WO2014148415A1 - 電荷輸送性ワニス - Google Patents
電荷輸送性ワニス Download PDFInfo
- Publication number
- WO2014148415A1 WO2014148415A1 PCT/JP2014/057073 JP2014057073W WO2014148415A1 WO 2014148415 A1 WO2014148415 A1 WO 2014148415A1 JP 2014057073 W JP2014057073 W JP 2014057073W WO 2014148415 A1 WO2014148415 A1 WO 2014148415A1
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- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- charge transporting
- substituted
- thin film
- Prior art date
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- 239000002966 varnish Substances 0.000 title claims abstract description 64
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 48
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 30
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 30
- 125000005843 halogen group Chemical group 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 23
- 239000002019 doping agent Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 19
- 125000003277 amino group Chemical group 0.000 claims abstract description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 14
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 13
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 115
- -1 diphenylamino group Chemical group 0.000 claims description 93
- 239000010409 thin film Substances 0.000 claims description 57
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical group C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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]
- H10K50/17—Carrier injection layers
Definitions
- the present invention relates to a charge transporting varnish, and more specifically, a charge that can provide a thin film that is excellent in transparency and charge transportability and can realize high brightness when applied to an organic electroluminescence (hereinafter referred to as organic EL) device. It relates to transportable varnish.
- organic EL organic electroluminescence
- a charge transporting thin film obtained from an organic solvent-based charge transporting varnish using a charge transporting material comprising a low molecular weight oligoaniline compound exhibits excellent electroluminescence device characteristics.
- the low-molecular oligoaniline compound constituting the charge transporting material has the same repeating unit structure in the molecule, and is colored as the conjugated system is extended. When it is a thin film, it has the property of increasing absorption in the visible region.
- coloring of a charge transporting thin film decreases the color purity and color reproducibility of the organic EL element. Moreover, this coloring becomes a problem in various full-color technologies for organic EL displays such as a three-color light emission method, a white color method, and a color conversion method, and becomes a significant obstacle in stably producing organic EL elements. As described above, it is desired that the charge transporting thin film of the organic EL element has high transmittance in the visible region and high transparency.
- the present inventors use an oligoaniline compound partially containing a conjugated system composed of a repeating unit structure different from an aniline unit or an oligoaniline compound obtained by partially cutting a conjugated system in a molecule.
- a charge-transporting thin film excellent in transparency with suppressed coloring in the visible region can be obtained (see Patent Document 2), but more transparent for improving the light extraction efficiency and the like.
- a thin film having high properties has been desired, and the organic EL element provided with the thin film described in Patent Document 2 has room for improvement in terms of element characteristics and life performance.
- JP 2002-151272 A International Publication No. 2008/032616 Japanese Patent Laid-Open No. 10-088123
- the present invention has been made in view of such circumstances, and has a high transparency and a high charge transport property, and is a charge transport thin film that can exhibit good device characteristics when applied to an organic EL device. It is an object to provide a charge transporting varnish that imparts.
- Patent Document 3 discloses an organic EL element using N, N′-diphenylbenzidine as a hole transport material. However, it is disclosed that a thin film having excellent transparency can be obtained by using the compound. Not disclosed.
- a charge transporting substance comprising an oligoaniline derivative represented by the formula (1), a charge transporting substance comprising an N, N′-diarylbenzidine derivative represented by the formula (2), a dopant and an organic solvent Charge transport varnish.
- each R 1 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1 , an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms.
- R 2 to R 7 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or Z 1.
- Y 1 to Y 12 are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 , or Z 2 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with 2 , Z 1 represents a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a
- R 8 to R 15 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms
- Ar 1 and Ar 2 each independently represent a group represented by the formula (3) or (4).
- R 16 to R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms
- X 1 and X 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diphenylamino group, or 1-naphthylphenyl.
- the charge transporting varnish of the present invention By using the charge transporting varnish of the present invention, a highly transparent charge transporting thin film with suppressed absorption in the visible region can be obtained.
- this thin film it is possible to ensure the color reproducibility of the element without degrading the color purity of the electroluminescent light or the light transmitted through the color filter. This can greatly contribute to the improvement of efficiency, and it is possible to reduce the size of the organic EL element and reduce the driving voltage.
- a charge transporting thin film having high transparency and conductivity can be obtained, and by applying this thin film to a hole injection layer of an organic EL element in particular, An organic EL element having excellent luminance characteristics can be obtained.
- the thin film obtained from the charge transporting varnish of the present invention can be used as an antistatic film, an anode buffer layer of an organic thin film solar cell, or the like.
- the charge transporting varnish of the present invention contains a charge transporting material composed of an oligoaniline derivative represented by the formula (1).
- the charge transportability is synonymous with conductivity and is synonymous with hole transportability.
- the charge transporting substance itself may be charge transporting, or may be charge transporting when used with an electron accepting substance.
- the charge transporting varnish may itself have a charge transporting property, and the resulting solid film may have a charge transporting property.
- Each R 1 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1 , an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, or Z 2 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with 2 .
- the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, straight chain having 1 to 20 carbon atoms such as s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc.
- branched alkyl group cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclo Examples thereof include cyclic alkyl groups having 3 to 20 carbon atoms such as octyl group, bicyclononyl group and bicyclodecyl group.
- alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, n- 1-pentenyl group, n-1-decenyl group, n-1-eicocenyl group and the like can be mentioned.
- alkynyl group having 2 to 20 carbon atoms examples include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n-2-butynyl group, and n-3-butynyl.
- aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group. Group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
- heteroaryl group having 2 to 20 carbon atoms include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4 -Imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group and the like.
- R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with Z 1 , or an aryl group having 6 to 20 carbon atoms which may be substituted with Z 2.
- a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 1 , or an aryl group having 6 to 14 carbon atoms which may be substituted with Z 2 is more preferable.
- more preferably substituted with Z 1 substituted an alkyl group or a Z 2 good 1-4 carbon atoms is also a phenyl group, it is most preferably a hydrogen atom.
- a plurality of R 1 may be the same or different.
- R 2 to R 7 are each independently substituted with a hydrogen atom, a halogen atom, a nitro group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group, a carboxylic acid group, or Z 1.
- Y 1 to Y 12 are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, which may be substituted with Z 1 , or Z 2 represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms which may be substituted with 2 .
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group represented by R 2 to R 7 and Y 1 to Y 12 are the same as those exemplified as R 1 .
- R 2 to R 5 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 1 , or a carbon atom having 6 to 14 carbon atoms which may be substituted with Z 2 . It is preferably an aryl group, more preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 1 , and even more preferably a hydrogen atom or a halogen atom. It is optimal that all are hydrogen atoms.
- R 6 and R 7 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 1 , or an aryl group having 6 to 14 carbon atoms which may be substituted with Z 2.
- Y 2 and Y 3 are a phenyl group optionally substituted with Z 2 —NY 2 Y 3 group
- a hydrogen atom, halogen It is more preferably an atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with Z 1 , or a diphenylamino group which may be substituted with Z 2 , and may be substituted with a hydrogen atom or Z 2
- a good diphenylamino group is even more preferable, and a hydrogen atom or a diphenylamino group is still more preferable.
- R 6 and R 7 are both hydrogen atoms or diphenylamino groups.
- n represents an integer of 2 to 20, and is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less, from the viewpoint of increasing the solubility of the oligoaniline derivative. From the viewpoint of enhancing the charge transport property of the thin film, it is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more.
- the alkyl group, alkenyl group and alkynyl group of R 1 to R 7 and Y 1 to Y 12 are a halogen atom, nitro group, cyano group, amino group, aldehyde group, hydroxyl group, thiol group, sulfonic acid group, carboxylic acid group, or Z 3 may be substituted with Z 1 is a heteroaryl group aryl or C 2 -C 20 is 1-6 carbon atoms which may be 20 substituted by, R 1 - R 7 and Y 1
- the aryl group and heteroaryl group of Y 12 may be substituted with a halogen atom, nitro group, cyano group, amino group, aldehyde group, hydroxyl group, thiol group, sulfonic acid group, carboxylic acid group, or Z 3.
- alkyl group having 1 to 20 carbon atoms may be substituted with Z 2 is an alkenyl group or an alkynyl group having 2 to 20 carbon atoms having 2 to 20 carbon atoms, these radicals may be further halogen atoms, nitro Group, a cyano group, an amino group, an aldehyde group, a hydroxyl group, a thiol group, a sulfonic acid group or may be substituted with Z 3 is a carboxylic acid group (the halogen atom include the same as above.) .
- Z 1 is preferably an aryl group having a halogen atom or Z carbon atoms 6 substituted 3-20, a halogen atom or Z 3 More preferably, it is a phenyl group which may be substituted with, and most preferably it is not present (that is, unsubstituted).
- Z 2 is preferably a halogen atom or an alkyl group of Z 3 are optionally to 1 to 20 carbon atoms substituted with a halogen atom or an alkyl group Z 3 carbon atoms which may be substituted with 1-4 More preferably, it is optimal that it is not present (ie, unsubstituted).
- Z 3 is preferably a halogen atom, more preferably fluorine, and most preferably not present (that is, unsubstituted).
- the carbon number of the alkyl group, alkenyl group and alkynyl group represented by R 1 to R 7 and Y 1 to Y 12 is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. is there.
- the carbon number of the aryl group and heteroaryl group is preferably 14 or less, more preferably 10 or less, and even more preferably 6 or less.
- the charge transporting varnish of the present invention includes a charge transporting material composed of an N, N′-diarylbenzidine derivative represented by the formula (2).
- R 8 to R 15 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms.
- alkyl group, alkenyl group and alkynyl group include the same groups as those exemplified as R 1 .
- R 8 to R 15 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, It is more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and most preferably all hydrogen atoms.
- Ar 1 and Ar 2 each independently represent a group represented by Formula (3) or (4).
- R 16 to R 25 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. Represents a group.
- R 16 to R 25 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, It is more preferably an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and most preferably all hydrogen atoms.
- X 1 and X 2 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diphenylamino group, or 1-naphthylphenyl. It represents an amino group, 2-naphthylphenylamino group, di (1-naphthyl) amino group, di (2-naphthyl) amino group or 1-naphthyl-2-naphthylamino group.
- X 1 and X 2 are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a diphenylamino group, a 1-naphthylphenylamino group, a 2-naphthylphenylamino group, a di (1-naphthyl) amino group, A di (2-naphthyl) amino group or 1-naphthyl-2-naphthylamino group is preferable, and a hydrogen atom, diphenylamino group, 1-naphthylphenylamino group, 2-naphthylphenylamino group, di (1-naphthyl) is preferred.
- an amino group a di (2-naphthyl) amino group or a 1-naphthyl-2-naphthylamino group, still more preferably a hydrogen atom or a diphenylamino group, and all of them being hydrogen atoms. Is optimal.
- the carbon number of the alkyl group, alkenyl group and alkynyl group represented by R 8 to R 25 , X 1 and X 2 is preferably 10 or less, more preferably 6 or less, and even more preferably 4 It is as follows.
- the molecular weights of the oligoaniline derivatives and N, N′-diarylbenzidine derivatives used in the present invention are usually 200 to 5,000, but are preferably 3,000 or less, more preferably from the viewpoint of enhancing the solubility of these derivatives. 2,000 or less.
- oligoaniline derivative a commercially available product may be used, or one synthesized by a known method may be used.
- the synthesis method is not particularly limited. For example, Bulletin Chemical Society ⁇ Japan (1994, Vol. 67, pp. 1749-1752), Synthetic Metals (Synthetic Metals) Metals) (1997, 84, pp. 119-120), International Publication No. 2008/032617, International Publication No. 2008-032616, International Publication No. 2008-129947, and the like.
- the N, N′-diarylbenzidine derivative may be a commercially available product, and a known method (for example, the method described in ThinThSolid Films, 520 (24), pp. 7157-7163 (2012)) or Although what was synthesize
- 1,4-dioxane, tetrahydrofuran or the like can be used as the solvent.
- the N, N′-diarylbenzidine derivative represented by the formula (2) is obtained, for example, by reacting a biphenyl compound represented by the formula (5) with an aromatic amine compound represented by the formula (6). be able to.
- R 8 to R 15 are the same as above.
- Ar 3 is the same as Ar 1 and Ar 2.
- Y represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom.
- Examples of the biphenyl compound represented by the formula (5) include 4,4′-dichlorobiphenyl, 4,4′-dibromobiphenyl, 4,4′-diiodobiphenyl, 4-chloro-4′-bromobiphenyl, 4- Examples include chloro-4'-iodobiphenyl, 4-bromo-4'-iodobiphenyl, and the like.
- aromatic amine compound represented by the formula (6) examples include aniline, 1-naphthylamine, 4- (diphenylamino) aniline, 4-diphenylamino-1-naphthylamine and the like.
- the charging ratio of the biphenyl compound represented by the formula (5) and the aromatic amine compound represented by the formula (6) should be about 1.8 to 4.0 mol of the aromatic amine compound with respect to 1 mol of the biphenyl compound. However, about 2.0 to 3.0 mol is preferable.
- Examples of the catalyst used in the above reaction include copper catalysts such as copper chloride, copper bromide, copper iodide, Pd (PPh 3 ) 4 (tetrakis (triphenylphosphine) palladium), Pd (PPh 3 ) 2 Cl 2. (Bis (triphenylphosphine) dichloropalladium), Pd (dba) 2 (bis (benzylideneacetone) palladium), Pd 2 (dba) 3 (tris (benzylideneacetone) dipalladium), Pd (Pt-Bu 3 ) 2 Palladium catalyst such as (bis (tri (t-butylphosphine) palladium)). These catalysts may be used alone or in combination of two or more. These catalysts may also be used with an appropriate ligand.
- copper catalysts such as copper chloride, copper bromide, copper iodide, Pd (PPh 3 ) 4 (tetrakis (triphenylphosphine)
- the amount of the catalyst used can be about 0.001 to 0.5 mol with respect to 1 mol of the biphenyl compound, but about 0.01 to 0.2 mol is preferable.
- the above reaction may be performed in a solvent.
- any solvent may be used as long as it does not adversely affect the reaction.
- the solvent include aliphatic hydrocarbons (pentane, n-hexane, n-octane, n-decane, decalin, etc.), halogenated aliphatic hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.) , Aromatic hydrocarbons (benzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), halogenated aromatic hydrocarbons (chlorobenzene, bromobenzene, o-dichlorobenzene, m-di) Chlorobenzene, p-dichlorobenzene, etc.), ethers (diethyl ether, diisoprop
- the reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent to be used, but is preferably about 0 to 200 ° C, more preferably 20 to 150 ° C.
- the desired N, N′-diarylbenzidine derivative can be obtained by post-treatment according to a conventional method.
- N, N′-diarylbenzidine derivatives that can be suitably used in the present invention include, but are not limited to, the following.
- the charge transporting varnish of the present invention contains a dopant.
- the dopant is not particularly limited as long as it is soluble in at least one solvent used for the varnish, and any of an inorganic dopant and an organic dopant can be used.
- inorganic acids such as hydrogen chloride, sulfuric acid, nitric acid, phosphoric acid; aluminum chloride (III) (AlCl 3 ), titanium tetrachloride (IV) (TiCl 4 ), boron tribromide (BBr 3 ) Boron trifluoride ether complex (BF 3 ⁇ OEt 2 ), iron (III) chloride (FeCl 3 ), copper (II) chloride (CuCl 2 ), antimony pentachloride (V) (SbCl 5 ), antimony pentafluoride Metal halides such as (V) (SbF 5 ), arsenic pentafluoride (V) (AsF 5 ), phosphorus pentafluoride (PF 5 ), tris (4-bromophenyl) aluminum hexachloroantimonate (TBPAH); Cl 2 , halogens such as Br 2 , I 2 , ICl, ICl 3
- organic dopants include benzenesulfonic acid, tosylic acid, p-styrenesulfonic acid, 2-naphthalenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-sulfosalicylic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5-dihexylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, 6,7-dibutyl-2-naphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl- 1-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalen
- aryl sulfonic acid compounds are preferred, and aryl sulfonic acid compounds represented by formula (7) are more preferred.
- M represents an oxygen atom
- A represents a naphthalene ring or anthracene ring
- B represents a divalent to tetravalent perfluorobiphenyl group
- p represents the number of sulfonic acid groups bonded to A
- q represents the number of bonds between B and M, and is an integer that satisfies 2 to 4.
- the N, N′-diarylbenzidine derivative represented by the formula (2) is 0.01% with respect to the oligoaniline derivative 1 represented by the formula (1) in a mass ratio (mol ratio).
- the charge transporting thin film that gives high luminance when used in an organic EL device can be obtained by adjusting the thickness to about 100 to 100, preferably about 0.1 to 30, more preferably about 0.8 to 20. It can be obtained with good reproducibility.
- the charge transporting varnish of the present invention has a substance amount of the N, N′-diarylbenzidine derivative represented by the formula (2) with respect to the substance amount (M H1 ) of the oligoaniline derivative represented by the formula (1) (The ratio of M H2 ) satisfies 0.01 ⁇ M H2 / M H1 ⁇ 100, preferably 0.1 ⁇ M H2 / M H1 ⁇ 30, more preferably 0.8 ⁇ M H2 / M H1 ⁇ 20.
- a dopant preferably an aryl sulfonic acid compound, more preferably an aryl sulfonic acid compound represented by formula (7), and still more preferably an aryl sulfonic acid compound represented by formula (8)
- substance amount ratio refers to a charge transporting substance (an oligoaniline derivative represented by formula (1) and an N, N′-diarylbenzidine derivative represented by formula (2). ) It can be about 0.01 to 100 with respect to 1, but is preferably about 0.1 to 10, more preferably about 0.3 to 5, which is high when used for an organic EL device. A charge transporting thin film that provides brightness can be obtained with good reproducibility.
- the ratio of the dopant material amount (M D ) to the charge transport material amount (M H ) is 0.01 ⁇ M D / M H ⁇ 100, preferably 0. 0.1 ⁇ M D / M H ⁇ 10, more preferably 0.3 ⁇ M D / M H ⁇ 5.
- Organic solvent As the organic solvent used in preparing the charge transporting varnish of the present invention, a highly soluble solvent capable of dissolving the charge transporting substance and the dopant satisfactorily can be used.
- highly soluble solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, diethylene glycol monomethyl ether, and the like. .
- These solvents can be used singly or in combination of two or more, and the amount used can be 5 to 100% by mass with respect to the total solvent used in the varnish.
- the charge transporting substance and the dopant are preferably either completely dissolved or uniformly dispersed in the solvent, and more preferably completely dissolved.
- the charge transporting varnish of the present invention has a viscosity of 10 to 200 mPa ⁇ s, particularly 35 to 150 mPa ⁇ s at 25 ° C., and a boiling point of 50 to 300 ° C., particularly 150 to 250 ° C. at normal pressure (atmospheric pressure). These high-viscosity organic solvents may be included. This makes it easy to adjust the viscosity of the varnish. As a result, it is possible to prepare a varnish according to the coating method to be used, which gives a highly flat thin film with good reproducibility.
- High viscosity organic solvents include cyclohexanol, ethylene glycol, ethylene glycol diglycidyl ether, 1,3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2, Examples include, but are not limited to, 3-butanediol, 1,4-butanediol, propylene glycol, hexylene glycol, and the like. These solvents may be used alone or in combination of two or more.
- the addition ratio of the high-viscosity organic solvent to the entire solvent used in the varnish of the present invention is preferably in the range where no solid precipitates, and the addition ratio is preferably 5 to 80% by mass as long as no solid precipitates.
- adjusting the surface tension of the solvent, adjusting the polarity, adjusting the boiling point, etc. 1 to 90% by mass, preferably 1 It is also possible to mix at a ratio of ⁇ 50 mass%.
- solvents examples include ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoacetate.
- solvents include, but are not limited to, ethyl ether, diacetone alcohol, ⁇ -butyrolactone, ethyl lactate, n-hexyl acetate and the like. These solvents can be used alone or in combination of two or more.
- the viscosity of the varnish of the present invention is appropriately set according to the thickness of the thin film to be produced, the solid content concentration, etc., but is usually 1 to 50 mPa ⁇ s at 25 ° C.
- the solid content concentration of the charge transporting varnish in the present invention is appropriately set in consideration of the viscosity and surface tension of the varnish, the thickness of the thin film to be produced, etc., but usually 0.1 to 10 In consideration of improving the coatability of the varnish, it is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass.
- a charge transporting thin film can be formed on a base material by applying the charge transporting varnish of the present invention on the base material and baking it.
- the method for applying the varnish is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating, an ink jet method, and a spray method. It is preferable to adjust the viscosity and the surface tension.
- the firing atmosphere is not particularly limited, and a thin film having a uniform film formation surface and a high charge transport property not only in the air atmosphere but also in an inert gas such as nitrogen or in a vacuum. It is possible to obtain.
- the firing temperature is appropriately set within a range of about 100 to 260 ° C. in consideration of the use of the obtained thin film, the degree of charge transportability imparted to the obtained thin film, and the like.
- the temperature is preferably about 140 to 250 ° C, more preferably about 145 to 240 ° C.
- two or more steps of temperature change may be applied for the purpose of expressing higher uniform film forming property or allowing the reaction to proceed on the substrate. Heating may be performed using an appropriate device such as a hot plate or an oven.
- the thickness of the charge transporting thin film is not particularly limited, but is preferably 5 to 200 nm when used as a hole injection layer in an organic EL device.
- a method of changing the film thickness there are methods such as changing the solid content concentration in the varnish and changing the amount of the solution on the substrate during coating.
- Organic EL device examples of materials and methods for producing an OLED element using the charge transporting varnish of the present invention include, but are not limited to, the following.
- the electrode substrate to be used is preferably cleaned in advance by liquid cleaning with a detergent, alcohol, pure water or the like.
- the anode substrate is subjected to surface treatment such as UV ozone treatment or oxygen-plasma treatment immediately before use. It is preferable.
- the surface treatment may not be performed.
- An example of a method for producing an OLED element having a hole injection layer made of a thin film obtained from the charge transporting varnish of the present invention is as follows.
- the charge transporting varnish of the present invention is applied to the anode substrate and baked to form a hole injection layer on the electrode.
- This is introduced into a vacuum deposition apparatus, and a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode metal are sequentially deposited to form an OLED element.
- a carrier block layer may be provided between arbitrary layers.
- anode material examples include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and those subjected to planarization are preferable.
- ITO indium tin oxide
- IZO indium zinc oxide
- Polythiophene derivatives and polyaniline derivatives having high charge transporting properties can also be used.
- TPD triphenylamine dimer derivative
- ⁇ -NPD N, N′-di (1-
- Materials for forming the light emitting layer include tris (8-quinolinolato) aluminum (III) (Alq 3 ), bis (8-quinolinolato) zinc (II) (Znq 2 ), bis (2-methyl-8-quinolinolato) ( p-phenylphenolate) aluminum (III) (BAlq) and 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi), and the like.
- the light emitting layer may be formed by co-evaporation.
- electron transport materials examples include Alq 3 , BAlq, DPVBi, 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD), and triazole derivatives (TAZ). , Bathocuproine (BCP), silole derivatives and the like.
- luminescent dopants examples include quinacridone, rubrene, coumarin 540, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM), tris (2-phenylpyridine) iridium ( III) (Ir (ppy) 3 ), (1,10-phenanthroline) -tris (4,4,4-trifluoro-1- (2-thienyl) -butane-1,3-dionate) europium (III) ( Eu (TTA) 3 phen) and the like.
- Examples of the material for forming the carrier block layer include PBD, TAZ, and BCP.
- Materials for forming the electron injection layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride ( MgF 2 ), strontium fluoride (SrF 2 ), Liq, Li (acac), lithium acetate, lithium benzoate and the like.
- cathode material examples include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium and the like.
- the method for producing a PLED element using the charge transporting varnish of the present invention is not particularly limited, and examples thereof include the following methods.
- the hole transport polymer layer and the light emitting polymer layer are sequentially formed.
- a PLED element having a charge transporting thin film formed by the charge transporting varnish of the invention can be produced.
- the charge transporting varnish of the present invention is applied on the anode substrate to prepare a hole injection layer by the above method, and a hole transporting polymer layer and a light emitting polymer layer are sequentially formed thereon. Then, a cathode electrode is vapor-deposited to obtain a PLED element.
- the same materials as those used in the production of the OLED element can be used, and the same cleaning treatment and surface treatment can be performed.
- a hole transporting polymer material or a light emitting polymer material, or a material in which a dopant is added to these materials are added and dissolved.
- coating on a positive hole injection layer or a positive hole transportable polymer layer, and baking each is mentioned.
- Examples of the light-emitting polymer material include polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH). And polyphenylene vinylene derivatives such as -PPV), polythiophene derivatives such as poly (3-alkylthiophene) (PAT), and polyvinylcarbazole (PVCz).
- polyfluorene derivatives such as poly (9,9-dialkylfluorene) (PDAF), poly (2-methoxy-5- (2′-ethylhexoxy) -1,4-phenylenevinylene) (MEH).
- polyphenylene vinylene derivatives such as -PPV
- polythiophene derivatives such as poly (3-alkylthiophene) (PAT)
- PVCz polyvinylcarbazole
- Examples of the solvent include toluene, xylene, chloroform and the like, and examples of the dissolution or uniform dispersion method include stirring, heating and stirring, and ultrasonic dispersion.
- the coating method is not particularly limited, and examples include an inkjet method, a spray method, a dip method, a spin coating method, a transfer printing method, a roll coating method, and a brush coating.
- the application is preferably performed under an inert gas such as nitrogen or argon.
- Transmittance measurement Visible ultraviolet absorption spectrum measuring device UV-3100PC manufactured by Shimadzu Corporation (6)
- Manufacture of EL elements Multi-function vapor deposition system C-E2L1G1-N manufactured by Choshu Sangyo (7) Measurement of luminance etc. of EL element: (Yes) Tech World's IVL measurement system
- N, N′-diphenylbenzidine was recrystallized using 1,4-dioxane, dried well under reduced pressure, and used for the preparation of varnish.
- Example 1-2 0.083 g (0.121 mmol), 0.143 g (0.425 mmol) and 0.274 g (0.303 mmol) (Example 1-3); 0.109 g (0.159 mmol), 0 121 g (0.359 mmol) and 0.270 g (0.299 mmol) (Example 1-4); 0.054 g (0.078 mmol), 0.092 g (0.274 mmol) and 0.354 g (0.392 mmol) (Example 1-5); 0.071 g (0.104 mmol), 0.078 g (0.233 mmol) and And 0.351 g (0.388 mmol) (Example 1-6); and 0.088 g (0.128 mmol), 0.065 g (0.192 mmol) and 0.347 g (0.385 mmol) (Example 1-7)
- a charge transporting varnish was prepared in the same manner as in Example 1-1 except that.
- N′-diarylbenzidine derivative B represented by the formula (9) produced according to the method described in WO2008 / 032616 and 0.111 g (0.345 mmol) of arylsulfonic acid C
- the mixture was dissolved in 17.5 g of 1,3-dimethyl-2-imidazolidinone under a nitrogen atmosphere.
- 3.5 g of cyclohexanol and 3.5 g of propylene glycol were added and further stirred.
- the obtained solution was filtered using a PTFE filter having a pore size of 0.2 ⁇ m to obtain a charge transporting varnish.
- the transmittance of the prepared thin film was measured.
- the transmittance was scanned at a wavelength of 400 to 800 nm which is a visible light region.
- Table 1 shows the transmittance at 400, 500, 600, 700, and 800 nm, and the average transmittance at 400 to 800 nm.
- the thin films prepared using the charge transporting varnishes of Examples 1-1 to 1-7 are varnishes (comparative examples) containing an oligoaniline compound whose conjugated system has been cut as a charge transporting material.
- the transmittance in the visible region was higher than that of the thin film prepared by using 1-1 to 1-2).
- Example 3-1 Production and characteristic evaluation of organic EL device
- the varnish obtained in Example 1-1 was applied to an ITO substrate using a spin coater, then dried at 50 ° C. for 5 minutes, and further baked at 230 ° C. for 15 minutes in an air atmosphere to be 30 nm on the ITO substrate. A uniform thin film was formed.
- As the ITO substrate a glass substrate of 25 mm ⁇ 25 mm ⁇ 0.7 t in which indium tin oxide (ITO) is patterned on the surface with a film thickness of 150 nm is used, and an O 2 plasma cleaning apparatus (150 W, 30 seconds) before use. To remove impurities on the surface.
- ITO indium tin oxide
- N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -) is applied to the ITO substrate on which the thin film has been formed using a vapor deposition apparatus (degree of vacuum: 1.0 ⁇ 10 ⁇ 5 Pa).
- NPD tris (8-quinolinolato) aluminum (III) (Alq 3 ), lithium fluoride, and aluminum thin films were sequentially laminated to obtain an organic EL device.
- the deposition rate was 0.2 nm / second for ⁇ -NPD, Alq 3 and aluminum, and 0.02 nm / second for lithium fluoride, and the film thicknesses were 30 nm, 40 nm, and 0.2 nm, respectively.
- the characteristic was 5 nm and 120 nm.
- Sealing was performed according to the following procedure. In a nitrogen atmosphere having an oxygen concentration of 2 ppm or less and a dew point of ⁇ 85 ° C. or less, the organic EL element was placed between the sealing substrates, and the sealing substrate was bonded with an adhesive (XNR5516Z-B1 manufactured by Nagase ChemteX Corporation). . At this time, a water-absorbing agent (HD-071010W-40 manufactured by Dynic Co., Ltd.) was placed in the sealing substrate together with the organic EL element. The bonded sealing substrate was irradiated with UV light (wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2 ), and then annealed at 80 ° C. for 1 hour to cure the adhesive.
- UV light wavelength: 365 nm, irradiation amount: 6,000 mJ / cm 2
- Example 3-7 In place of the varnish obtained in Example 1-1, Example 3-1 except that the varnish obtained in Examples 1-2 to 1-7 and Comparative Examples 1-1 to 1-2 was used.
- the organic EL element was produced by the same method as 1.
- Example 3-3 Instead of forming a thin film using varnish, it consists of N, N'-diphenylbenzidine only on the ITO substrate by an evaporation method (deposition rate 0.2 nm / sec) using N, N'-diphenylbenzidine as an evaporation source.
- An organic EL device was produced in the same manner as in Example 3-1, except that a 30 nm uniform thin film was formed.
- the organic EL device of the example showed higher luminance than the device of the comparative example.
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Abstract
Description
1.式(1)で表されるオリゴアニリン誘導体からなる電荷輸送性物質、式(2)で表されるN,N'-ジアリールベンジジン誘導体からなる電荷輸送性物質、ドーパント及び有機溶媒を含むことを特徴とする電荷輸送性ワニス。
R2~R7は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基、カルボン酸基、Z1で置換されていてもよい炭素数1~20のアルキル基、炭素数2~20のアルケニル基若しくは炭素数2~20のアルキニル基、Z2で置換されていてもよい炭素数6~20のアリール基若しくは炭素数2~20のヘテロアリール基、-NHY1、-NY2Y3、-C(O)Y4、-OY5、-SY6、-SO3Y7、-C(O)OY8、-OC(O)Y9、-C(O)NHY10又は-C(O)NY11Y12基を表し、
Y1~Y12は、それぞれ独立して、Z1で置換されていてもよい炭素数1~20のアルキル基、炭素数2~20のアルケニル基若しくは炭素数2~20のアルキニル基、又はZ2で置換されていてもよい炭素数6~20のアリール基若しくは炭素数2~20のヘテロアリール基を表し、
Z1は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基、カルボン酸基、又はZ3で置換されていてもよい炭素数6~20のアリール基若しくは炭素数2~20のヘテロアリール基を表し、
Z2は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基、カルボン酸基、又はZ3で置換されていてもよい炭素数1~20のアルキル基、炭素数2~20のアルケニル基若しくは炭素数2~20のアルキニル基を表し、
Z3は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基又はカルボン酸基を表し、
nは、2~20の整数を表す。)
Ar1及びAr2は、それぞれ独立して、式(3)又は(4)で表される基を表す。
X1及びX2は、それぞれ独立して、水素原子、炭素数1~20のアルキル基、炭素数2~20のアルケニル基、炭素数2~20のアルキニル基、ジフェニルアミノ基、1-ナフチルフェニルアミノ基、2-ナフチルフェニルアミノ基、ジ(1-ナフチル)アミノ基、ジ(2-ナフチル)アミノ基又は1-ナフチル-2-ナフチルアミノ基を表す。)]
2.1の電荷輸送性ワニスを用いて作製される電荷輸送性薄膜。
3.2の電荷輸送性薄膜を有する電子デバイス。
4.2の電荷輸送性薄膜を有する有機EL素子。
5.電荷輸送性薄膜が、正孔注入層又は正孔輸送層である4の有機EL素子。
6.1の電荷輸送性ワニスを基材上に塗布して焼成することを特徴とする電荷輸送性薄膜の製造方法。
7.2の電荷輸送性薄膜を用いることを特徴とする有機EL素子の製造方法。
本発明の電荷輸送性ワニスは、式(1)で表されるオリゴアニリン誘導体からなる電荷輸送性物質を含む。ここで、電荷輸送性とは、導電性と同義であり、正孔輸送性と同義である。電荷輸送性物質は、それ自体に電荷輸送性があるものでもよく、電子受容性物質と共に用いた際に電荷輸送性があるものでもよい。なお、電荷輸送性ワニスは、それ自体に電荷輸送性があるものでもよく、それにより得られる固形膜が電荷輸送性を有するものでもよい。
R2~R7及びY1~Y12で表されるアルキル基、アルケニル基、アルキニル基、アリール基及びヘテロアリール基としては、R1として例示したものと同様のものが挙げられる。
Z2は、ハロゲン原子又はZ3で置換されていてもよい炭素数1~20のアルキル基であることが好ましく、ハロゲン原子又はZ3で置換されていてもよい炭素数1~4のアルキル基であることがより好ましく、存在しないこと(すなわち、非置換であること)が最適である。
Z3は、ハロゲン原子であることが好ましく、フッ素であることがより好ましく、存在しないこと(すなわち、非置換であること)が最適である。
反応終了後は、常法に従って後処理をし、目的とするN,N'-ジアリールベンジジン誘導体を得ることができる。
本発明の電荷輸送性ワニスは、ドーパントを含む。ドーパントは、ワニスに使用する少なくとも1種の溶媒に溶解するものであれば特に限定されず、無機系のドーパント、有機系のドーパントのいずれも使用できる。
本発明の電荷輸送性ワニスを調製する際に用いられる有機溶媒としては、電荷輸送性物質及びドーパントを良好に溶解し得る高溶解性溶媒を用いることができる。このような高溶解性溶媒としては、例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン、1,3-ジメチル-2-イミダゾリジノン、ジエチレングリコールモノメチルエーテル等が挙げられる。これらの溶媒は1種単独で又は2種以上混合して用いることができ、その使用量は、ワニスに使用する溶媒全体に対して5~100質量%とすることができる。なお、電荷輸送性物質及びドーパントは、いずれも上記溶媒に完全に溶解しているか、均一に分散している状態となっていることが好ましく、完全に溶解していることがより好ましい。
本発明の電荷輸送性ワニスを基材上に塗布して焼成することで、基材上に電荷輸送性薄膜を形成させることができる。
ワニスの塗布方法としては、特に限定されるものではなく、ディップ法、スピンコート法、転写印刷法、ロールコート法、刷毛塗り、インクジェット法、スプレー法等が挙げられ、塗布方法に応じてワニスの粘度及び表面張力を調節することが好ましい。
本発明の電荷輸送性ワニスを用いてOLED素子を作製する場合の使用材料や作製方法としては、下記のようなものが挙げられるが、これらに限定されない。
(1)1H-NMR測定:バリアン製 高分解能核磁気共鳴装置
(2)基板洗浄:長州産業(株)製 基板洗浄装置(減圧プラズマ方式)
(3)ワニスの塗布:ミカサ(株)製 スピンコーターMS-A100
(4)膜厚測定:(株)小坂研究所製 微細形状測定機サーフコーダET-4000
(5)透過率測定:(株)島津製作所製 可視紫外線吸収スペクトル測定装置UV-3100PC
(6)EL素子の作製:長州産業(株)製 多機能蒸着装置システムC-E2L1G1-N
(7)EL素子の輝度等の測定:(有)テック・ワールド製 I-V-L測定システム
その後、反応混合液を濾過し、その濾液に飽和食塩水を加えて分液処理をした後、有機層から溶媒を留去して得られた固体を1,4-ジオキサンを用いて再結晶し、アニリン誘導体Aを得た(収量:22.37g、収率:65%)。
室温まで放冷後、反応後に析出しているアリールスルホン酸Cを再溶解させるために、N,N-ジメチルホルムアミドを更に500mL加え、室温で90分間攪拌した。攪拌終了後、この溶液を濾過して炭酸カリウム残渣を除去し、減圧濃縮した。更に、残存している不純物を除去するために、残渣にメタノール100mLを加え、室温で30分間攪拌した。攪拌終了後、懸濁溶液を濾過し、濾物を濾取した。濾物に超純水300mLを加えて溶解し、陽イオン交換樹脂ダウエックス650C(ダウ・ケミカル社製、Hタイプ約200mL、留出溶媒:超純水)を用いたカラムクロマトグラフィーによりイオン交換した。
pH1以下の分画を減圧下で濃縮乾固し、残渣を減圧下で乾固してアリールスルホン酸Cを得た(収量:11g、収率:85%)。
[実施例1-1]
合成例1で製造したアニリン誘導体A0.029g(0.042mmol)、N,N'-ジフェニルベンジジン(東京化成工業(株))0.189g(0.563mmol)及び合成例2で製造したアリールスルホン酸C0.282g(0.313mmol)の混合物を、窒素雰囲気下で1,3-ジメチル-2-イミダゾリジノン17.5gに溶解させた。そこへ、シクロヘキサノール3.5g及びプロピレングリコール3.5gを加えて更に攪拌した。得られた溶液を孔径0.2μmのPTFE製フィルターを用いて濾過し、電荷輸送性ワニスを得た。なお、N,N'-ジフェニルベンジジンは、1,4-ジオキサンを用いて再結晶し、減圧下でよく乾燥してからワニスの調製に用いた。
アニリン誘導体A、N,N'-ジフェニルベンジジン及びアリールスルホン酸Cの使用量を、それぞれ0.056g(0.082mmol)、0.166g(0.493mmol)及び0.278g(0.308mmol)(実施例1-2);0.083g(0.121mmol)、0.143g(0.425mmol)及び0.274g(0.303mmol)(実施例1-3);0.109g(0.159mmol)、0.121g(0.359mmol)及び0.270g(0.299mmol)(実施例1-4);0.054g(0.078mmol)、0.092g(0.274mmol)及び0.354g(0.392mmol)(実施例1-5);0.071g(0.104mmol)、0.078g(0.233mmol)及び0.351g(0.388mmol)(実施例1-6);並びに0.088g(0.128mmol)、0.065g(0.192mmol)及び0.347g(0.385mmol)(実施例1-7)とした以外は実施例1-1と同様の方法で電荷輸送性ワニスを調製した。
国際公開第2008/032616号記載の方法に従って製造した式(9)で表されるN,N'-ジアリールベンジジン誘導体B0.189g(0.345mmol)及びアリールスルホン酸C0.311g(0.345mmol)の混合物を、窒素雰囲気下で1,3-ジメチル-2-イミダゾリジノン17.5gに溶解させた。そこへ、シクロヘキサノール3.5g及びプロピレングリコール3.5gを加えて更に攪拌した。得られた溶液を孔径0.2μmのPTFE製フィルターを用いて濾過し、電荷輸送性ワニスを得た。
アニリン誘導体A0.031g(0.045mmol)、N,N'-ジアリールベンジジン誘導体B0.166g(0.303mmol)及びアリールスルホン酸C0.304g(0.336mmol)の混合物を、窒素雰囲気下で1,3-ジメチル-2-イミダゾリジノン17.5gに溶解させた。そこへ、シクロヘキサノール3.5g及びプロピレングリコール3.5gを加えて更に攪拌した。得られた溶液を孔径0.2μmのPTFE製フィルターを用いて濾過し、電荷輸送性ワニスを得た。
N,N'-ジフェニルベンジジン0.742g、1,3-ジメチル-2-イミダゾリジノン17.5g、シクロヘキサノール3.5g及びプロピレングリコール3.5gを用いてワニスの調製を試みたが、ワニスは懸濁し、有機EL素子用の電荷輸送性薄膜の形成に用い得る均一なワニスを得ることができなかった。
[実施例2-1~2-7及び比較例2-1~2-2]
実施例1-1~1-7及び比較例1-1~1-2で得られたワニスをそれぞれスピンコーターを用いて石英基板に塗布した後、大気中50℃で5分間乾燥し、更に230℃で15分間焼成し、石英基板上に膜厚30nmの均一な薄膜を形成した。なお、石英基板は、プラズマ洗浄装置(150W、30秒間)を用い、表面上の不純物を除却してから使用した。
[実施例3-1]
実施例1-1で得られたワニスをスピンコーターを用いてITO基板に塗布した後、50℃で5分間乾燥し、更に、大気雰囲気下、230℃で15分間焼成し、ITO基板上に30nmの均一な薄膜を形成した。ITO基板としては、インジウム錫酸化物(ITO)が表面上に膜厚150nmでパターニングされた25mm×25mm×0.7tのガラス基板を用い、使用前にO2プラズマ洗浄装置(150W、30秒間)によって表面上の不純物を除却した。
次いで、薄膜を形成したITO基板に対し、蒸着装置(真空度1.0×10-5Pa)を用いてN,N'-ジ(1-ナフチル)-N,N'-ジフェニルベンジジン(α-NPD)、トリス(8-キノリノラート)アルミニウム(III)(Alq3)、フッ化リチウム、及びアルミニウムの薄膜を順次積層し、有機EL素子を得た。この際、蒸着レートは、α-NPD,Alq3及びアルミニウムについては0.2nm/秒、フッ化リチウムについては0.02nm/秒の条件でそれぞれ行い、膜厚は、それぞれ30nm、40nm、0.5nm及び120nmとした。
なお、空気中の酸素、水等の影響による特性劣化を防止するため、有機EL素子は封止基板により封止した後、その特性を評価した。封止は以下の手順で行った。
酸素濃度2ppm以下、露点-85℃以下の窒素雰囲気中で、有機EL素子を封止基板の間に収め、封止基板を接着材(ナガセケムテックス(株)製XNR5516Z-B1)により貼り合わせた。この際、捕水剤(ダイニック(株)製HD-071010W-40)を有機EL素子と共に封止基板内に収めた。貼り合わせた封止基板に対し、UV光を照射(波長:365nm、照射量:6,000mJ/cm2)した後、80℃で1時間、アニーリング処理して接着材を硬化させた。
実施例1-1で得られたワニスの代わりに、それぞれ、実施例1-2~1-7、比較例1-1~1-2で得られたワニスを用いた以外は、実施例3-1と同様の方法で有機EL素子を作製した
ワニスを用いて薄膜を形成する代わりに、N,N'-ジフェニルベンジジンを蒸着源とする蒸着法(蒸着レート0.2nm/秒)で、ITO基板上にN,N'-ジフェニルベンジジンのみからなる30nmの均一な薄膜を形成した以外は、実施例3-1と同様の方法で有機EL素子を作製した。
Claims (7)
- 式(1)で表されるオリゴアニリン誘導体からなる電荷輸送性物質、式(2)で表されるN,N'-ジアリールベンジジン誘導体からなる電荷輸送性物質、ドーパント及び有機溶媒を含むことを特徴とする電荷輸送性ワニス。
R2~R7は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基、カルボン酸基、Z1で置換されていてもよい炭素数1~20のアルキル基、炭素数2~20のアルケニル基若しくは炭素数2~20のアルキニル基、Z2で置換されていてもよい炭素数6~20のアリール基若しくは炭素数2~20のヘテロアリール基、-NHY1、-NY2Y3、-C(O)Y4、-OY5、-SY6、-SO3Y7、-C(O)OY8、-OC(O)Y9、-C(O)NHY10又は-C(O)NY11Y12基を表し、
Y1~Y12は、それぞれ独立して、Z1で置換されていてもよい炭素数1~20のアルキル基、炭素数2~20のアルケニル基若しくは炭素数2~20のアルキニル基、又はZ2で置換されていてもよい炭素数6~20のアリール基若しくは炭素数2~20のヘテロアリール基を表し、
Z1は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基、カルボン酸基、又はZ3で置換されていてもよい炭素数6~20のアリール基若しくは炭素数2~20のヘテロアリール基を表し、
Z2は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基、カルボン酸基、又はZ3で置換されていてもよい炭素数1~20のアルキル基、炭素数2~20のアルケニル基若しくは炭素数2~20のアルキニル基を表し、
Z3は、ハロゲン原子、ニトロ基、シアノ基、アミノ基、アルデヒド基、水酸基、チオール基、スルホン酸基又はカルボン酸基を表し、
nは、2~20の整数を表す。)
Ar1及びAr2は、それぞれ独立して、式(3)又は(4)で表される基を表す。
X1及びX2は、それぞれ独立して、水素原子、炭素数1~20のアルキル基、炭素数2~20のアルケニル基、炭素数2~20のアルキニル基、ジフェニルアミノ基、1-ナフチルフェニルアミノ基、2-ナフチルフェニルアミノ基、ジ(1-ナフチル)アミノ基、ジ(2-ナフチル)アミノ基又は1-ナフチル-2-ナフチルアミノ基を表す。)] - 請求項1記載の電荷輸送性ワニスを用いて作製される電荷輸送性薄膜。
- 請求項2記載の電荷輸送性薄膜を有する電子デバイス。
- 請求項2記載の電荷輸送性薄膜を有する有機エレクトロルミネッセンス素子。
- 前記電荷輸送性薄膜が、正孔注入層又は正孔輸送層である請求項4記載の有機エレクトロルミネッセンス素子。
- 請求項1記載の電荷輸送性ワニスを基材上に塗布して焼成することを特徴とする電荷輸送性薄膜の製造方法。
- 請求項2記載の電荷輸送性薄膜を用いることを特徴とする有機エレクトロルミネッセンス素子の製造方法。
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JP6004083B2 (ja) | 2016-10-05 |
JPWO2014148415A1 (ja) | 2017-02-16 |
CN105190929B (zh) | 2017-05-10 |
TWI614317B (zh) | 2018-02-11 |
KR20150130432A (ko) | 2015-11-23 |
KR102176623B1 (ko) | 2020-11-09 |
CN105190929A (zh) | 2015-12-23 |
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