JP2007070282A - Novel triarylboron derivative and organic electroluminescent device containing the same - Google Patents
Novel triarylboron derivative and organic electroluminescent device containing the same Download PDFInfo
- Publication number
- JP2007070282A JP2007070282A JP2005258545A JP2005258545A JP2007070282A JP 2007070282 A JP2007070282 A JP 2007070282A JP 2005258545 A JP2005258545 A JP 2005258545A JP 2005258545 A JP2005258545 A JP 2005258545A JP 2007070282 A JP2007070282 A JP 2007070282A
- Authority
- JP
- Japan
- Prior art keywords
- group
- voltage
- linear
- triarylboron
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 claims abstract description 70
- 238000005401 electroluminescence Methods 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 150000001638 boron Chemical class 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 238000001296 phosphorescence spectrum Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000001769 aryl amino group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- -1 4,6-difluorophenyl Chemical group 0.000 description 251
- 239000010410 layer Substances 0.000 description 137
- 230000005525 hole transport Effects 0.000 description 38
- 238000002347 injection Methods 0.000 description 32
- 239000007924 injection Substances 0.000 description 32
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 30
- 239000000243 solution Substances 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000001194 electroluminescence spectrum Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- NSABRUJKERBGOU-UHFFFAOYSA-N iridium(3+);2-phenylpyridine Chemical compound [Ir+3].[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1 NSABRUJKERBGOU-UHFFFAOYSA-N 0.000 description 16
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 15
- 235000019341 magnesium sulphate Nutrition 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 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 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- IZOWAAYDURJWLW-UHFFFAOYSA-N CC1=C(C(=CC(=C1C=1C=NC=CC=1)C)C)B Chemical compound CC1=C(C(=CC(=C1C=1C=NC=CC=1)C)C)B IZOWAAYDURJWLW-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- 239000012267 brine Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 230000005281 excited state Effects 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- KSLRMBMUSPREKG-UHFFFAOYSA-N tris(3-bromo-2,4,6-trimethylphenyl)borane Chemical compound CC1=C(Br)C(C)=CC(C)=C1B(C=1C(=C(Br)C(C)=CC=1C)C)C1=C(C)C=C(C)C(Br)=C1C KSLRMBMUSPREKG-UHFFFAOYSA-N 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
- BHVDTLKQNMCWNY-UHFFFAOYSA-N 3-(1-chlorocyclohexa-2,4-dien-1-yl)pyridine Chemical compound C=1C=CN=CC=1C1(Cl)CC=CC=C1 BHVDTLKQNMCWNY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- LTSSSVHTLGQZAQ-UHFFFAOYSA-N 1,3,5-tribromo-2,4,6-trimethylbenzene Chemical group CC1=C(Br)C(C)=C(Br)C(C)=C1Br LTSSSVHTLGQZAQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XAGZJIQIVXSURR-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]piperidin-2-one Chemical group C1=CC(C(F)(F)F)=CC=C1N1C(=O)CCCC1 XAGZJIQIVXSURR-UHFFFAOYSA-N 0.000 description 2
- MMHFCEWVMQXVEV-UHFFFAOYSA-N 3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]pyridine Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=2C=NC=CC=2)C=C1 MMHFCEWVMQXVEV-UHFFFAOYSA-N 0.000 description 2
- UOJCDDLTVQJPGH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(B2OC(C)(C)C(C)(C)O2)C=C1 UOJCDDLTVQJPGH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group 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
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- VLRICFVOGGIMKK-UHFFFAOYSA-N pyrazol-1-yloxyboronic acid Chemical compound OB(O)ON1C=CC=N1 VLRICFVOGGIMKK-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- ZRXVCYGHAUGABY-UHFFFAOYSA-O tris(4-bromophenyl)azanium Chemical compound C1=CC(Br)=CC=C1[NH+](C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 ZRXVCYGHAUGABY-UHFFFAOYSA-O 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JPDUPGAVXNALOL-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetraphenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 JPDUPGAVXNALOL-UHFFFAOYSA-N 0.000 description 1
- CIHJFEWFZJQTFE-UHFFFAOYSA-N 2,4-dibromo-1,3,5-trimethylbenzene Chemical group CC1=CC(C)=C(Br)C(C)=C1Br CIHJFEWFZJQTFE-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- YMXIIVIQLHYKOT-UHFFFAOYSA-N 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline Chemical group O1C(C)(C)C(C)(C)OB1C1=CC=CC(N)=C1 YMXIIVIQLHYKOT-UHFFFAOYSA-N 0.000 description 1
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 1
- 125000005977 3-phenylpropyloxy group Chemical group 0.000 description 1
- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 description 1
- ZNJRONVKWRHYBF-VOTSOKGWSA-N 4-(dicyanomethylene)-2-methyl-6-julolidyl-9-enyl-4h-pyran Chemical compound O1C(C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(CCCN2CCC3)=C2C3=C1 ZNJRONVKWRHYBF-VOTSOKGWSA-N 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- QKWORTBZGYIMOM-UHFFFAOYSA-N 9-(2-carbazol-9-ylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 QKWORTBZGYIMOM-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- WYZWJLZUSHFFOR-UHFFFAOYSA-N C1=CC=C2SC(C3=CC=4C=C5CCCN6CCCC(=C56)C=4OC3=O)=NC2=C1 Chemical compound C1=CC=C2SC(C3=CC=4C=C5CCCN6CCCC(=C56)C=4OC3=O)=NC2=C1 WYZWJLZUSHFFOR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- GMQUEDBQYNHEEM-UHFFFAOYSA-N [B].[B].CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O Chemical compound [B].[B].CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O GMQUEDBQYNHEEM-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- VZSNNUDOANMGNX-UHFFFAOYSA-K aluminum;4-phenylphenolate Chemical compound [Al+3].C1=CC([O-])=CC=C1C1=CC=CC=C1.C1=CC([O-])=CC=C1C1=CC=CC=C1.C1=CC([O-])=CC=C1C1=CC=CC=C1 VZSNNUDOANMGNX-UHFFFAOYSA-K 0.000 description 1
- 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
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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
- 125000004429 atom Chemical group 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- BCDSSSXUYLVMQY-UHFFFAOYSA-N bis(2,4,6-trimethylphenyl)boron Chemical compound CC1=CC(C)=CC(C)=C1[B]C1=C(C)C=C(C)C=C1C BCDSSSXUYLVMQY-UHFFFAOYSA-N 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 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
- 150000004775 coumarins Chemical class 0.000 description 1
- KFGVRWGDTLZAAO-UHFFFAOYSA-N cyclopenta-1,3-diene dicyclohexyl(cyclopenta-1,3-dien-1-yl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.C1CCC(CC1)P(C1CCCCC1)c1ccc[cH-]1 KFGVRWGDTLZAAO-UHFFFAOYSA-N 0.000 description 1
- 125000006312 cyclopentyl amino group Chemical group [H]N(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005446 heptyloxy 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])O* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000006316 iso-butyl amino group Chemical group [H]N(*)C([H])([H])C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl 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])C([H])([H])C([H])([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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([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
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 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
- 239000003921 oil Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000004880 oxines Chemical class 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
- 150000002940 palladium Chemical class 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000000913 palmityl 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])C([H])([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
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000002958 pentadecyl 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])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
- 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004894 pentylamino group Chemical group C(CCCC)N* 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-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
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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
- 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
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
- 125000001935 tetracenyl group Chemical class C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 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
- 125000005259 triarylamine group Chemical group 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
Description
本発明は、新規なリン光材料、とくに青色リン光材料に適したワイドギャップな電子輸送層を形成するのに有用な新規なトリアリールホウ素誘導体およびそれを含む有機エレクトロルミネッセンス素子に関する。 The present invention relates to a novel triarylboron derivative useful for forming a wide-gap electron transport layer suitable for a novel phosphorescent material, particularly a blue phosphorescent material, and an organic electroluminescence device including the same.
有機EL素子は、電極から注入されたホールと電子の再結合によって生成した励起エネルギーが発光過程を経て基底状態に緩和されることにより自発光する。しかしながら、ホールと電子の再結合によって生成する励起状態には一重項励起状態と三重項励起状態の2種類がそれぞれ1対3の割合で存在する。これまでの多くは一重項励起状態からの発光を利用した蛍光材料が発光材料に利用されていたため、内部量子効率が最大で25%であるので、この時取り出し効率を20%とすると、最大外部量子効率は5%が理論限界であった。 The organic EL element emits light when excitation energy generated by recombination of holes and electrons injected from an electrode is relaxed to a ground state through a light emission process. However, there are two types of excited states generated by recombination of holes and electrons, a singlet excited state and a triplet excited state, in a ratio of 1: 3. In many cases, a fluorescent material utilizing light emission from a singlet excited state has been used as a light emitting material, and therefore, the internal quantum efficiency is 25% at the maximum. The quantum efficiency was the theoretical limit of 5%.
近年、イリジウムやプラチナなどの重原子効果を利用した錯体化合物を用い三重項励起状態からの発光、すなわちリン光発光を用いることにより発光効率の向上が報告されるようになった(例えば、非特許文献1)。一重項励起状態に加え、三重項励起状態からの発光を利用することで最大内部量子効率は理論上100%に到達することが可能で、リン光材料は発光材料として注目を浴びている。 In recent years, improvement in luminous efficiency has been reported by using light emission from a triplet excited state, that is, phosphorescence emission, using a complex compound utilizing a heavy atom effect such as iridium or platinum (for example, non-patented) Reference 1). The maximum internal quantum efficiency can theoretically reach 100% by utilizing light emission from the triplet excited state in addition to the singlet excited state, and phosphorescent materials are attracting attention as light emitting materials.
例えば緑色材料として、下記式
また安達らによる非特許文献2などにより青色発光材料である下記式
その結果最近ではS.R.Forrestらによる非特許文献3では下記式
これら発光材料を効率よく発光させるにはホールと電子の注入バランスを整えて、発光層の中で十分にこれらのキャリアーの再結合が行えるようにホール輸送剤や電子輸送剤などを選択しなければならない。
特に青色リン光材料についてはエネルギーギャップが大きいためにワイドギャップ化されたホール輸送剤や電子輸送剤が必要になってくる。現在これらリン光材料については、電子輸送材料に従来から使用されているAlq3〔トリス(8−キノリノラト)アルミニウム〕やBAlq2〔ビス(2−メチル−8−キノリノラト)アルミニウム−p−フェニルフェノラート〕等が使用されているが、リン光材料に使用するには十分なエネルギーギャップを持ち合わせていないため新規なワイドギャップな電子輸送材料の開発が必要である。
In particular, since the blue phosphorescent material has a large energy gap, a hole transport agent and an electron transport agent having a wide gap are required. For these phosphorescent materials, Alq 3 [tris (8-quinolinolato) aluminum] and BAlq 2 [bis (2-methyl-8-quinolinolato) aluminum-p-phenylphenolate, which are conventionally used for electron transport materials, are used. However, since it does not have a sufficient energy gap for use in phosphorescent materials, it is necessary to develop a new wide gap electron transport material.
本発明の第1の目的は、新規なトリアリールホウ素誘導体を提供する点にある。本発明の第2の目的は、それを用いた新規な有機エレクトロルミネッセンス素子を提供する点にある。 The first object of the present invention is to provide a novel triarylboron derivative. The second object of the present invention is to provide a novel organic electroluminescence device using the same.
本発明の第1は、下記一般式(1)
よりなる群から選ばれたトリアリールホウ素誘導体に関する。
本発明の第2は、3.4eV以上の広いエネルギーギャップ(Eg)を有する請求項1記載のトリアリールホウ素誘導体に関する。
本発明の有機エレクトロルミネッセンス素子に用いられる一般式(1)〜(6)で表される化合物はバンドギャップが3.4eV以上の値を示すことが好ましい。バンドギャップが上記の値を示すことで電子輸送性を保持しホールブロック効果が期待でき、発光効率の向上が期待できる。また特に青色リン光材料を発光させるには大きなバンドギャップが必要である。
バンドギャップとは、化合物のイオン化ポテンシャル(Ip)と電子親和力(Ea)の差を表す。化合物のイオン化ポテンシャル(Ip)と電子親和力(Ea)は一般に真空準位を基準に決定される。イオン化ポテンシャル(Ip)は化合物のHOMO(最高被占分子軌道)レベルにある電子を真空準位に放出するのに必要なエネルギーのことであり、一方、電子親和力(Ea)は真空準位にある電子が物質のLUMO(最低空分子軌道)レベルに落ちて安定化するエネルギーのことである。
イオン化ポテンシャル(Ip)と電子親和力(Ea)の差は、エネルギーギャップ(Eg)として化合物の吸収スペクトルの吸収端より求めることができる。
一般に以下の式で求めることができる。吸収端の波長をWnmとすればそのときのエネルギーギャップEgは
Eg=1240÷W
で求めることができる。
本発明の第3は、500nmよりも短波長に低温リン光スペクトルの発光端を示す請求項1または2記載のトリアリールホウ素誘導体に関する。
本発明の有機エレクトロルミネッセンス素子に用いられる一般式(1)〜(6)で表される化合物は低温リン光の発光端が500nm以下の値を示すことが好ましい。低温リン光スペクトルの測定は、リン光材料が一般に室温で測定することが困難であり、被測定物を液体ヘリウムなどで冷却した状態で測定する。これを測定することで組み合せるリン光発光材料へのエネルギーの移動がスムーズに起こるかどうかの判断がつく。特に青色リン光材料との組合せの場合、発光端の値が500nm以下でないとスムーズなエネルギー移動が起こりえない。
本発明の第4は、一般式(1)〜(6)におけるAr′がピリジル基である請求項1〜3いずれか記載のトリアリールホウ素誘導体に関する。
本発明の第5は、一般式(1)〜(6)におけるArが単結合またはフェニレン基である請求項1〜4いずれか記載のトリアリールホウ素誘導体に関する。
本発明の第6は、一般式(1)、(2)、(4)、(5)、(6)におけるArが3′−位および/または、5′−位に結合している請求項1〜5いずれか記載のトリアリールホウ素誘導体に関する。
本発明の第7は、請求項1〜6いずれか記載のトリアリールホウ素誘導体を含有す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に関する。
本発明の第8は、請求項1〜6いずれか記載のトリアリールホウ素誘導体を電子輸送材料として使用したことを特徴とする有機エレクトロルミネッセンス素子に関する。
本発明の第9は、請求項2記載のトリアリールホウ素誘導体とリン光発光材料を併用したことを特徴とする有機エレクトロルミネッセンス素子に関する。
本発明の第10は、請求項3記載のトリアリールホウ素誘導体とリン光発光材料を併用したことを特徴とする有機エレクトロルミネッセンス素子に関する。
The first of the present invention is the following general formula (1)
And a triarylboron derivative selected from the group consisting of:
The second aspect of the present invention relates to the triarylboron derivative according to claim 1, which has a wide energy gap (Eg) of 3.4 eV or more.
The compounds represented by the general formulas (1) to (6) used in the organic electroluminescence device of the present invention preferably have a band gap of 3.4 eV or more. When the band gap shows the above value, the electron transport property can be maintained, the hole blocking effect can be expected, and the light emission efficiency can be improved. In particular, a large band gap is required for emitting a blue phosphorescent material.
The band gap represents the difference between the ionization potential (Ip) and the electron affinity (Ea) of the compound. The ionization potential (Ip) and electron affinity (Ea) of a compound are generally determined based on the vacuum level. The ionization potential (Ip) is the energy required to release electrons at the HOMO (highest occupied molecular orbital) level of a compound to the vacuum level, while the electron affinity (Ea) is at the vacuum level. This is the energy at which electrons fall to the LUMO (lowest molecular orbital) level of a material and stabilize.
The difference between the ionization potential (Ip) and the electron affinity (Ea) can be obtained from the absorption edge of the absorption spectrum of the compound as an energy gap (Eg).
Generally, it can obtain | require with the following formula | equation. If the wavelength of the absorption edge is Wnm, then the energy gap Eg is
Eg = 1240 ÷ W
Can be obtained.
3rd of this invention is related with the triaryl boron derivative of Claim 1 or 2 which shows the light emission edge of a low-temperature phosphorescence spectrum in a wavelength shorter than 500 nm.
The compounds represented by the general formulas (1) to (6) used in the organic electroluminescence device of the present invention preferably have a low-temperature phosphorescence emission edge having a value of 500 nm or less. The measurement of the low-temperature phosphorescence spectrum is generally difficult for a phosphorescent material to be measured at room temperature, and the measurement is performed in a state where an object to be measured is cooled with liquid helium or the like. By measuring this, it is possible to judge whether or not energy transfer to the phosphorescent material to be combined occurs smoothly. In particular, in the case of a combination with a blue phosphorescent material, smooth energy transfer cannot occur unless the value of the emission edge is 500 nm or less.
A fourth aspect of the present invention relates to the triarylboron derivative according to any one of claims 1 to 3, wherein Ar 'in the general formulas (1) to (6) is a pyridyl group.
5th of this invention is related with the triaryl boron derivative in any one of Claims 1-4 whose Ar in General formula (1)-(6) is a single bond or a phenylene group.
According to a sixth aspect of the present invention, Ar in the general formulas (1), (2), (4), (5) and (6) is bonded to the 3'-position and / or the 5'-position. It relates to the triarylboron derivative according to any one of 1 to 5.
7th of this invention is related with the organic electroluminescent element characterized by containing the triaryl boron derivative in any one of Claims 1-6.
An eighth aspect of the present invention relates to an organic electroluminescence device using the triarylboron derivative according to any one of claims 1 to 6 as an electron transport material.
A ninth aspect of the present invention relates to an organic electroluminescence device comprising the triarylboron derivative according to claim 2 and a phosphorescent material in combination.
A tenth aspect of the present invention relates to an organic electroluminescent device characterized by using the triarylboron derivative according to claim 3 and a phosphorescent material together.
本発明の一般式(1)〜(6)で示されるトリアリールホウ素誘導体は、下記一般式(7)〜(12)
で示されるハロゲン化トリアリールホウ素化合物を原料とし、塩基、触媒および溶媒の存在下において、下記一般式(13)
In the presence of a base, a catalyst and a solvent, a halogenated triarylboron compound represented by the following general formula (13)
これらの反応で使用する溶媒は、トルエン、トルエン−アルコール混合溶媒、ジメトキシエタンなどが使用できる。またこの反応で使用する塩基については、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸水素ナトリウム、炭酸水素カリウム、リン酸カリウム、水酸化リチウム、水酸化ナトリウム、水酸化カリウムのような無機アルカリ金属塩、トリエチルアミンのような有機塩基、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムt−ブトキシド、カリウムt−ブトキシドのような有機アルカリ金属塩、テトラブチルアンモニウムヒドロキシド1Mメタノール溶液等の有機塩基化合物の有機溶液等が使用できる。また、触媒で使用するパラジウム触媒については、テトラキス(トリフェニルホスフィノ)パラジウムが好ましいが、酢酸パラジウムやビス(トリフェニルホスフィン)パラジウムジクロライド、ビス(1、1′−ビス(ジフェニルホスフィノ)フェロセン)パラジウムジクロライド、ビス(1,4−ビス(ジフェニルホスフィノ)ブタン)パラジウムジクロライドなどの0価の有機パラジウム錯体が使用できる。
また、これらの反応で使用するアリールホウ酸化合物については、対応するアリールハロゲン化合物を無水のジエチルエーテルやテトラヒドロフランなどのエーテル溶媒中でn−ブチルリチウムなどでリチオ化し、これにトリメトキシボラン、トリエトキシボロン、トリイソプロピルボロン、ピナコールボロンやビス(ピナコラート)ジボロンなどと作用させることにより容易に合成することができる。
As a solvent used in these reactions, toluene, a toluene-alcohol mixed solvent, dimethoxyethane, or the like can be used. Regarding the base used in this reaction, inorganic alkali metal salts such as sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, Organic bases such as triethylamine, organic alkali metal salts such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide, organic base compounds such as tetrabutylammonium hydroxide 1M methanol solution, etc. Can be used. The palladium catalyst used in the catalyst is preferably tetrakis (triphenylphosphino) palladium, but palladium acetate, bis (triphenylphosphine) palladium dichloride, bis (1,1′-bis (diphenylphosphino) ferrocene). Zero-valent organic palladium complexes such as palladium dichloride and bis (1,4-bis (diphenylphosphino) butane) palladium dichloride can be used.
For the aryl boric acid compounds used in these reactions, the corresponding aryl halogen compounds are lithiated with n-butyllithium in an ether solvent such as anhydrous diethyl ether or tetrahydrofuran, and trimethoxyborane or triethoxyboron is added thereto. , Triisopropylboron, pinacolboron, bis (pinacolato) diboron and the like can be easily synthesized.
これらの反応は下記反応式に示すとおりである。
前記R1〜R14におけるアルキル基としては、メチル、エチル、プロピル、n−ブチル、sec−ブチル、t−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、エイコシルなどを挙げることができる。 Examples of the alkyl group for R 1 to R 14 include methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Examples include pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.
置換もしくは無置換のアルコキシ基としては、メトキシ基、エトキシ基、2−メトキシエトキシ基、2−(2−メトキシエトキシ)エトキシ基、2−エトキシエトキシ基、2−ブトキシエトキシ基、2−(ジメチルアミノ)エトキシ基、2−(ジブチルアミノ)エトキシ基、プロポキシ基、イソプロポキシ基、3−メトキシプロポキシ基、3−エトキシプロポキシ基、3−(ジメチルアミノ)プロポキシ基、ブトキシ基、イソブトキシ基、sec−ブトキシ基、tert−ブトキシ基、ペントキシ基、イソペントキシ基、2−ペントキシ基、3−ペントキシ基、ネオペントキシ基、ヘキシロキシ基、2−ヘキシロキシ基、2−エチルヘキシロキシ基、2−ブチルヘキシロキシ基、ヘプチロキシ基、オクトキシ基、2−オクトキシ基、ノニロキシ基、デシロキシ基、ドデシロキシ基、アリロキシ基、ベンジロキシ基、4−メトキシベンジロキシ基、4−フルオロベンジロキシ基、3−(ジメチルアミノ)ベンジロキシ基、4−フェニルベンジロキシ基、1−ナフチルメトキシ基、2−ナフチルメトキシ基、1−(2−メトキシナフチル)メトキシ基、9−アントリルメトキシ基、ジフェニルメトキシ基、ジ(p−トリル)メトキシ基、ジ(4−メトキシフェニル)メトキシ基、ジ(1−ナフチル)メトキシ基、トリフェニルメトキシ基、3−フェニルプロピロキシ基等が挙げられる。 Examples of the substituted or unsubstituted alkoxy group include methoxy group, ethoxy group, 2-methoxyethoxy group, 2- (2-methoxyethoxy) ethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, and 2- (dimethylamino). ) Ethoxy group, 2- (dibutylamino) ethoxy group, propoxy group, isopropoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group, 3- (dimethylamino) propoxy group, butoxy group, isobutoxy group, sec-butoxy Group, tert-butoxy group, pentoxy group, isopentoxy group, 2-pentoxy group, 3-pentoxy group, neopentoxy group, hexyloxy group, 2-hexyloxy group, 2-ethylhexyloxy group, 2-butylhexyloxy group, heptyloxy group , Octoxy group, 2-octoxy group, nonyloxy Group, decyloxy group, dodecyloxy group, allyloxy group, benzyloxy group, 4-methoxybenzyloxy group, 4-fluorobenzyloxy group, 3- (dimethylamino) benzyloxy group, 4-phenylbenzyloxy group, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1- (2-methoxynaphthyl) methoxy group, 9-anthrylmethoxy group, diphenylmethoxy group, di (p-tolyl) methoxy group, di (4-methoxyphenyl) methoxy group, di (1 -Naphthyl) methoxy group, triphenylmethoxy group, 3-phenylpropyloxy group and the like.
置換もしくは無置換のアルキルアミノ基としては、メチルアミノ基、エチルアミノ基、プロピルアミノ基、イソプロピルアミノ基、ブチルアミノ基、イソブチルアミノ基、ペンチルアミノ基、ヘキシルアミノ基、シクロペンチルアミノ基、シクロヘキシルアミノ基、オクチルアミノ基、ヘプチルアミノ基、デシルアミノ基、ドデシルアミノ基、ジメチルアミノ基、エチルメチルアミノ基、ジエチルアミノ基、メチルプロピルアミノ基、イソプロピルメチルアミノ基、ブチルメチルアミノ基、イソブチルメチルアミノ基、エチルプロピルアミノ基、ジプロピルアミノ基、ジイソプロピルアミノ基、ブチルエチルアミノ基、エチルイソブチルアミノ基、ジブチルアミノ基、ジイソブチルアミノ基、メチルペンチルアミノ基、エチルペンチルアミノ基、ヘキシルメチルアミノ基、エチルヘキシルアミノ基、ブチルヘキシルアミノ基、ヘキシルペンチルアミノ基、ジヘキシルアミノ基、ジシクロペンチルアミノ基、シクロヘキシルメチルアミノ基、シクロヘキシルエチルアミノ基、シクロヘキシルイソプロピルアミノ基、ジシクロヘキシルアミノ基、メチルオクチルアミノ基、ヘプチルメチルアミノ基、ヘプチルイソプロピルアミノ基、ジヘプチルアミノ基、メチルオクチルアミノ基、オクチルプロピルアミノ基、ジオクチルアミノ基、デシルエチルアミノ基、デシルイソプロピルアミノ基、ジ(2−エチルヘキシル)アミノ基、ドデシルメチルアミノ基、ドデシルヘキシルアミノ基、シクロヘキシルドデシルアミノ基、ジドデシルアミノ基等が挙げられる。 Examples of the substituted or unsubstituted alkylamino group include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, pentylamino group, hexylamino group, cyclopentylamino group, and cyclohexylamino group. Octylamino group, heptylamino group, decylamino group, dodecylamino group, dimethylamino group, ethylmethylamino group, diethylamino group, methylpropylamino group, isopropylmethylamino group, butylmethylamino group, isobutylmethylamino group, ethylpropyl Amino group, dipropylamino group, diisopropylamino group, butylethylamino group, ethylisobutylamino group, dibutylamino group, diisobutylamino group, methylpentylamino group, ethylpentylamino , Hexylmethylamino group, ethylhexylamino group, butylhexylamino group, hexylpentylamino group, dihexylamino group, dicyclopentylamino group, cyclohexylmethylamino group, cyclohexylethylamino group, cyclohexylisopropylamino group, dicyclohexylamino group, methyloctyl Amino group, heptylmethylamino group, heptylisopropylamino group, diheptylamino group, methyloctylamino group, octylpropylamino group, dioctylamino group, decylethylamino group, decylisopropylamino group, di (2-ethylhexyl) amino group , Dodecylmethylamino group, dodecylhexylamino group, cyclohexyldodecylamino group, didodecylamino group and the like.
置換もしくは無置換のアリール基としては、フェニル基、1−ナフチル基、2−ナフチル基、4−フェニル−1−ナフチル基、4−フェニル−2−ナフチル基、1−フェニル−5−ナフチル基、1−アントリル基、2−アントリル基、9−アントリル基、10−フェニル−9−アントリル基、1−フェナントリル基、2−フェナントリル基、3−フェナントリル基、4−フェナントリル基、9−フェナントリル基、1−ピレニル基、2−ピレニル基、2−ペリレニル基、3−ペリレニル基、1−フルオランテニル基、2−フルオランテニル基、3−フルオランテニル基、8−フルオランテニル基、2−トリフェニレニル基、9,9−ジメチルフルオレン−2−イル基、9,9−ジブチルフルオレン−2−イル基、9,9−ジヘキシルフルオレン−2−イル基、9,9−ジオクチルフルオレン−2−イル基、9,9−ジフェニルフルオレン−2−イル基、2−ビフェニリル基、3−ビフェニリル基、4−ビフェニリル基、p−テルフェニル−3−イル基、p−テルフェニル−4−イル基、m−テルフェニル−3−イル基、m−テルフェニル−4−イル基、o−テルフェニル−3−イル基、o−テルフェニル−4−イル基、4−(1−ナフチル)−1−ナフチル基、o−トリル基、m−トリル基、p−トリル基、p−tert−ブチルフェニル基、4−メトキシフェニル基、4−フルオロフェニル基、4−ジメチルアミノフェニル基、4−シアノフェニル基、4−(トリフルオロメチル)フェニル基、4−メチル−1−ナフチル基、2−メトキシ−1−ナフチル基、10−メチル−9−アントリル基、10−メトキシ−9−アントリル基、4−フェニル−8−フルオランテニル基、7−ジメチルアミノ−9,9−ジメチルフルオレン−2−イル基、3′,5′−ジフェニルビフェニル−4−イル基等が挙げられる Examples of the substituted or unsubstituted aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 4-phenyl-1-naphthyl group, 4-phenyl-2-naphthyl group, 1-phenyl-5-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 10-phenyl-9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1 -Pyrenyl group, 2-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 1-fluoranthenyl group, 2-fluoranthenyl group, 3-fluoranthenyl group, 8-fluoranthenyl group, 2-triphenylenyl Group, 9,9-dimethylfluoren-2-yl group, 9,9-dibutylfluoren-2-yl group, 9,9-dihexylfluore 2-yl group, 9,9-dioctylfluoren-2-yl group, 9,9-diphenylfluoren-2-yl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl- 3-yl group, p-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-4-yl group, o-terphenyl-3-yl group, o-terphenyl- 4-yl group, 4- (1-naphthyl) -1-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, p-tert-butylphenyl group, 4-methoxyphenyl group, 4-fluoro Phenyl group, 4-dimethylaminophenyl group, 4-cyanophenyl group, 4- (trifluoromethyl) phenyl group, 4-methyl-1-naphthyl group, 2-methoxy-1-naphthyl group, 10-methyl-9- Enthryl group, 10-methoxy-9-anthryl group, 4-phenyl-8-fluoranthenyl group, 7-dimethylamino-9,9-dimethylfluoren-2-yl group, 3 ', 5'-diphenylbiphenyl-4 -Yl group etc. are mentioned
炭素数1〜20の直鎖または分岐のアルキル基を置換基として有することもあるアリーロキシ基としては、前記例示の各種アリール基の結合手部分に酸素が導入されたものを挙げることができる。例えば、置換もしくは無置換のアリーロキシ基としては、フェノキシ基、1−ナフトキシ基、2−ナフトキシ基、4−フェニル−1−ナフトキシ基、4−フェニル−2−ナフトキシ基、1−フェニル−5−ナフトキシ基、1−アントリロキシ基、2−アントリロキシ基、9−アントリロキシ基、10−フェニル−9−アントリロキシ基、1−フェナントリロキシ基、2−フェナントリロキシ基、3−フェナントリロキシ基、4−フェナントリロキシ基、9−フェナントリロキシ基、1−ピレニロキシ基、2−ピレニロキシ基、1−ペリレノキシ基、2−ペリレノキシ基、3−ペリレノキシ基、1−フルオランテノキシ基、2−フルオランテノキシ基、3−フルオランテノキシ基、8−フルオランテノキシ基、2−トリフェニレノキシ基、9,9−ジメチルフルオレン−2−イロキシ基、9,9−ジブチルフルオレン−2−イロキシ基、9,9−ジヘキシルフルオレン−2−イロキシ基、9,9−ジオクチルフルオレン−2−イロキシ基、9,9−ジフェニルフルオレン−2−イロキシ基、2−ビフェニルイロキシ基、3−ビフェニルイロキシ基、4−ビフェニルイロキシ基、p−ターフェニル−3−イロキシ基、p−ターフェニル−4−イロキシ基、m−ターフェニル−3−イロキシ基、m−ターフェニル−4−イロキシ基、o−ターフェニル−3−イロキシ基、o−ターフェニル−4−イロキシ基、4−(1−ナフチル)−1−ナフトキシ基、o−トリロキシ基、m−トリロキシ基、p−トリロキシ基、p−tert−ブチルフェノキシ基、4−メトキシフェノキシ基、4−フルオロフェノキシ基、4−ジメチルアミノフェノキシ基、4−シアノフェノキシ基、4−(トリフルオロメチル)フェノキシ基、4−メチル−1−ナフトキシ基、4−フェニル−1−ナフトキシ基、2−メトキシ−ナフトキシ基、10−メチル−9−アントリロキシ基、10−メトキシ−9−アントリロキシ基、4−フェニル−フルオランテン−8−イロキシ基、7−ジメチルアミノ−9,9−ジメチルフルオランテン−2−イロキシ基、3′,5′−ジフェニルビフェニル−4−イロキシ基等が挙げられる。 Examples of the aryloxy group that may have a linear or branched alkyl group having 1 to 20 carbon atoms as a substituent include those in which oxygen is introduced into the bond part of the various aryl groups exemplified above. For example, the substituted or unsubstituted aryloxy group includes phenoxy group, 1-naphthoxy group, 2-naphthoxy group, 4-phenyl-1-naphthoxy group, 4-phenyl-2-naphthoxy group, 1-phenyl-5-naphthoxy group. Group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 10-phenyl-9-anthryloxy group, 1-phenanthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group, 4-phena Nutryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 2-pyrenyloxy group, 1-peryleneoxy group, 2-peryleneoxy group, 3-peryleneoxy group, 1-fluoranthenoxy group, 2-fluoranthenoxy group Group, 3-fluoranthenoxy group, 8-fluoranthenoxy group, 2-triphenylenoxy group, 9, -Dimethylfluorene-2-yloxy group, 9,9-dibutylfluorene-2-iroxy group, 9,9-dihexylfluorene-2-iroxy group, 9,9-dioctylfluorene-2-iroxy group, 9,9-diphenyl Fluorene-2-iroxy group, 2-biphenyliroxy group, 3-biphenyliroxy group, 4-biphenyliroxy group, p-terphenyl-3-iroxy group, p-terphenyl-4-iroxy group, m- Terphenyl-3-Iroxy group, m-Terphenyl-4-Iroxy group, o-Terphenyl-3-Iroxy group, o-Terphenyl-4-Iroxy group, 4- (1-Naphtyl) -1-naphthoxy group , O-triloxy group, m-triloxy group, p-triloxy group, p-tert-butylphenoxy group, 4-methoxyphenoxy group, 4-full Lophenoxy group, 4-dimethylaminophenoxy group, 4-cyanophenoxy group, 4- (trifluoromethyl) phenoxy group, 4-methyl-1-naphthoxy group, 4-phenyl-1-naphthoxy group, 2-methoxy-naphthoxy group Group, 10-methyl-9-anthryloxy group, 10-methoxy-9-anthryloxy group, 4-phenyl-fluoranthene-8-iroxy group, 7-dimethylamino-9,9-dimethylfluoranthene-2-yloxy group, 3 ', 5'-diphenylbiphenyl-4-iroxy group and the like can be mentioned.
置換もしくは無置換のアリールアミノ基の例としては、前記アリール基として挙げた1価の基にアミノ基が置換した基であり、たとえば、1−フェニルアミノ基、N−o−トリルアミノ基、N−m−トリルアミノ基、N−p−トリルアミノ基、N−1−ナフチルアミノ基、N−2−ナフチルアミノ基、N−(4−メトキシフェニル)アミノ基、N−(4−エチルフェニル)アミノ基、N−(4−フルオロフェニル)アミノ基、N−(4−ジメチルアミノフェニル)−アミノ基、2−ナフチルアミノ基、N−(1−アントリル)アミノ基、N−(2−アントリル)アミノ基、N−(9−アントリル)アミノ基、N−(10−メチル−9−アントリル)アミノ基、N−(9−フェナントリル)アミノ基、N−(9,9−ジメチルフルオレン−2−イル)アミノ基、N−(3−フルオランテニル)アミノ基、N−(1−ピレニル)アミノ基、N−(1−ピレニル)アミノ基、N−(3−ペリレニル)アミノ基、ジフェニルアミノ基、N,N−ジ(o−トリル)アミノ基、N,N−ジ(m−トリル)アミノ基、N,N−ジ(p−トリル)アミノ基、N,N−ジ(1−ナフチル)アミノ基、N,N−ジ(2−ナフチル)アミノ基、N−(1−ナフチル)−N−フェニルアミノ基、N−(4−メトキシフェニル)−N−フェニルアミノ基、N−(4−エチルフェニル)−N−フェニルアミノ基、N−(4−フルオロフェニル)−N−フェニルアミノ基、N−(4−ジメチルアミノフェニル)−N−フェニルアミノ基、N−(2−ナフチル)−N−フェニルアミノ基、N−(1−ナフチル)−N−(o−トリル)アミノ基、N−(2−ナフチル)−N−(o−トリル)アミノ基、N−(1−アントリル)フェニルアミノ基、N−(2−アントリル)−N−フェニルアミノ基、N−(9−アントリル)−N−フェニルアミノ基、N−(10−メチル−9−アントリル)−N−フェニルアミノ基、N−(1−アントリル)−N−(1−ナフチル)アミノ基、N−(2−アントリル)−N−(1−ナフチル)アミノ基、N−(9−アントリル)−N−(2−ナフチル)アミノ基、N−(10−メチル−9−アントリル)−N−(2−ナフチル)アミノ基、N−(9−フェナントリル)−N−フェニルアミノ基、N−(9−フェナントリル)−N−(p−トリル)アミノ基、N−(1−ナフチル)−N−(9−フェナントリル)アミノ基、N−(9,9−ジメチルフルオレン−2−イル)−N−フェニルアミノ基、N−(9,9−ジメチルフルオレン−2−イル)−N−(m−トリル)アミノ基、N−(9,9−ジメチルフルオレン−2−イル)−N−(1−ナフチル)アミノ基、N−(9,9−ジメチルフルオレン−2−イル)−N−(4−メトキシフェニル)アミノ基、N−(1−アントリル)−N−(9,9−ジメチルフルオレン−2−イル)アミノ基、N−(9,9−ジメチルフルオレン−2−イル)−N−(9−フェナントリル)アミノ基、N,N−ビス(9,9−ジメチルフルオレン−2−イル)アミノ基、N−(3−フルオランテニル)−N−フェニルアミノ基、N−(3−フルオランテニル)−N−(p−トリル)アミノ基、N−(3−フルオランテニル)−N−(4−メトキシフェニル)アミノ基、N−(3−フルオランテニル)−N−(1−ナフチル)アミノ基、N−(3−フルオランテニル)−N−(2−ナフチル)アミノ基、N−(1−アントリル)−N−(3−フルオランテニル)アミノ基、N−(9−アントリル)−N−(3−フルオランテニル)アミノ基、N−(3−フルオランテニル)−N−(9−フェナントリル)アミノ基、N−(3−フルオランテニル)−N−(9,9−ジメチルフルオレン−2−イル)アミノ基、N,N−ジ(3−フルオランテニル)アミノ基、N−フェニル−N−(1−ピレニル)アミノ基、N−(1−ピレニル)−N−(p−トリル)アミノ基、N−(4−ジメチルアミノフェニル)−N−(1−ピレニル)アミノ基、N−(1−ナフチル)−N−(1−ピレニル)アミノ基、N−(2−ナフチル)−N−(1−ピレニル)アミノ基、N−(1−アントリル)−N−(1−ピレニル)アミノ基、N−(9−アントリル)−N−(1−ピレニル)アミノ基、N−(1−ピレニル)−N−(9−フェナントリル)アミノ基、N−(9,9−ジメチルフルオレン−2−イル)−N−(1−ピレニル)アミノ基、N−(3−フルオランテニル)−N−(1−ピレニル)アミノ基、N−(9−フルオランテニル)−N−(1−ピレニル)アミノ基、N−(3−ペリレニル)−N−フェニルアミノ基、N−(3−ペリレニル)−N−(m−トリル)アミノ基、N−(4−ジメチルアミノメチル)−N−(3−ペリレニル)アミノ基、N−(1−ナフチル)−N−(3−ペリレニル)アミノ基、N−(2−ナフチル)−N−(3−ペリレニル)アミノ基、N−(1−アントリル)−N−(3−ペリレニル)アミノ基、N−(3−ペリレニル)−N−(9−フェナントリル)アミノ基、N−(9,9−ジメチルフルオレン−2−イル)−N−(3−ペリレニル)アミノ基、N−(9−フルオランテニル)−N−(3−ペリレニル)アミノ基、ビス(4−ジメチルアミノフェニル)アミノ基、ビス(4−ジフェニルアミノフェニル)アミノ基等が挙げられる。 Examples of the substituted or unsubstituted arylamino group are groups in which an amino group is substituted for the monovalent group mentioned as the aryl group, and examples thereof include a 1-phenylamino group, an N-o-tolylamino group, an N- m-tolylamino group, Np-tolylamino group, N-1-naphthylamino group, N-2-naphthylamino group, N- (4-methoxyphenyl) amino group, N- (4-ethylphenyl) amino group, N- (4-fluorophenyl) amino group, N- (4-dimethylaminophenyl) -amino group, 2-naphthylamino group, N- (1-anthryl) amino group, N- (2-anthryl) amino group, N- (9-anthryl) amino group, N- (10-methyl-9-anthryl) amino group, N- (9-phenanthryl) amino group, N- (9,9-dimethylfluorene-2- L) amino group, N- (3-fluoranthenyl) amino group, N- (1-pyrenyl) amino group, N- (1-pyrenyl) amino group, N- (3-perylenyl) amino group, diphenylamino group N, N-di (o-tolyl) amino group, N, N-di (m-tolyl) amino group, N, N-di (p-tolyl) amino group, N, N-di (1-naphthyl) Amino group, N, N-di (2-naphthyl) amino group, N- (1-naphthyl) -N-phenylamino group, N- (4-methoxyphenyl) -N-phenylamino group, N- (4- Ethylphenyl) -N-phenylamino group, N- (4-fluorophenyl) -N-phenylamino group, N- (4-dimethylaminophenyl) -N-phenylamino group, N- (2-naphthyl) -N -Phenylamino group, N- (1-naphthyl) -N- o-tolyl) amino group, N- (2-naphthyl) -N- (o-tolyl) amino group, N- (1-anthryl) phenylamino group, N- (2-anthryl) -N-phenylamino group, N- (9-anthryl) -N-phenylamino group, N- (10-methyl-9-anthryl) -N-phenylamino group, N- (1-anthryl) -N- (1-naphthyl) amino group, N- (2-anthryl) -N- (1-naphthyl) amino group, N- (9-anthryl) -N- (2-naphthyl) amino group, N- (10-methyl-9-anthryl) -N- (2-naphthyl) amino group, N- (9-phenanthryl) -N-phenylamino group, N- (9-phenanthryl) -N- (p-tolyl) amino group, N- (1-naphthyl) -N- (9-phenanthryl) amino group, N- (9 , 9-dimethylfluoren-2-yl) -N-phenylamino group, N- (9,9-dimethylfluoren-2-yl) -N- (m-tolyl) amino group, N- (9,9-dimethyl) Fluoren-2-yl) -N- (1-naphthyl) amino group, N- (9,9-dimethylfluoren-2-yl) -N- (4-methoxyphenyl) amino group, N- (1-anthryl) -N- (9,9-dimethylfluoren-2-yl) amino group, N- (9,9-dimethylfluoren-2-yl) -N- (9-phenanthryl) amino group, N, N-bis (9 , 9-dimethylfluoren-2-yl) amino group, N- (3-fluoranthenyl) -N-phenylamino group, N- (3-fluoranthenyl) -N- (p-tolyl) amino group, N -(3-Fluoranthenyl) -N- (4- Toxiphenyl) amino group, N- (3-fluoranthenyl) -N- (1-naphthyl) amino group, N- (3-fluoranthenyl) -N- (2-naphthyl) amino group, N- (1 -Anthryl) -N- (3-fluoranthenyl) amino group, N- (9-anthryl) -N- (3-fluoranthenyl) amino group, N- (3-fluoranthenyl) -N- (9 -Phenanthryl) amino group, N- (3-fluoranthenyl) -N- (9,9-dimethylfluoren-2-yl) amino group, N, N-di (3-fluoranthenyl) amino group, N- Phenyl-N- (1-pyrenyl) amino group, N- (1-pyrenyl) -N- (p-tolyl) amino group, N- (4-dimethylaminophenyl) -N- (1-pyrenyl) amino group, N- (1-naphthyl) -N- (1-pyrenyl Amino group, N- (2-naphthyl) -N- (1-pyrenyl) amino group, N- (1-anthryl) -N- (1-pyrenyl) amino group, N- (9-anthryl) -N- ( 1-pyrenyl) amino group, N- (1-pyrenyl) -N- (9-phenanthryl) amino group, N- (9,9-dimethylfluoren-2-yl) -N- (1-pyrenyl) amino group, N- (3-fluoranthenyl) -N- (1-pyrenyl) amino group, N- (9-fluoranthenyl) -N- (1-pyrenyl) amino group, N- (3-perylenyl) -N- Phenylamino group, N- (3-perylenyl) -N- (m-tolyl) amino group, N- (4-dimethylaminomethyl) -N- (3-perylenyl) amino group, N- (1-naphthyl)- N- (3-perylenyl) amino group, N- (2-naphthyl) -N -(3-perylenyl) amino group, N- (1-anthryl) -N- (3-perylenyl) amino group, N- (3-perylenyl) -N- (9-phenanthryl) amino group, N- (9, 9-dimethylfluoren-2-yl) -N- (3-perylenyl) amino group, N- (9-fluoranthenyl) -N- (3-perylenyl) amino group, bis (4-dimethylaminophenyl) amino group And bis (4-diphenylaminophenyl) amino group.
Arにおけるアリーレン基は、前記アリール基の例に挙げたものに対応するアリーレン基を挙げることができ、またAr′のヘテロアリール基としては、1個〜3個の窒素を1つの環内に有するもの、1個の硫黄を環内に有するもの、1個の硫黄と窒素を1つの環内に有するもの、1個の窒素と酸素を1つの環内に有するもの、1個の酸素と硫黄を1つの環内に有するものなどを挙げることができる。 Examples of the arylene group in Ar include an arylene group corresponding to those exemplified in the examples of the aryl group, and the heteroaryl group of Ar ′ has 1 to 3 nitrogen atoms in one ring. One having one sulfur in the ring One having one sulfur and nitrogen in one ring One having one nitrogen and oxygen in one ring One oxygen and sulfur The thing etc. which have in one ring can be mentioned.
Ar′−Ar−として具体的な例を以下に示す。 Specific examples of Ar′-Ar— are shown below.
本発明のトリアリールホウ素誘導体の例を以下に示す。なお、本明細書における式中、環から突き出している結合手以外の線はすべて−CH3(メチル基)の略号である。
Examples of the triarylboron derivative of the present invention are shown below. In the formulas in this specification, all lines other than the bond protruding from the ring are abbreviations for —CH 3 (methyl group).
本発明のトリアリールホウ素誘導体は高い電子輸送性能を有する。従って、電子注入材料及び電子輸送材料として使用することができる。 The triarylboron derivative of the present invention has high electron transport performance. Therefore, it can be used as an electron injection material and an electron transport material.
本発明のトリアリールホウ素誘導体を有機エレクトロルミネッセンス素子に使用する場合、適当な発光材料(ドーパント)と組み合わせて使用することもできる。 When the triarylboron derivative of the present invention is used in an organic electroluminescence device, it can also be used in combination with a suitable light emitting material (dopant).
本発明のトリアリールホウ素化合物を電子輸送層に用いる場合、電子注入材料、電子輸送材料として使用できる。また他の電子輸送材料と組み合わせて使用することもできる。 When the triarylboron compound of the present invention is used for an electron transport layer, it can be used as an electron injection material or an electron transport material. It can also be used in combination with other electron transport materials.
次に本発明の有機エレクトロルミネッセンス素子について説明する。本発明の有機エレクトロルミネッセンス素子は、陽極と陰極間に一層もしくは多層の有機化合物を積層した素子であり、該有機化合物層の少なくとも一層が本発明トリアリールホウ素誘導体を含有する。有機エレクトロルミネッセンス素子が一層の場合、陽極と陰極間に発光層を設けている。発光層は、発光材料を含有しそれに加えて陽極から注入した正孔もしくは陰極から注入した電子を発光材料まで輸送するのが目的で、正孔注入材料もしくは電子注入材料を含有していても良い。多層型の有機エレクトロルミネッセンス素子の構成例としては、例えば陽極/正孔輸送層/発光層/電子輸送層/陰極、陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/陰極、陽極/正孔輸送層/発光層/電子輸送層/電子注入層/陰極、陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極等の多層構成で積層されたものがあげられる。また、必要に応じて陰極上に封止層を有していても良い。 Next, the organic electroluminescence element of the present invention will be described. The organic electroluminescence device of the present invention is a device in which a single layer or a multilayer organic compound is laminated between an anode and a cathode, and at least one layer of the organic compound layer contains the triarylboron derivative of the present invention. When the organic electroluminescence element is a single layer, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material and may contain a hole injecting material or an electron injecting material for the purpose of transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. . Examples of the configuration of the multilayer organic electroluminescence device include, for example, anode / hole transport layer / light emitting layer / electron transport layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode. , Anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, etc. Laminated ones are examples. Moreover, you may have a sealing layer on a cathode as needed.
正孔輸送層、電子輸送層、および発光層のそれぞれの層は、一層構造であっても、多層構造であっても良い。また正孔輸送層、電子輸送層はそれぞれの層で注入機能を受け持つ層(正孔注入層及び電子注入層)と輸送機能を受け持つ層(正孔輸送層および電子輸送層)を別々に設けることもできる。 Each of the hole transport layer, the electron transport layer, and the light emitting layer may have a single layer structure or a multilayer structure. In addition, the hole transport layer and the electron transport layer should be provided separately with a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer). You can also.
本発明の有機エレクトロルミネッセンス素子は、上記構成例に限らず、種々の構成とすることができる。必要に応じて、正孔輸送層成分と発光層成分、あるいは電子輸送層成分と発光層成分を混合した層を設けても良い。 The organic electroluminescence element of the present invention is not limited to the above configuration example, and can have various configurations. If necessary, a layer in which a hole transport layer component and a light emitting layer component or an electron transport layer component and a light emitting layer component are mixed may be provided.
以下本発明の有機エレクトロルミネッセンス素子の構成要素に関して、陽極/正孔輸送層/発光層/電子輸送層/陰極からなる素子構成を例として取り上げて詳細に説明する。本発明の有機エレクトロルミネッセンス素子は、基板に支持されていることが好ましい。 Hereinafter, the constituent elements of the organic electroluminescence element of the present invention will be described in detail by taking as an example an element structure comprising an anode / hole transport layer / light emitting layer / electron transport layer / cathode. The organic electroluminescence device of the present invention is preferably supported on a substrate.
基板の素材については特に制限はなく、従来の有機エレクトロルミネッセンス素子に慣用されているものであれば良く、例えばガラス、石英ガラス、透明プラスチックなどからなるものを用いることができる。 There is no restriction | limiting in particular about the raw material of a board | substrate, What is necessary is just used for the conventional organic electroluminescent element, For example, what consists of glass, quartz glass, a transparent plastic etc. can be used.
本発明の有機エレクトロルミネッセンス素子の陽極としては、仕事関数の大きな金属単体(4eV以上)、仕事関数の大きな金属同士の合金(4eV以上)または導電性物質およびこれらの混合物を電極材料とすることが好ましい。このような電極材料の具体例としては、金、銀、銅等の金属、ITO(インジウム−スズオキサイド)、酸化スズ(SnO2)、酸化亜鉛(ZnO)などの導電性透明材料、ポリピロール、ポリチオフェン等の導電性高分子材料が挙げられる。陽極はこれらの電極材料を、例えば蒸着、スパッタリング、塗布などの方法により基板上に形成することができる。陽極のシート電気抵抗は数百Ω/cm2以下が好ましい。陽極の膜厚は材料にもよるが、一般に5〜1,000nm程度、好ましくは10〜500nmである。 As an anode of the organic electroluminescence device of the present invention, an electrode material may be a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof. preferable. Specific examples of such electrode materials include metals such as gold, silver, and copper, conductive transparent materials such as ITO (indium-tin oxide), tin oxide (SnO 2 ), and zinc oxide (ZnO), polypyrrole, and polythiophene. Examples thereof include conductive polymer materials such as For the anode, these electrode materials can be formed on the substrate by a method such as vapor deposition, sputtering, or coating. The sheet electrical resistance of the anode is preferably several hundred Ω / cm 2 or less. The thickness of the anode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm.
陰極としては、仕事関数の小さな金属単体(4eV以下)、仕事関数の小さな金属同士の合金(4eV以下)または導電性物質およびこれらの混合物を電極材料とすることが好ましい。このような電極材料の具体例としては、リチウム、リチウム−インジウム合金、ナトリウム、ナトリウム−カリウム合金、マグネシウム、マグネシウム−銀合金、マグネシウム−インジウム合金、アルミニウム、アルミニウム−リチウム合金、アルミニウム−マグネシウム合金などが挙げられる。陰極はこれらの電極材料を、例えば蒸着、スパッタリングなどの方法により、薄膜を形成させることにより作製することができる。陰極のシート電気抵抗は数百Ω/cm2以下が好ましい。陰極の膜厚は材料にもよるが、一般に5〜1,000nm程度、好ましくは10〜500nmである。本発明の有機エレクトロルミネッセンス素子の発光を効率良く取り出すために、陽極または陰極の少なくとも一方の電極は、透明もしくは半透明であることが好ましい。 As the cathode, an electrode material is preferably a single metal having a small work function (4 eV or less), an alloy of metals having a small work function (4 eV or less), a conductive substance, or a mixture thereof. Specific examples of such electrode materials include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy. Can be mentioned. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet electrical resistance of the cathode is preferably several hundred Ω / cm 2 or less. The thickness of the cathode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm. In order to efficiently extract light emitted from the organic electroluminescence device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent.
本発明の有機エレクトロルミネッセンス素子の正孔輸送層は、正孔伝達化合物からなるもので、陽極より注入された正孔を発光層に伝達する機能を有している。電界が与えた2つの電極間に正孔伝達化合物が配置されて陽極から正孔が注入された場合、少なくとも10−6cm2/V・秒以上の正孔移動度を有する正孔伝達物質が好ましい。本発明の有機エレクトロルミネッセンス素子に使用する正孔輸送層に使用する正孔伝達物質は、前記の好ましい性質を有するものであれば特に制限はない。従来から光導電材料において正孔の電荷注入輸送材料として慣用されているものや有機エレクトロルミネッセンス素子の正孔輸送層に使用されている公知の材料の中から任意のものを選択して用いることができる。 The hole transport layer of the organic electroluminescence device of the present invention is made of a hole transfer compound and has a function of transferring holes injected from the anode to the light emitting layer. When a hole transport compound is disposed between two electrodes to which an electric field is applied and holes are injected from the anode, a hole transport material having a hole mobility of at least 10 −6 cm 2 / V · second or more is obtained. preferable. The hole transport material used for the hole transport layer used in the organic electroluminescence device of the present invention is not particularly limited as long as it has the above-mentioned preferable properties. It is possible to select and use any of the materials conventionally used as hole charge injection / transport materials in photoconductive materials and known materials used for the hole transport layer of organic electroluminescent devices. it can.
前記の正孔伝達物質としては、例えば銅フタロシアニンなどのフタロシアニン誘導体、N,N,N′,N′−テトラフェニル−1,4−フェニレンジアミン、N,N′−ジ(m−トリル)−N,N′−ジフェニル−4,4′−ジアミノビフェニル(TPD)、N,N′−ジ(1−ナフチル)−N,N′−ジフェニル−4,4′−ジアミノビフェニル(α−NPD)、等のトリアリールアミン誘導体、ポリフェニレンジアミン誘導体、ポリチオフェン誘導体、および水溶性のPEDOT−PSS(ポリエチレンジオキサチオフェン−ポリスチレンスルホン酸)が挙げられる。正孔輸送層は、これらの他の正孔伝達化合物一種または二種以上からなる一層で構成されたもので良く、前記の正孔伝達物質とは別の化合物からなる正孔輸送層を積層したものでもよい。 Examples of the hole transfer material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, and N, N′-di (m-tolyl) -N. , N′-diphenyl-4,4′-diaminobiphenyl (TPD), N, N′-di (1-naphthyl) -N, N′-diphenyl-4,4′-diaminobiphenyl (α-NPD), etc. And triarylamine derivatives, polyphenylenediamine derivatives, polythiophene derivatives, and water-soluble PEDOT-PSS (polyethylenedioxathiophene-polystyrenesulfonic acid). The hole transport layer may be composed of one or more of these other hole transport compounds, and a hole transport layer composed of a compound different from the hole transport material is laminated. It may be a thing.
本発明の有機エレクトロルミネッセンス素子の発光層の発光物質については特に制限されることはなく、従来の公知の化合物の中から任意のものを選択して用いることができる。 The light emitting material of the light emitting layer of the organic electroluminescence device of the present invention is not particularly limited, and any one of conventionally known compounds can be selected and used.
発光材料としては、ペリレン誘導体、ナフタセン誘導体、キナクリドン誘導体、クマリン誘導体(例えばクマリン1、クマリン540、クマリン545など)、ピラン誘導体(例えばDCM−1、DCM−2、DCJTBなど)、有機金属錯体(トリス(8−ヒドロキシキノリノラト)アルミニウム(Alq3)、トリス(4−メチル−8−ヒドロキシキノリノラト)アルミニウム(Almq3)等の蛍光材料や[2−(4,6−ジフルオロフェニル)ピリジル−N,C2′]イリジウム(III)ピコリレート(FIrpic)、トリス[1−(4−(トリフルオロメチル)フェニル)−1H−ピラゾラート,N,C2′]イリジウム(III)(Irtfmppz3)、ビス[2−(4′,6′−ジフルオロフェニル)ピリジナト−N,C2′]テトラキス(1−ピラゾリル)ボレート(Fir6)、トリス(2−フェニルピリジナト)イリジウム(III)[Ir(ppy)3]などのリン光材料などを挙げることができる。 Examples of the light-emitting material include perylene derivatives, naphthacene derivatives, quinacridone derivatives, coumarin derivatives (eg, coumarin 1, coumarin 540, coumarin 545, etc.), pyran derivatives (eg, DCM-1, DCM-2, DCJTB, etc.), organometallic complexes (tris). Fluorescent materials such as (8-hydroxyquinolinolato) aluminum (Alq 3 ), tris (4-methyl-8-hydroxyquinolinolato) aluminum (Almq 3 ), and [2- (4,6-difluorophenyl) pyridyl- N, C2 ′] iridium (III) picolylate (FIrpic), tris [1- (4- (trifluoromethyl) phenyl) -1H-pyrazolate, N, C2 ′] iridium (III) (Irtfmpppz3), bis [2- (4 ', 6'-difluorophenyl) pyridinato-N, C2' And phosphorescent materials such as tetrakis (1-pyrazolyl) borate (Fir6), tris (2-phenylpyridinato) iridium (III) [Ir (ppy) 3 ], and the like.
発光層は、ホスト材料とゲスト材料(ドーパント)から形成することもできる[Appl.Phys.Lett.,65 3610(1989)]。特にリン光材料を発光層に使用する場合、ホスト材料の使用が必要でありこの時使用されるホスト材料としては4,4′−ジ(N−カルバゾリル)−1,1′−ビフェニル(CBP)、1,4−ジ(N−カルバゾリル)ベンゼン、2,2′−ジ(4″−(N−カルバゾリル)フェニル)−1,1′−ビフェニル(4CzPBP)等があげられる。 The light-emitting layer can also be formed of a host material and a guest material (dopant) [Appl. Phys. Lett. 65 3610 (1989)]. In particular, when a phosphorescent material is used for the light emitting layer, it is necessary to use a host material, and the host material used at this time is 4,4'-di (N-carbazolyl) -1,1'-biphenyl (CBP). 1,2-di (N-carbazolyl) benzene, 2,2′-di (4 ″-(N-carbazolyl) phenyl) -1,1′-biphenyl (4CzPBP) and the like.
ゲスト材料は、ホスト材料に対して、好ましくは0.01〜40重量%であり、より好ましくは0.1〜20重量%である。 The guest material is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight, based on the host material.
本発明の有機エレクトロルミネッセンス素子の電子輸送層の材料としては、本発明のトリアリールホウ素誘導体が好ましい。このものは単独で使用できるが他の電子輸送材料と併用しても構わない。 As a material for the electron transport layer of the organic electroluminescence device of the present invention, the triarylboron derivative of the present invention is preferable. Although this thing can be used independently, you may use together with another electron transport material.
本発明の有機エレクトロルミネッセンス素子は、電子注入性をさらに向上させる目的で、陰極と有機層の間に絶縁体で構成される電子注入層をさらに設けても良い。ここで使用される絶縁体としては、アルカリ金属ハロゲン化物、アルカリ土類金属ハロゲン化物から選択される少なくとも一つの金属化合物を使用することが好ましい。アルカリ金属ハロゲン化物としては、フッ化リチウム、フッ化ナトリウム、フッ化カリウム、フッ化セシウム、塩化リチウム等が挙げられる。アルカリ土類ハロゲン化物としては、フッ化マグネシウム、フッ化カルシウム、フッ化バリウム、フッ化ストロンチウム等が挙げられる。 The organic electroluminescent device of the present invention may further include an electron injection layer composed of an insulator between the cathode and the organic layer for the purpose of further improving the electron injection property. As the insulator used here, it is preferable to use at least one metal compound selected from alkali metal halides and alkaline earth metal halides. Examples of the alkali metal halide include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride. Examples of the alkaline earth halide include magnesium fluoride, calcium fluoride, barium fluoride, and strontium fluoride.
正孔輸送層、発光層の形成方法については特に限定されるものではない。例えば乾式成膜法(例えば真空蒸着法、イオン化蒸着法など)、湿式成膜法(溶液塗布法(例えば、スピンコート法、キャスト法、インクジェット法など))を使用することができる。本発明のトリアリールホウ素化合物の電子輸送層の形成方法については、乾式成膜法(例えば真空蒸着法、イオン化蒸着法)が好ましい。また素子の作製については上記の成膜方法を併用しても構わない。 The method for forming the hole transport layer and the light emitting layer is not particularly limited. For example, a dry film forming method (for example, vacuum vapor deposition method, ionization vapor deposition method) or a wet film forming method (solution coating method (for example, spin coating method, cast method, ink jet method)) can be used. As a method for forming the electron transport layer of the triarylboron compound of the present invention, a dry film forming method (for example, a vacuum evaporation method or an ionization evaporation method) is preferable. In addition, the above-described film formation method may be used in combination for manufacturing the element.
真空蒸着法により正孔輸送層、発光層、電子輸送層等の各層を形成する場合、真空蒸着条件は、特に限定されるものではない。通常10−5Torr程度以下の真空下で50〜500℃程度のボート温度(蒸着源温度)、−50〜300℃程度の基板温度で、0.01〜50nm/sec.程度蒸着することが好ましい。正孔輸送層、発光層、電子輸送層の各層を複数の化合物を使用して形成する場合、化合物を入れた各ボートをそれぞれ温度制御しながら共蒸着することが好ましい。 When forming each layer such as a hole transport layer, a light emitting layer, and an electron transport layer by a vacuum deposition method, the vacuum deposition conditions are not particularly limited. Usually, at a boat temperature (deposition source temperature) of about 50 to 500 ° C. under a vacuum of about 10 −5 Torr or less, at a substrate temperature of about −50 to 300 ° C., 0.01 to 50 nm / sec. Vapor deposition is preferred. When forming each layer of a positive hole transport layer, a light emitting layer, and an electron carrying layer using a some compound, it is preferable to co-evaporate each boat which put the compound, temperature-controlling each.
正孔輸送層、発光層を溶媒塗布法で形成する場合、各層を構成する成分を溶媒に溶解または分散させて塗布液とする。溶媒としては、炭化水素系溶媒(例えば、ヘプタン、トルエン、キシレン、シクロヘキサン等)、ケトン系溶媒(例えばアセトン、メチルエチルケトン、メチルイソブチルケトン等)、ハロゲン系溶媒(例えばジクロロメタン、クロロホルム、クロロベンゼン、ジクロロベンゼン等)、エステル系溶媒(例えば酢酸エチル、酢酸ブチル等)、アルコール系溶媒(例えばメタノール、エタノール、ブタノール、メチルセロソルブ、エチルセロソルブ等)、エーテル系溶媒(例えばジブチルエーテル、テトラヒドロフラン、1,4−ジオキサン、1,2−ジメトキシエタン等)、非プロトン性溶媒(例えばN,N′−ジメチルアセトアミド、ジメチルスルホキシド等)、水等が挙げられる。溶媒は単独で使用しても良く、複数の溶媒を併用しても良い。 When forming the hole transport layer and the light emitting layer by a solvent coating method, the components constituting each layer are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) ), Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like), aprotic solvents (for example, N, N'-dimethylacetamide, dimethyl sulfoxide and the like), water and the like. The solvent may be used alone, or a plurality of solvents may be used in combination.
正孔輸送層、発光層、電子輸送層等の各層の膜厚は、特に限定されるものではないが、通常5〜5,000nmになるようにする。 The thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited, but is usually 5 to 5,000 nm.
本発明の有機エレクトロルミネッセンス素子は、酸素や水分等との接触を遮断する目的で保護層(封止層)を設けたり、不活性物質中に素子を封入して保護することができる。不活性物質としては、パラフィン、シリコンオイル、フルオロカーボン等が挙げられる。保護層に使用する材料としては、フッ素樹脂、エポキシ樹脂、シリコーン樹脂、ポリエステル、ポリカーボネート、光硬化性樹脂等が挙げられる。 The organic electroluminescence device of the present invention can be protected by providing a protective layer (sealing layer) for the purpose of blocking contact with oxygen, moisture, or the like, or by encapsulating the device in an inert substance. Examples of the inert substance include paraffin, silicon oil, and fluorocarbon. Examples of the material used for the protective layer include fluorine resin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.
本発明の有機エレクトロルミネッセンス素子は、通常直流駆動の素子として使用できる。直流電圧を印加する場合、陽極をプラス、陰極をマイナスの極性として電圧を通常1.5〜20V程度印加すると発光が観測される。また、本発明の有機エレクトロルミネッセンス素子は交流駆動の素子としても使用できる。交流電圧を印加する場合には、陽極がプラス、陰極がマイナスの状態になった時に発光する。本発明の有機エレクトロルミネッセンス素子は、例えば電子写真感光体、フラットパネルディスプレイなどの平面発光体、複写機、プリンター、液晶ディスプレイのバックライト、計器等の光源、各種発光素子、各種表示素子、各種標識、各種センサー、各種アクセサリーなどに使用することができる。 The organic electroluminescence device of the present invention can be used as a normal DC drive device. When a DC voltage is applied, light emission is observed when a voltage of about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. Moreover, the organic electroluminescent element of this invention can be used also as an element of an alternating current drive. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state. The organic electroluminescent device of the present invention is, for example, a flat light emitter such as an electrophotographic photosensitive member or a flat panel display, a copying machine, a printer, a backlight of a liquid crystal display, a light source such as an instrument, various light emitting devices, various display devices, various signs. It can be used for various sensors and various accessories.
図47〜60に、本発明の有機エレクトロルミネッセンス素子の好ましい例を示す。 47-60 show preferred examples of the organic electroluminescence device of the present invention.
図47は、本発明の有機エレクトロルミネッセンス素子の一例を示す断面図である。図47は、基板1上に陽極2、発光層3および陰極4を順次設けた構成のものである。ここで使用する発光素子は、それ自体がホール輸送性、電子輸送性及び発光性の機能を単一で有している場合や、それぞれの機能を有する化合物を混合して使用する場合に有用である。 FIG. 47 is a cross-sectional view showing an example of the organic electroluminescence element of the present invention. FIG. 47 shows a structure in which an anode 2, a light emitting layer 3 and a cathode 4 are sequentially provided on a substrate 1. The light-emitting element used here is useful when it has a single function of hole transport, electron transport, and light emission, or when a compound having each function is used in combination. is there.
図48は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図48は、基板1上に、陽極2、ホール輸送層5、発光層3及び陰極4を順次設けた構成のものである。この場合、発光層は電子輸送性の機能を有している場合に有用である。 FIG. 48 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 48 shows a structure in which an anode 2, a hole transport layer 5, a light emitting layer 3, and a cathode 4 are sequentially provided on a substrate 1. In this case, the light emitting layer is useful when it has an electron transporting function.
図49は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図49は、基板1上に、陽極2、発光層3、電子輸送層6及び陰極4を順次設けた構成のものである。この場合、発光層はホール輸送性の機能を有している場合に有用である。 FIG. 49 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 49 shows a structure in which an anode 2, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, the light emitting layer is useful when it has a hole transporting function.
図50は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図50は、基板1上に、陽極2、ホール輸送層5、発光層3、電子輸送層6及び陰極4を順次設けた構成のものである。これは、キャリア輸送と発光の機能を分離したものであり、材料選択の自由度が増すために、発光の高効率化や発光色の自由度が増すことになる。 FIG. 50 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 50 shows a structure in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. This separates the functions of carrier transport and light emission, and the degree of freedom in material selection increases, so that the efficiency of light emission and the degree of freedom in light emission color increase.
図51は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図51は、基板1上に、陽極2、ホール注入層7、ホール輸送層5、発光層3、電子輸送層6及び陰極4を順次設けた構成のものである。この場合、ホール注入層7を設けることにより、陽極2とホール輸送層5の密着性を高めたり、陽極からホールの注入を良くし、発光素子の低電圧駆動に効果がある。 FIG. 51 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 51 shows a structure in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, the provision of the hole injection layer 7 improves the adhesion between the anode 2 and the hole transport layer 5, improves the injection of holes from the anode, and is effective in driving the light emitting element at a low voltage.
図52は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図52は、基板1上に、陽極2、ホール輸送層5、発光層3、電子輸送層6、電子注入層8及び陰極4を順次設けた構成のものである。この場合、陰極4から電子の注入を良くし、発光素子の低電圧駆動に効果がある。 FIG. 52 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 52 shows a structure in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. In this case, injection of electrons from the cathode 4 is improved, which is effective for low voltage driving of the light emitting element.
図53は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図53は、基板1上に、陽極2、ホール注入層7、ホール輸送層5、発光層3、電子輸送層6、電子注入層8及び陰極4を順次設けた構成のものである。この場合、陽極2からホールの注入を良くし、陰極4からは電子の注入を良くし、最も低電圧駆動に効果がある構成である。 FIG. 53 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 53 shows a structure in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. In this case, hole injection from the anode 2 is improved and electron injection from the cathode 4 is improved, which is the most effective for low voltage driving.
図54〜60は、本発明の有機エレクトロルミネッセンス素子における他の例を示す断面図である。図54〜60は、発光層3と陰極4あるいは電子輸送層6の間にホールブロック層9を挿入した構成のものである。陽極から注入されたホール、あるいは発光層3で再結合により生成した励起子が、陰極4側に抜けることを防止する効果があり、有機エレクトロルミネッセンス素子の発光効率の向上に効果がある。 54-60 is sectional drawing which shows the other example in the organic electroluminescent element of this invention. 54 to 60 show a configuration in which a hole blocking layer 9 is inserted between the light emitting layer 3 and the cathode 4 or the electron transporting layer 6. This has the effect of preventing holes injected from the anode or excitons generated by recombination in the light-emitting layer 3 from escaping to the cathode 4 side, and is effective in improving the light emission efficiency of the organic electroluminescence element.
図54〜60で、ホール輸送層5、ホール注入層7、電子輸送層6、電子注入層8、発光層3、ホールブロック層9のそれぞれの層は、一層構造であっても、多層構造であってもよい。 54 to 60, each of the hole transport layer 5, the hole injection layer 7, the electron transport layer 6, the electron injection layer 8, the light emitting layer 3, and the hole blocking layer 9 has a single layer structure or a multilayer structure. There may be.
図47〜60は、あくまで基本的な素子構成であり、本発明の化合物を用いた有機エレクトロルミネッセンス素子の構成は、これに限定されるものではない。 47 to 60 are basic device configurations to the last, and the configuration of the organic electroluminescence device using the compound of the present invention is not limited to this.
本発明のトリアリールホウ素誘導体は、これまで知られている代表的な電子輸送材料Alq3よりも高い電子輸送性能を示すだけでなく、ホールブロック性が高いため、青色リン光発光素子に用いることで、従来の有機エレクトロルミネッセンス素子よりも高効率発光が可能となった。従って、本発明のトリアリールホウ素誘導体は、工業的に極めて重要なものである。 The triarylboron derivative of the present invention not only exhibits higher electron transport performance than a typical electron transport material Alq 3 known so far, but also has a high hole blocking property, so that it is used for a blue phosphorescent light emitting device. Thus, it is possible to emit light with higher efficiency than the conventional organic electroluminescence element. Therefore, the triarylboron derivative of the present invention is extremely important industrially.
本発明のトリアリールホウ素誘導体は、実施例に示されるようにこれまで知られている代表的な電子輸送材料Alq3よりも遙かに高い電子輸送性能を示すことがわかる。このため有機エレクトロルミネッセンス素子、有機半導体トランジスタ等の有機半導体デバイスに適した材料を提供することが可能になった。また本発明のトリアリールホウ素誘導体を用いることにより、従来の有機エレクトロルミネッセンス素子よりも低い駆動電圧で作動し、発光特性に優れ且つ安定性に優れた長寿命の有機エレクトロルミネッセンス素子を提供することが可能になった。従って本発明のトリアリールホウ素誘導体は、工業的に極めて重要なものである。
またトリアリールホウ素誘導体は、可視領域に蛍光を持たないためAlq3のような発光機能を示さない。従って電子輸送層として使用した場合Alq3のように有機エレクトロルミネッセンス素子の駆動電圧をあげると発光してくると言うことはない。このため発光材料の選択決定が容易である。
Triarylboron derivatives of the present invention is found to exhibit high electron transporting performance much than typical electron transporting material Alq 3 known heretofore as shown in the Examples. Therefore, it has become possible to provide materials suitable for organic semiconductor devices such as organic electroluminescence elements and organic semiconductor transistors. In addition, by using the triarylboron derivative of the present invention, it is possible to provide a long-life organic electroluminescence device that operates at a driving voltage lower than that of a conventional organic electroluminescence device and has excellent light emission characteristics and excellent stability. It became possible. Therefore, the triarylboron derivative of the present invention is extremely important industrially.
In addition, since the triarylboron derivative does not have fluorescence in the visible region, the triarylboron derivative does not exhibit a light emitting function like that of Alq 3 . Therefore, when it is used as an electron transport layer, it does not say that light is emitted when the driving voltage of the organic electroluminescence element is increased as in Alq 3 . For this reason, the selection of the light emitting material is easy.
以下に、実施例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例1
(1)トリ(4−ブロモメシチル)ボラン(TBrMB)の合成
(1) Synthesis of tri (4-bromomesityl) borane (TBrMB)
(2)トリ[4−(3−ピリジル)−メシチル]ボラン(TPYMB)の合成
実施例2
(1)3−(1−クロロフェニル)−ピリジン(ClPHPY)の合成
(1) Synthesis of 3- (1-chlorophenyl) -pyridine (ClPHPY)
(2)1−(3−ピリジル)−4−(4,4,5,5,−テトラメチル−1,3,2−ジオキサボロラン−2−イル)−ベンゼン(PHPYDOB)の合成
乾燥ジオキサン250mlを投入し、撹拌しながら40分窒素フローした。この溶液を80℃に加熱し、24時間反応させた。反応終了後30℃まで冷却し、クロロホルム300mlを投入し、5%食塩水で3回分液洗浄した。この液を硫酸マグネシウムで乾燥し、ろ過して濃縮し褐色粘体を得た。この粘体をシリカゲルカラム(展開液酢酸エチル/クロロホルム=1/1)で精製し1−(3−ピリジル)−4−(4,4,5,5,−テトラメチル−1,3,2−ジオキサボロラン−2−イル)−ベンゼン(PHPYDOB)の薄黄色粘体6.7gを得た。1H−NMRで構造を確認した。(収率67.3% 理論収量10.1g)
(2) Synthesis of 1- (3-pyridyl) -4- (4,4,5,5, -tetramethyl-1,3,2-dioxaborolan-2-yl) -benzene (PHPYDOB)
250 ml of dry dioxane was added, and nitrogen flow was performed for 40 minutes with stirring. This solution was heated to 80 ° C. and reacted for 24 hours. After completion of the reaction, the reaction mixture was cooled to 30 ° C., and 300 ml of chloroform was added thereto, followed by separation and washing three times with 5% saline. The solution was dried over magnesium sulfate, filtered and concentrated to obtain a brown viscous body. This viscous body was purified with a silica gel column (developing solution ethyl acetate / chloroform = 1/1) to give 1- (3-pyridyl) -4- (4,4,5,5, -tetramethyl-1,3,2-dioxaborolane. 6.7 g of light yellow viscous body of 2-yl) -benzene (PHPYDOB) was obtained. The structure was confirmed by 1 H-NMR. (Yield 67.3% Theoretical yield 10.1 g)
(3)トリ[4−(4−フェニル−3−ピリジル)−メシチル]ボラン(TPPYMB)の合成
Td:分解温度、Tg:二次転移温度、Tc:結晶化温度、Tm:融点、Ip:イオン化ポテンシャル、Eg:エネルギーギャップ、Ea:エレクトロアフィニティ(電子親和力)、n.d.:検出されず。
Tg(二次転移温度)については、DSC(Diffirential Scanning Calorimeter 示差熱量計)中にサンプルを加え、溶融させたものを急冷し、2〜3回繰り返すとガラス転移を表すカーブがチャート上に現れるので、そのカーブを接線で結び、その交点の温度をTgとして採用する。
Tc(結晶化温度)は、一度融解した結晶が再び結晶化する温度である。Tgをもつものは、一般にTcは有しない。
Tm(融点)は、同じくDSCにサンプルを加え、昇温していくと吸熱カーブが現れるのでその極大のところとの温度を読んで、その温度をTmとする。
Td(分解温度)は、DTA(Differential thermal analyzer 示差熱分析装置)にサンプルを加え、加熱していくとサンプルが熱によって分解し、重量が減少しだす。その減少が開始しだしたところの温度を読んで、その温度をTdとする。
エネルギーギャップ(Eg)については、蒸着機で作成した薄膜を紫外−可視吸光度計で薄膜の吸収曲線を測定する。その薄膜の短波長側の立ち上がりの所に接線を引き、求まった交点の波長W(nm)を次の式に代入し目的の値を求める。それによって得た値がEgになる。
Eg=1240÷W
例えば接線を引いて求めた値W(nm)が470nmだったとしたらこの時のEgの値は
Eg=1240÷470=2.63(eV)
と言うことになる。
Ip(イオン化ポテンシャル)は、イオン化ポテンシャル測定装置(例えば理研計器AC−1)を使用して測定し、測定するサンプルがイオン化を開始しだしたところの電圧(eV)の値を読む。
Ea(電子親和力)は、IpからEgを引いた値である。
本明細書における波長に対する強度(intensity a.u.)の測定は、浜松ホトニクス社製ストリークカメラを用いて、クライオスタット中で4.2Kにおいて測定した。
Td: decomposition temperature, Tg: secondary transition temperature, Tc: crystallization temperature, Tm: melting point, Ip: ionization potential, Eg: energy gap, Ea: electroaffinity (electron affinity), n. d. : Not detected.
As for Tg (secondary transition temperature), a sample is added to DSC (Differential Scanning Calorimeter), the melted sample is rapidly cooled, and a curve representing the glass transition appears on the chart when repeated 2-3 times. The curves are connected by tangent lines, and the temperature at the intersection is adopted as Tg.
Tc (crystallization temperature) is a temperature at which a crystal once melted is crystallized again. Those with Tg generally do not have Tc.
As for Tm (melting point), an endothermic curve appears when a sample is added to the DSC and the temperature is raised, so the temperature at the maximum is read and the temperature is defined as Tm.
As for Td (decomposition temperature), when a sample is added to DTA (Differential Thermal Analyzer) and heated, the sample is decomposed by heat and the weight starts to decrease. The temperature at which the decrease starts is read and the temperature is defined as Td.
Regarding the energy gap (Eg), an absorption curve of the thin film prepared with a vapor deposition machine is measured with an ultraviolet-visible absorptiometer. A tangent line is drawn at the rising edge of the thin film on the short wavelength side, and the wavelength W (nm) at the obtained intersection is substituted into the following equation to obtain the target value. The value obtained thereby becomes Eg.
Eg = 1240 ÷ W
For example, if the value W (nm) obtained by drawing a tangent is 470 nm, the value of Eg at this time is Eg = 1240 ÷ 470 = 2.63 (eV)
It will be said.
Ip (ionization potential) is measured using an ionization potential measuring apparatus (for example, Riken Keiki AC-1), and the value of the voltage (eV) at which the sample to be measured starts ionization is read.
Ea (electron affinity) is a value obtained by subtracting Eg from Ip.
Intensity au in this specification was measured at 4.2K in a cryostat using a streak camera manufactured by Hamamatsu Photonics.
実施例3
(1)2−(ジメシチルボリル)−4,6−ジブロモメシチレン(MBDBrMES)の合成
(1) Synthesis of 2- (dimesitylboryl) -4,6-dibromomesitylene (MBDBrMES)
(2)1,4−ビス(4,4,5,5−テトラメチル−1,3,2−ジオキサボロラン−2−イル)−ベンゼン(BDOBBz)
(3)1−(3−ピリジル)−4−(4,4,5,5−テトラメチル−1,3,2−ジオキサボロラン−2−イル)−ベンゼン(PHPYDOB)の合成
3−ピリジル)−4−(4,4,5,5−テトラメチル−1,3,2−ジオキサボロラン−2−イル)−ベンゼン(PHPYDOB)の薄黄色粘体1.91gを得た。1H−NMRにより構造を確認した。(収率40.5% 理論収量4.7g)
(3) Synthesis of 1- (3-pyridyl) -4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -benzene (PHPYDOB)
A pale yellow viscous substance 1.91 g of 3-pyridyl) -4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -benzene (PHPYDOB) was obtained. The structure was confirmed by 1 H-NMR. (Yield 40.5% Theoretical yield 4.7 g)
(4)2−(ジメシチルボリル)−4,6−ビス(3−ピリジルフェニル)メシチレン(PPYTMB)の合成
実施例4、比較例1
Alq〔(8−キノリラート)アルミニウム〕を用いた有機EL素子(比較例1)と本実施例1のトリ[4−(3−ピリジル)−メシチル]ボラン(TPYMB)を用いた有機EL素子(実施例4)の対比
(1)素子構成
比較例1:ITO/NPD(50nm)/Alq(70nm)/LiF(0.5nm)/Al(100nm)
実施例4:ITO/NPD(50nm)/Alq(40nm)/TPYMB(30nm)/LiF(0.5nm)/Al(100nm)
Organic EL device using Alq [(8-quinolylato) aluminum] (Comparative Example 1) and organic EL device using tri [4- (3-pyridyl) -mesityl] borane (TPYMB) of Example 1 (implementation) Comparison of Example 4) (1) Device Configuration Comparative Example 1: ITO / NPD (50 nm) / Alq (70 nm) / LiF (0.5 nm) / Al (100 nm)
Example 4: ITO / NPD (50 nm) / Alq (40 nm) / TPYMB (30 nm) / LiF (0.5 nm) / Al (100 nm)
Current density:電流密度
P.E.:視感効率
C.E.:電流効率
実施例5
本実施例1のトリ[4−(3−ピリジル)−メシチル]ボラン(TPYMB)を用いた青色リン光素子(実施例4)と、TPYMBの代りに3−(4−ビフェニリル)−4−フェニル−5−(4−t−ブチルフェニル)−1,2,4−トリアゾール(TAZ)を用いた青色リン光素子(比較例2)との対比
(1)素子構成
比較例2:ITO/TPDPES:TBPAH(10wt%:20nm)/DTASI(20nm)/4CZPBP:FIrpic(9wt%:30nm)/TAZ(30nm)/LiF(0.5nm)/Al(100nm)
実施例5:ITO/TPDPES:TBPAH(10wt%:20nm)/DTASI(20nm)/4CZPBP:FIrpic(9wt%:30nm)/TPYMB(30nm)/LiF(0.5nm)/Al(100nm)
A blue phosphorescent device (Example 4) using tri [4- (3-pyridyl) -mesityl] borane (TPYMB) of Example 1 and 3- (4-biphenylyl) -4-phenyl instead of TPYMB Comparison with blue phosphorescent device (Comparative Example 2) using -5- (4-t-butylphenyl) -1,2,4-triazole (TAZ) (1) Device configuration Comparative Example 2: ITO / TPDPES: TBPAH (10 wt%: 20 nm) / DTASI (20 nm) / 4CZPBP: FIrpic (9 wt%: 30 nm) / TAZ (30 nm) / LiF (0.5 nm) / Al (100 nm)
Example 5: ITO / TPDPES: TBPAH (10 wt%: 20 nm) / DTASI (20 nm) / 4CZPBP: FIrpic (9 wt%: 30 nm) / TPYMB (30 nm) / LiF (0.5 nm) / Al (100 nm)
実施例6(TPYMBを電子輸送材料とした緑リン光素子)
(1)素子構成
ITO/TPDPES:TBPAH10wt%(20nm)/m−DTATPB(30nm)/CBP:Ir(ppy)39wt%/TPYMB/LiF(0.5nm)/Al(100nm)
その1:発光層=CBP:Ir(ppy)39wt%(30nm)
電子輸送層=TPYMB(30nm)
その2:発光層=CBP:Ir(ppy)39wt%(20nm)
電子輸送層=TPYMB(40nm)
その3:発光層=CBP:Ir(ppy)39wt%(10nm)
電子輸送層=TPYMB(50nm)
TPDPESは、ポリ〔オキシ−1,4−フェニレンスルホニル−1,4−フェニレンオキシ−1,4−フェニレン(フェニルイミノ)(1,1′−ビフェニル)−4,4′−ジイル(フェニルイミノ)−1,4−フェニレン〕{poly〔oxy−1,4−phenylensulfonyl−1,4−phenyleneoxy−1,4−phenylene)(phenylimino)(1,1′−biphenyl)−4,4′−diyl(phenylimino)−1,4−phenylene〕}(9CI)(CA INDEX NAME)の略称である。
TBPAHはトリス(4−ブロモフェニル)アミニウム ヘキサクロロアンチモネート〔Tris(4−bromophenyl)aminium hexachloroantimonate〕である。
図16〜19に電圧−電流密度、電圧−輝度、電圧−視感効率、電圧−電流効率特性を図20に輝度−電流効率特性を示す。また図21にELスペクトルを示す。表5に得られた素子特性をまとめた。いずれの素子からもIr(ppy)3のみの発光が観測されたことがELスペクトルを見て分かった。発光層の膜厚を薄くし、TPYMBを厚くするに伴い図16の電流特性からみて、電流注入性が向上する傾向がある。発光層10nm(100Å)とした素子では、視感効率、電流効率は発光層30nm(300Å)の素子よりも劇的に向上し、100cd/m2時において視感効率87.7ルーメン/W、外部量子効率24.3%という非常に高効率的な結果が得られた。これは、TPYMBの電子移動度が発光層の電子移動より高いために発光層を薄くすると電流注入性が向上し、結果的に低電圧駆動するため高効率化したのではないかと考えられる。
Example 6 (Green phosphorescent device using TPYMB as electron transport material)
(1) Element configuration ITO / TPDPES: TBPAH 10 wt% (20 nm) / m-DTATPB (30 nm) / CBP: Ir (ppy) 3 9 wt% / TPYMB / LiF (0.5 nm) / Al (100 nm)
Part 1: Light emitting layer = CBP: Ir (ppy) 3 9 wt% (30 nm)
Electron transport layer = TPYMB (30 nm)
Part 2: Light emitting layer = CBP: Ir (ppy) 3 9 wt% (20 nm)
Electron transport layer = TPYMB (40 nm)
Part 3: Light emitting layer = CBP: Ir (ppy) 3 9 wt% (10 nm)
Electron transport layer = TPYMB (50 nm)
TPDPES is a poly [oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene (phenylimino) (1,1'-biphenyl) -4,4'-diyl (phenylimino)- 1,4-phenylene] {poly [oxy-1,4-phenylsulfonyl-1,4-phenylene-1,4-phenylene) (phenylimino) (1,1′-biphenyl) -4,4′-diyl (phenylimino) -1,4-phenylene]} (9CI) (CA INDEX NAME).
TBPAH is tris (4-bromophenyl) aminium hexachloroantimonate [Tris (4-bromophenyl) aminium hexachloroantimonate].
実施例7〜9(TPYMBを電子輸送層とした緑リン光素子におけるホール輸送層の検討)
さらなる低電圧駆動を狙って、最も高効率である発光層10nm/電子輸送層TPYMB50nm型素子のホール輸送層を比較的ホール移動度が高いとされているTAPCとホール注入性に優れていると考えられるDTNTPHをホール輸送層とした素子をそれぞれ作製し評価した。
(1)素子構成
実施例7:ITO/TPDPES:TBPAH10wt%(20nm)/m−DTATPB(30nm)/CBP:Ir(ppy)39wt%(10nm)/TPYMB(50nm)/LiF(0.5nm)/Al(100nm)
実施例8:ITO/TPDPES:TBPAH10wt%(20nm)/TAPC(30nm)/CBP:Ir(ppy)39wt%(10nm)/TPYMB(50nm)/LiF(0.5nm)/Al(100nm)
実施例9:ITO/TPDPES:TBPAH10wt%(20nm)/DTNTPH(30nm)/CBP:Ir(ppy)39wt%(10nm)/TPYMB(50nm)/LiF(0.5nm)/Al(100nm)
TPDPES、TBPAH、CBP、Ir(ppy)3は前記と同一。
それぞれの素子の電圧−電流密度特性(対数)、電圧−電流密度特性(線形)、電圧−輝度特性(対数)、電圧−輝度特性(線形)、電圧−視感効率特性、電圧−電流効率特性、25mA/cm2時のELスペクトルを、図22〜28に示すと共に、各素子の特性を表6に示す。
図22、23の電圧−電流特性の対数および線形プロット、図24、25に電圧−輝度特性の対数および線形プロット、図26、27の電圧−視感効率特性、電圧−電流効率特性を表6にまとめた。ELスペクトルよりいずれの素子からもIr(ppy)3のみの発光が観測されている。図22、23の電圧−電流特性より、期待どおり、TAPC、DTNTPHを用いた素子はm−DTATPBよりも電流注入性が向上していることがわかる。しかし図24、25の電圧−輝度特性より、TAPCでは輝度も向上しているが、DTNTPHでは逆に低下していることがわかる。
TAPCを用いた素子では、m−DTATPBを用いた素子よりも低電圧駆動したため、さらに効率が向上し100cd/m2時の視感効率92.7ルーメン/W、外部量子効率24.2%と極めて高効率な発光が得られた。これはTAPCの励起子閉じこめ効果に加えて、極めてキャリアバランスが良いことが起因していると考えられる。逆にDTNTPHを用いた素子では最も電流注入がよいのにもかかわらず、効率は逆に最も低い。
Examples 7 to 9 (Examination of hole transport layer in green phosphor element using TPYMB as electron transport layer)
Aiming for further low voltage driving, the hole transport layer of the light emitting layer 10 nm / electron transport layer TPYMB 50 nm type element, which is the most efficient, is considered to have excellent TAPC and hole injection properties, which are said to have relatively high hole mobility. Each of the devices using DTNTPH as a hole transport layer was prepared and evaluated.
(1) Device Configuration Example 7: ITO / TPDPES: TBPAH 10 wt% (20 nm) / m-DTATPB (30 nm) / CBP: Ir (ppy) 3 9 wt% (10 nm) / TPYMB (50 nm) / LiF (0.5 nm) / Al (100 nm)
Example 8: ITO / TPDPES: TBPAH 10 wt% (20 nm) / TAPC (30 nm) / CBP: Ir (ppy) 3 9 wt% (10 nm) / TPYMB (50 nm) / LiF (0.5 nm) / Al (100 nm)
Example 9: ITO / TPDPES: TBPAH 10 wt% (20 nm) / DTNTPH (30 nm) / CBP: Ir (ppy) 3 9 wt% (10 nm) / TPYMB (50 nm) / LiF (0.5 nm) / Al (100 nm)
TPDPES, TBPAH, CBP, and Ir (ppy) 3 are the same as described above.
Logarithmic and linear plots of voltage-current characteristics in FIGS. 22 and 23, logarithmic and linear plots of voltage-luminance characteristics in FIGS. 24 and 25, voltage-luminous efficiency characteristics and voltage-current efficiency characteristics in FIGS. Summarized in From the EL spectrum, light emission of only Ir (ppy) 3 is observed from any element. From the voltage-current characteristics shown in FIGS. 22 and 23, it can be seen that the device using TAPC and DTNTPH has improved current injection properties than m-DTATPB as expected. However, from the voltage-luminance characteristics of FIGS. 24 and 25, it can be seen that TAPC has improved brightness but DTNTPH has decreased.
Since the device using TAPC was driven at a lower voltage than the device using m-DTATPB, the efficiency was further improved, and the luminous efficiency at 100 cd / m 2 was 92.7 lumen / W and the external quantum efficiency was 24.2%. Extremely efficient light emission was obtained. This is considered to be due to the fact that the carrier balance is extremely good in addition to the exciton confinement effect of TAPC. On the contrary, in the element using DTNTPH, although the current injection is the best, the efficiency is the lowest.
実施例10(TPYMBを電子輸送材料とした青リン光素子)、比較例3
(1)素子構成
実施例10:ITO/TPDPES:TBPAH10wt%(20nm)/DTASI(30nm)/4CZPBP:Flrpic9wt%(30nm)/TPYMB(30nm)/LiF(0.5nm)/Al(100nm)
比較例3:ITO/TPDPES:TBPAH10wt%(20nm)/DTASI(30nm)/4CZPBP:Flrpic9wt%(30nm)/TAZ(30nm)/LiF(0.5nm)/Al(100nm)
TPDPES、TBPAH、DTASI、4CZPBP、TAZは、前記と同一。
(2)素子の評価
図29〜32に電圧−電流密度、電圧−輝度、電圧−視感効率、電圧−電流効率特性を示す。また図33に25mA/cm2時のELスペクトルを示す、図34に300〜450nmの部分の拡大したELスペクトルを示す。図33、34のELスペクトルより、TPYMBを用いた素子からはFlrpicのみの発光が観測されているのに対し、TAZを用いた素子からはFlrpic以外に380nm付近にピークをもつTAZと思われる微弱な発光が観測されている。この結果よりTPYMBのホールブロック性はTAZを上回っていると考えられる。図29の電圧−電流特性よりTPYMBを用いた素子ではTAZよりも大きな電流密度が観測されている。また図30の輝度特性からも9Vまでの領域では低電圧駆動していることがわかる。これは明らかに、TPYMBの励起子閉じこめ効果よりも、電子移動度がTAZより上回っていることに起因すると考えられる。表7から明らかなように、TPYMBを用いた素子(実施例10)の効率は向上し、100cd/m2時で視感効率29.1ルーメン/W、外部量子効率17.5%という高効率な発光が得られている。
Example 10 (blue phosphorescent device using TPYMB as an electron transport material), Comparative Example 3
(1) Device Configuration Example 10: ITO / TPDPES: TBPAH 10 wt% (20 nm) / DTASI (30 nm) / 4CZPBP: Flrpic 9 wt% (30 nm) / TPYMB (30 nm) / LiF (0.5 nm) / Al (100 nm)
Comparative Example 3: ITO / TPDPES: TBPAH 10 wt% (20 nm) / DTASI (30 nm) / 4CZPBP: Flrpic 9 wt% (30 nm) / TAZ (30 nm) / LiF (0.5 nm) / Al (100 nm)
TPDPES, TBPAH, DTASI, 4CZPBP, and TAZ are the same as described above.
(2) Evaluation of device FIGS. 29 to 32 show voltage-current density, voltage-luminance, voltage-luminous efficiency, and voltage-current efficiency characteristics. FIG. 33 shows an EL spectrum at 25 mA / cm 2 , and FIG. 34 shows an enlarged EL spectrum of a portion of 300 to 450 nm. From the EL spectra of FIGS. 33 and 34, only Flrpic emission is observed from the element using TPYMB, whereas the element using TAZ is considered to be TAZ having a peak near 380 nm other than Flrpic. Luminescence is observed. From this result, it is considered that the hole block property of TPYMB exceeds TAZ. From the voltage-current characteristics of FIG. 29, a current density larger than TAZ is observed in the element using TPYMB. It can also be seen from the luminance characteristics of FIG. This is apparently due to the fact that the electron mobility is higher than TAZ than the exciton confinement effect of TPYMB. As is apparent from Table 7, the efficiency of the device using TPYMB (Example 10) was improved, with a luminous efficiency of 29.1 lumen / W and an external quantum efficiency of 17.5% at 100 cd / m 2. Light emission is obtained.
実施例11(TPYMBを電子輸送材料とした青リン光素子)
(1)素子構成
ITO/TPDPES:TBPAH10wt%(20nm)/DTASI(20nm)/4CZPBP:Flrpic9wt%/TPYMB/LiF(0.5nm)/Al(100nm)
その1:4CZPBP:Flrpic9wt%(30nm)
TPYMB(30nm)
その2:4CZPBP:Flrpic9wt%(20nm)
TPYMB(40nm)
その3:4CZPBP:Flrpic9wt%(10nm)
TPYMB(50nm)
Ir(ppy)3を用いた緑リン光素子同様、発光層(4CZPBP:Flrpic9wt%)/電子輸送層(TPYMB)の膜厚を30nm/30nm、20nm/40nm、10nm/50nmとしたものをそれぞれ製作し、評価した。
(2)素子の評価
図35〜39に電圧−電流密度、電圧−輝度、電圧−視感効率、電圧−電流効率、輝度−電流効率特性をそれぞれ示す。また図40に25mA/cm2時のELスペクトルを示す。表8に素子特性をまとめる。図35の電圧−電流特性より発光層が薄くなるに伴い、電流密度が増大する傾向がある。Ir(ppy)3を用いた緑リン光素子でも同様の傾向が観測されており、TPYMBの電子移動度が発光層の電子移動度を上回るため電流が注入されやすくなるのではないかと考えられる。
10nm/50nmの素子において100cd/m2時の視感効率は33.6ルーメン/W、外部量子効率20.6%と最も高効率な結果が得られている。
Example 11 (Blue phosphor element using TPYMB as electron transport material)
(1) Element configuration ITO / TPDPES: TBPAH 10 wt% (20 nm) / DTASI (20 nm) / 4 CZPBP: Flrpic 9 wt% / TPYMB / LiF (0.5 nm) / Al (100 nm)
Part 1: 4CZPBP: Flrpic 9wt% (30nm)
TPYMB (30nm)
Part 2: 4CZPBP: Flrpic 9wt% (20nm)
TPYMB (40nm)
Part 3: 4CZPBP: Flrpic 9wt% (10nm)
TPYMB (50nm)
Like green phosphorescent devices using Ir (ppy) 3 , light emitting layer (4CZPBP: Flrpic 9 wt%) / electron transport layer (TPYMB) film thicknesses of 30 nm / 30 nm, 20 nm / 40 nm, 10 nm / 50 nm were produced, respectively. And evaluated.
(2) Evaluation of device FIGS. 35 to 39 show voltage-current density, voltage-luminance, voltage-luminous efficiency, voltage-current efficiency, and luminance-current efficiency characteristics, respectively. FIG. 40 shows an EL spectrum at 25 mA / cm 2 . Table 8 summarizes the device characteristics. From the voltage-current characteristics of FIG. 35, the current density tends to increase as the light emitting layer becomes thinner. A similar tendency is observed even in a green phosphor element using Ir (ppy) 3, and it is considered that current is likely to be injected because the electron mobility of TPYMB exceeds the electron mobility of the light emitting layer.
In a 10 nm / 50 nm device, the luminous efficiency at 100 cd / m 2 is 33.6 lumens / W, and the external quantum efficiency is 20.6%.
実施例12(TPYMBを電子輸送材料とした青リン光素子のFlrpicドープ濃度の検討)
(1)素子構成
ITO/TPDPES:TBPAH10wt%(20nm)/DTASI(20nm)/4CZPBP:Flrpic9wt%、13wt%、18wt%(10nm)/TPYMB(50nm)/LiF(0.5nm)/Al(100nm)
発光層は10nmに固定し、Flrpicドープ濃度を9wt%から13wt%、18wt%と濃くした素子を作製し評価した。
(2)素子の評価
図41、42に電圧−電流密度特性の対数プロットとその線形プロット、図43〜45に電圧−輝度、電圧−視感効率、電圧−電流効率をそれぞれ示す。また25mA/cm2時のELスペクトルを図46に示す。表9に素子特性をまとめる。現在9wt%、13wt%、18wt%の3種類のデータであるが、13wt%で100cd/m2時の視感効率38.2ルーメン/W、外部量子効率20.9%という非常に高効率な発光が得られている。1000cd/m2時の視感効率もドープ濃度9wt%では8.5ルーメン/Wであったのに対し、13wt%では16.5ルーメン/Wと大きく改善されている。
図41、42の電流密度特性より、ドープ濃度18wt%の素子では電流注入は最も良いことが確認できる。
Example 12 (Investigation of Flrpic doping concentration of blue phosphorescent device using TPYMB as electron transport material)
(1) Element configuration ITO / TPDPES: TBPAH 10 wt% (20 nm) / DTASI (20 nm) / 4 CZPBP: Flrpic 9 wt%, 13 wt%, 18 wt% (10 nm) / TPYMB (50 nm) / LiF (0.5 nm) / Al (100 nm)
A light emitting layer was fixed at 10 nm, and a device having a Flrpic doping concentration increased from 9 wt% to 13 wt% and 18 wt% was evaluated.
(2) Evaluation of device FIGS. 41 and 42 show logarithmic plots and linear plots of voltage-current density characteristics, and FIGS. 43 to 45 show voltage-luminance, voltage-luminous efficiency, and voltage-current efficiency, respectively. In addition, FIG. 46 shows an EL spectrum at 25 mA / cm 2 . Table 9 summarizes the device characteristics. Currently 9wt%, 13wt%, although three types of data 18 wt%, 13 wt% in 100 cd / m 2 o'clock luminous efficiency 38.2 lumens / W, very high efficiency of external quantum efficiency 20.9 percent Luminescence is obtained. The luminous efficiency at 1000 cd / m 2 was 8.5 lumens / W at a doping concentration of 9 wt%, but greatly improved to 16.5 lumens / W at 13 wt%.
From the current density characteristics of FIGS. 41 and 42, it can be confirmed that the current injection is the best in the element having a doping concentration of 18 wt%.
1 基板
2 陽極
3 発光層
4 陰極
5 ホール輸送層
6 電子輸送層
7 ホール注入層
8 電子注入層
9 ホールブロック層
DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Light emitting layer 4 Cathode 5 Hole transport layer 6 Electron transport layer 7 Hole injection layer 8 Electron injection layer 9 Hole block layer
Claims (10)
よりなる群から選ばれたトリアリールホウ素誘導体。 The following general formula (1)
A triarylboron derivative selected from the group consisting of:
An organic electroluminescence device comprising the triarylboron derivative according to claim 3 and a phosphorescent material in combination.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005258545A JP2007070282A (en) | 2005-09-06 | 2005-09-06 | Novel triarylboron derivative and organic electroluminescent device containing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005258545A JP2007070282A (en) | 2005-09-06 | 2005-09-06 | Novel triarylboron derivative and organic electroluminescent device containing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2007070282A true JP2007070282A (en) | 2007-03-22 |
Family
ID=37932044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005258545A Pending JP2007070282A (en) | 2005-09-06 | 2005-09-06 | Novel triarylboron derivative and organic electroluminescent device containing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2007070282A (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100892986B1 (en) | 2007-09-20 | 2009-04-10 | 제일모직주식회사 | Organic compound, and organic photoelectric device comprising the same |
WO2009072582A1 (en) | 2007-12-06 | 2009-06-11 | Kyoto University | Novel boron compound, method for producing the same, and functional electronic device using the same |
WO2009107574A1 (en) * | 2008-02-25 | 2009-09-03 | 昭和電工株式会社 | Organic electroluminescent element, and manufacturing method and uses therefor |
JP2011512673A (en) * | 2008-02-19 | 2011-04-21 | ゼネラル・エレクトリック・カンパニイ | Organic optoelectronic device and manufacturing method thereof |
JP2011529050A (en) * | 2008-07-24 | 2011-12-01 | ゼネラル・エレクトリック・カンパニイ | Compounds containing phenylpyridine units |
US20120217869A1 (en) * | 2011-02-28 | 2012-08-30 | Kyushu University National University Corporation | Delayed fluorescence material and organic electroluminescence device |
US8277957B2 (en) | 2009-08-28 | 2012-10-02 | Industrial Technology Research Institute | Quinoxaline derivatives and organic light-emitting diodes comprising the same |
WO2013031638A1 (en) * | 2011-08-31 | 2013-03-07 | 住友化学株式会社 | Composition containing borane compound and conjugated polymer compound, and element |
US8486544B2 (en) | 2009-08-28 | 2013-07-16 | Industrial Technology Research Institute | Quinoxaline derivatives and organic light-emitting diodes comprising the same |
EP3147958A1 (en) | 2015-09-28 | 2017-03-29 | Novaled GmbH | Organic electroluminescent devices comprising borane compounds |
CN110423243A (en) * | 2018-09-10 | 2019-11-08 | 广东聚华印刷显示技术有限公司 | Electron transport material and preparation method thereof and organic electroluminescence device |
CN113501834A (en) * | 2021-06-21 | 2021-10-15 | 兰州大学 | Single-component organic triaryl boron room-temperature phosphorescent material with adjustable excitation |
CN114149458A (en) * | 2021-11-29 | 2022-03-08 | 苏州大学 | B/N organic electroluminescent material and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001093670A (en) * | 1999-09-28 | 2001-04-06 | Konica Corp | Organic electroluminescence element |
JP2003234192A (en) * | 2001-12-06 | 2003-08-22 | Konica Corp | Organic electroluminescent element and display device |
JP2004014440A (en) * | 2002-06-11 | 2004-01-15 | Konica Minolta Holdings Inc | Organic electroluminescent element and display device |
JP2004311405A (en) * | 2003-03-27 | 2004-11-04 | Konica Minolta Holdings Inc | Organic electroluminescent element, display device, and lighting system |
WO2005062675A1 (en) * | 2003-12-24 | 2005-07-07 | Konica Minolta Holdings, Inc. | Material for organic electroluminescent device, organic electroluminescent device, illuminating device and display |
WO2005062676A1 (en) * | 2003-12-24 | 2005-07-07 | Konica Minolta Holdings, Inc. | Material for organic electroluminescent device, organic electroluminescent device, illuminating device and display |
-
2005
- 2005-09-06 JP JP2005258545A patent/JP2007070282A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001093670A (en) * | 1999-09-28 | 2001-04-06 | Konica Corp | Organic electroluminescence element |
JP2003234192A (en) * | 2001-12-06 | 2003-08-22 | Konica Corp | Organic electroluminescent element and display device |
JP2004014440A (en) * | 2002-06-11 | 2004-01-15 | Konica Minolta Holdings Inc | Organic electroluminescent element and display device |
JP2004311405A (en) * | 2003-03-27 | 2004-11-04 | Konica Minolta Holdings Inc | Organic electroluminescent element, display device, and lighting system |
WO2005062675A1 (en) * | 2003-12-24 | 2005-07-07 | Konica Minolta Holdings, Inc. | Material for organic electroluminescent device, organic electroluminescent device, illuminating device and display |
WO2005062676A1 (en) * | 2003-12-24 | 2005-07-07 | Konica Minolta Holdings, Inc. | Material for organic electroluminescent device, organic electroluminescent device, illuminating device and display |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100892986B1 (en) | 2007-09-20 | 2009-04-10 | 제일모직주식회사 | Organic compound, and organic photoelectric device comprising the same |
WO2009072582A1 (en) | 2007-12-06 | 2009-06-11 | Kyoto University | Novel boron compound, method for producing the same, and functional electronic device using the same |
US8436173B2 (en) | 2007-12-06 | 2013-05-07 | Kyoto University | Boron compounds, their production processes, and functional electronic devices using same |
JP2011512673A (en) * | 2008-02-19 | 2011-04-21 | ゼネラル・エレクトリック・カンパニイ | Organic optoelectronic device and manufacturing method thereof |
WO2009107574A1 (en) * | 2008-02-25 | 2009-09-03 | 昭和電工株式会社 | Organic electroluminescent element, and manufacturing method and uses therefor |
EP2249410A1 (en) * | 2008-02-25 | 2010-11-10 | Showa Denko K.K. | Organic electroluminescent element, and manufacturing method and uses therefor |
EP2249410A4 (en) * | 2008-02-25 | 2012-03-28 | Showa Denko Kk | Organic electroluminescent element, and manufacturing method and uses therefor |
JP2011529050A (en) * | 2008-07-24 | 2011-12-01 | ゼネラル・エレクトリック・カンパニイ | Compounds containing phenylpyridine units |
US8486544B2 (en) | 2009-08-28 | 2013-07-16 | Industrial Technology Research Institute | Quinoxaline derivatives and organic light-emitting diodes comprising the same |
US8277957B2 (en) | 2009-08-28 | 2012-10-02 | Industrial Technology Research Institute | Quinoxaline derivatives and organic light-emitting diodes comprising the same |
US20120217869A1 (en) * | 2011-02-28 | 2012-08-30 | Kyushu University National University Corporation | Delayed fluorescence material and organic electroluminescence device |
US9783734B2 (en) * | 2011-02-28 | 2017-10-10 | Kyulux, Inc. | Delayed fluorescence material and organic electroluminescence device |
JP2013049806A (en) * | 2011-08-31 | 2013-03-14 | Sumitomo Chemical Co Ltd | Composition and device containing borane compound and conjugated polymer compound |
US9255221B2 (en) | 2011-08-31 | 2016-02-09 | Sumitomo Chemical Company, Limited | Composition containing borane compound and conjugated polymer compound, and element |
WO2013031638A1 (en) * | 2011-08-31 | 2013-03-07 | 住友化学株式会社 | Composition containing borane compound and conjugated polymer compound, and element |
EP3147958A1 (en) | 2015-09-28 | 2017-03-29 | Novaled GmbH | Organic electroluminescent devices comprising borane compounds |
WO2017055263A1 (en) | 2015-09-28 | 2017-04-06 | Novaled Gmbh | Organic electroluminescent devices comprising borane compounds |
CN110423243A (en) * | 2018-09-10 | 2019-11-08 | 广东聚华印刷显示技术有限公司 | Electron transport material and preparation method thereof and organic electroluminescence device |
CN110423243B (en) * | 2018-09-10 | 2022-06-10 | 广东聚华印刷显示技术有限公司 | Electron transport material, preparation method thereof and organic electroluminescent device |
CN113501834A (en) * | 2021-06-21 | 2021-10-15 | 兰州大学 | Single-component organic triaryl boron room-temperature phosphorescent material with adjustable excitation |
CN114149458A (en) * | 2021-11-29 | 2022-03-08 | 苏州大学 | B/N organic electroluminescent material and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4878819B2 (en) | Novel triazine derivative and organic electroluminescence device containing the same | |
JP5063992B2 (en) | Novel di (pyridylphenyl) derivative, electron transport material comprising the same, and organic electroluminescence device including the same | |
JP5207760B2 (en) | Novel pyrimidine-based or triazine-based derivative, electron transport material comprising the same, and organic electroluminescence device including the same | |
JP2007070282A (en) | Novel triarylboron derivative and organic electroluminescent device containing the same | |
US6479172B2 (en) | Electroluminescent (EL) devices | |
TWI541320B (en) | Novel compound for organic photoelectric device and organic photoelectric device including the same | |
KR101195863B1 (en) | Aromatic compound and organic electroluminescent device using the same | |
KR101401639B1 (en) | Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same | |
KR20150105201A (en) | New organic electroluminescent compounds and organic electroluminescent device comprising the same | |
KR20090028943A (en) | Hole injection/transporting layer material and organic electroluminescent device comprising same | |
JP4960045B2 (en) | Heteroaryl compound having novel biphenyl central skeleton and organic electroluminescence device comprising the same | |
WO2008105349A1 (en) | Light-emitting element using spirofluorene derivative and electronic appliance | |
KR101916572B1 (en) | Compound and organic light electronic device comprising the same | |
TW201408626A (en) | Compound for organic electroluminescent device and organic electroluminescent device including the same | |
KR101026175B1 (en) | Fluorenecarbazole derivative and organic electroluminescent device comprising same | |
JP5201956B2 (en) | Novel di (pyridylphenyl) derivative, electron transport material comprising the same, and organic electroluminescence device including the same | |
JP5086608B2 (en) | Novel di (phenanthroline) derivative, electron transport material comprising the same, and organic electroluminescence device including the same | |
KR100994765B1 (en) | Organic electroluminescent device comprising fluorene-based light emitting material | |
KR20170013373A (en) | Organic compounds for an organic electroluminescent device and an organic electroluminescent device comprising the same | |
JP5220429B2 (en) | NOVEL DIPYLENE DERIVATIVE, ELECTRON TRANSPORT MATERIAL, LIGHT EMITTING MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE CONTAINING THE SAME | |
KR101226701B1 (en) | Aromatic compound and organic electroluminescent device using the same | |
JP5114070B2 (en) | Fluorene derivative, electron transport material comprising the same, electron injection material, and organic electroluminescence device using the same | |
JP5349889B2 (en) | Novel terphenyl derivative, electron transport material comprising the same, and organic electroluminescence device including the same | |
KR20090016048A (en) | Fluorescent green/blue-emitting material and organic electroluminescent device comprising same | |
KR100951441B1 (en) | Hole injection/transporting layer material and organic electroluminescent device comprising same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080903 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100511 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20101006 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101130 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110405 |