JPWO2015178407A1 - 電荷輸送性ワニス - Google Patents
電荷輸送性ワニス Download PDFInfo
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- JPWO2015178407A1 JPWO2015178407A1 JP2016521123A JP2016521123A JPWO2015178407A1 JP WO2015178407 A1 JPWO2015178407 A1 JP WO2015178407A1 JP 2016521123 A JP2016521123 A JP 2016521123A JP 2016521123 A JP2016521123 A JP 2016521123A JP WO2015178407 A1 JPWO2015178407 A1 JP WO2015178407A1
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- thin film
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- 239000002966 varnish Substances 0.000 title claims abstract description 69
- -1 silane compound Chemical class 0.000 claims abstract description 206
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 138
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 72
- 239000010409 thin film Substances 0.000 claims abstract description 64
- 125000005843 halogen group Chemical group 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 239000000126 substance Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 35
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 35
- 125000001072 heteroaryl group Chemical group 0.000 claims description 30
- 238000005401 electroluminescence Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- 125000000304 alkynyl group Chemical group 0.000 claims description 17
- 230000005525 hole transport Effects 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000003107 substituted aryl group Chemical group 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 description 43
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 125000001153 fluoro group Chemical group F* 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 150000001448 anilines Chemical class 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000002019 doping agent Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000003172 aldehyde group Chemical group 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 3
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 3
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229940051250 hexylene glycol Drugs 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
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- WFQFDAGQJUVDKP-UHFFFAOYSA-N 2,8-ditert-butyl-5,11-bis(4-tert-butylphenyl)-6,12-diphenyltetracene Chemical compound C1=CC(C(C)(C)C)=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC(=CC=C2C(C=2C=CC(=CC=2)C(C)(C)C)=C11)C(C)(C)C)=C(C=CC(=C2)C(C)(C)C)C2=C1C1=CC=CC=C1 WFQFDAGQJUVDKP-UHFFFAOYSA-N 0.000 description 2
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- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- YERGTYJYQCLVDM-UHFFFAOYSA-N iridium(3+);2-(4-methylphenyl)pyridine Chemical compound [Ir+3].C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1 YERGTYJYQCLVDM-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 2
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- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- GWFGARXUJNKOMY-UHFFFAOYSA-N [3,5-di(carbazol-9-yl)phenyl]-triphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)(C=1C=CC=CC=1)C1=CC=CC=C1 GWFGARXUJNKOMY-UHFFFAOYSA-N 0.000 description 1
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 description 1
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- HDGNFKSZZTUTIF-UHFFFAOYSA-N [Ru+3].CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1.CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1.CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 Chemical compound [Ru+3].CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1.CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1.CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 HDGNFKSZZTUTIF-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
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- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
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- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
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- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
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- GQVWHWAWLPCBHB-UHFFFAOYSA-L beryllium;benzo[h]quinolin-10-olate Chemical compound [Be+2].C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21.C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21 GQVWHWAWLPCBHB-UHFFFAOYSA-L 0.000 description 1
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- FCDNEESKPPIAJZ-UHFFFAOYSA-N bis[3,5-di(carbazol-9-yl)phenyl]-diphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)(C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 FCDNEESKPPIAJZ-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- HFUZCVTVOQHYBZ-UHFFFAOYSA-N c1ccc2c(cccc2c1)-c1c2ccccc2c(-c2ccc(cc2)-c2ccc(cc2)-c2c3ccccc3c(-c3cccc4ccccc34)c3ccccc23)c2ccccc12 Chemical group c1ccc2c(cccc2c1)-c1c2ccccc2c(-c2ccc(cc2)-c2ccc(cc2)-c2c3ccccc3c(-c3cccc4ccccc34)c3ccccc23)c2ccccc12 HFUZCVTVOQHYBZ-UHFFFAOYSA-N 0.000 description 1
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
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- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- UWCPBTNCCSZKGT-UHFFFAOYSA-N platinum 25,26,27,28-tetrazahexacyclo[16.6.1.13,6.18,11.113,16.019,24]octacosa-1(25),2,4,6,8(27),9,11,13,15,17,19,21,23-tridecaene Chemical compound [Pt].N1C(C=C2C3=CC=CC=C3C(C=C3NC(=C4)C=C3)=N2)=CC=C1C=C1C=CC4=N1 UWCPBTNCCSZKGT-UHFFFAOYSA-N 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- JCBJVAJGLKENNC-UHFFFAOYSA-N potassium;ethoxymethanedithioic acid Chemical group [K+].CCOC(S)=S JCBJVAJGLKENNC-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 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
- 230000001681 protective effect Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical group C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 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
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 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
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-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
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000004784 trichloromethoxy group Chemical group ClC(O*)(Cl)Cl 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- FCIABWJRBPKYJO-UHFFFAOYSA-N triethoxy(furan-3-yl)silane Chemical compound CCO[Si](OCC)(OCC)C=1C=COC=1 FCIABWJRBPKYJO-UHFFFAOYSA-N 0.000 description 1
- SAWDTKLQESXBDN-UHFFFAOYSA-N triethoxy(heptyl)silane Chemical compound CCCCCCC[Si](OCC)(OCC)OCC SAWDTKLQESXBDN-UHFFFAOYSA-N 0.000 description 1
- OYGYKEULCAINCL-UHFFFAOYSA-N triethoxy(hexadecyl)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC OYGYKEULCAINCL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- FHVAUDREWWXPRW-UHFFFAOYSA-N triethoxy(pentyl)silane Chemical compound CCCCC[Si](OCC)(OCC)OCC FHVAUDREWWXPRW-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- QALDFNLNVLQDSP-UHFFFAOYSA-N triethoxy-(2,3,4,5,6-pentafluorophenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=C(F)C(F)=C(F)C(F)=C1F QALDFNLNVLQDSP-UHFFFAOYSA-N 0.000 description 1
- CUVIJHAPWYUQIV-UHFFFAOYSA-N triethoxy-[3-(1,1,1,2,3,3,3-heptafluoropropan-2-yloxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOC(F)(C(F)(F)F)C(F)(F)F CUVIJHAPWYUQIV-UHFFFAOYSA-N 0.000 description 1
- PBTDWUVVCOLMFE-UHFFFAOYSA-N triethoxy-[4-(trifluoromethyl)phenyl]silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C(C(F)(F)F)C=C1 PBTDWUVVCOLMFE-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- XFFHTZIRHGKTBQ-UHFFFAOYSA-N trimethoxy-(2,3,4,5,6-pentafluorophenyl)silane Chemical compound CO[Si](OC)(OC)C1=C(F)C(F)=C(F)C(F)=C1F XFFHTZIRHGKTBQ-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XSVXWCZFSFKRDO-UHFFFAOYSA-N triphenyl-(3-triphenylsilylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XSVXWCZFSFKRDO-UHFFFAOYSA-N 0.000 description 1
- LNQMQGXHWZCRFZ-UHFFFAOYSA-N triphenyl-[4-(4-triphenylsilylphenyl)phenyl]silane Chemical group C1=CC=CC=C1[Si](C=1C=CC(=CC=1)C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LNQMQGXHWZCRFZ-UHFFFAOYSA-N 0.000 description 1
- HITRWHKLCHWBNZ-UHFFFAOYSA-N triphenyl-[4-(9-phenylfluoren-9-yl)phenyl]silane Chemical compound C1=CC=CC=C1C1(C=2C=CC(=CC=2)[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 HITRWHKLCHWBNZ-UHFFFAOYSA-N 0.000 description 1
- KIGXXTRUJYDDKP-UHFFFAOYSA-N triphenyl-[4-[4-(4-triphenylsilylphenyl)phenyl]phenyl]silane Chemical group C1=CC=CC=C1[Si](C=1C=CC(=CC=1)C=1C=CC(=CC=1)C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 KIGXXTRUJYDDKP-UHFFFAOYSA-N 0.000 description 1
- RFDGVZHLJCKEPT-UHFFFAOYSA-N tris(2,4,6-trimethyl-3-pyridin-3-ylphenyl)borane Chemical compound CC1=C(B(C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C(C)=CC(C)=C1C1=CC=CN=C1 RFDGVZHLJCKEPT-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- GWDUZCIBPDVBJM-UHFFFAOYSA-L zinc;2-(2-hydroxyphenyl)-3h-1,3-benzothiazole-2-carboxylate Chemical compound [Zn+2].OC1=CC=CC=C1C1(C([O-])=O)SC2=CC=CC=C2N1.OC1=CC=CC=C1C1(C([O-])=O)SC2=CC=CC=C2N1 GWDUZCIBPDVBJM-UHFFFAOYSA-L 0.000 description 1
- HTPBWAPZAJWXKY-UHFFFAOYSA-L zinc;quinolin-8-olate Chemical compound [Zn+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 HTPBWAPZAJWXKY-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C09D179/02—Polyamines
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
この有機EL素子ではその性能を高める観点から複数の機能性薄膜が用いられるが、中でも正孔注入層や正孔輸送層は、陽極と発光層との電荷の授受を担い、有機EL素子の電圧駆動の低下および輝度向上を達成するために重要な機能を果たす。
なお、ポリスチレンスルホン酸やポリアニリン等の導電性ポリマーを含む組成物に、グリシドオキシプロピルトリメトキシシランや所定のシロキサン系物質を含めることで、当該組成物から得られる薄膜を備える有機EL素子の輝度特性や寿命を向上できることが報告されている(特許文献1,2参照)が、本発明で用いる有機シラン化合物を含む電荷輸送性ワニスに関する報告はない。
1. 電荷輸送性物質と、有機シラン化合物と、有機溶媒とを含み、前記有機シラン化合物が、予めアルコキシシラン化合物を加水分解縮合して調製された重量平均分子量500〜10000の重合体であり、前記アルコキシシラン化合物が、式(1−1)および(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種を含むことを特徴とする電荷輸送性ワニス、
SiR1(OR2)3 (1−1)
SiR1 2(OR2)2 (1−2)
(式中、R1は、それぞれ独立に、Z1で置換された炭素数1〜20のアルキル基、またはZ2で置換された炭素数6〜20のアリール基を表し、R2は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、Z1は、ハロゲン原子、シアノ基、ニトロ基、Z3で置換された炭素数1〜20のアルコキシ基、Z3で置換された炭素数6〜20のアリール基、またはZ3で置換された炭素数2〜20のヘテロアリール基を表し、Z2は、ハロゲン原子、シアノ基、ニトロ基、またはZ3で置換された炭素数1〜20のアルキル基を表し、Z3は、ハロゲン原子、シアノ基、またはニトロ基を表す。)
2. 前記アルコキシシラン化合物が、前記式(1−1)および式(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種と、式(2−1)〜(2−3)で表されるアルコキシシラン化合物から選ばれる少なくとも1種とを含む1の電荷輸送性ワニス、
Si(OR3)4 (2−1)
SiR4 2(OR3)2 (2−2)
SiR4(OR3)3 (2−3)
(式中、R3は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、R4は、それぞれ独立に、炭素数1〜20のアルキル基、Z4で置換されていてもよい炭素数2〜20のアルケニル基、Z4で置換されていてもよい炭素数2〜20のアルキニル基、炭素数6〜20のアリール基、またはZ5で置換されていてもよい炭素数2〜20のヘテロアリール基を表し、Z3は、前記と同じ意味を表し、Z4は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシル基、チオール基、Z6で置換されていてもよい炭素数6〜20のアリール基、またはZ6で置換されていてもよい炭素数2〜20のヘテロアリール基を表し、Z5は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシル基、チオール基、Z6で置換されていてもよい炭素数1〜20のアルキル基、Z6で置換されていてもよい炭素数1〜20のアルケニル基、またはZ6で置換されていてもよい炭素数1〜20のアルキニル基を表し、Z6は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシル基、またはチオール基を表す。)
3. 前記アルコキシシラン化合物が、前記式(1−1)で表されるアルコキシラン化合物と、前記式(2−1)で表されるアルコキシシラン化合物とを含む1または2の電荷輸送性ワニス、
4. 前記電荷輸送性物質が、アニリン誘導体である1〜3のいずれかの電荷輸送性ワニス、
5. 1〜4のいずれか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、
6. 5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、
7. 前記電荷輸送性薄膜が、正孔注入層または正孔輸送層である6の有機エレクトロルミネッセンス素子、
8. 1〜4のいずれかの電荷輸送性ワニスを基材上に塗布し、溶媒を蒸発させることを特徴とする電荷輸送性薄膜の製造方法、
9. 5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、
10. 電荷輸送性物質と有機溶媒とを含む電荷輸送性ワニスから得られる電荷輸送性薄膜のイオン化ポテンシャル深化方法であって、前記電荷輸送性ワニス中に、式(1−1)および(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種を含むアルコキシシラン化合物を加水分解縮合して調製された重量平均分子量500〜10000の重合体を添加することを特徴とする電荷輸送性薄膜のイオン化ポテンシャル深化方法、
SiR1(OR2)3 (1−1)
SiR1 2(OR2)2 (1−2)
(式中、R1は、それぞれ独立に、Z1で置換された炭素数1〜20のアルキル基、またはZ2で置換された炭素数6〜20のアリール基を表し、R2は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、Z1は、ハロゲン原子、シアノ基、ニトロ基、Z3で置換された炭素数1〜20のアルコキシ基、Z3で置換された炭素数6〜20のアリール基、またはZ3で置換された炭素数2〜20のヘテロアリール基を表し、Z2は、ハロゲン原子、シアノ基、ニトロ基、またはZ3で置換された炭素数1〜20のアルキル基を表し、Z3は、ハロゲン原子、シアノ基、またはニトロ基を表す。)
11. 電荷輸送性物質を含む電荷輸送性薄膜のイオン化ポテンシャル深化方法であって、前記電荷輸送性薄膜作製時に、前記電荷輸送性物質とともに式(1−1)および(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種を含むアルコキシシラン化合物を加水分解縮合して調製された重量平均分子量500〜10000の重合体を用い、前記電荷輸送性薄膜内に前記重合体を導入することを特徴とする電荷輸送性薄膜のイオン化ポテンシャル深化方法
SiR1(OR2)3 (1−1)
SiR1 2(OR2)2 (1−2)
(式中、R1は、それぞれ独立に、Z1で置換された炭素数1〜20のアルキル基、またはZ2で置換された炭素数6〜20のアリール基を表し、R2は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、Z1は、ハロゲン原子、シアノ基、ニトロ基、Z3で置換された炭素数1〜20のアルコキシ基、Z3で置換された炭素数6〜20のアリール基、またはZ3で置換された炭素数2〜20のヘテロアリール基を表し、Z2は、ハロゲン原子、シアノ基、ニトロ基、またはZ3で置換された炭素数1〜20のアルキル基を表し、Z3は、ハロゲン原子、シアノ基、またはニトロ基を表す。)
を提供する。
また、本発明の電荷輸送性ワニスは、所定の有機シラン化合物を含むことから、これを含まないワニスを用いた場合と比較し、得られる薄膜のイオン化ポテンシャルが深くなり、その結果、当該薄膜とそれに接する陰極側の機能性薄膜との間の電荷輸送の障壁が低減されたものとなり得る。
この平坦性が良好で、好適なイオン化ポテンシャルを有する本発明の電荷輸送性薄膜を、有機EL素子の正孔注入層や正孔輸送層、好ましくは正孔輸送層に適用することで、素子の輝度特性の向上を図ることができる。
また、本発明の電荷輸送性ワニスは、スピンコート法やスリットコート法等、大面積に成膜可能な各種ウェットプロセスを用いた場合でも電荷輸送性に優れた薄膜を再現性よく製造できるため、近年の有機EL素子の分野における進展にも十分対応できる。
なお、本発明の電荷輸送性薄膜は、コンデンサ電極保護膜、帯電防止膜、有機薄膜太陽電池の陽極バッファ層等への応用も期待される。
本発明に係る電荷輸送性ワニスは、電荷輸送性物質と、予めアルコキシシラン化合物を加水分解縮合して調製された重量平均分子量500〜10000の重合体からなる有機シラン化合物と、有機溶媒とを含み、上記アルコキシシラン化合物が、式(1−1)および(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種を含むものであるが、重合体の分子量をより高めることを考慮すると、式(1−1)で表されるトリアルコキシシラン化合物を含むものが好ましい。
SiR1(OR2)3 (1−1)
SiR1 2(OR2)2 (1−2)
炭素数1〜20のアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、例えば、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、s−ブチル基、t−ブチル基、n−ペンチル基、n−ヘキシル基、n−ヘプチル基、n−オクチル基、n−ノニル基、n−デシル基等の炭素数1〜20の直鎖または分岐鎖状アルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、ビシクロブチル基、ビシクロペンチル基、ビシクロヘキシル基、ビシクロヘプチル基、ビシクロオクチル基、ビシクロノニル基、ビシクロデシル基等の炭素数3〜20の環状アルキル基などが挙げられる。
炭素数2〜20のヘテロアリール基の具体例としては、2−チエニル基、3−チエニル基、2−フラニル基、3−フラニル基、2−オキサゾリル基、4−オキサゾリル基、5−オキサゾリル基、3−イソオキサゾリル基、4−イソオキサゾリル基、5−イソオキサゾリル基、2−チアゾリル基、4−チアゾリル基、5−チアゾリル基、3−イソチアゾリル基、4−イソチアゾリル基、5−イソチアゾリル基、2−イミダゾリル基、4−イミダゾリル基、2−ピリジル基、3−ピリジル基、4−ピリジル基等が挙げられる。
また、アリール基およびヘテロアリール基の炭素数は、好ましくは14以下であり、より好ましくは10以下であり、より一層好ましくは6以下である。
Z1およびZ2としては、ハロゲン原子が好ましく、フッ素原子が最適であり、Z3としては、R2においては存在しない(すなわち、非置換である)ことが好ましく、Z1およびZ2においてはハロゲン原子が好ましく、フッ素原子が最適である。
Z2で置換された炭素数6〜20のアリール基としては、上記Z3で置換された炭素数6〜20のアリール基で例示した基に加え、4−トリクロロメチルフェニル基、4−トリブロモメチルフェニル基、4−トリフルオロメチルフェニル基等のハロゲン化アルキル基を有するアリール基等が挙げられるが、フッ化アルキル基を有するアリール基が好ましい。
Si(OR3)4 (2−1)
SiR4 2(OR3)2 (2−2)
SiR4(OR3)3 (2−3)
その他、ハロゲン原子、炭素数1〜20のアルキル基、炭素数6〜20のアリール基、炭素数2〜20のヘテロアリール基の具体例としては、上記と同様のものが挙げられる。
また、アリール基およびヘテロアリール基の炭素数は、好ましくは14以下であり、より好ましくは10以下であり、より一層好ましくは6以下である。
また、R4としては、炭素数1〜20のアルキル基または炭素数6〜20のアリール基が好ましく、炭素数1〜10のアルキル基または炭素数6〜14のアリール基がより好ましく、炭素数1〜6のアルキル基または炭素数6〜10のアリール基がより一層好ましく、炭素数1〜4のアルキル基またはフェニル基がさらに好ましい。
なお、複数のR3は、すべて同一でも異なっていてもよく、複数のR4も、すべて同一でも異なっていてもよい。
また、Z4としては、ハロゲン原子、Z6で置換されていてもよいフェニル基、Z6で置換されていてもよいフラニル基が好ましく、ハロゲン原子がより好ましく、フッ素原子、または存在しないこと(すなわち、非置換であること)がより一層好ましい。
また、Z5としては、ハロゲン原子、Z6で置換されていてもよい炭素数1〜20のアルキル基、Z6で置換されていてもよいフラニル基が好ましく、ハロゲン原子がより好ましく、フッ素原子、または存在しないこと(すなわち、非置換であること)がより一層好ましい。
そして、Z6としては、ハロゲン原子が好ましく、フッ素原子または存在しないこと(すなわち、非置換であること)がより好ましい。
上記式(2−2)で表されるジアルコキシシラン化合物の具体例としては、ジメチルジメトキシシラン、ジメチルジエトキシシラン、メチルエチルジメトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、メチルプロピルジメトキシシラン、メチルプロピルジエトキシシラン、ジイソプロピルジメトキシシラン、フェニルメチルジメトキシシラン、ビニルメチルジメトキシシラン等が挙げられる。
上記式(2−3)で表されるトリアルコキシシラン化合物の具体例としては、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ペンチルトリメトキシシラン、ペンチルトリエトキシシラン、ヘプチルトリメトキシシラン、ヘプチルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、ドデシルトリメトキシシラン、ドデシルトリエトキシシラン、ヘキサデシルトリメトキシシラン、ヘキサデシルトリエトキシシラン、オクタデシルトリメトキシシラン、オクタデシルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、トリエトキシ−2−チエニルシラン、3−(トリエトキシシリル)フラン等が挙げられる。
加水分解の手法としては、特に限定されるものではなく一般的な手法を用いればよい。一例を挙げると、アルコキシシラン化合物を、水系溶媒中で20〜100℃程度で1〜24時間処理する手法が挙げられる。この際、酸または塩基を触媒として用いることもできる。
Y1は、互いに独立して、水素原子、Z7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のアルケニル基もしくは炭素数2〜20のアルキニル基、またはZ8で置換されていてもよい、炭素数6〜20のアリール基もしくは炭素数2〜20のヘテロアリール基を表す。
なお、アルキル基、アルケニル基、アルキニル基、アリール基、およびヘテロアリール基の具体例としては、上記と同様のものが挙げられる。
Y2〜Y13は、互いに独立して、Z7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のアルケニル基もしくは炭素数2〜20のアルキニル基、またはZ8で置換されていてもよい、炭素数6〜20のアリール基もしくは炭素数2〜20のヘテロアリール基を表す。
Z8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、またはZ9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のアルケニル基もしくは炭素数2〜20のアルキニル基である。
Z9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、またはカルボン酸基である。
なお、Lが2以上である場合、複数のR11は、互いに同一であっても異なっていてもよく、複数のR12も、互いに同一であっても異なっていてもよい。
また、置換基Z8は、ハロゲン原子、またはZ9で置換されていてもよい炭素数1〜20のアルキル基が好ましく、ハロゲン原子、またはZ9で置換されていてもよい炭素数1〜4のアルキル基がより好ましく、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。
そして、置換基Z9は、ハロゲン原子が好ましく、フッ素がより好ましく、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。
また、アリール基およびヘテロアリール基の炭素数は、好ましくは14以下であり、より好ましくは10以下であり、より一層好ましくは6以下である。
正孔輸送性低分子材料としては、(トリフェニルアミン)ダイマー誘導体、[(トリフェニルアミン)ダイマー]スピロダイマー、N,N’−ビス(ナフタレン−1−イル)−N,N’−ビス(フェニル)−ベンジジン(α−NPD)、N,N’−ビス(ナフタレン−2−イル)−N,N’−ビス(フェニル)−ベンジジン、N,N’−ビス(3−メチルフェニル)−N,N’−ビス(フェニル)−ベンジジン、N,N’−ビス(3−メチルフェニル)−N,N’−ビス(フェニル)−9,9−スピロビフルオレン、N,N’−ビス(ナフタレン−1−イル)−N,N’−ビス(フェニル)−9,9−スピロビフルオレン、N,N’−ビス(3−メチルフェニル)−N,N’−ビス(フェニル)−9,9−ジメチル−フルオレン、N,N’−ビス(ナフタレン−1−イル)−N,N’−ビス(フェニル)−9,9−ジメチル−フルオレン、N,N’−ビス(3−メチルフェニル)−N,N’−ビス(フェニル)−9,9−ジフェニル−フルオレン、N,N’−ビス(ナフタレン−1−イル)−N,N’−ビス(フェニル)−9,9−ジフェニル−フルオレン、N,N’−ビス(ナフタレン−1−イル)−N,N’−ビス(フェニル)−2,2’−ジメチルベンジジン、2,2’,7,7’−テトラキス(N,N−ジフェニルアミノ)−9,9−スピロビフルオレン、9,9−ビス[4−(N,N−ビス−ビフェニル−4−イル−アミノ)フェニル]−9H−フルオレン、9,9−ビス[4−(N,N−ビス−ナフタレン−2−イル−アミノ)フェニル]−9H−フルオレン、9,9−ビス[4−(N−ナフタレン−1−イル−N−フェニルアミノ)−フェニル]−9H−フルオレン、2,2’,7,7’−テトラキス[N−ナフタレニル(フェニル)−アミノ]−9,9−スピロビフルオレン、N,N’−ビス(フェナントレン−9−イル)−N,N’−ビス(フェニル)−ベンジジン、2,2’−ビス[N,N−ビス(ビフェニル−4−イル)アミノ]−9,9−スピロビフルオレン、2,2’−ビス(N,N−ジフェニルアミノ)−9,9−スピロビフルオレン、ジ−[4−(N,N−ジ(p−トリル)アミノ)−フェニル]シクロヘキサン、2,2’,7,7’−テトラ(N,N−ジ(p−トリル))アミノ−9,9−スピロビフルオレン、N,N,N’,N’−テトラ−ナフタレン−2−イル−ベンジジン、N,N,N’,N’−テトラ−(3−メチルフェニル)−3,3’−ジメチルベンジジン、N,N’−ジ(ナフタレニル)−N,N’−ジ(ナフタレン−2−イル)−ベンジジン、N,N,N’,N’−テトラ(ナフタレニル)−ベンジジン、N,N’−ジ(ナフタレン−2−イル)−N,N’−ジフェニルベンジジン−1,4−ジアミン、N1,N4−ジフェニル−N1,N4−ジ(m−トリル)ベンゼン−1,4−ジアミン、N2,N2,N6,N6−テトラフェニルナフタレン−2,6−ジアミン、トリス(4−(キノリン−8−イル)フェニル)アミン、2,2’−ビス(3−(N,N−ジ(p−トリル)アミノ)フェニル)ビフェニル、4,4’,4”−トリス[3−メチルフェニル(フェニル)アミノ]トリフェニルアミン(m−MTDATA)、4,4’,4”−トリス[1−ナフチル(フェニル)アミノ]トリフェニルアミン(1−TNATA)等のトリアリールアミン類、5,5”−ビス−{4−[ビス(4−メチルフェニル)アミノ]フェニル}−2,2’:5’,2”−ターチオフェン(BMA−3T)等のオリゴチオフェン類などが挙げられる。
ドーパント物質としては、ワニスに使用する少なくとも一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物質、有機系のドーパント物質のいずれも使用できる。
これら無機系および有機系のドーパント物質は、1種類単独で用いてもよく、2種類以上組み合わせて用いてもよい。
なお、これらの有機溶媒は、それぞれ単独で、または2種以上混合して用いることができる。
また、本発明における電荷輸送性ワニスの固形分濃度は、ワニスの粘度および表面張力等や、作製する薄膜の厚み等を勘案して適宜設定されるものではあるが、通常、0.1〜10.0質量%程度であり、ワニスの塗布性を向上させることを考慮すると、好ましくは0.5〜5.0質量%程度、より好ましくは1.0〜3.0質量%程度である。なお、ここでいう固形分とは、本発明の電荷輸送性ワニスに含まれる電荷輸送性物質およびドーパント物質を意味する。
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、スリットコート法等が挙げられ、塗布方法に応じてワニスの粘度および表面張力を調節することが好ましい。
なお、焼成の際、より高い均一成膜性を発現させたり、基材上で反応を進行させたりする目的で、2段階以上の温度変化をつけてもよく、加熱は、例えば、ホットプレートやオーブン等、適当な機器を用いて行えばよい。
したがって、本発明の電荷輸送性薄膜を、有機EL素子の正孔注入層や正孔輸送層、好ましくは正孔輸送層に適用することで、当該薄膜とその陰極側に積層される機能性薄膜との間の電荷輸送の障壁が小さくなり、有機素子の輝度特性の向上を図ることができる。
使用する電極基板は、洗剤、アルコール、純水等による液体洗浄を予め行って浄化しておくことが好ましく、例えば、陽極基板では使用直前にUVオゾン処理、酸素−プラズマ処理等の表面処理を行うことが好ましい。ただし陽極材料が有機物を主成分とする場合、表面処理を行わなくともよい。
上記の方法により、陽極基板上、あるいは必要に応じて陽極基板上に設けられた正孔注入層上に本発明の電荷輸送性ワニスを塗布して焼成し、電極上に正孔輸送層を作製する。これを真空蒸着装置内に導入し、発光層、電子輸送層、電子輸送層/ホールブロック層、陰極金属を順次蒸着してOLED素子とする。なお、必要に応じて、発光層と正孔輸送層との間に電子ブロック層を設けてよい。
陽極材料としては、インジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)に代表される透明電極や、アルミニウムに代表される金属やこれらの合金等から構成される金属陽極が挙げられ、平坦化処理を行ったものが好ましい。高電荷輸送性を有するポリチオフェン誘導体やポリアニリン誘導体を用いることもできる。
なお、金属陽極を構成するその他の金属としては、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ガリウム、イットリウム、ジルコニウム、ニオブ、モリブデン、ルテニウム、ロジウム、パラジウム、カドミウム、インジウム、スカンジウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ハフニウム、タリウム、タングステン、レニウム、オスミウム、イリジウム、プラチナ、金、チタン、鉛、ビスマスやこれらの合金等が挙げられるが、これらに限定されるわけではない。
陰極材料としては、アルミニウム、マグネシウム−銀合金、アルミニウム−リチウム合金、リチウム、ナトリウム、カリウム、セシウム等が挙げられる。
電子ブロック層を形成する材料としては、トリス(フェニルピラゾール)イリジウム等が挙げられる。
なお、正孔輸送層に用いる電荷輸送性物質としては、先に例示した電荷輸送性物質の中で、正孔輸送性高分子材料以外の化合物が用いられる。
上記OLED素子作製において、発光層、電子輸送層、電子注入層の真空蒸着操作を行う代わりに、発光性高分子層を形成することによって本発明の電荷輸送性ワニスによって形成される正孔輸送性高分子層を有するPLED素子を作製することができる。
具体的には、陽極基板あるいは陽極基板上に必要に応じて形成された正孔注入層上に、本発明の電荷輸送性ワニスを塗布して上記の方法により正孔輸送層を作製し、その上に発光性高分子層を順次形成し、さらに陰極を蒸着してPLED素子とする。
発光性高分子層の形成法としては、発光性高分子材料、またはこれにドーパント物質を加えた材料に溶媒を加えて溶解するか、均一に分散し、正孔輸送層の上に塗布した後、それぞれ焼成することで成膜する方法が挙げられる。
なお、正孔輸送層に用いる電荷輸送性物質としては、先に例示した正孔輸送性高分子材料が用いられる。
塗布方法としては、特に限定されるものではなく、インクジェット法、スプレー法、ディップ法、スピンコート法、転写印刷法、ロールコート法、刷毛塗り等が挙げられる。なお、塗布は、窒素、アルゴン等の不活性ガス下で行うことが好ましい。
焼成する方法としては、不活性ガス下または真空中、オーブンまたはホットプレートで加熱する方法が挙げられる。
(1)分子量測定:昭和電工(株)製、常温ゲル浸透クロマトグラフィー(GPC)装置(GPC−101)およびShodex製カラム(KD−803L)
(測定条件)
・カラム温度:40℃
・溶離液:テトラヒドロフラン(THF),10ml/L
・流速:1.0ml/分
・検量線作成用標準サンプル:昭和電工(株)製、SL−105,標準ポリスチレン(分子量約580,2970,7200,19900,52400)
(2)1H−NMR測定:日本電子(株)製、JNM−ECP300 FT NMR SYSTEM
(3)基板洗浄:長州産業(株)製、基板洗浄装置(減圧プラズマ方式)
(4)ワニスの塗布:ミカサ(株)製、スピンコーターMS−A100
(5)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
(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
(8)イオン化ポテンシャルの測定:理研計器(株)製、大気中光電子分光装置AC−3
[合成例1]有機シラン化合物の合成
温度計および還流管を備え付けた200mLの四つ口反応フラスコ中で、ヘキシレングリコール18.4g、ブチルセロソルブ6.1g、テトラエトキシシラン23.3g、および3,3,3−トリフルオロプロピルトリメトキシシラン10.5gを混合し、アルコキシシランモノマーの溶液を調製した。
この溶液に、予めヘキシレングリコール9.2g、ブチルセロソルブ3.1g、水8.6gおよび触媒として蓚酸0.7gを混合した溶液を、室温下で30分かけて滴下し、さらに室温で30分撹拌した。その後、オイルバスを用いて加熱して1時間還流させた後、放冷して、SiO2換算濃度が12質量%のポリシロキサン溶液を得た。
得られたポリシロキサンの数平均分子量は2,500であり、重量平均分子量は3,500であった。
なお、得られたポリシロキサン溶液10.0g、ヘキシレングリコール42.0g、およびブチルセロソルブ14.0gを混合し、SiO2換算濃度が5質量%のポリシロキサン溶液を調製し、このポリシロキサン溶液を電荷輸送性ワニスの調製に用いた。
[実施例1−1]
窒素雰囲気下で、電荷輸送性ポリマーであるポリ[(9,9−ジヘキシルフルオレニル−2,7−ジイル)−co−(N,N’−ビス{p−ブチルフェニル}−1,4−ジアミノフェニレン)](ADS250BE,American Dye Source,Inc製、以下同様)0.05gと、合成例1で得られたポリシロキサン溶液0.0151gと、トルエン10gとをよく混合して、電荷輸送性ワニスを調製した。
電荷輸送性ポリマー(ADS250BE)の使用量を0.0251g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。
窒素雰囲気下で、電荷輸送性ポリマー(ADS250BE)0.05gと、トルエン10gとをよく混合して、電荷輸送性ワニスを調製した。
[実施例2−1]
まず、窒素雰囲気下で、国際公開第2013/084664号記載の方法に従って合成した式(A1)で表されるアニリン誘導体0.165gと、国際公開第2006/025342号記載の方法に従って合成した式(S1)で表されるアリールスルホン酸0.325gとを、1,3−ジメチル−2−イミダゾリジノン8.0gに溶解させた。そこへ、シクロヘキサノール12.0gおよびプロピレングリコール4.0gを加えて撹拌し、さらにそこへ3,3,3−トリフルオロプロピルトリメトキシシラン0.016gおよびフェニルトリメトキシシラン0.033gを溶解させて撹拌して正孔注入層形成用ワニスを得た。
次いで、ITO基板上に形成された薄膜の上に、スピンコーターを用いて実施例1−1で得られた電荷輸送性ワニスを塗布した後、大気雰囲気下、150℃で10分間焼成し、30nmの均一な薄膜(正孔輸送層)を形成した。
その上に、蒸着装置(真空度1.0×10-5Pa)を用いてCBPとIr(PPy)3を共蒸着した。共蒸着はIr(PPy)3の濃度が6%になるように蒸着レートをコントロールし、40nm積層させた。次いで、BAlq、フッ化リチウムおよびアルミニウムの薄膜を順次積層して有機EL素子を得た。この際、蒸着レートは、BAlqおよ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20nm、0.5nmおよび100nm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((株)MORESCO製、モレスコモイスチャーカット WB90US(P))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、比較例1で得られたワニスを用いた以外は、実施例2−1と同様の方法で有機EL素子を製造した。
[実施例3−1]
実施例1−1で得られたワニスをインジウム錫酸化物(ITO)が膜厚150nmとなるように成膜された25mm×25mm×0.7tのガラス基板に塗布した後、大気雰囲気下、150℃で10分間焼成し、30nmの均一な薄膜を形成した。基板は使用前に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去した。
得られた薄膜について、大気中光電子分光装置AC−3を用いてイオン化ポテンシャルを測定した。具体的な測定方法とイオン化ポテンシャルの決定方法を下記に示す。
まず、装置本体内に圧搾空気(0.5〜0.7MPa)と圧搾窒素(純度:99.9%以上、圧力:0.5〜0.6MPa)を供給し、装置を暖機した。その後、本体とパソコンを接続し、通信の確立、光量調節装置の初期化、検知器電圧設定を行った。次に、光量を20nWに設定し、4.8〜7.0eVの光量補正係数を測定した。続いて、サンプルを挿入し、測定した光量補正係数を用いて4.8〜7.0eVの光電子収率を測定した。測定終了後、横軸が照射光のエネルギー、縦軸が光電子収率実測値の平方根のグラフを作成し、最小二乗法で得られた外挿直線とグランドレベルとの交点からイオン化ポテンシャルを決定した。結果を表2に示す。
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、比較例1で得られたワニスを用いた以外は、実施例3−1と同様の方法でイオン化ポテンシャルを測定した。結果を併せて表2に示す。
Claims (11)
- 電荷輸送性物質と、有機シラン化合物と、有機溶媒とを含み、
前記有機シラン化合物が、予めアルコキシシラン化合物を加水分解縮合して調製された重量平均分子量500〜10000の重合体であり、
前記アルコキシシラン化合物が、式(1−1)および(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種を含むことを特徴とする電荷輸送性ワニス。
SiR1(OR2)3 (1−1)
SiR1 2(OR2)2 (1−2)
(式中、R1は、それぞれ独立に、Z1で置換された炭素数1〜20のアルキル基、またはZ2で置換された炭素数6〜20のアリール基を表し、
R2は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、
Z1は、ハロゲン原子、シアノ基、ニトロ基、Z3で置換された炭素数1〜20のアルコキシ基、Z3で置換された炭素数6〜20のアリール基、またはZ3で置換された炭素数2〜20のヘテロアリール基を表し、
Z2は、ハロゲン原子、シアノ基、ニトロ基、またはZ3で置換された炭素数1〜20のアルキル基を表し、
Z3は、ハロゲン原子、シアノ基、またはニトロ基を表す。) - 前記アルコキシシラン化合物が、前記式(1−1)および式(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種と、式(2−1)〜(2−3)で表されるアルコキシシラン化合物から選ばれる少なくとも1種類とを含む請求項1記載の電荷輸送性ワニス。
Si(OR3)4 (2−1)
SiR4 2(OR3)2 (2−2)
SiR4(OR3)3 (2−3)
(式中、R3は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、
R4は、それぞれ独立に、炭素数1〜20のアルキル基、Z4で置換されていてもよい炭素数2〜20のアルケニル基、Z4で置換されていてもよい炭素数2〜20のアルキニル基、炭素数6〜20のアリール基、またはZ5で置換されていてもよい炭素数2〜20のヘテロアリール基を表し、
Z3は、前記と同じ意味を表し、
Z4は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシル基、チオール基、Z6で置換されていてもよい炭素数6〜20のアリール基、またはZ6で置換されていてもよい炭素数2〜20のヘテロアリール基を表し、
Z5は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシル基、チオール基、Z6で置換されていてもよい炭素数1〜20のアルキル基、Z6で置換されていてもよい炭素数1〜20のアルケニル基、またはZ6で置換されていてもよい炭素数1〜20のアルキニル基を表し、
Z6は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシル基、またはチオール基を表す。) - 前記アルコキシシラン化合物が、前記式(1−1)で表されるアルコキシラン化合物と、前記式(2−1)で表されるアルコキシシラン化合物とを含む請求項1または2記載の電荷輸送性ワニス。
- 前記電荷輸送性物質が、アニリン誘導体である請求項1〜3のいずれか1項記載の電荷輸送性ワニス。
- 請求項1〜4のいずれか1項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5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、正孔注入層または正孔輸送層である請求項6記載の有機エレクトロルミネッセンス素子。
- 請求項1〜4のいずれか1項記載の電荷輸送性ワニスを基材上に塗布し、溶媒を蒸発させることを特徴とする電荷輸送性薄膜の製造方法。
- 請求項5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。
- 電荷輸送性物質と有機溶媒とを含む電荷輸送性ワニスから得られる電荷輸送性薄膜のイオン化ポテンシャル深化方法であって、
前記電荷輸送性ワニス中に、式(1−1)および(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種を含むアルコキシシラン化合物を加水分解縮合して調製された重量平均分子量500〜10000の重合体を添加することを特徴とする電荷輸送性薄膜のイオン化ポテンシャル深化方法。
SiR1(OR2)3 (1−1)
SiR1 2(OR2)2 (1−2)
(式中、R1は、それぞれ独立に、Z1で置換された炭素数1〜20のアルキル基、またはZ2で置換された炭素数6〜20のアリール基を表し、
R2は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、
Z1は、ハロゲン原子、シアノ基、ニトロ基、Z3で置換された炭素数1〜20のアルコキシ基、Z3で置換された炭素数6〜20のアリール基、またはZ3で置換された炭素数2〜20のヘテロアリール基を表し、
Z2は、ハロゲン原子、シアノ基、ニトロ基、またはZ3で置換された炭素数1〜20のアルキル基を表し、
Z3は、ハロゲン原子、シアノ基、またはニトロ基を表す。) - 電荷輸送性物質を含む電荷輸送性薄膜のイオン化ポテンシャル深化方法であって、
前記電荷輸送性薄膜作製時に、前記電荷輸送性物質とともに式(1−1)および(1−2)で表されるアルコキシシラン化合物から選ばれる少なくとも1種を含むアルコキシシラン化合物を加水分解縮合して調製された重量平均分子量500〜10000の重合体を用い、前記電荷輸送性薄膜内に前記重合体を導入することを特徴とする電荷輸送性薄膜のイオン化ポテンシャル深化方法。
SiR1(OR2)3 (1−1)
SiR1 2(OR2)2 (1−2)
(式中、R1は、それぞれ独立に、Z1で置換された炭素数1〜20のアルキル基、またはZ2で置換された炭素数6〜20のアリール基を表し、
R2は、それぞれ独立に、Z3で置換されていてもよい炭素数1〜20のアルキル基を表し、
Z1は、ハロゲン原子、シアノ基、ニトロ基、Z3で置換された炭素数1〜20のアルコキシ基、Z3で置換された炭素数6〜20のアリール基、またはZ3で置換された炭素数2〜20のヘテロアリール基を表し、
Z2は、ハロゲン原子、シアノ基、ニトロ基、またはZ3で置換された炭素数1〜20のアルキル基を表し、
Z3は、ハロゲン原子、シアノ基、またはニトロ基を表す。)
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