WO2019128343A1 - 一种电致发光材料及其在光电器件中的应用 - Google Patents
一种电致发光材料及其在光电器件中的应用 Download PDFInfo
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- WO2019128343A1 WO2019128343A1 PCT/CN2018/107243 CN2018107243W WO2019128343A1 WO 2019128343 A1 WO2019128343 A1 WO 2019128343A1 CN 2018107243 W CN2018107243 W CN 2018107243W WO 2019128343 A1 WO2019128343 A1 WO 2019128343A1
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 230000005669 field effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 1
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 abstract 1
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 abstract 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
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- 230000006798 recombination Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 0 Cc1c2[n](*)c3ccc(*)cc3c2ccc1 Chemical compound Cc1c2[n](*)c3ccc(*)cc3c2ccc1 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
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- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MLBLYPGYMLZUMG-UHFFFAOYSA-N c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c2cc(-[n]3c4ccccc4c4c3cccc4)ccc2)c2cc(-[n]3c4ccccc4c4c3cccc4)ccc2)cc1 Chemical compound c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c2cc(-[n]3c4ccccc4c4c3cccc4)ccc2)c2cc(-[n]3c4ccccc4c4c3cccc4)ccc2)cc1 MLBLYPGYMLZUMG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- MITGKKFYIJJQGL-UHFFFAOYSA-N 9-(4-chlorobenzoyl)-6-methylsulfonyl-2,3-dihydro-1H-carbazol-4-one Chemical compound ClC1=CC=C(C(=O)N2C3=CC=C(C=C3C=3C(CCCC2=3)=O)S(=O)(=O)C)C=C1 MITGKKFYIJJQGL-UHFFFAOYSA-N 0.000 description 1
- SWKRZWXWRDTDLV-UHFFFAOYSA-N BrC(Br)=C1c2ncccc2C(c2ccccc2)(c2ccccc2)c2ncccc12 Chemical compound BrC(Br)=C1c2ncccc2C(c2ccccc2)(c2ccccc2)c2ncccc12 SWKRZWXWRDTDLV-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- IDQUIFLAFFZYEX-UHFFFAOYSA-N OB(c1cc(-[n]2c(cccc3)c3c3c2cccc3)ccc1)O Chemical compound OB(c1cc(-[n]2c(cccc3)c3c3c2cccc3)ccc1)O IDQUIFLAFFZYEX-UHFFFAOYSA-N 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FCMFLIXQBFZFPI-UHFFFAOYSA-N c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c(cc2)ccc2-[n]2c(cccc3)c3c3c2cccc3)c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)cc1 Chemical compound c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c(cc2)ccc2-[n]2c(cccc3)c3c3c2cccc3)c(cc2)ccc2-[n]2c3ccccc3c3c2cccc3)cc1 FCMFLIXQBFZFPI-UHFFFAOYSA-N 0.000 description 1
- HFGYOMQFVHXETC-UHFFFAOYSA-N c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c(cc2)ccc2-c(cc2c3c4cccc3)ccc2[n]4-c2ccccc2)c(cc2)ccc2-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)cc1 Chemical compound c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c(cc2)ccc2-c(cc2c3c4cccc3)ccc2[n]4-c2ccccc2)c(cc2)ccc2-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)cc1 HFGYOMQFVHXETC-UHFFFAOYSA-N 0.000 description 1
- QXWJSDFAXSIOOU-UHFFFAOYSA-N c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c(cccc2)c2-[n]2c(cccc3)c3c3c2cccc3)c2ccccc2-[n]2c(cccc3)c3c3c2cccc3)cc1 Chemical compound c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c(cccc2)c2-[n]2c(cccc3)c3c3c2cccc3)c2ccccc2-[n]2c(cccc3)c3c3c2cccc3)cc1 QXWJSDFAXSIOOU-UHFFFAOYSA-N 0.000 description 1
- RSKJMNUYXSKQAB-UHFFFAOYSA-N c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c2ccccc2)c2ccccc2)cc1 Chemical compound c1ccc(C(c2ccccc2)(c2cccnc22)c3ncccc3C2=C(c2ccccc2)c2ccccc2)cc1 RSKJMNUYXSKQAB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
Definitions
- the invention relates to a novel organic light emitting diode electroluminescent material and application in the photoelectric device, in particular to an electroluminescent material based on a carbazole and pyridine building unit, which is used as a light emitting layer material for an organic light emitting diode device.
- OLEDs organic light-emitting diodes
- OLED devices have the characteristics of self-luminous, wide viewing angle, short reaction time and the ability to fabricate flexible devices, making them a strong competitor for next-generation display and lighting technologies.
- OLED still has problems such as low efficiency and short life, which needs further research.
- PHOLEDs electrophosphorescent devices
- High-efficiency PHOLED devices are typically multilayer structures with the advantage of facilitating carrier injection, transport, and recombination processes.
- concentration quenching and T 1 -T 1 quenching occur, resulting in a decrease in luminous efficiency.
- the guest material is typically doped in the host material to "dilute" the concentration of the guest material.
- Excitons formed in the body The method of energy transfer from Dexter is transmitted to the object, and the excited object radiates back to the ground state. Therefore, in order to obtain high-efficiency PHOLED devices, it is particularly important to develop new high-performance host materials.
- the host material can be classified into three types: a hole type, an electron type, and a bipolar type.
- a hole-type host material When a hole-type host material is used, hole and electron recombination usually occurs at the interface between the light-emitting layer and the electron transport layer; when an electron-type host material is used, hole and electron recombination generally occur at the interface between the light-emitting layer and the hole transport layer. on.
- the monopolar host material is liable to cause the carrier recombination region to be narrowed.
- the narrow composite region causes the local exciton density to increase and accelerates the T 1 -T 1 annihilation, which is not conducive to the improvement of device performance.
- the bipolar body material can effectively solve the above problems.
- the use of bipolar host materials can balance the holes and electrons in the device, broaden the carrier recombination region, and simplify the device structure, which has attracted great interest from researchers in this field.
- the object of the present invention is to provide a novel bipolar host material based on pyridine and carbazole building units, which is used in an organic light emitting diode device to obtain good luminous efficiency.
- Ar is one of the following groups:
- R 1 and R 2 are independently selected from hydrogen, C1-C4 substituted or unsubstituted alkyl, C2-C4 substituted or unsubstituted olefinic alkyl, C2-C4 substituted or unsubstituted alkynyl, C6-C10 a substituted or unsubstituted aryl group, an aromatic hydrocarbon group having one or more substituents, a C1-C8 heteroaryl group containing one or more substituents substituted or unsubstituted, having one or more hetero atoms; It is substituted by a halogen element, a C1-C4 alkyl group.
- R 1 and R 2 are independently selected from hydrogen, C1-C4 alkyl, and C6-C10 contains one or more substituted or unsubstituted aryl or aromatic hydrocarbon groups;
- R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, tert-butyl, phenyl, tolyl, naphthyl;
- R 1 and R 2 are the same substituent selected from the group consisting of hydrogen, methyl, tert-butyl, and phenyl;
- Ar is the following group:
- R 1 and R 2 are the same substituents selected from the group consisting of hydrogen, tert-butyl, and phenyl.
- Ar is one of the following groups:
- R 1 is hydrogen and R 2 is tert-butyl, phenyl, tolyl or naphthyl.
- An organic electroluminescent diode device comprising a cathode, an anode and an organic layer, the organic layer being one or more layers of a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, the organic layers not necessarily being each layer All exist.
- the hole transport layer, the hole blocking layer, the light-emitting layer, and/or the electron transport layer contain the compound of the formula (I).
- the compound of the formula (I) is a host material applied to the light-emitting layer.
- the total thickness of the organic layer of the device of the present invention is from 1 to 1000 nm, preferably from 1 to 500 nm, more preferably from 5 to 300 nm.
- the organic layer may be formed into a film by a vaporization or solution method.
- the compound represented by the formula (I) has the following structure:
- the above compounds are used in organic electroluminescent devices, electroluminescent devices, organic field effect transistors, organic solar cells and chemical sensors.
- the experimental results show that the organic host material of the invention has high luminous efficiency and is potential to be applied in the field of organic electroluminescent devices.
- Figure 1 is a structural view of an organic electroluminescent device of the present invention
- 10 represents a glass substrate
- 20 represents an anode
- 30 represents a hole injection layer
- 40 represents a hole transport layer
- 50 represents a light-emitting layer
- 60 represents a hole blocking layer
- 70 represents an electron injection layer
- 80 represents a cathode.
- the OLED is prepared by using the organic host material of the invention, as shown in FIG.
- the transparent conductive ITO glass substrate 10 (with the anode 20 on the surface) was sequentially washed with a detergent solution and deionized water, ethanol, acetone, deionized water, and then treated with oxygen plasma for 30 seconds.
- the compound TAPC was distilled to form a hole transport layer 40 having a thickness of 40 nm.
- TmPyPb 50 nm thick TmPyPb was vapor-deposited on the light-emitting layer as the hole blocking layer 60.
- LiF was vaporized into an electron injection layer 70 and 100 nm Al as a device cathode 80.
- the organic light-emitting device 2 was prepared in the same manner by replacing the above compound 1 with CBP (structure is shown below).
- the maximum luminous efficiency and the external quantum efficiency are 65.7 cd/A and 20.6%, respectively; under the same conditions, the maximum luminous efficiency and external quantum efficiency of the organic light-emitting device 2 based on CBP in the comparative example They were 58.9 cd/A and 16.7%, respectively. It can be seen that the device prepared by using the organic material of the invention has good electroluminescence performance and meets the requirements of the high performance OLED device for the host material.
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Abstract
提供了一种电致发光材料及其在光电器件中的应用，其具有式(I)所述的结构，Ar为式(II)、(III)中的一个，其中，R 1、R 2独立选自氢，C1-C4取代或未取代的烷基，C2-C4取代或者未取代的烯烷基，C2-C4取代或者未取代的炔烷基，C6-C10的含有一个或者多个取代基取代或未取代的芳基、芳烃基，C3-C8的含有一个或者多个取代基取代或未取代的含有一个或者多个杂原子的杂芳基。实验结果表明，该电致发光材料应用于OLED中，具有较高的发光效率，有潜力应用于有机电致发光器件领域。
Description
本发明涉及新型有机发光二极管电致发光材料及在光电器件中的应用，特别是涉及一种基于咔唑及吡啶构建单元的电致发光材料，作为发光层材料用于有机发光二极管器件。
近年来，有机发光二极管(OLED)作为一种有巨大应用前景的照明、显示技术，受到了学术界与产业界的广泛关注。OLED器件具有自发光、广视角、反应时间短及可制备柔性器件等特性，成为下一代显示、照明技术的有力竞争者。但目前OLED仍然存在效率低、寿命短等问题，有待人们进一步研究。
自1998年Forrest等人报道电致磷光器件(PHOLED)以来，PHOLED因其可以高效利用三线态和单线态激子发光而备受关注。高效PHOLED器件通常为多层结构，其优点在于可以方便地调节载流子注入、传输及复合等过程。在发光层中，当客体掺杂浓度较高时，会出现浓度淬灭和T
1-T
1湮灭，导致发光效率降低。为了解决这些问题，通常将客体材料掺杂在主体材料中，从而“稀释”客体材料的浓度。主体中形成的激子通过
和Dexter能量转移的方式传递给客体，受激发的客体辐射发光回到基态。因此，为了获得高效PHOLED器件，开发新型高性能的主体材料尤为重要。
主体材料可以分为空穴型、电子型和双极型三种类型。当使用空穴型主体材料时，空穴、电子复合通常发生在发光层和电子传输层界面上；当使用电子型主体材料时，空穴、电子复合通常发生在发光层和空穴传输层界面上。可见，单极型主体材料易于导致载流子复合区域变窄。窄的复合区域会导致局部激子密度升高而加速T
1-T
1湮灭，不利于器件性能的提升。而双极型主体材料则可以有效地解决上述问题。使用双极型主体材料，既可以平衡器件中的空穴和电子、拓宽载流子复合区域，又可以简化器件结构，引起了该领域研究者的极大兴趣。
发明内容
本发明目的在于提供一种新型基于吡啶和咔唑构建单元的双极型主体材料，将该材料用于有机发光二极管器件，获得了很好的发光效率。
基于咔唑及吡啶构建单元的电致发光材料，具有化学式(I)的结构：
Ar为下列基团中的一个：
其中，R
1、R
2独立选自氢，C1-C4取代或未取代的烷基，C2-C4取代或者未取代的烯烷基，C2-C4取代或者未取代的炔烷基，C6-C10的含有一个或者多个取代基取代或未取代的芳基、芳烃基，C3-C8的含有一个或者多个取代基取代或未取代的含有一个或者多个杂原子的杂芳基；所述取代为被卤元素、C1－C4的烷基所取代。
优选地，R
1、R
2独立选自氢，C1-C4烷基，C6-C10的含有一个或者多个取代或未取代的芳基、芳烃基；
更优选地，R
1、R
2独立选自氢，甲基，叔丁基，苯基，甲苯基，萘基；
进一步优选，R
1、R
2为相同取代基，选自氢，甲基，叔丁基，苯基；
特别优选，其中Ar为下列基团：
进一步优选，其中Ar为下列基团之一：
特别优选：R
1为氢，R
2为叔丁基，苯基，甲苯基，萘基。
有机电致发光二极管器件，包括阴极、阳极和有机层，所述有机层为空穴传输层、发光层、空穴阻挡层、电子传输层中的一层或多层，这些有机层不必每层都存在。
所述空穴传输层、空穴阻挡层、发光层和/或电子传输层中含有式(I)所述的化合物。
所述式(I)所述的化合物为应用于发光层中的主体材料。
本发明的器件有机层的总厚度为1-1000nm，优选1-500nm，更优选5-300nm。
所述有机层可以通过蒸渡或溶液法形成薄膜。
如上面提到的，本发明的式(I)所述的化合物如下，但不限于所列举的结构：
再优选：式(I)所表示化合物为以下结构：
上述化合物在有机电致发光器件，力致发光器件，有机场效应晶体管，有机太阳能电池和化学传感器上的应用。
实验结果表明，本发明的有机主体材料应用于OLED中，具有较高的发光效率，有潜力应用于有机电致发光器件领域。
图1为本发明的有机电致发光器件结构图，
其中10代表为玻璃基板，20代表为阳极，30代表为空穴注入层，40代表为空穴传输层，50代表发光层，60代表空穴阻挡层，70代表电子注入层，80代表为阴极。
为了更详细叙述本发明，特举以下例子，但是不限于此。
实施例1
化合物1的合成路线
化合物1c的合成
氮气保护下，将1b(5.0g,23.8mmol,参考Bioorgan.Med.Chem.,2014,12,6505.合成)和二苯甲烷(4.0g,23.8mmol)溶于无水四氢呋喃中，冷至-20℃。缓慢将叔丁醇钾(5.0g,45.0mmol)加入上述溶液中，逐渐升至室温反应2h。将上述反应液加入水中，经二氯甲烷萃取三次，合并有机相。有机相经无水硫酸钠干燥后，旋除溶剂，剩余物经柱层析分离得浅黄色固体(3.6g,产率43％)。
化合物1a的合成
氮气保护下，将化合物1c(3.5g,10.0mmol)、三苯基膦(3.9g,15.0mmol)和四溴化碳(4.0g,12.0mmol)加入甲苯中，升温至80℃反应6h。冷至室温后，将上述反应液加入水中，经二氯甲烷萃取三次，合并有机相。有机相经无水硫酸钠干燥后，旋除溶剂，剩余物经柱层析分离得浅黄色固体(3.6g,产率71％)。
化合物1的合成
氮气保护下，将化合物1a(3.0g,6.0mmol)、化合物1d(3.6g,12.6mmol)(参考文献J.Mater.Chem.C,2015,3,12529-12538合成)、Pd(PPh
3)
4(100mg,0.1mmol)、二氧六环(40mL)和碳酸钾水溶液(2M,5mL)依次加入Schlenk管中。加热至80℃，反应12小时。冷至室温后，将上述反应液加入水中，经二氯甲烷萃取三次，合并有机相。有机相经无水硫酸钠干燥后，旋除溶剂，剩余物经柱层析分离得浅黄色固体(3.8g,产率76％)。MS(EI):m/z:828.5(M
+)
实施例2
化合物2的合成路线
化合物2的合成
参考文献J.Mater.Chem.C,2015,3,12529-12538合成化合物2a。参考化合物1的合成方法制备化合物2得浅黄色固体(2.8g,产率72％)。MS(EI):m/z:828.5(M
+)
实施例3
化合物3的合成路线
化合物3的合成
参考文献J.Mater.Chem.C,2015,3,12529-12538合成化合物3a。参考化合物1的合成方法制备化合物3得浅黄色固体(1.7g,产率72％)。MS(EI):m/z:828.5(M
+)
实施例4
化合物12的合成路线
化合物12的合成
参考文献CN105601613A合成化合物12a(1.1g,3.83mmol)。参考化合物1的合成方法制备化合物12得浅黄色固体(4.6g,产率80％)。MS(EI):m/z:981.5(M
+)
实施例5
有机电致发光器件1的制备
使用本发明的有机主体材料制备OLED，见图1
首先，将透明导电ITO玻璃基板10(上面带有阳极20)依次经：洗涤剂溶液和去离子水，乙醇，丙酮，去离子水洗净，再用氧等离子处理30秒。
然后，在ITO上蒸渡10nm厚的HATCN作为空穴注入层30。
然后，蒸渡化合物TAPC,形成40nm厚的空穴传输层40。
然后，在空穴传输层上蒸渡30nm厚的AG-Pt-1(15％)与化合物1(85％)作为发光层50。
然后，在发光层上蒸渡50nm厚的TmPyPb作为空穴阻挡层60。
最后，蒸渡1nm LiF为电子注入层70和100nm Al作为器件阴极80。
器件中所述结构式
对比例1
有机电致发光器件2的制备
使用CBP(结构见下式)替换上述化合物1,依照相同方法制备有机发光器件2。
基于化合物1有机发光器件1发射绿光，最大发光效率和外量子效率分别为65.7cd/A和20.6％；相同条件下，对比例中，基于CBP的有机发光器件2最大发光效率和外量子效率分别为58.9cd/A和16.7％。可见，使用本发明的有机材料制备的器件具有很好的电致发光性能，符合高性能OLED器件对主体材料的要求。
Claims (10)
- 基于咔唑及吡啶构建单元的电致发光材料，具有化学式(I)的结构：
Ar为下列基团中的一个：
其中，R 1、R 2独立选自氢，C1-C4取代或未取代的烷基，C2-C4取代或者未取代的烯烷基，C2-C4取代或者未取代的炔烷基，C6-C10的被一个或者多个取代基取代或未取代的芳基、芳烃基，C3-C8的被一个或者多个取代基取代或未取代的含有一个或者多个杂原子的杂芳基；所述取代为被卤元素、C1－C4的烷基所取代。 - 根据权利要求1所述的电致发光材料，其中R 1、R 2独立选自氢，C1-C4烷基，C6-C10的被一个或者多个取代基取代或未取代的芳基、芳烃基；所述取代为被卤元素、C1－C4的烷基所取代。
- 根据权利要求2所述的电致发光材料，其中R 1、R 2独立选自氢，甲基，叔丁基，苯基，甲苯基，萘基。
- 根据权利要求3所述的电致发光材料，其中R 1、R 2为相同取代基，选自氢，甲基，叔丁基，苯基。
- 根据权利要求4所述的电致发光材料，其中Ar为下列基团：
其中R 1、R 2为相同取代基，选自氢，叔丁基，苯基。 - 根据权利要求2所述的电致发光材料，其中Ar为下列基团之一：
- 根据权利要求6所述的电致发光材料，R 1为氢，R 2为叔丁基，苯基，甲苯基，萘基。
- 根据权利要求2所述的电致发光材料，所述式(I)的结构为下列化合物中的一个：
- 根据权利要求8所述的电致发光材料，所述式(I)的结构为下列化合物：
- 权利要求1-9任一材料在有机电致发光器件，有机场效应晶体管，有机太阳能电池和化学传感器上的应用。
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