JP5897171B2 - 有機電界発光素子用の有機イリジウム錯体 - Google Patents
有機電界発光素子用の有機イリジウム錯体 Download PDFInfo
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- JP5897171B2 JP5897171B2 JP2015045467A JP2015045467A JP5897171B2 JP 5897171 B2 JP5897171 B2 JP 5897171B2 JP 2015045467 A JP2015045467 A JP 2015045467A JP 2015045467 A JP2015045467 A JP 2015045467A JP 5897171 B2 JP5897171 B2 JP 5897171B2
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- organic
- iridium complex
- ligand
- diketone
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- 150000002503 iridium Chemical class 0.000 title description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 91
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 91
- 239000003446 ligand Substances 0.000 claims description 57
- 238000006862 quantum yield reaction Methods 0.000 claims description 18
- 125000000623 heterocyclic group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 76
- 239000002904 solvent Substances 0.000 description 56
- 239000002243 precursor Substances 0.000 description 46
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 45
- 238000005401 electroluminescence Methods 0.000 description 42
- 239000000203 mixture Substances 0.000 description 42
- 230000015572 biosynthetic process Effects 0.000 description 38
- 238000003786 synthesis reaction Methods 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 24
- 238000001914 filtration Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- 229910052938 sodium sulfate Inorganic materials 0.000 description 24
- 235000011152 sodium sulphate Nutrition 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- 239000012299 nitrogen atmosphere Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- 239000010410 layer Substances 0.000 description 20
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 20
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 20
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 16
- 229940093475 2-ethoxyethanol Drugs 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 11
- 235000019341 magnesium sulphate Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- -1 butoxy-substituted benzene rings Chemical group 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 125000002524 organometallic group Chemical group 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 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 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 5
- AVTSEHYNSNELMQ-UHFFFAOYSA-N 1,3-bis(3,5-ditert-butylphenyl)propane-1,3-dione Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C(=O)CC(=O)C=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)=C1 AVTSEHYNSNELMQ-UHFFFAOYSA-N 0.000 description 4
- UGRCKSONAWDLEI-UHFFFAOYSA-N 1,3-bis(5,5,8,8-tetramethyl-6,7-dihydronaphthalen-2-yl)propane-1,3-dione Chemical compound C1(C)(C2=CC=C(C(=O)CC(=O)C3=CC=C4C(C)(C)CCC(C)(C)C4=C3)C=C2C(C)(C)CC1)C UGRCKSONAWDLEI-UHFFFAOYSA-N 0.000 description 4
- UCVINTIEPYMTAQ-UHFFFAOYSA-N 2-dibenzofuran-4-ylquinoline Chemical compound C1=CC=CC2=NC(C3=C4OC=5C(C4=CC=C3)=CC=CC=5)=CC=C21 UCVINTIEPYMTAQ-UHFFFAOYSA-N 0.000 description 4
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 230000005283 ground state Effects 0.000 description 4
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- BRZLLJSRIPVXFR-UHFFFAOYSA-N 1-dibenzofuran-4-ylisoquinoline Chemical compound C1=CC=C2C(C3=C4OC=5C(C4=CC=C3)=CC=CC=5)=NC=CC2=C1 BRZLLJSRIPVXFR-UHFFFAOYSA-N 0.000 description 3
- FYYZLNTYBLXDKM-UHFFFAOYSA-N 1-dibenzothiophen-4-ylisoquinoline Chemical compound C1=CC=C(C=2SC3=C(C=21)C=CC=C3)C1=NC=CC2=CC=CC=C12 FYYZLNTYBLXDKM-UHFFFAOYSA-N 0.000 description 3
- FYLUMWHKJHEKGF-UHFFFAOYSA-N 2-dibenzothiophen-4-ylquinoline Chemical compound C1=CC=CC2=NC(C3=C4SC=5C(C4=CC=C3)=CC=CC=5)=CC=C21 FYLUMWHKJHEKGF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 3
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- ZEIOQJMJXFVPOG-UHFFFAOYSA-N methyl 3,5-ditert-butylbenzoate Chemical compound COC(=O)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 ZEIOQJMJXFVPOG-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- CCQKWSZYTOCEIB-UHFFFAOYSA-N 1,1,4,4-tetramethyl-2,3-dihydronaphthalene Chemical compound C1=CC=C2C(C)(C)CCC(C)(C)C2=C1 CCQKWSZYTOCEIB-UHFFFAOYSA-N 0.000 description 2
- MSQCQINLJMEVNJ-UHFFFAOYSA-N 1-chloroisoquinoline Chemical compound C1=CC=C2C(Cl)=NC=CC2=C1 MSQCQINLJMEVNJ-UHFFFAOYSA-N 0.000 description 2
- OFUFXTHGZWIDDB-UHFFFAOYSA-N 2-chloroquinoline Chemical compound C1=CC=CC2=NC(Cl)=CC=C21 OFUFXTHGZWIDDB-UHFFFAOYSA-N 0.000 description 2
- NCTSLPBQVXUAHR-UHFFFAOYSA-N 3,5-ditert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC(C(O)=O)=CC(C(C)(C)C)=C1 NCTSLPBQVXUAHR-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(C)(CC)c(ccc1c2[o]c3c1cccc3)c2-c1ccc(cccc2)c2*1[C@@](C)N Chemical compound CCC(C)(CC)c(ccc1c2[o]c3c1cccc3)c2-c1ccc(cccc2)c2*1[C@@](C)N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- XZCJVWCMJYNSQO-UHFFFAOYSA-N butyl pbd Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)O1 XZCJVWCMJYNSQO-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- IDSWJMDPKPOHRX-UHFFFAOYSA-N thiophen-3-yloxyboronic acid Chemical compound OB(O)OC=1C=CSC=1 IDSWJMDPKPOHRX-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- AFVLVVWMAFSXCK-UHFFFAOYSA-N α-cyano-4-hydroxycinnamic acid Chemical compound OC(=O)C(C#N)=CC1=CC=C(O)C=C1 AFVLVVWMAFSXCK-UHFFFAOYSA-N 0.000 description 2
- CLTHBVPJKLDVAS-UHFFFAOYSA-N 1,3-ditert-butyl-5-ethylbenzene Chemical compound CCC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 CLTHBVPJKLDVAS-UHFFFAOYSA-N 0.000 description 1
- WZSMQEXDKGEYOW-UHFFFAOYSA-N 1-(3,5-ditert-butylphenyl)ethanone Chemical compound CC(=O)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 WZSMQEXDKGEYOW-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZXHUJRZYLRVVNP-UHFFFAOYSA-N dibenzofuran-4-ylboronic acid Chemical compound C12=CC=CC=C2OC2=C1C=CC=C2B(O)O ZXHUJRZYLRVVNP-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- KHBKYYUHCSVLIX-UHFFFAOYSA-N furan-3-yloxyboronic acid Chemical compound OB(O)OC=1C=COC=1 KHBKYYUHCSVLIX-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000003097 hole (electron) Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- GRWIABMEEKERFV-UHFFFAOYSA-N methanol;oxolane Chemical compound OC.C1CCOC1 GRWIABMEEKERFV-UHFFFAOYSA-N 0.000 description 1
- CCWOAEHVQLCSTC-UHFFFAOYSA-N methyl 2,3-dibutylbenzoate Chemical compound C(CCC)C=1C(=C(C(=O)OC)C=CC=1)CCCC CCWOAEHVQLCSTC-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Description
[量子効率]
外部量子効率=(光取出し効率)×内部量子効率
内部量子効率=(励起子生成効率)×(PL量子収率)×(キャリアバランス)
ジブチル安息香酸メチルと、(ジブチル安息香酸メチル)エタン−1−オンとを合成した後、これら2つの化合物を用いた合成反応により、β‐ジケトン化合物(A)を得た。
3,5−ジ−tert−ブチル安息香酸(3.00g,12.8mmol)とメタノール(9mL)の混合物に濃硫酸(0.9mL)を窒素雰囲気下、0℃にて滴下し、その後、撹拌しながら1時間加熱還流させた。放冷後、クロロホルム(100mL)を加え、さらに水(100mL)を加えて分液漏斗内で振とうし、有機層を分離した。この操作をもう一度繰り返した後、分離した有機層を一つに合わせた。この有機層をさらに、飽和炭酸水素ナトリウム水溶液(50mL)及び飽和食塩水(50mL)で洗浄した後、無水硫酸マグネシウムを適量加えて乾燥させた。ろ過により硫酸マグネシウムを除去した後、エバポレーターにて溶媒を留去し、残渣をデシケーター内で減圧下乾燥させることで3,5−ジ−tert−ブチル安息香酸メチルを得た。得られた化合物は白色固体であり、収率は92%であった(2.92g,11.8mmol)。以上により合成した化合物の特性(1H NMR、TOF MS)は、以下の通りであった。
1H NMR(CDCl3):d1.35(s,18H),3.91(s,3H),7.62(t,J=2.0Hz,1H),7.89(d,J=2.0Hz,2H).
MALDI−TOF MS:m/z 249([M+H]+).
3,5−ジ−tert−ブチル安息香酸(3.00g,12.8mmol)を乾燥テトラヒドロフラン(120mL)に加え、窒素雰囲気下、0℃以下になるまで撹拌しながら冷却した。この混合物にメチルリチウムの3.0Mジエトキシメタン溶液(15mL)を滴下し、その後室温まで昇温して2時間撹拌した。この反応混合物に6M塩酸を加えて酸性にした後、クロロホルム(100mL×2)で抽出した。得られた有機層を一つに合わせ、水(50mL×2)、飽和炭酸水素ナトリウム水溶液(50mL)及び飽和食塩水(50mL)で洗浄した後、無水硫酸マグネシウムを適量加えて乾燥させた。ろ過により硫酸マグネシウムを除去した後、エバポレーターにて溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で精製することで1−(3,5−ジ−tert−ブチルフェニル)エタン−1−オンを得た。得られた化合物は、無色の液体であり、収率75%であった(2.23g,9.60mmol)。以上により合成した化合物の特性は、以下の通りであった。
1H NMR(CDCl3)d1.37(s,18H),2.60(s,3H),7.64(t,J=1.6Hz,1H),7.80(d,J=1.6Hz,2H).
MALDI−TOF MS:m/z 232(M+).
3,5−ジ−tert−ブチル安息香酸メチル(2.92g,11.8mmol)と水素化ナトリウム(60%油分散;1.27g,31.8mmol)を乾燥THF(23mL)に入れ、窒素雰囲気下、室温にて撹拌した。そこへ1−(3,5−ジ−tert−ブチルフェニル)エタン−1−オン(2.23g,9.60mmol)を乾燥THF(23mL)に溶かした溶液を30分かけて滴下した。その後、得られた反応混合物を60℃下、24時間撹拌した。放冷後、1M塩酸を加えて酸性にした後、クロロホルム(100mL×2)で抽出した。得られた有機層を一つに合わせ、水(50mL×2)、飽和炭酸水素ナトリウム水溶液(50mL)及び飽和食塩水(50mL)で洗浄した後、無水硫酸マグネシウムを適量加えて乾燥させた。ろ過により硫酸マグネシウムを除去した後、エバポレーターにて溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;クロロホルム)で精製することで1,3−ビス(3,5−ジ−tert−ブチルフェニル)プロパン−1,3−ジオン(β−ジケトンA)を得た。得られた化合物は、こはく色のシロップ状物質であり、収率49%であった(2.12g,4.73mmol)。以上により合成した化合物の特性は、以下の通りであった。
1H NMR(CDCl3)d1.38(s,36H),6.78(s,1H),7.63(t,J=2.0Hz,2H),7.78(d,J=2.0Hz,4H),16.9(brs,1H).
MALDI−TOF MS:m/z 449([M+H]+).
1,2,3,4−テトラヒドロ−1,1,4,4−テトラメチルナフタレンとマロニルクロリドを用いた合成反応により、β‐ジケトン化合物(B)を得た。
1,2,3,4−テトラヒドロ−1,1,4,4−テトラメチルナフタレン(5.00g,26.6mmol)、マロニルクロリド(1.35g、9.58mmol)及び塩化アルミニウム(5.51g、41.3mmol)を二硫化炭素(27mL)に入れ、50℃にて3時間加熱撹拌した。次に、放冷後、冷やした2mol/Lの塩酸(27mL)を加えて分液ロートに移し、クロロホルムで抽出した。有機層を更に水で洗浄し、エバポレーターで溶媒を留去した後、残渣に濃塩酸(3.5mL)とクロロホルム(35mL)を加え、9時間加熱還流させた。放冷後、混合物を分液ロートに移し、水及び飽和食塩水で洗浄した。有機層を無水硫酸マグネシウムで乾燥させた後、ロータリーエバポレーターで溶媒を留去した。残渣をシリカゲルカラムクロマトグラフィー(展開溶媒;酢酸エチル:ヘキサン=1:2(v/v))で精製することにより、β−ジケトン(B)を収率39%で得た(1.66g,3.74mmol)。以上により合成した化合物の特性は、以下の通りであった。
1H NMR(CDCl3):δ1.30(s,12H),1.34(s,12H),1.71(m,8H),6.76(s,1H),7.40(d,J=8.0Hz,2H),7.68(dd,J=8.0 and 2.0Hz,2H),7.94(d,J=2.0Hz,2H),16.96(brs,1H)
MALDI−TOF MS:m/z 445([M+H]+).
1H NMR(CDCl3):δ7.39(t,J=7.6Hz,1H),7.48−7.53(m,1H),7.55−7.59(m,2H),7.66(d,J=8.7Hz,1H),7.76(dt,J=1.4and7.6Hz,1H),7.89(d,J=7.6Hz,1H),8.02(d,J=7.6Hz,1H),8.06(dd,J=1.4and7.6Hz,1H),8,23(d,J=8.7Hz,1H),8.34(d,J=8.7Hz,1H),8.43(dd,J=1.4and7.6Hz,1H),8.52(d,J=8.7Hz,1H).
MALDI−TOF MS:m/z 296([M+H]+).
下記式に従い、C−N配位子(1)と塩化イリジウムとを反応させて前駆体(1)を得た。2−(ジベンゾ[b,d]フラン−4−イル)キノリン(3.50g,11.9mmol)と2−エトキシエタノール(210mL)の混合物を窒素雰囲気下、油浴上で加熱した。溶液の温度が100℃に達したら、塩化イリジウム・三水和物(1.60g,4.54mmol)と水(70mL)の混合物を加え、得られた反応混合物を120℃で10時間撹拌した。放冷後、水(175mL)を反応混合物に加え、ろ過して沈殿を回収し、適量のメタノールで洗浄することによって、前駆体(1)を83%の収率で得た(3.08g,1.89mmol)。得られた化合物は難溶性の固体であった。さらなる精製は行わずに、下記イリジウム錯体の合成に用いた。
1H NMR(CDCl3):d7.36−7.40(m,1H),7.41−7.42(m,2H),7.46−7.55(m,2H),7.67−7.74(m,2H),7.77(d,J=6.0Hz,1H),7.83(d,J=8.8Hz,1H),7.94(d,J=8.4Hz,1H),8.00−8.04(m,1H),8.11(dd,J=1.4Hz and 5.6Hz,1H)8.72(d,J=5.6Hz,1H)
MALDI−TOF MS:m/z 296([M+H]+).
下記式に従い、C−N配位子(2)と塩化イリジウムとを反応させて前駆体(2)を得た。1−(ジベンゾ[b,d]フラン−4−イル)イソキノリン(3.07g,10.4mmol)と2−エトキシエタノール(180mL)の混合物を窒素雰囲気下、油浴上で加熱した。溶液の温度が100℃に達したら、塩化イリジウム・三水和物(1.21g,4.04mmol)と水(60mL)の混合物を加え、得られた反応混合物を120℃で10時間撹拌した。放冷後、水(150mL)を反応混合物に加え、ろ過して沈殿を回収し、適量のメタノールで洗浄することによって、前駆体(2)を69%の収率で得た(2.28g,1.40mmol)。前駆体(2)は難溶性の固体のため、さらなる精製は行わずに、下記イリジウム錯体の合成に用いた。
1H NMR(CDCl3):δ7.46−7.53(m,2H),7.58(dt,J=1.4 and 7.6Hz,1H),7.63(t,J=7.8Hz,1H),7.80(dt,J=1.4 and 7.6Hz,1H),7.86(d,J=7.8Hz,1H),7.99(m,1H),8.10(d,J=8.7Hz,1H),8.17(dd,J=1.4 and 7.6Hz,1H),8.21−8.24(m,1H),8.26(d,J=8.7Hz,1H),8.30(dd,J=0.9 and 7.8Hz,1H),8.42(d,J=7.8Hz,1H).
MALDI−TOF MS:m/z 311(M+).
1H NMR(CDCl3):δ7.44−7.53(m,3H),7.64(t,J=7.8Hz,1H),7.69−7.72(m,2H),7.74−7.79(m,2H),7.94(d,J=8.3Hz,1H),7.98(d,J=7.8Hz,1H),8.21−8.24(m,1H),8.29(dd,J=7.6Hz,1H),8.71(d,J=6.0Hz,1H).
MALDI−TOF MS:m/z 311(M+).
1H NMR(CDCl3):δ1.17(s,36H),5.75(s,1H),6.67(d,J=8.2Hz,2H),7.06(d,J=1.8Hz,4H),7.19−7.23(m,4H),7.28(d,J=8.2Hz,2H),7.31(t,J=1.8Hz,2H),7.37−7.42(m,4H),7.69(d,J=8.2Hz,2H),7.77−7.81(m,4H),8.37(d,J=9.2Hz,2H),8.52(d,J=9.2Hz,2H),9.31(d,J=9.2Hz,2H).
MALDI−TOF MS:m/z 1229([M+H]+).
Anal. Calcd for C73H67IrN2O4: C,71.37;H,5.50;N,2.28. Found:C,71.74;H,5.84;N,2.13.
1H NMR(CDCl3):δ1.08(s,6H),1.10(s,6H),1.16(s,6H),1.18(s,6H),1.57(m,8H),5.79(s,1H),6.65(d,J=8.2Hz,2H),7.09(d,J=8.2Hz,2H),7.13−7.18(m,4H),7.21−7.29(m,6H),7.34−7.43(m,4H),7.69(d,J=8.2Hz,2H),7.77−7.79(m,4H),8.34(d,J=8.3Hz,2H),8.50(d,J=8.3Hz,2H),9.29(d,J=8.2Hz,2H).
MALDI−TOF MS:m/z 1225([M+H]+).
Anal. Calcd for C73H63IrN2O4: C,71.60;H,5.19;N,2.29. Found:C,71.72;H,5.52;N,2.15.
1H NMR(CDCl3):δ5.94(s,1H),6.64(d,J=8.2Hz,2H),7.12−7.23(m,8H),7.28−7.30(m,4H),7.35(t,J=7.8Hz,2H),7.41(t,J=7.8Hz,2H),7.48(d,J=7.3Hz,4H),7.70(d,J=8.2Hz,2H),7.77−7.80(m,4H),8.32(d,J=8.2Hz,2H),8.50(d,J=8.7Hz,2H),9.26(d,J=8.7Hz,2H).
MALDI−TOF MS:m/z 1004(M+).
1H NMR(CDCl3):δ1.08(s,36H),6.42(s,1H),6.60(d,J=8.7Hz,2H),7.22−7.26(m,2H),7.30−7.34(m,10H),7.36(t,J=1.8Hz,2H),7.49−7.52(m,2H),7.71−7.79(m,6H),7.90(d,J=8.7Hz,2H),8.61(d,J=6.4Hz,2H),9.18(d,J=8.7Hz,2H).
MALDI−TOF MS:1228(M+).
Anal. Calcd for C73H67IrN2O4: C,71.37;H,5.50;N,2.28. Found:C,71.21;H,5.72;N,2.04.
1H NMR(CDCl3):δ1.08(s,6H),1.15(s,6H),1.16(s,6H),1.18(s,6H),1.57(m,8H),6.47(s,1H),6.49(d,J=1.8Hz,2H),7.13(d,J=8.2Hz,2H),7.32−7.36(m,4H),7.41(dd,J=1.8 and 8.2Hz,2H),7.49−7.54(m,6H),7.71−7.79(m,6H),7.90−7.93(m,4H),8.59(d,J=6.4Hz,2H),9.15(d,J=8.2Hz,2H).
MALDI−TOF MS:m/z 1224(M+).
Anal. Calcd for C73H63IrN2O4: C,71.60;H,5.19;N,2.29. Found:C,71.72;H,5.45;N,2.11.
1H NMR(CDCl3):δ6.44(d,J=8.2Hz,2H),6.57(s,1H),7.18−7.24(m,4H),7.30−7.38(m,8H),7.50(d,J=8.2Hz,2H),7.53(d,J=6.4Hz,2H),7.69(dd,J=1.3and 8.2Hz,4H),7.71−7.79(m,6H),7.91(d,J=8.2Hz,2H),8.58(d,J=6.4Hz,2H),9.15(d,J=8.2Hz,2H).
MALDI−TOF MS:1004(M+).
1H NMR(CDCl3):δ1.18(s,36H),5.68(s,1H),6.87(d,J=8.2Hz,2H),7.01(d,J=1.8Hz,4H),7.19(dt,J=1.4 and 8.2Hz,2H),7.31(t,J=1.8Hz,2H),7.35−7.41(m,6H),7.46(d,J=8.2Hz,2H),7.81(d,J=6.8Hz,2H),7.92(dd,J=1.4 and 8.2Hz,2H),7.97(dd,J=1.4 and 6.9Hz,2H),8.43(d,J=8.7Hz,2H),8.46(d,J=8.7Hz,2H),8.83(d,J=8.7Hz,2H).
MALDI−TOF MS:m/z 1260(M+).
Anal. Calcd for C73H67IrN2O2S2: C,69.55;H,5.36;N,2.22. Found:C,69.55;H,5.36;N,2.54.
1H NMR(CDCl3):δ1.08(s,6H),1.10(s,6H),1.16(s,6H),1.18(s,6H),1.57(m,8H),5.80(s,1H),6.65(d,J=8.2Hz,2H),7.09(d,J=8.2Hz,2H),7.13−7.16(m,4H),7.18−7.30(m,6H),7.34−7.42(m,4H),7.69(d,J=8.2Hz,2H),7.77−7.90(m,4H),8.34(d,J=8.7Hz,2H),8.50(d,J=8.7Hz,2H),9.29(d,J=8.7Hz,2H).
MALDI−TOF MS:m/z 1256(M+).
Anal. Calcd for C73H63IrN2O2S2: C,69.77;H,5.05;N,2.23. Found:C,69.49;H,5.25;N,2.54.
1H NMR(CDCl3):δ5.87(s,1H),6.85(d,J=8.2Hz,2H),7.10−7.20(m,6H),7.32−7.51(m,14H),7.78(dd,1.8 and 8.2Hz,2H),7.92(dd,J=1.4 and 6.9Hz,2H),7.99(dd,J=1.4 and 6.9Hz,2H),8.36(d,J=8.7Hz,2H),8.44(d,J=8.7Hz,2H),8.74(d,J=8.7Hz,2H).
MALDI−TOF MS:m/z 1036(M+).
Anal. Calcd for C57H35IrN2O2S2: C,66.07;H,3.40;N,2.70. Found:C,66.20;H,3.51;N,2.61.
1H NMR(CDCl3):δ1.07(s,36H),6.41(s,1H),6.59(d,J=8.2Hz,2H),7.22−7.26(m,2H),7.29(d,J=1.8Hz,4H),7.31−7.35(m,6H),7.49−7.52(m,4H),7.71−7.77(m,6H),7.90(d,J=8.2Hz,2H),8.61(d,J=5.9Hz,2H),9.18(d,J=8.2Hz,2H).
MALDI−TOF MS:m/z 1261([M+H]+).
Anal. Calcd for C73H67IrN2O2S2: C,69.55;H,5.36;N,2.22. Found:C,69.38;H,5.33;N,2.37.
1H NMR(CDCl3):δ0.96(s,6H),1.07(s,6H),1.14(s,6H),1.17(s,6H),6.47(d,J=7.7Hz,2H),6.48(s,1H),7.13(d,J=8.2Hz,2H),7,22−7.26(m,2H),7.31−7.35(m,4H),7.40(dd,J=1.8 and 8.7Hz,2H),7.49(d,J=6.8Hz,4H),7.53(d,J=1.8Hz,2H),7.70−7.78(m,6H),7.90(d,J=7.7Hz,2H),8.59(d,J=6.8Hz,2H),9.14(d,J=8.7Hz,2H).
MALDI−TOF MS:m/z 1256(M+).
Anal. Calcd for C73H63IrN2O2S2: C,69.77;H,5.05;N,2.23. Found:C,70.10;H,5.31;N,2.54.
1H NMR(CDCl3):δ6.45(d,J=7.7Hz,2H),6.58(s,1H),7.21(t,J=7.6Hz,4H),7.23−7.27(m,2H),7.32-7.37(m,6H),7.50(d,J=8.2Hz,2H),7.53(d,J=6.4Hz,2H),7.70(d,J=7.6Hz,4H),7.72−7.80(m,6H),7.92(dd,J=1.3 and 8.2Hz,2H),8.59(d,J=6.4Hz,2H),9.16(d,J=7.7Hz,2H).
MALDI−TOF MS:m/z 1036(M+).
Anal. Calcd for C57H35IrN2O2S2: C,66.07;H,3.40;N,2.70. Found:C,66.07;H,3.69;N,2.70.
上記で得られた各イリジウム錯体について、発光(PL)スペクトル及びPL量子収率ΦPLを測定した。PLスペクトルの測定では、堀場製作所社製Fluorolog−3分光光度計を用いた。PL量子収率の測定では、浜松ホトニクス社製C9920−12量子収率測定装置を用いた。これらPLスペクトル及びPL量子収率の評価は、媒質として、有機溶媒(ジクロロメタン(CH2Cl2))中、及び、高分子薄膜(ポリメタクリル酸メチル、PMMA)中の両方について行った。尚、溶液試料は、アルゴンガスを封入して脱酸素溶液として測定し、高分子薄膜試料については窒素雰囲気下で測定を行った。高分子薄膜試料については、PMMA中に各イリジウム錯体を4重量%ドープして測定を行った。結果を下記表に示す。
イリジウム錯体熱分解特性は、熱重量分析(TG)により評価した。TG測定装置として、リガク社製TG8120熱重量分析装置を用いて、窒素気流下(200mL/min)、2mgのイリジウム錯体を昇温速度10℃/minにて、約50℃から約450℃まで加熱した際の試料の重量変化を観察した。測定結果を、図1及び表2に示す。表2における重量減少率は、初期重量に対する重量減少率とした。
イリジウム錯体1‐A、2‐A、1‐X、及び2‐Xを用いて、下記の手順で、図2に示す有機EL素子(1)を作製し、特性評価を行った。
(a)ホール注入層(5)の形成
ITO−ガラス基板(三容真空工業製,ITO、膜厚150nm)にパターニング処理を施し、洗浄することにより陽極(2)を準備した。次いで、ITO薄膜を、オゾンにより表面処理した。表面処理後、速やかに、ホール注入材料をスピンコート法によりITO膜上に成膜し、120℃にて1時間焼成することにより、厚み40nmのホール注入層(5)を形成した。ホール注入材料としては、PEDOTとPSSとを含む導電性ポリマー(Heraeus Clevios製、P VP CH8000)を用いた。
脱水トルエンに、ポリ(9−ビニルカルバゾール)(PVCz、Sigma−Aldrich製、数平均分子量Mn,25000−50000、THF−メタノールから再沈殿により精製)、2−(4−ビフェニリル)−5−(4−tert−ブチルフェニル)−1,3,4−オキサジアゾール(PBD)、及びイリジウム錯体1−Aを溶解させ、メンブレンフィルター(メルクミリポア製、0.2μm Millex−FG)でろ過することにより、発光層用インクInk(1−A)を調製した。PVCz、PBD,及びイリジウム錯体の重量比を10:3.0:1.0とし、PVCz10mgに対して0.7mlのトルエンをインク溶媒として用いた。得られた発光層用インクInk(1−A)を用いて、ホール注入層(5)上に、スピンコート法により成膜し、120℃で一時間焼成することにより、厚み80nmの発光層4を形成した。
シャドウマスクを用いて、真空蒸着により、電子注入材料としてのフッ化セシウムの薄膜(電子注入層(6)、厚み1nm)を形成し、次いで、アルミニウムの薄膜(陰極(3)、厚み250nm)を作製した。このとき、発光部の面積が、10mm2(2mm×5mm)となるように、電子注入層(6)及び陰極(3)を作製した。このようにして、有機EL素子EL(1−A)を完成させた。
イリジウム錯体1−Aに代えて、各イリジウム錯体(1−B、1−X、2−A、2−B、2−X、3−A、3−B、3−X、4−A、4−B、4−X)を用いて、各発光層用インクInkを調製した。この発光層用インクInkを用いる以外は、上記の手順と同様にして、各有機EL素子ELを得た。
上記工程で得られた有機EL素子を、紫外線硬化樹脂を用いて、キャビティガラス中に封止し、有機EL特性評価用のサンプルを作製した。
ELスペクトル、最大輝度Lmax(cd/m2)、最大外部量子効率ηext,max(%)及びCIE表色系(x,y)等の有機EL素子特性を、輝度配光特性測定装置(浜松ホトニクス社製、C−9920−11)により測定した。
Claims (4)
- C−N配位子のヘテロ原子Xは、酸素原子(O)又は硫黄原子(S)である請求項1に記載の有機イリジウム錯体。
- 高分子薄膜中に4wt%ドープしたときのPL量子収率ΦPLが0.4以上である請求項1又は請求項2に記載の有機イリジウム錯体。
- 請求項1〜3のいずれかに記載された有機イリジウム錯体を含む発光層を備える有機電界発光素子。
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TW104118471A TWI621621B (zh) | 2014-06-13 | 2015-06-08 | 用於有機電場發光元件的有機銥錯合物 |
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