounds of the invention of formula (I) or the preferred embodiments described above and below result in a low operating voltage when used in electronic devices.
  • optical loss channels can be avoided in electronic devices, particularly organic electroluminescent devices. As a result, these devices are characterized by high PL and thus high EL efficiency of emitters and excellent energy transfer from the matrices to dopants.
  • the compounds according to formula (I) or the preferred embodiments described above and below have a deep triplet level Ti, which can be, for example, in the range from 2.50 eV to 2.90 eV.
  • the present invention further relates to the use of a compound according to formula (I), in particular formula (Ia), or a mixture according to the invention or a formulation according to the invention in an organic electroluminescent device.
  • the compound according to formula (I), in particular formula (Ia), or a mixture according to the invention or a formulation according to the invention is used as an electron-transporting material, electron-injecting material, matrix material, hole-transporting and/or hole-blocking material, more preferably as an electron-transporting material, matrix material, hole-transporting material and/or hole-blocking material.
  • the precipitated solid is filtered off with suction, washed once with 200 ml of water, once with 150 ml of water/ethanol (EtOH) (1:1 vv), and three times with 100 ml of EtOH, and dried in vacuo.
  • the crude product is purified by chromatography (Torrent column system from A. Semrau) and/or repeated hot extraction crystallization (common organic solvents or combinations thereof, preferably acetonitrile/DCM, 1:3 to 3:1 vv), as well as fractional sublimation or annealing under high vacuum. Yield: 30.4 g (78 mmol) 78%;

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne de nouveaux composés (matériaux) et des dispositifs électroluminescents organiques tels que des OLED (diodes électroluminescentes organiques) qui contiennent ces composés, par exemple en tant que matériaux de transport d'électrons et/ou matériaux matriciels, éventuellement combinés avec un autre matériau matriciel. L'invention concerne également des mélanges et des formulations contenant ces nouveaux composés.
PCT/EP2024/086537 2023-12-20 2024-12-16 Nouveaux matériaux pour dispositifs électroluminescents organiques Pending WO2025132194A1 (fr)

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EP23218859 2023-12-20

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