JP2006269472A - Organic electroluminescence element - Google Patents
Organic electroluminescence element Download PDFInfo
- Publication number
- JP2006269472A JP2006269472A JP2005081131A JP2005081131A JP2006269472A JP 2006269472 A JP2006269472 A JP 2006269472A JP 2005081131 A JP2005081131 A JP 2005081131A JP 2005081131 A JP2005081131 A JP 2005081131A JP 2006269472 A JP2006269472 A JP 2006269472A
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- Japan
- Prior art keywords
- group
- substituted
- unsubstituted
- general formula
- light emitting
- 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.)
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- -1 poly (3,4-ethylenedioxy) Polymers 0.000 claims description 63
- 238000002347 injection Methods 0.000 claims description 35
- 239000007924 injection Substances 0.000 claims description 35
- 125000000732 arylene group Chemical group 0.000 claims description 25
- 125000005549 heteroarylene group Chemical group 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- 125000003277 amino group Chemical group 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 7
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000004450 alkenylene group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 75
- 230000032258 transport Effects 0.000 description 26
- 239000010408 film Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 14
- 238000004528 spin coating Methods 0.000 description 12
- 0 CC(*(C)C)c(cc1)ccc1N(c1ccc(C)cc1)c1ccc(C)cc1 Chemical compound CC(*(C)C)c(cc1)ccc1N(c1ccc(C)cc1)c1ccc(C)cc1 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 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 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 125000005309 thioalkoxy group Chemical group 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical compound N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OGNSDRMLWYNUED-UHFFFAOYSA-N 1-cyclohexyl-4-[4-[4-(4-cyclohexylcyclohexyl)cyclohexyl]cyclohexyl]cyclohexane Chemical group C1CCCCC1C1CCC(C2CCC(CC2)C2CCC(CC2)C2CCC(CC2)C2CCCCC2)CC1 OGNSDRMLWYNUED-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- HGPVZVIPOXMTJD-UHFFFAOYSA-N 2,5-bis(4-bromophenyl)-1,3,4-oxadiazole Chemical compound C1=CC(Br)=CC=C1C1=NN=C(C=2C=CC(Br)=CC=2)O1 HGPVZVIPOXMTJD-UHFFFAOYSA-N 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 description 1
- CMSGUKVDXXTJDQ-UHFFFAOYSA-N 4-(2-naphthalen-1-ylethylamino)-4-oxobutanoic acid Chemical compound C1=CC=C2C(CCNC(=O)CCC(=O)O)=CC=CC2=C1 CMSGUKVDXXTJDQ-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- ZYASLTYCYTYKFC-UHFFFAOYSA-N 9-methylidenefluorene Chemical compound C1=CC=C2C(=C)C3=CC=CC=C3C2=C1 ZYASLTYCYTYKFC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FGUQGBWJHQIHQD-UHFFFAOYSA-N CC(C)c(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound CC(C)c(cc1)ccc1N(c1ccccc1)c1ccccc1 FGUQGBWJHQIHQD-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFTJFFPVMJLXPD-UHFFFAOYSA-N Cc(cc1)ccc1N(c1ncccc1)c1ncccc1 Chemical compound Cc(cc1)ccc1N(c1ncccc1)c1ncccc1 UFTJFFPVMJLXPD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl 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
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
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- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 150000004697 chelate complex Chemical class 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 125000003336 coronenyl group Chemical group C1(=CC2=CC=C3C=CC4=CC=C5C=CC6=CC=C1C1=C6C5=C4C3=C21)* 0.000 description 1
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- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 125000002541 furyl group Chemical group 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
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003824 heptacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC6=CC7=CC=CC=C7C=C6C=C5C=C4C=C3C=C12)* 0.000 description 1
- 125000002192 heptalenyl group Chemical group 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
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001633 hexacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC6=CC=CC=C6C=C5C=C4C=C3C=C12)* 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
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NBGMRMDAEWWFIR-UHFFFAOYSA-N imidazole-2-thione Chemical compound S=C1N=CC=N1 NBGMRMDAEWWFIR-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000003933 pentacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C12)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-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
- 125000001828 phenalenyl group Chemical group C1(C=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 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
- 125000001388 picenyl group Chemical group C1(=CC=CC2=CC=C3C4=CC=C5C=CC=CC5=C4C=CC3=C21)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 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
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、高発光効率の有機電界発光（ＥＬ）素子に関するものである。 The present invention relates to an organic electroluminescence (EL) device having high luminous efficiency.
有機エレクトロルミネッセンス（EL）素子は、低電圧で高輝度の発光を得ることができ、有望な表示素子として注目されている。 An organic electroluminescence (EL) element has been attracting attention as a promising display element because it can emit light with high luminance at a low voltage.
具体的には、１０Ｖ以下の低電圧で発光する高い蛍光量子効率を持った有機化合物を含有した薄膜を積層した有機電界発光素子が報告されている（非特許文献１）。この方法は、金属キレート錯体を発光層、アミン系化合物を正孔注入層に使用して、高輝度の緑色発光を得ており、６〜７Ｖの直流電圧で輝度は数１０００ｃｄ／ｍ2に達している。しかしながら、有機化合物の蒸着操作を伴う有機電界発光素子作成は、生産性に問題が有り、製造工程の簡略化、大面積化の観点から、塗布方式の素子作成が望ましい。 Specifically, an organic electroluminescent element in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported (Non-Patent Document 1). This method uses a metal chelate complex as a light emitting layer and an amine compound as a hole injection layer to obtain high luminance green light emission, and the luminance reaches several thousand cd / m 2 at a DC voltage of 6 to 7V. ing. However, the production of an organic electroluminescent device involving an organic compound vapor deposition operation has a problem in productivity, and it is desirable to create a coating-type device from the viewpoint of simplifying the manufacturing process and increasing the area.
また、近年、りん光発光材料がより注目されるようになった。以下のような理由で原理的に高発光効率が期待できるからである。
キャリア再結合により生成される励起子は１重項励起子と３重項励起子からなり，その確率は１：３である。これまでの有機ＥＬ素子は、蛍光発光を利用していたが、原理的にその発光収率は生成された励起子数に対して、２５％でありこれが上限であった。しかし３重項励起子から発生する燐光を用いれば、原理的に少なくとも３倍の収率が期待され、さらにエネルギー的に高い１重項から３重項への項間交差による転移を考え合わせると、原理的には４倍の１００％の発光収率が期待できる。
In recent years, more attention has been paid to phosphorescent materials. This is because high luminous efficiency can be expected in principle for the following reasons.
The excitons generated by the carrier recombination are composed of singlet excitons and triplet excitons, and the probability is 1: 3. Conventional organic EL devices have used fluorescence emission, but in principle, the emission yield is 25% of the number of excitons generated, which is the upper limit. However, if phosphorescence generated from triplet excitons is used, a yield of at least three times is expected in principle, and the transition due to intersystem crossing from singlet to triplet, which is higher in energy, is considered. In principle, a light emission yield of 100%, which is 4 times, can be expected.
塗布型りん光発光素子として、正孔輸送層と発光層を塗布により素子を作成した例が報告されている（非特許文献２）。正孔輸送層には、PEDOT/PSS、発光層には、非共役高分子の側鎖にホスト部位、発光部位をペンダント状にした化合物が用いられていた。ただし、正孔輸送層と発光層の二層構成のため、駆動電圧が高くなってしまうという問題があった。 As a coating type phosphorescent light emitting device, an example in which a device is prepared by coating a hole transport layer and a light emitting layer has been reported (Non-patent Document 2). For the hole transport layer, PEDOT / PSS was used, and for the light emitting layer, a compound having a pendant host portion and a light emitting portion on the side chain of the nonconjugated polymer was used. However, there is a problem that the drive voltage becomes high due to the two-layer structure of the hole transport layer and the light emitting layer.
一方、駆動電圧を下げるために、塗布により電子輸送層を積層した例がある(非特許文献 ３)。具体的には、有機溶媒への溶解性を上げるために高分子中にアンモニウム塩を有する電子輸送材料を用いていた。正孔注入層と蛍光系高分子発光層を塗布し、さらに電子輸送材料を塗布することにより、駆動電圧を下げられた。しかしながら、蛍光発光材料を用いているために輝度、電流効率、電力効率が低いという問題点があった。
三重項励起子からの発光が可能な発光材料を含む発光層と正孔注入層からなる有機電界発光素子は、電子輸送性、電子注入性、正孔輸送性、正孔注入性、発光性など種々の機能を有する材料を複数発光素子に混合して使用できる。しかしながら駆動電圧が高く、かつ、発光効率も低いという問題点がある。
本発明の目的は、三重項励起子からの発光が可能な発光材料を含む有機電界発光素子であって、塗布方式で積層化しても、駆動電圧が低く、発光効率が高い電界発光素子を提供する事にある。
Organic electroluminescent devices consisting of a light-emitting layer containing a light-emitting material capable of emitting light from triplet excitons and a hole injection layer have electron transport properties, electron injection properties, hole transport properties, hole injection properties, light emission properties, etc. A material having various functions can be mixed and used in a plurality of light emitting elements. However, there are problems that the drive voltage is high and the light emission efficiency is low.
An object of the present invention is to provide an organic electroluminescent device including a luminescent material capable of emitting light from triplet excitons, and has a low driving voltage and high luminous efficiency even when stacked by a coating method. There is to do.
本発明は、陽極層および陰極層の両電極層間に、正孔注入層と発光層と電子輸送層を含む複数層の有機化合物薄膜を形成してなる有機電界発光素子において、
前記発光層を形成する発光層形成材料が、三重項励起子からの発光が可能な発光材料を含み、かつ、前記電子輸送層を形成する電子輸送層形成材料が下記一般式[1]で示される繰り返し単位を含む化合物を有する有機電界発光素子に関する。
一般式［１］
Ｄ1、Ｄ2は、置換もしくは未置換のアルキレン基、置換もしくは未置換のアルケニレン基、置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、置換もしくは未置換の縮合アリーレン基、置換もしくは未置換の縮合ヘテロアリーン基、ヘテロ原子またはこれらの組み合わせより選ばれてなる2価の有機残基を表す。
ｍ1およびｍ2は、０または1であり、ｎは、0から１０である。
Ｑ11、Ｑ21、Ｑ12およびＱ22は、独立して、Ｈ、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキル基、置換もしくは未置換のヘテロアルキル基からなる群より選ばれてなる1価の有機残基を表す。そしてＱ31およびＱ32は、置換もしくは未置換のアルキル基、置換もしくは未置換のヘテロアルキル基からなる群より選ばれてなる1価の有機残基を表し、ただし、ｍ1およびｍ2が１である場合、Ｑ11、Ｑ21、Ｑ12およびＱ22は、Ｈ以外であり、Ｅ1 -およびＥ2 -は、負に荷電した対イオンを表す。］
The present invention relates to an organic electroluminescent device in which a plurality of organic compound thin films including a hole injection layer, a light emitting layer, and an electron transport layer are formed between both electrode layers of an anode layer and a cathode layer.
The light emitting layer forming material for forming the light emitting layer includes a light emitting material capable of emitting light from triplet excitons, and the electron transport layer forming material for forming the electron transport layer is represented by the following general formula [1]. The present invention relates to an organic electroluminescent device having a compound containing a repeating unit.
General formula [1]
D 1 and D 2 are substituted or unsubstituted alkylene group, substituted or unsubstituted alkenylene group, substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted condensed arylene group, substituted Alternatively, it represents a divalent organic residue selected from an unsubstituted condensed heteroarylene group, a heteroatom, or a combination thereof.
m 1 and m 2 are 0 or 1, and n is 0 to 10.
Q 11 , Q 21 , Q 12 and Q 22 are independently H, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted alkyl group, substituted or unsubstituted hetero Represents a monovalent organic residue selected from the group consisting of alkyl groups; Q 31 and Q 32 represent a monovalent organic residue selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted heteroalkyl group, provided that m 1 and m 2 are 1 , Q 11 , Q 21 , Q 12 and Q 22 are other than H, and E 1 − and E 2 − represent a negatively charged counterion. ]
また、本発明は、電子輸送層が、電子輸送層形成材料を溶媒に溶解させ、塗布方式で形成されたものである上記有機電界発光素子に関する。 The present invention also relates to the above organic electroluminescent device, wherein the electron transport layer is formed by dissolving an electron transport layer forming material in a solvent and coating.
また、本発明は、発光層が、発光層形成材料を溶媒に溶解させ、塗布方式で形成されたものである上記有機電界発光素子に関する。 The present invention also relates to the above organic electroluminescent device, wherein the light emitting layer is formed by dissolving a light emitting layer forming material in a solvent and applying the same.
また、本発明は、発光層形成材料が、下記一般式［２］で表されるユニットと、アミノ基を有するユニットとの共重合体、および、を含む上記有機電界発光素子に関する。
一般式［２］
Cは下記一般式［３］または一般式［４］で表される一価の有機残基を表す。］
一般式［３］
Xは直接結合、−O−、−S−、−Se−、−NH−、−NR23−（R23はアルキル基またはアリール基を表す。）、−S (＝O)2−、−（CO）−、−COO−、−OCO−、−CH2−を示し、
R16〜R22は互いに結合してアリール環を形成しても良く、さらにそのアリール環に置換基を有しても良い。］
一般式［４］
General formula [2]
C represents a monovalent organic residue represented by the following general formula [3] or general formula [4]. ]
General formula [3]
X is a direct bond, —O—, —S—, —Se—, —NH—, —NR 23 — (R 23 represents an alkyl group or an aryl group), —S (═O) 2 —, — ( CO) -, - COO -, - OCO -, - CH 2 - indicates,
R 16 to R 22 may be bonded to each other to form an aryl ring, and further the aryl ring may have a substituent. ]
General formula [4]
また、本発明は、正孔注入層を形成する正孔注入層形成材料を溶媒に溶解させ、塗布方式で形成されたものである上記有機電界発光素子に関する。 The present invention also relates to the organic electroluminescence device described above, wherein the hole injection layer forming material for forming the hole injection layer is dissolved in a solvent and formed by a coating method.
また、本発明は、正孔注入層を形成する正孔注入層形成材料が、ＰＥＤＯＴ・ＰＳＳ（ポリ（３，４−エチレンジオキシ）−２，５−チオフェン・ポリスチレンスルホン酸）であることを特徴とする上記有機電界発光素子に関する。
に関する。
In the present invention, the hole injection layer forming material for forming the hole injection layer is PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrenesulfonic acid). It is related with the said organic electroluminescent element characterized.
About.
本発明により、塗布方式を用いても駆動電圧が低く、発光効率が高い電界発光素子を提供することができた。
According to the present invention, it is possible to provide an electroluminescent device having a low driving voltage and high luminous efficiency even when a coating method is used.
本発明の課題を解決するためには、具体的には、図１〜図２などで示される有機電界発光素子において、陰極より素子内部に注入された電子（電荷）を効率的に陽極より注入されたホール（正孔）と再結合させる為に、陰極より素子内部に電子を効率的に注入させる役割をする層（電子輸送層）が必要である。 In order to solve the problems of the present invention, specifically, in the organic electroluminescence device shown in FIGS. 1 and 2, etc., electrons (charges) injected into the device from the cathode are efficiently injected from the anode. In order to recombine with the generated holes (holes), a layer (electron transport layer) that functions to efficiently inject electrons from the cathode into the device is necessary.
この役割を果たすのが電子輸送層である。しかし、三重項励起子からの発光が可能な発光材料を含む塗布型界発光素子の場合、塗布方式で、この電子輸送層を成膜することは困難であった。それは、電子輸送層を形成する電子輸送材料を塗布し溶剤揮散した後の膜安定性に欠けるなどの理由により、均一に製膜可能な材料が見いだせなかったからである。電子輸送層を塗布できない為、陰極より直接発光層に電子が注入する構成となる。しかし、この場合、陰極（例えば、Ca、Ba）と発光層の間のエネルギーバンドギャップが非常に大きく、電子の注入が困難になり、駆動電圧が高く、電力効率が低下した。従って、さらに、この電子輸送層と電極の間に電子注入層を入れる事により、さらなる低電圧駆動化が期待される。 The electron transport layer plays this role. However, in the case of a coating type field light emitting device containing a light emitting material capable of emitting light from triplet excitons, it has been difficult to form this electron transport layer by a coating method. This is because a material capable of forming a film uniformly could not be found due to lack of film stability after applying an electron transport material for forming an electron transport layer and evaporating the solvent. Since the electron transport layer cannot be applied, electrons are directly injected from the cathode into the light emitting layer. However, in this case, the energy band gap between the cathode (for example, Ca, Ba) and the light emitting layer is very large, it becomes difficult to inject electrons, the driving voltage is high, and the power efficiency is lowered. Therefore, further lower voltage driving is expected by inserting an electron injection layer between the electron transport layer and the electrode.
本発明では、三重項励起子からの発光が可能な発光材料を含む有機電界発光素子において、一般式［１］で示されるような高分子化合物は、塗布後の膜安定性に優れ、電子を発光層に効率的に送ることができるので、電子輸送層形成材料して用いることができる。
一般式［１］において、式中、Ａｒは、置換もしくは未置換の縮合アリーレン基、置換もしくは未置換の縮合ヘテロアリーレン基、または、これらの組み合わせである２価の有機残基を表す。
Ｄ1、Ｄ2は、置換もしくは未置換のアルキレン基、置換もしくは未置換のアルケニレン基、置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、置換もしくは未置換の縮合アリーレン基、置換もしくは未置換の縮合ヘテロアリーン基、ヘテロ原子またはこれらの組み合わせより選ばれてなる2価の有機残基を表す。
ｍ1およびｍ2は、０または1であり、ｎは、0から１０である。
Ｑ11、Ｑ21、Ｑ12およびＱ22は、それぞれ独立して、水素原子、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキル基、置換もしくは未置換のヘテロアルキル基からなる群より選ばれてなる1価の有機残基を表す。そしてＱ31およびＱ32は、それぞれ独立して、置換もしくは未置換のアルキル基、置換もしくは未置換のヘテロアルキル基からなる群より選ばれてなる1価の有機残基を表し、ただし、ｍ1およびｍ2が１である場合、Ｑ11、Ｑ21、Ｑ12およびＱ22は、水素原子以外であり、Ｅ1 -およびＥ2 -は、負に荷電した対イオン（例えば、塩素アニオン、臭素アニオン、ヨウ素アニオンのようなハロゲンのアニオン種や、過塩素酸アニオン、テトラフルオロホウ酸アニオン、テトラペンタフルオロホウ酸アニオン、トリフルオロ酢酸アニオン、トリフルオロメタンスルホン酸アニオン、ヘキサフルオロリン酸アニオンまたはシアンアニオン）である。
In the present invention, in an organic electroluminescent device containing a light emitting material capable of emitting light from triplet excitons, the polymer compound represented by the general formula [1] is excellent in film stability after coating, and has an electron. Since it can send efficiently to a light emitting layer, it can be used as an electron carrying layer forming material.
In the general formula [1], Ar represents a divalent organic residue which is a substituted or unsubstituted condensed arylene group, a substituted or unsubstituted condensed heteroarylene group, or a combination thereof.
D 1 and D 2 are substituted or unsubstituted alkylene group, substituted or unsubstituted alkenylene group, substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted condensed arylene group, substituted Alternatively, it represents a divalent organic residue selected from an unsubstituted condensed heteroarylene group, a heteroatom, or a combination thereof.
m 1 and m 2 are 0 or 1, and n is 0 to 10.
Q 11 , Q 21 , Q 12 and Q 22 are each independently a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, substituted or unsubstituted Represents a monovalent organic residue selected from the group consisting of: Q 31 and Q 32 each independently represent a monovalent organic residue selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted heteroalkyl group, provided that m 1 And when m 2 is 1, Q 11 , Q 21 , Q 12 and Q 22 are other than a hydrogen atom, and E 1 − and E 2 − are negatively charged counter ions (for example, chlorine anion, bromine Anion, halogen anion species such as iodine anion, perchlorate anion, tetrafluoroborate anion, tetrapentafluoroborate anion, trifluoroacetate anion, trifluoromethanesulfonate anion, hexafluorophosphate anion or cyanide anion ).
本発明で言う有機残基、あるいは置換基としては、特に断らない限り、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキル基、置換もしくは未置換のアルケニル基置換もしくは未置換のアルコキシ基、置換もしくは未置換のチオアルコキシ基、シアノ基、アミノ基、モノもしくはジ置換アミノ基、水酸基、メルカプト基、エーテル基、チオエーテル基、カルボニル基、およびこれらの組み合わせが挙げられる。 Unless otherwise specified, the organic residue or substituent referred to in the present invention is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl. Group-substituted or unsubstituted alkoxy groups, substituted or unsubstituted thioalkoxy groups, cyano groups, amino groups, mono- or di-substituted amino groups, hydroxyl groups, mercapto groups, ether groups, thioether groups, carbonyl groups, and combinations thereof. Can be mentioned.
置換もしくは未置換のアリール基としては、好ましくは炭素数６〜６０の単環または縮合環のアリール基であり、フェニル基、ビフェニレニル基、トリフェニレニル基、テトラフェニレニル基、３−ニトロフェニル基、４−メチルチオフェニル基、３，５−ジシアノフェニル基、ｏ−，ｍ−およびｐ−トリル基、キシリル基、ｏ−，ｍ−およびｐ−クメニル基、メシチル基、ペンタレニル基、インデニル基、ナフチル基、アントラセニル基、アズレニル基、ヘプタレニル基、アセナフチレニル基、フェナレニル基、フルオレニル基、アントリル基、アントラキノニル基、３−メチルアントリル基、フェナントリル基、ピレニル基、クリセニル基、２−エチル−１−クリセニル基、ピセニル基、ペリレニル基、６−クロロペリレニル基、ペンタフェニル基、ペンタセニル基、テトラフェニレニル基、ヘキサフェニル基、ヘキサセニル基、ルビセニル基、コロネニル基、トリナフチレニル基、ヘプタフェニル基、ヘプタセニル基、ピラントレニル基、オバレニル基等がある。 The substituted or unsubstituted aryl group is preferably a monocyclic or condensed ring aryl group having 6 to 60 carbon atoms, and includes a phenyl group, a biphenylenyl group, a triphenylenyl group, a tetraphenylenyl group, a 3-nitrophenyl group, 4-methylthiophenyl group, 3,5-dicyanophenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, indenyl group, naphthyl group Anthracenyl group, azulenyl group, heptalenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, anthryl group, anthraquinonyl group, 3-methylanthryl group, phenanthryl group, pyrenyl group, chrysenyl group, 2-ethyl-1-chrysenyl group, Picenyl group, perylenyl group, 6-chloroperylenyl group, penta Eniru group, pentacenyl group, tetraphenylenyl les group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.
置換もしくは未置換のヘテロアリール基としては、好ましくは炭素数４ないし６０の単環または縮合環の芳香族ヘテロアリール基であり、より好ましくは窒素原子、酸素原子または硫黄原子の少なくとも一つを含有する炭素数４ないし６０の単環または縮合環の芳香族ヘテロアリール基であり、更に好ましくは炭素数４ないし３０の５員または６員の芳香族ヘテロアリール基である。チオニル基、フリル基、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、インドリル基、キノリル基、イソキノリル基、フタラジニル基、キノキサリニル基、キナゾリニル基、カルバゾリル基、アクリジニル基、フェナジニル基、フルフリル基、イソチアゾリル基、イソキサゾリル基、フラザニル基、フェノキサジニル基、ベンゾチアゾリル基、ベンゾオキサゾリル基、ベンズイミダゾリル基、２−メチルピリジル基、３−シアノピリジル基等がある。 The substituted or unsubstituted heteroaryl group is preferably a monocyclic or condensed aromatic heteroaryl group having 4 to 60 carbon atoms, and more preferably contains at least one of a nitrogen atom, an oxygen atom or a sulfur atom. And a monocyclic or condensed aromatic heteroaryl group having 4 to 60 carbon atoms, more preferably a 5- or 6-membered aromatic heteroaryl group having 4 to 30 carbon atoms. Thionyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl Phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, 2-methylpyridyl group, 3-cyanopyridyl group and the like.
置換もしくは未置換のアルキル基としてはメチル基、エチル基、プロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基、イソオクチル基、ステアリル基、トリクロロメチル基、トリフロロメチル基、シクロプロピル基、シクロヘキシル基、１，３−シクロヘキサジエニル基、２−シクロペンテン−１−イル基、２，４−シクロペンタジエン−１−イリデニル基などがある。 Substituted or unsubstituted alkyl groups include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl , Stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexadienyl group, 2-cyclopenten-1-yl group, 2,4-cyclopentadiene-1-ylidenyl group, etc. There is.
置換もしくは未置換のアルケニル基としては、エチニル基、１−プロペニル基、１，３−ブタジエニル基、２−ペンテンー４−イニル基、３−メチル−２−ブテニル基、１−ペンチニル基、トリクロロエチニル基、トリフルオロエチニル基、３−α，α−ジトリフルオロメチル−２−ブテニル基等の炭素数１〜２０のアルケニル基およびその置換体がある。 Examples of the substituted or unsubstituted alkenyl group include ethynyl group, 1-propenyl group, 1,3-butadienyl group, 2-pentene-4-ynyl group, 3-methyl-2-butenyl group, 1-pentynyl group, and trichloroethynyl group. , An alkenyl group having 1 to 20 carbon atoms such as a trifluoroethynyl group and a 3-α, α-ditrifluoromethyl-2-butenyl group, and substituted products thereof.
また、発明において、アリーレン基、ヘテロアリーレン基、アルキレン基、アルケニレン基は、上記アリール基、ヘテロアリール基、アルキル基、アルケニル基の対応する２価の残基が挙げられる。 In the invention, the arylene group, heteroarylene group, alkylene group, and alkenylene group include the corresponding divalent residues of the aryl group, heteroaryl group, alkyl group, and alkenyl group.
置換もしくは未置換のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、２−エチルヘキシルオキシ基、ステアリルオキシ基、トリフロロメトキシ基等がある。 Examples of substituted or unsubstituted alkoxy groups include methoxy, ethoxy, propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, stearyloxy Group, trifluoromethoxy group and the like.
置換もしくは未置換のチオアルコキシ基としては、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ｓｅｃ−ブチルチオ基、ｔｅｒｔ−ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基、オクチルチオ基等がある。 Examples of the substituted or unsubstituted thioalkoxy group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
置換もしくは未置換のアリールオキシ基としては、フェノキシ基、ｐ−ｔｅｒｔ−ブチルフェニキシ基、３−フルオロフェニキシ基等がある。
置換もしくは未置換のアリールチオ基としては、フェニルチオ基、３−フルオロフェニルチオ基等がある。
Examples of the substituted or unsubstituted aryloxy group include a phenoxy group, a p-tert-butylphenoxy group, and a 3-fluorophenoxy group.
Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a 3-fluorophenylthio group.
モノまたはジ置換アミノ基としては、メチルアミノ基、ジメチルアミノ基、エチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基、ジフェニルアミノ基、ビス（アセトオキシメチル）アミノ基、ビス（アセトオキシエチル）アミノ基、ビス（アセトオキシプロピル）アミノ基、ビス（アセトオキシブチル）アミノ基、ジベンジルアミノ基等がある。 Mono- or di-substituted amino groups include methylamino, dimethylamino, ethylamino, diethylamino, dipropylamino, dibutylamino, diphenylamino, bis (acetoxymethyl) amino, bis (acetoxy) And ethyl) amino group, bis (acetoxypropyl) amino group, bis (acetoxybutyl) amino group, and dibenzylamino group.
好ましい置換基しては、水素原子、炭素数が１〜２０のアルキル基、もしくはアルコキシ基である。また、隣接した置換基同士で５ないし７員環の酸素原子、窒素原子、硫黄原子等が含まれてもよい脂肪族、炭素環式芳香族、複素環式芳香族、複素環を形成してもよく、これらの環の任意の位置にさらに置換基を有してもよい。 Preferred substituents are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group. Further, adjacent substituents form an aliphatic, carbocyclic aromatic, heterocyclic aromatic or heterocyclic ring which may contain a 5- to 7-membered oxygen atom, nitrogen atom, sulfur atom, etc. It may also have a substituent at any position of these rings.
一般式［１］のAr部分の具体例をＡ−１〜Ａ−１２ に示すがこれらに限定されるものではない。 Specific examples of the Ar portion of the general formula [1] are shown in A-1 to A-12, but are not limited thereto.
本発明の一般式［１］のＤ1、Ｄ2としては、好ましくは、置換もしくは未置換のアルキレン基、置換もしくは未置換のアルケニレン基、置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、置換もしくは未置換の縮合アリーレン基、置換もしくは未置換の縮合ヘテロアリーン基、ヘテロ原子またはこれらの組み合わせより選ばれてなる2価の有機残基である。具体例を下記に示すが、これに限定されるものではない。 D 1 and D 2 in the general formula [1] of the present invention are preferably a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted hetero group. A divalent organic residue selected from an arylene group, a substituted or unsubstituted condensed arylene group, a substituted or unsubstituted condensed heteroarylene group, a heteroatom, or a combination thereof. Although a specific example is shown below, it is not limited to this.
本発明の一般式［１］のＱ11、Ｑ21、Ｑ12およびＱ22としては、好ましくは、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキル基、置換もしくは未置換のヘテロアルキル基からなる群より選ばれてなる1価の有機残基である。具体例を下記に示すが、これに限定されるものではない。 Q 11 , Q 21 , Q 12 and Q 22 in the general formula [1] of the present invention are preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group. , A monovalent organic residue selected from the group consisting of substituted or unsubstituted heteroalkyl groups. Although a specific example is shown below, it is not limited to this.
本発明の一般式［１］のＥ1 -およびＥ2 -としては、負に荷電した対イオンが挙げられる。これらは、対イオンであればよく、必ずしも１価のイオンである必要はない。具体例を下記に示すが、これに限定されるものではない。 Examples of E 1 − and E 2 − in the general formula [1] of the present invention include a negatively charged counter ion. These may be counter ions, and are not necessarily monovalent ions. Although a specific example is shown below, it is not limited to this.
本発明の一般式［１］で示される繰り返し単位を含む化合物は耐熱性、薄膜状態の安定性を考えると重量平均分子量は特に限定しないが、たとえばゲルパーミエイションクロマトグラフィー測定法によるポリスチレン換算で１０００〜１００００００、特に３０００〜５０００００であることが好ましい。
一般式［１］の繰り返し単位の構造例を表１に具体的に示すが、本発明の繰り返し単位は以下の代表例に限定されるものではない。表１は、各繰り返し単位の構造を示すのみで、その重合形態を示したものではない。また、表中の％は、モル％を表す。
The weight average molecular weight of the compound containing the repeating unit represented by the general formula [1] of the present invention is not particularly limited in consideration of heat resistance and stability in a thin film state. For example, in terms of polystyrene by gel permeation chromatography measurement It is preferably 1000 to 1000000, particularly 3000 to 500000.
Although the structural example of the repeating unit of General formula [1] is specifically shown in Table 1, the repeating unit of this invention is not limited to the following representative examples. Table 1 only shows the structure of each repeating unit, and does not show its polymerization form. Moreover,% in a table | surface represents mol%.
表１
一般式［２］においてAはB、Cを側鎖に有する非共役主鎖骨格を形成することのできる任意の３価の有機残基を表す。有機残基については、一般式［２］と同様のものが例示できるが、非共役主鎖となるように選択される。
Ａの具体例をＦ−１〜Ｆ−１２に示すがこれらに限定されるものではない。
In the general formula [2], A represents an arbitrary trivalent organic residue capable of forming a non-conjugated main chain skeleton having B and C in the side chain. Examples of the organic residue are the same as those in the general formula [2], but are selected so as to be a non-conjugated main chain.
Specific examples of A are shown in F-1 to F-12, but are not limited thereto.
共重合体を形成する際の非共役主鎖骨格モノマーの重合様式はラジカル重合、カチオン重合、アニオン重合などのビニル重合、縮重合、開環重合、種々の重合反応による共重合体形成を行うことができ、重合方法は特に限定しないが、本発明では特にビニル重合モノマーの重合による共重合体形成反応が好ましい。 The polymerization mode of the non-conjugated main chain skeleton monomer in forming the copolymer is to perform copolymer formation by vinyl polymerization such as radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, ring-opening polymerization, and various polymerization reactions. The polymerization method is not particularly limited, but in the present invention, a copolymer formation reaction by polymerization of a vinyl polymerization monomer is particularly preferable.
本発明の一般式［２］のＢは、直接結合、または、置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、および置換もしくは未置換のエテニレン基からなる群より一つ以上選ばれてなる２価の有機残基である。前記アリーレン基もしくはヘテロアリーレン基が置換基を有する場合、置換基同士が一体となって新たな環を形成することがあってもよい。 B in the general formula [2] of the present invention is one or more selected from the group consisting of a direct bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group. This is a divalent organic residue. When the arylene group or heteroarylene group has a substituent, the substituents may be combined to form a new ring.
本発明の一般式［２］のＣは、一般式［３］および／または一般式［４］で表される。R16〜R28の置換基は、一般式［２］の有機残基の説明したものと同様のものが挙げられる。 C in the general formula [2] of the present invention is represented by the general formula [3] and / or the general formula [4]. Examples of the substituent for R 16 to R 28 include the same as those described for the organic residue of the general formula [2].
本発明の一般式［２］のＣとしては、具体例を下記に示すが、これに限定されるものではない。 Specific examples of C in the general formula [2] of the present invention are shown below, but are not limited thereto.
また、一般式［２］のＢ、Ｃからなる一価の有機残基は、あるいは、アミノ基を有するユニットのアミノ基が側鎖にある場合のアミノ基を含む有機残基は、非共役主鎖骨格モノマーの段階で導入されていなくとも、非共役主鎖骨格が形成されたあと、導入・変性されてもよい。 In addition, the monovalent organic residue composed of B and C in the general formula [2], or the organic residue containing an amino group when the amino group of the unit having an amino group is in the side chain is a non-conjugated main group. Even if it is not introduced at the stage of the chain skeleton monomer, it may be introduced / modified after the non-conjugated main chain skeleton is formed.
一般式［２］で表されるユニット、およびアミノ基を有するユニットの共重合体において、アミノ基を有するユニットの、アミノ基は、共重合体の主鎖または側鎖に存在する。
好ましくは、下記一般式［５］で表される構造を有するユニットである。
In the copolymer of the unit represented by the general formula [2] and the unit having an amino group, the amino group of the unit having an amino group is present in the main chain or side chain of the copolymer.
A unit having a structure represented by the following general formula [5] is preferable.
一般式［５］
［式中Ｅ、およびＦは、それぞれ独立に置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、置換もしくは未置換のエテニレン基からなる群より１つ以上選ばれてなる２価の有機残基を表す（ただし、エテニレン基が選ばれる場合は、２つの、アリーレン基もしくはヘテロアリーレン基の間になる場合である。）。］ [Wherein E and F are each independently a divalent group selected from one or more selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group. Represents an organic residue (however, when an ethenylene group is selected, it is a case between two arylene groups or heteroarylene groups). ]
また、好ましくは下記一般式［６］で表される構造を有するユニットである。
一般式［６］
General formula [6]
［式中Ｄ、Ｅ、Ｆは、それぞれ独立に置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、置換もしくは未置換のエテニレン基からなる群より１つ以上選ばれてなる２価の有機残基を表す（ただし、エテニレン基が選ばれる場合は、２つの、アリーレン基もしくはヘテロアリーレン基の間になる場合である。）。］ [Wherein D, E and F are each independently a divalent selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted ethenylene group. (However, when an ethenylene group is selected, it is a case between two arylene groups or heteroarylene groups.) ]
アミノ基を有するユニットはさらに好ましくは下記一般式［７］で表される。
一般式［７］
General formula [7]
［式中Dは、置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、置換もしくは未置換のエテニレン基からなる群より１つ以上選ばれてなる２価の有機残基を（ただし、エテニレン基が選ばれる場合は、２つの、アリーレン基もしくはヘテロアリーレン基の間になる場合である。）を表し、ＨおよびＩは置換もしくは未置換のアリール基または置換もしくは未置換のヘテロアリール基群より１つまたは２つ選ばれてなる１価の有機残基を表し、Gは非共役の３価の有機残基を表す。］
一般式［７］のＧは、前述の例一般式［２］のＡの同様のものが例示できる。
[Wherein D represents a divalent organic residue selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group (provided that And an ethenylene group is a case between two arylene groups or heteroarylene groups.) And H and I are substituted or unsubstituted aryl groups or substituted or unsubstituted
Examples of G in the general formula [7] are the same as those in A in the above-described general formula [2].
アミノ基を有するユニットは、さらに好ましくは以下、H−１からH−１２に示す構造が挙げられるがこれらに限定されるものではない。 More preferably, examples of the unit having an amino group include, but are not limited to, the structures shown in H-1 to H-12 below.
本発明で用いられる発光層形成材料は、一般式［２］で表されるユニットと、その他のユニットとの共重合体であることが好ましい。その他のユニットとしては、アミノ基を有するユニット、電子輸送性の骨格を有するユニットなどが挙げられる。 The light emitting layer forming material used in the present invention is preferably a copolymer of a unit represented by the general formula [2] and other units. Examples of other units include a unit having an amino group and a unit having an electron transporting skeleton.
一般式［２］、［５］〜［７］におけるアリーレン基は、一般式［１］で説明したアリーレン基と同様のものが挙げられる。 Examples of the arylene group in the general formulas [2] and [5] to [7] include the same arylene groups as described in the general formula [1].
一般式［２］、［５］〜［７］におけるヘテロアリーレン基は、一般式［１］で説明したヘテロアリーレン基と同様のものが挙げられる。 Examples of the heteroarylene group in the general formulas [2] and [5] to [7] include the same heteroarylene groups as described in the general formula [1].
一般式［２］、［５］〜［７］におけるエテニレン基としては、エテニレン基、１−メチルエテニレン基、１−エチルエテニレン基などが挙げられる。 Examples of ethenylene groups in the general formulas [2] and [5] to [7] include an ethenylene group, a 1-methylethenylene group, and a 1-ethylethenylene group.
なお、本発明の一般式［２］で表されるユニットとアミノ基を有するユニットの共重合体は、ランダム、ブロック、またはグラフト共重合体であってもよく、それらの中間的な構造を有する高分子たとえばブロック性をもつランダム共重合体であってもよい。
本発明の一般式［２］で表されるユニットとアミノ基を有するユニットの共重合体はさらにスチレンおよびその誘導体、アクリル酸およびその誘導体、マレイン酸およびその誘導体、有機酸ビニルエステルなどと共重合体としてもよい。
The copolymer of the unit represented by the general formula [2] of the present invention and the unit having an amino group may be a random, block, or graft copolymer, and has an intermediate structure thereof. The polymer may be a random copolymer having block property.
The copolymer of the unit represented by the general formula [2] of the present invention and the unit having an amino group is further co-polymerized with styrene and its derivatives, acrylic acid and its derivatives, maleic acid and its derivatives, organic acid vinyl ester and the like. It may be combined.
本発明の一般式［２］で表されるユニットとアミノ基を有するユニットの共重合体は耐熱性、薄膜状態の安定性を考えると重量平均分子量は特に限定しないが、たとえばゲルパーミエイションクロマトグラフィー測定法によるポリスチレン換算で１０００〜１００００００、特に３０００〜５０００００であることが好ましい。
ポリマーに用いられるユニットの構造例を表２に具体的に示すが、本発明のポリマーは以下の代表例に限定されるものではない。表２は、各ユニットモノマーの構造を示すのみで、その重合形態を示したものではない。また、表中の％は、モル％を表す。
The copolymer of the unit represented by the general formula [2] and the unit having an amino group of the present invention is not particularly limited in terms of weight average molecular weight in view of heat resistance and stability in a thin film state. For example, gel permeation chromatography It is preferably 1,000 to 1,000,000, and particularly preferably 3,000 to 500,000 in terms of polystyrene by the graphic measurement method.
Although the structural example of the unit used for a polymer is specifically shown in Table 2, the polymer of this invention is not limited to the following representative examples. Table 2 shows only the structure of each unit monomer, and does not show its polymerization form. Moreover,% in a table | surface represents mol%.
表２
本発明で用いられる一般式［２］で表されるユニットとアミノ基を有するユニットの共重合体は、さらに、発光材料あるいはドーピング材料と併用して用いる。 The copolymer of the unit represented by the general formula [2] and the unit having an amino group used in the present invention is further used in combination with a light emitting material or a doping material.
一般式［２］で表されるユニットとアミノ基を有するユニットの共重合体の、発光材料またはドーパント材料として特に三重項励起子からの発光が可能な発光材料が好ましい。三重項励起子からの発光が可能な発光材料としては、三重項発光性の金属錯体があり、イリジウム錯体Ir(ppy)3（Tris-Ortho-Metalated Complexof Iridium (III) with 2-Phenylpyridine）等が知られている。Ir(ppy)3を用いた緑色発光素子は８％の外部量子収率を達成しており、従来有機発光素子の限界といわれていた外部量子収率５％を凌駕した（Applied Physics Letters 75, 4(1999)）。その他Ir錯体化合物、金属配位ポリフィリン化合物が本発明の有機発光素子用材料と共に使用可能であるがこれらに限定されるものではない。 A light emitting material capable of emitting light from triplet excitons is particularly preferable as the light emitting material or dopant material of the copolymer of the unit represented by the general formula [2] and the unit having an amino group. Examples of luminescent materials that can emit light from triplet excitons include triplet luminescent metal complexes, such as the iridium complex Ir (ppy) 3 (Tris-Ortho-Metalated Complex of Iridium (III) with 2-Phenylpyridine). Are known. The green light-emitting device using Ir (ppy) 3 has achieved an external quantum yield of 8%, exceeding the external quantum yield of 5%, which was previously considered the limit of organic light-emitting devices (Applied Physics Letters 75, 4 (1999)). Other Ir complex compounds and metal coordination porphyrin compounds can be used with the organic light emitting device material of the present invention, but are not limited thereto.
発光層には、必要があればさらに正孔注入材料や電子注入材料を使用することもできる。有機電界発光素子は、多層構造にすることにより、クエンチングによる輝度や寿命の低下を防ぐことができる。また、ドーパント材料により、発光輝度や発光効率の向上、赤色や青色の発光を得ることもできる。また、正孔注入帯域、発光層、電子注入帯域は、それぞれ三層以上の層構成により形成されても良い。その際には、正孔注入帯域の場合、電極から正孔を注入する層を正孔注入層、正孔注入層から正孔を受け取り発光層まで正孔を輸送する層を正孔輸送層と呼ぶ。同様に、電子注入帯域の場合、電極から電子を注入する層を電子注入層、電子注入層から電子を受け取り発光層まで電子を輸送する層を電子輸送層と呼ぶ。これらの各層は、材料のエネルギー準位、耐熱性、有機層もしくは金属電極との密着性等の各要因により選択されて使用される。 If necessary, a hole injection material or an electron injection material can be further used for the light emitting layer. The organic electroluminescent element can prevent a decrease in luminance and lifetime due to quenching by adopting a multilayer structure. Further, with the dopant material, it is possible to improve light emission luminance and light emission efficiency and to obtain red or blue light emission. Moreover, the hole injection zone, the light emitting layer, and the electron injection zone may each be formed with a layer configuration of three or more layers. In that case, in the case of the hole injection zone, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection zone, a layer for injecting electrons from an electrode is referred to as an electron injection layer, and a layer for receiving electrons from the electron injection layer and transporting electrons to a light emitting layer is referred to as an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or metal electrode.
正孔注入層形成材料としては、正孔を輸送する能力を持ち、陽極からの正孔注入効果、発光層または発光材料に対して優れた正孔注入効果を有し、発光層で生成した励起子の電子注入帯域または電子注入材料への移動を防止し、かつ薄膜形成能力の優れた化合物が挙げられる。具体的には、PEDOT・PSS、PANI、フタロシアニン誘導体、ナフタロシアニン誘導体、ポルフィリン誘導体、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、イミダゾールチオン、ピラゾリン、ピラゾロン、テトラヒドロイミダゾール、ヒドラゾン、アシルヒドラゾン、ポリアリールアルカン、スチルベン、ブタジエン、ベンジジン型トリフェニルアミン、スチリルアミン型トリフェニルアミン、ジアミン型トリフェニルアミン等と、それらの誘導体、およびポリビニルカルバゾール、ポリシラン、導電性高分子等の高分子材料等があるが、これらに限定されるものではない。 As a hole injection layer forming material, it has the ability to transport holes, has a hole injection effect from the anode, an excellent hole injection effect for the light emitting layer or light emitting material, and the excitation generated in the light emitting layer Examples thereof include a compound that prevents migration of a child to an electron injection zone or an electron injection material and has an excellent thin film forming ability. Specifically, PEDOT / PSS, PANI, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, hydrazone, acyl hydrazone, polyaryl There are alkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, etc., and their derivatives, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers. However, it is not limited to these.
本発明において、電子注入層形成材料は、例えば、フルオレノン、アントラキノジメタン、ジフェノキノン、チオピランジオキシド、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、ペリレンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等とそれらの誘導体をさらに含むことができるが、これらに限定されるものではない。 In the present invention, the electron injection layer forming material is, for example, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodi. Methane, anthrone and the like and derivatives thereof may be further included, but are not limited thereto.
本発明で使用される有機化合物薄膜の塗布方法としては、特に限定はなく、例えば溶媒に溶解した後、塗布する方法（例えばインクジェット法、スプレイ法、印刷法、スピンコーテング法、キャスティング法、ディッピング法、バーコート法、ロールコート法など）などを用いることが出来る。塗布方式で成膜する場合に用いる溶媒としては、水、およびメタノール、エタノール、プロピルアルコール、ブタノール等のアルコール系計溶媒、メチルセロソルブ、エチルセロソルブ、ブチルセルブ等のセロソルブ系溶媒、ジクロロエタン、ジクロロメタン、クロロホルム、などの有機ハロゲン系溶媒、テトラヒドロフラン、1.4-ジオキサンなどのエーテル系溶媒、トルエン、キシレンなどの芳香族炭化水素系溶媒、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド系溶媒、酢酸エチル、酢酸ブチルなどのエステル系溶媒、またはこれらの混合溶媒であっても良い。高分子の構造、分子量によっても異なるが、通常溶媒の０．０１から１０重量％、好ましくは０．１から５重量％溶解した溶液を用いて成膜する。 The organic compound thin film coating method used in the present invention is not particularly limited, for example, a method of coating after dissolving in a solvent (for example, an ink jet method, a spray method, a printing method, a spin coating method, a casting method, a dipping method). , Bar coating method, roll coating method, etc.) can be used. Solvents used in the case of forming a film by a coating method include water and alcohol based solvents such as methanol, ethanol, propyl alcohol, and butanol, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butylselve, dichloroethane, dichloromethane, chloroform, Organic halogen solvents such as tetrahydrofuran, ether solvents such as 1.4-dioxane, aromatic hydrocarbon solvents such as toluene and xylene, amide solvents such as dimethylformamide and dimethylacetamide, ester systems such as ethyl acetate and butyl acetate A solvent or a mixed solvent thereof may be used. Although it depends on the structure and molecular weight of the polymer, the film is usually formed using a solution of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, of a solvent.
有機電界発光素子の陽極に使用される導電性物質としては、４ｅＶより大きな仕事関数を持つものが好適であり、炭素、アルミニウム、セシウム、バナジウム、鉄、コバルト、ニッケル、タングステン、銀、金、白金、パラジウム等およびそれらの合金、ＩＴＯ基板、ＮＥＳＡ基板と称される酸化スズ、酸化インジウム等の酸化金属、さらにはポリチオフェンやポリピロール等の有機導電性樹脂が用いられる。
陰極に使用される導電性物質としては、４.０ｅＶより小さな仕事関数を持つものが好適であり、マグネシウム、バリウム、カルシウム、セシウム、錫、鉛、チタニウム、イットリウム、リチウム、ルテニウム、マンガン等およびそれらの合金が用いられるが、これらに限定されるものではない。陽極および陰極は、必要があれば二層以上の層構成により形成されていても良い。
As the conductive material used for the anode of the organic electroluminescence device, a material having a work function larger than 4 eV is preferable, and carbon, aluminum, cesium, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum Further, palladium, etc. and alloys thereof, ITO substrate, metal oxide such as tin oxide and indium oxide called NESA substrate, and organic conductive resin such as polythiophene and polypyrrole are used.
As the conductive material used for the cathode, those having a work function smaller than 4.0 eV are preferable, such as magnesium, barium, calcium, cesium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, and the like. However, it is not limited to these. If necessary, the anode and the cathode may be formed of two or more layers.
本発明の有機電界発光素子は、壁掛けテレビ等のフラットパネルディスプレイや、平面発光体として、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等へ応用が考えられ、その工業的価値は非常に大きい。
The organic electroluminescent element of the present invention can be applied to flat panel displays such as wall-mounted televisions, flat light emitters, light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights. And its industrial value is very large.
以下、本発明を実施例に基づきさらに詳細に説明する。説明中、部は重量部、％は重量％を表す。
製造例１
B-1の合成方法
Hereinafter, the present invention will be described in more detail based on examples. In the description, parts represent parts by weight and% represents% by weight.
Production Example 1
Synthesis method of B-1
乾燥窒素気流下、2,7-dibromofluorene(1.6g、5.0mmol) 、tetrabutylammonium bromide(322mg、1.0mmol) 、1,6-dibromohexane(12g、50mmol) 、と溶媒として50wt%NaOH aq 100ml加え、75℃にて15分間撹拌した。反応液を室温まで冷却し、クロロホルムにて抽出した。有機層を水、1MHCl溶液、ブラインにてそれぞれ二回ずつ洗った。その後、溶媒、過剰な1,6-dibromohexaneを除去し、シリカゲルカラムクロマトグラフィーにて単離精製し、化合物（1）を得た。収率74％。この化合物（1）の構造決定は、ＮＭＲスペクトル等により行った。
Under a dry nitrogen stream, 2,7-dibromofluorene (1.6 g, 5.0 mmol), tetrabutylammonium bromide (322 mg, 1.0 mmol), 1,6-dibromohexane (12 g, 50 mmol), and 100 ml of 50 wt% NaOH aq as a solvent were added, 75 ° C. For 15 minutes. The reaction solution was cooled to room temperature and extracted with chloroform. The organic layer was washed twice with water, 1M HCl solution and brine. Thereafter, the solvent and
四つ口フラスコに冷却管をつけ、化合物（1）(650mg, 1.0mmol)、
2,5-bis(4-bromophenyl)-1,3,4-oxadiazole (380mg, 1.0mmol) 、1,4-phenylenebisboronic acid
(330mg, 2.0mmol)、 tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) (32mg, 27mmol)にTHF (24ml) を加えて撹拌した。ここに2M K2CO3 aq (12ml)を加えた。85℃で20時間還流した。反応液をメタノール再沈殿により精製し、化合物(2)を得た。収率63％。この化合物（2）の構造決定は、赤外線吸収スペクトル等により行った。
A four-necked flask was fitted with a condenser, and compound (1) (650 mg, 1.0 mmol),
2,5-bis (4-bromophenyl) -1,3,4-oxadiazole (380mg, 1.0mmol), 1,4-phenylenebisboronic acid
(330 mg, 2.0 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh 3 ) 4 ) (32 mg, 27 mmol) was added with THF (24 ml) and stirred. 2M K 2 CO 3 aq (12 ml) was added thereto. Refluxed at 85 ° C. for 20 hours. The reaction solution was purified by methanol reprecipitation to obtain compound (2). Yield 63%. The structure of this compound (2) was determined by infrared absorption spectrum or the like.
-78℃THF (10ml)に溶解した 化合物（2）(100mg)に、40wt% trimethylamine aq 6mlを加えて撹拌し、反応液を室温にした。その後、水20mlを加え、再び-78℃に冷却し40wt% trimethylamine aq 6mlを加え、反応液を室温にし24時間攪拌した。溶媒を除去後、アセトンで再沈殿により精製し、化合物（B-1）を得た。収率80％。この化合物（B-1）の構造決定は、赤外線吸収スペクトル等により行った。
化合物2の、赤外線吸収スペクトルを図３に示す。
To compound (2) (100 mg) dissolved in −78 ° C. THF (10 ml), 6 ml of 40 wt% trimethylamine aq was added and stirred, and the reaction solution was brought to room temperature. Thereafter, 20 ml of water was added, the mixture was cooled again to −78 ° C., 6 ml of 40 wt% trimethylamine aq was added, and the reaction solution was brought to room temperature and stirred for 24 hours. After removing the solvent, the residue was purified by reprecipitation with acetone to obtain Compound (B-1).
The infrared absorption spectrum of
以下に本発明の有機発光素子用材料を用いた実施例を具体的に示すが、本発明はこれにより限定されるものではない。 Examples using the organic light-emitting device material of the present invention are specifically shown below, but the present invention is not limited thereto.
実施例１
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ/ＰＳＳ（ポリ(3,4-エチレンジオキシ)-2,5-チオフェン/ポリスチレンスルホン酸）をスピンコート法で６０ｎｍの膜厚に製膜した。ついで、トルエン溶媒に溶解させた発光材料Ｐ−１およびイリジウム錯体（化合物（３）） (3%)を膜厚５０ｎｍでスピンコート法にて塗布した。さらに、電子輸送材料B−１を５０ｎｍの膜厚でスピンコート法にて塗布し、減圧乾燥を行った。さらに、ＬｉＦを１ｎｍ、Ａｌを２００ｎｍの膜厚で電極を形成させ、有機ＥＬ素子１を作製した。
Example 1
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid) was formed into a film thickness of 60 nm by spin coating on the cleaned glass plate with an ITO electrode. Subsequently, the luminescent material P-1 and iridium complex (compound (3)) (3%) dissolved in a toluene solvent were applied by spin coating at a film thickness of 50 nm. Further, the electron transport material B-1 was applied by a spin coating method with a film thickness of 50 nm, and dried under reduced pressure. Furthermore, an electrode was formed with a film thickness of 1 nm for LiF and 200 nm for Al, thereby producing an
化合物（３）
比較例１
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ/ＰＳＳ（ポリ(3,4-エチレンジオキシ)-2,5-チオフェン/ポリスチレンスルホン酸）をスピンコート法で６０ｎｍの膜厚に製膜した。ついで、トルエン溶媒に溶解させた発光材料Ｐ−１およびイリジウム錯体（化合物（３）） (3%)を膜厚５０ｎｍでスピンコート法にて塗布し、減圧乾燥を行った。さらに、Ｃａを２０ｎｍ、Ａｌを２００ｎｍの膜厚で電極を形成させ、有機ＥＬ素子２を作製した。
Comparative Example 1
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid) was formed into a film thickness of 60 nm by spin coating on the cleaned glass plate with an ITO electrode. Subsequently, the light-emitting material P-1 and iridium complex (compound (3)) (3%) dissolved in a toluene solvent were applied at a film thickness of 50 nm by a spin coating method and dried under reduced pressure. Furthermore, an electrode was formed with a film thickness of 20 nm for Ca and 200 nm for Al, thereby producing an
比較例２
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ/ＰＳＳ（ポリ(3,4-エチレンジオキシ)-2,5-チオフェン/ポリスチレンスルホン酸）をスピンコート法で６０ｎｍの膜厚に製膜した。ついで、ジクロロエタン溶媒に溶解させた発光材料（化合物（４））を膜厚５０ｎｍでスピンコート法にて塗布し、さらに、電子輸送材料B−１を５０ｎｍの膜厚でスピンコート法にて塗布し、減圧乾燥を行った。さらに、ＬｉＦを１ｎｍ、Ａｌを２００ｎｍの膜厚で電極を形成させ、有機ＥＬ素子３を作製した。
Comparative Example 2
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid) was formed into a film thickness of 60 nm by spin coating on the cleaned glass plate with an ITO electrode. Next, a light emitting material (compound (4)) dissolved in a dichloroethane solvent is applied by a spin coat method with a film thickness of 50 nm, and further, an electron transport material B-1 is applied by a spin coat method with a film thickness of 50 nm. Then, vacuum drying was performed. Further, an electrode was formed with a film thickness of 1 nm for LiF and 200 nm for Al, thereby producing an
化合物（４）
実施例２
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ/ＰＳＳ（ポリ(3,4-エチレンジオキシ)-2,5-チオフェン/ポリスチレンスルホン酸）をスピンコート法で６０ｎｍの膜厚に製膜した。ついで、トルエン溶媒に溶解させた発光材料Ｐ−１およびイリジウム錯体（化合物（３）） (3%)を膜厚５０ｎｍでスピンコート法にて塗布した。さらに、電子輸送材料B−２を１０ｎｍの膜厚でスピンコート法にて塗布し、減圧乾燥を行った。さらに、ＬｉＦを１ｎｍ、Ａｌを２００ｎｍの膜厚で電極を形成させ、有機ＥＬ素子４を作製した。
Example 2
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid) was formed into a film thickness of 60 nm by spin coating on the cleaned glass plate with an ITO electrode. Subsequently, the luminescent material P-1 and iridium complex (compound (3)) (3%) dissolved in a toluene solvent were applied by spin coating at a film thickness of 50 nm. Further, the electron transport material B-2 was applied by spin coating with a film thickness of 10 nm and dried under reduced pressure. Further, an electrode was formed with a film thickness of 1 nm for LiF and 200 nm for Al, and an
実施例３
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ/ＰＳＳ（ポリ(3,4-エチレンジオキシ)-2,5-チオフェン/ポリスチレンスルホン酸）をスピンコート法で６０ｎｍの膜厚に製膜した。ついで、トルエン溶媒に溶解させた発光材料Ｐ−１およびイリジウム錯体（化合物（３）） (3%)を膜厚５０ｎｍでスピンコート法にて塗布した。さらに、電子輸送材料B−３を１０ｎｍの膜厚でスピンコート法にて塗布し、減圧乾燥を行った。さらに、ＬｉＦを１ｎｍ、Ａｌを２００ｎｍの膜厚で電極を形成させ、有機ＥＬ素子５を作製した。
Example 3
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid) was formed into a film thickness of 60 nm by spin coating on the cleaned glass plate with an ITO electrode. Subsequently, the luminescent material P-1 and iridium complex (compound (3)) (3%) dissolved in a toluene solvent were applied by spin coating at a film thickness of 50 nm. Furthermore, the electron transport material B-3 was applied with a film thickness of 10 nm by a spin coat method, and dried under reduced pressure. Furthermore, an electrode was formed with a film thickness of 1 nm for LiF and 200 nm for Al, thereby producing an
実施例１〜３、および比較例１〜２のEL特性を表３に示す。
表３
Table 3
本発明の有機ＥＬ素子は低駆動電圧化、発光効率、発光輝度の向上を達成するものであり、併せて使用される発光材料、正孔注入材料、電子輸送材料、電極材料等および素子作製方法を限定するものではない。 The organic EL device of the present invention achieves low driving voltage, light emission efficiency, and improvement of light emission luminance. Light emitting material, hole injection material, electron transport material, electrode material, etc. used together and device manufacturing method It is not intended to limit.
表３から明らかなように本発明の電子輸送層を用いた有機電界発光素子（素子１）と用いない有機電界発光素子（素子２）を比較すると前者のほうが低駆動電圧、高効率発光であることが確認できる。また、共役高分子材料（化合物４）を用いた有機電界発光素子（素子３）を比較すると前者のほうが高効率発光であることが確認できる。 As is clear from Table 3, when comparing the organic electroluminescent device (device 1) using the electron transport layer of the present invention with the organic electroluminescent device (device 2) not used, the former has lower driving voltage and higher efficiency light emission. I can confirm that. Further, when comparing an organic electroluminescent element (element 3) using a conjugated polymer material (compound 4), it can be confirmed that the former is more efficient light emission.
１は陽極層
２は陰極層
３は正孔注入層
４は発光層
５は電子注入層
６は電子輸送層
1 is an
Claims (6)
前記発光層を形成する発光層形成材料が、三重項励起子からの発光が可能な発光材料を含み、かつ、
前記電子輸送層を形成する電子輸送層形成材料が下記一般式[1]で示される繰り返し単位を含む化合物を有する有機電界発光素子。
一般式［１］
Ｄ1、Ｄ2は、置換もしくは未置換のアルキレン基、置換もしくは未置換のアルケニレン基、置換もしくは未置換のアリーレン基、置換もしくは未置換のヘテロアリーレン基、置換もしくは未置換の縮合アリーレン基、置換もしくは未置換の縮合ヘテロアリーン基、ヘテロ原子またはこれらの組み合わせより選ばれてなる2価の有機残基を表す。
ｍ1およびｍ2は、０または1であり、ｎは、0から１０である。
Ｑ11、Ｑ21、Ｑ12およびＱ22は、それぞれ独立して、水素原子、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキル基、置換もしくは未置換のヘテロアルキル基からなる群より選ばれてなる1価の有機残基を表す。そしてＱ31およびＱ32は、それぞれ独立して、置換もしくは未置換のアルキル基、置換もしくは未置換のヘテロアルキル基からなる群より選ばれてなる1価の有機残基を表し、ただし、ｍ1およびｍ2が１である場合、Ｑ11、Ｑ21、Ｑ12およびＱ22は、水素原子以外であり、Ｅ1 -およびＥ2 -は、負に荷電した対イオンを表す。］ In an organic electroluminescent element formed by forming a plurality of organic compound thin films including a hole injection layer, a light emitting layer, and an electron transport layer between both the anode layer and the cathode layer,
The light emitting layer forming material forming the light emitting layer includes a light emitting material capable of emitting light from triplet excitons, and
An organic electroluminescent element, wherein the electron transport layer forming material forming the electron transport layer has a compound containing a repeating unit represented by the following general formula [1].
General formula [1]
D 1 and D 2 are substituted or unsubstituted alkylene group, substituted or unsubstituted alkenylene group, substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted condensed arylene group, substituted Alternatively, it represents a divalent organic residue selected from an unsubstituted condensed heteroarylene group, a heteroatom, or a combination thereof.
m 1 and m 2 are 0 or 1, and n is 0 to 10.
Q 11 , Q 21 , Q 12 and Q 22 are each independently a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group, substituted or unsubstituted Represents a monovalent organic residue selected from the group consisting of: Q 31 and Q 32 each independently represent a monovalent organic residue selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted heteroalkyl group, provided that m 1 And when m 2 is 1, Q 11 , Q 21 , Q 12 and Q 22 are other than a hydrogen atom, and E 1 − and E 2 − represent a negatively charged counter ion. ]
一般式［２］
Cは下記一般式［３］または一般式［４］で表される一価の有機残基を表す。］
一般式［３］
Xは直接結合、−O−、−S−、−Se−、−NH−、−NR23−（R23はアルキル基またはアリール基を表す。）、−S (＝O)2−、−（CO）−、−COO−、−OCO−、−CH2−を示し、
R16〜R22は互いに結合してアリール環を形成しても良く、さらにそのアリール環に置換基を有しても良い。］
一般式［４］
General formula [2]
C represents a monovalent organic residue represented by the following general formula [3] or general formula [4]. ]
General formula [3]
X is a direct bond, —O—, —S—, —Se—, —NH—, —NR 23 — (R 23 represents an alkyl group or an aryl group), —S (═O) 2 —, — ( CO) -, - COO -, - OCO -, - CH 2 - indicates,
R 16 to R 22 may be bonded to each other to form an aryl ring, and further the aryl ring may have a substituent. ]
General formula [4]
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012216815A (en) * | 2011-03-28 | 2012-11-08 | Sumitomo Chemical Co Ltd | Electronic device, polymer compound |
| JP2013532756A (en) * | 2010-08-02 | 2013-08-19 | メルク パテント ゲーエムベーハー | Polymers containing structural units with electron transport properties |
| JP2013243280A (en) * | 2012-05-22 | 2013-12-05 | Hitachi Chemical Co Ltd | Organic electronics material, ink composition, organic electronics element, organic electroluminescent element, and photoelectric conversion element |
| JP2015119194A (en) * | 2007-03-23 | 2015-06-25 | 株式会社半導体エネルギー研究所 | Composition |
| JP2017514303A (en) * | 2014-04-16 | 2017-06-01 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Organic light emitting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015119194A (en) * | 2007-03-23 | 2015-06-25 | 株式会社半導体エネルギー研究所 | Composition |
| JP2013532756A (en) * | 2010-08-02 | 2013-08-19 | メルク パテント ゲーエムベーハー | Polymers containing structural units with electron transport properties |
| US9368726B2 (en) | 2010-08-02 | 2016-06-14 | Merck Patent Gmbh | Polymers containing structural units which have electron-transport properties |
| JP2012216815A (en) * | 2011-03-28 | 2012-11-08 | Sumitomo Chemical Co Ltd | Electronic device, polymer compound |
| JP2013243280A (en) * | 2012-05-22 | 2013-12-05 | Hitachi Chemical Co Ltd | Organic electronics material, ink composition, organic electronics element, organic electroluminescent element, and photoelectric conversion element |
| JP2017514303A (en) * | 2014-04-16 | 2017-06-01 | ケンブリッジ ディスプレイ テクノロジー リミテッド | Organic light emitting device |
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