JP3755196B2 - Electroluminescent device using cyclopentadiene derivative - Google Patents
Electroluminescent device using cyclopentadiene derivative Download PDFInfo
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- JP3755196B2 JP3755196B2 JP18865396A JP18865396A JP3755196B2 JP 3755196 B2 JP3755196 B2 JP 3755196B2 JP 18865396 A JP18865396 A JP 18865396A JP 18865396 A JP18865396 A JP 18865396A JP 3755196 B2 JP3755196 B2 JP 3755196B2
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title description 33
- -1 formyloxy group Chemical group 0.000 claims description 42
- 239000000126 substance Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 10
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 8
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 5
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 5
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 5
- 229920001774 Perfluoroether Chemical group 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 4
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 4
- 125000005199 aryl carbonyloxy group Chemical group 0.000 claims description 4
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000005401 electroluminescence Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000005647 linker group Chemical group 0.000 claims 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims 2
- 239000000463 material Substances 0.000 description 37
- 230000032258 transport Effects 0.000 description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 18
- 229910052749 magnesium Inorganic materials 0.000 description 18
- 239000011777 magnesium Substances 0.000 description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 230000005525 hole transport Effects 0.000 description 16
- 229910052709 silver Inorganic materials 0.000 description 16
- 239000004332 silver Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 238000007740 vapor deposition Methods 0.000 description 16
- 238000000151 deposition Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 229910052783 alkali metal Inorganic materials 0.000 description 14
- 150000001340 alkali metals Chemical class 0.000 description 14
- 230000008021 deposition Effects 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- 229910003437 indium oxide Inorganic materials 0.000 description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 8
- UHXOHPVVEHBKKT-UHFFFAOYSA-N 1-(2,2-diphenylethenyl)-4-[4-(2,2-diphenylethenyl)phenyl]benzene Chemical group C=1C=C(C=2C=CC(C=C(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=2)C=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 UHXOHPVVEHBKKT-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 125000002971 oxazolyl group Chemical group 0.000 description 3
- 150000004880 oxines Chemical class 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- DPLKSHQZYSYFRQ-UHFFFAOYSA-N 1,1-dimethyl-2,3,4,5-tetraphenylgermole Chemical compound C[Ge]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 DPLKSHQZYSYFRQ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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 class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SJYHQNHZKXSOSL-UHFFFAOYSA-N C[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)F)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)F)C.C[Ge]1(C(=C(C(=C1C1=C(C=CC=C1)C(F)(F)F)C1=CC=CC=C1)C1=CC=CC=C1)C1=C(C=CC=C1)C(F)(F)F)C Chemical compound C[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)F)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)F)C.C[Ge]1(C(=C(C(=C1C1=C(C=CC=C1)C(F)(F)F)C1=CC=CC=C1)C1=CC=CC=C1)C1=C(C=CC=C1)C(F)(F)F)C SJYHQNHZKXSOSL-UHFFFAOYSA-N 0.000 description 2
- WRYDNIACOQBAOK-UHFFFAOYSA-N C[Ge]1(C(=C(C(=C1C=1OC2=C(N1)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2OC1=C(N2)C=CC=C1)C Chemical compound C[Ge]1(C(=C(C(=C1C=1OC2=C(N1)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2OC1=C(N2)C=CC=C1)C WRYDNIACOQBAOK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000005200 aryloxy carbonyloxy group Chemical group 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005290 ethynyloxy group Chemical group C(#C)O* 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
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- 125000002541 furyl group Chemical group 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000004866 oxadiazoles Chemical class 0.000 description 2
- 125000001715 oxadiazolyl group Chemical group 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 125000001567 quinoxalinyl group Chemical class N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- QKLPIYTUUFFRLV-YTEMWHBBSA-N 1,4-bis[(e)-2-(2-methylphenyl)ethenyl]benzene Chemical compound CC1=CC=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=CC=C1C QKLPIYTUUFFRLV-YTEMWHBBSA-N 0.000 description 1
- BCASZEAAHJEDAL-PHEQNACWSA-N 1,4-bis[(e)-2-(4-methylphenyl)ethenyl]benzene Chemical compound C1=CC(C)=CC=C1\C=C\C(C=C1)=CC=C1\C=C\C1=CC=C(C)C=C1 BCASZEAAHJEDAL-PHEQNACWSA-N 0.000 description 1
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- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
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- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QBLBTMIULCXHNE-UHFFFAOYSA-N C1(=CC=C(C=C1)[Ge]1(C(=C(C(=C1C1=CC=C(C=C1)C)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C.C[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)C)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)C)C Chemical compound C1(=CC=C(C=C1)[Ge]1(C(=C(C(=C1C1=CC=C(C=C1)C)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=C(C=C1)C)C1=CC=C(C=C1)C)C.C[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)C)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)C)C QBLBTMIULCXHNE-UHFFFAOYSA-N 0.000 description 1
- BTMHLGHBIZVYJF-UHFFFAOYSA-N C[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)OC)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)OC)CC[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)OC)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)OC)C Chemical compound C[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)OC)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)OC)CC[Ge]1(C(=C(C(=C1C1=CC(=CC=C1)OC)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC(=CC=C1)OC)C BTMHLGHBIZVYJF-UHFFFAOYSA-N 0.000 description 1
- LCTWLODICUHPRM-UHFFFAOYSA-N C[Ge]1(C(=C(C(=C1C=1SC2=C(C1C1=CC=CC=C1)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2SC1=C(C2C2=CC=CC=C2)C=CC=C1)C.C[Ge]1(C(=C(C(=C1C=1SC2=C(C1C)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2SC1=C(C2C)C=CC=C1)C Chemical compound C[Ge]1(C(=C(C(=C1C=1SC2=C(C1C1=CC=CC=C1)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2SC1=C(C2C2=CC=CC=C2)C=CC=C1)C.C[Ge]1(C(=C(C(=C1C=1SC2=C(C1C)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2SC1=C(C2C)C=CC=C1)C LCTWLODICUHPRM-UHFFFAOYSA-N 0.000 description 1
- WKBBUDHOFXQECC-UHFFFAOYSA-N C[Ge]1(C(=C(C(=C1C=1SC2=C(N1)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2SC1=C(N2)C=CC=C1)C.C[Ge]1(C(=C(C(=C1C1=C(SC2=C1C=CC=C2)C)C2=CC=CC=C2)C2=CC=CC=C2)C2=C(SC1=C2C=CC=C1)C)C Chemical compound C[Ge]1(C(=C(C(=C1C=1SC2=C(N1)C=CC=C2)C2=CC=CC=C2)C2=CC=CC=C2)C=2SC1=C(N2)C=CC=C1)C.C[Ge]1(C(=C(C(=C1C1=C(SC2=C1C=CC=C2)C)C2=CC=CC=C2)C2=CC=CC=C2)C2=C(SC1=C2C=CC=C1)C)C WKBBUDHOFXQECC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- MASVCBBIUQRUKL-UHFFFAOYSA-N POPOP Chemical compound C=1N=C(C=2C=CC(=CC=2)C=2OC(=CN=2)C=2C=CC=CC=2)OC=1C1=CC=CC=C1 MASVCBBIUQRUKL-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
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- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000006269 biphenyl-2-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C(*)C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006268 biphenyl-3-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C([H])C(*)=C([H])C([H])=C1[H] 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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- 239000010406 cathode material Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- YHOLMJGIIYTMRY-UHFFFAOYSA-L dichlorostannane Chemical class Cl[SnH2]Cl YHOLMJGIIYTMRY-UHFFFAOYSA-L 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical class Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- GQNMAZUQZDEAFI-UHFFFAOYSA-N lithium;1h-naphthalen-1-ide Chemical compound [Li+].[C-]1=CC=CC2=CC=CC=C21 GQNMAZUQZDEAFI-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- XPIGOSZCSQQSSF-UHFFFAOYSA-N lithium;n,n-dimethyl-1h-naphthalen-1-id-2-amine Chemical compound [Li+].C1=CC=CC2=[C-]C(N(C)C)=CC=C21 XPIGOSZCSQQSSF-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 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
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- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
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- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 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
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- ZBJSHDVMDCJOEZ-UHFFFAOYSA-N potassium;1h-naphthalen-1-ide Chemical compound [K+].[C-]1=CC=CC2=CC=CC=C21 ZBJSHDVMDCJOEZ-UHFFFAOYSA-N 0.000 description 1
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- 238000004528 spin coating Methods 0.000 description 1
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- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、電界発光（ELECTROLUMINESCENCE、以下ＥＬと略記する。）素子に関し、さらに詳しくはシクロペンタジエン誘導体を用いた有機ＥＬ素子に関する。
【０００２】
【従来の技術】
近年、これまでにない高輝度な平面ディスプレイの候補として有機ＥＬ素子が注目され、その研究開発が活発化している。有機ＥＬ素子は有機発光層を２つの電極で挟んだ構造であり、陽極から注入された正孔と陰極から注入された電子とが発光層中で再結合して光を発する。用いられる有機材料には低分子材料と高分子材料があり、共に高輝度の有機ＥＬ素子を与えることが知らされている。
【０００３】
このような有機ＥＬ素子には２つのタイプがある。１つは、タン（C.W.Tang）らによって発表された蛍光色素を電荷輸送層中に添加したもの（ジャーナル オブ ジ アプライド フィジックス(J.Appl.Phys.),65,3610(1989)）、もう１つは、蛍光色素を単独に用いたものである（例えば、ジャパニーズ ジャーナル オブ ジ アプライド フィジックス(Jpn.J.Appl.Phys.),27,L269(1988）に記載されている素子である。）。後者の素子では、蛍光色素が電荷の１つである正孔のみを輸送する正孔輸送層および／または電子のみを輸送する電子輸送層と積層しているような場合に発光効率が向上することが示されている。
【０００４】
有機ＥＬ素子に使用される正孔輸送材料については、トリフェニルアミン誘導体を中心にして多種多様の材料が知られているにもかかわらず、電子輸送材料について知られているものは少ない。また、既存の電子輸送材料は、既存の正孔輸送材料、例えば、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ジ（３−メチルフェニル）−４，４’−ジアミノビフェニル（以下ＴＰＤと略記する。）に比べ電荷の輸送能力が低く、有機ＥＬ素子に使用した場合、性能が用いた電子輸送材料により制限され十分な素子の特性を引き出すことができなかった。
【０００５】
従来の電子輸送材料の具体例としてオキシン誘導体の金属錯体（特開昭５９−１９４３９３などに記載のもの。）、２−（４−ビフェニルイル）−５−（４−tert−ブチルフェニル）−１，３，４−オキサジアゾール（以下ＰＢＤと略記する。）などが知られている。前者は、比較的低電圧で有機ＥＬ素子を駆動させることができるが、まだ十分ではなく、また、自身の発光が緑色であるためフルカラーデスプレ−用としては実用的ではない。後者を電子輸送層として用いた例としてジャパニーズジャーナルオブジアプライドフィジックス（Jpn.J.Appl.Phys.),27,L269(1988)に記載の有機ＥＬ素子をあげることができるが、結晶化を起こしやすいなど、薄膜の安定性に乏しいことが指摘されていた。
【０００６】
この問題を解決するためにオキサジアゾール環を複数持つ化合物（日本化学会誌,11,1540(1991)、特開平６ー１４５６５８、特開平６ー９２９４７、特開平５ー１５２０７２、特開平５ー２０２０１１および特開平６ー１３６３５９などに記載のもの。）が開発されたが、これらにおいても駆動電圧が高いなど実用上充分な性質を有していなかった。また、キノキサリン誘導体（特開平６−２０７１６９）を２量化させることにより分子量を増大させ薄膜の安定性を向上させることができることが報告されているが駆動電圧は依然として高く実用には十分ではなかった。
【０００７】
シクロペンタジエン誘導体（アプライド フィジックス レター（Appl.Phys.Lett.）,56,799(1990）、１，２，３，４，５−ペンタシクロペンタジエン）を用いた例も報告されているが、高効率、高発光な素子は得られていない。
【０００８】
このように、従来の有機ＥＬ素子に用いられる電子輸送材料は、電子輸送能に劣る上、フルカラー表示、薄膜の安定性、駆動電圧、発光効率等が不十分なものであった。優れた材料を使用することにより有機ＥＬ素子の効率を高める必要があり、何よりもまず電子輸送能に優れていることが必要であると考えられている。
【０００９】
【発明が解決しようとする課題】
本発明の目的は、低電圧、高発光効率な有機ＥＬ素子を提供することである。
【００１０】
【課題を解決するための手段】
本発明者らは、従来の有機ＥＬ素子が抱えている前記の問題を解決する為に、鋭意検討した結果、スタナシクロペンタジエン環あるいはゲルマシクロペンタジエン環誘導体を用いることにより、低電圧、高発光効率であることを見出し本発明を完成した。
【００１１】
スタナシクロペンタジエン環あるいはゲルマシクロペンタジエン環が有機ＥＬ素子として好適である理由について本発明者らが種々研究した結果、対応するシクロペンタジエン環、チオフェン環、ピロール環あるいはフラン環に比べて、最低非占有分子軌道が低く、電子を受け取りやすい構造であることが半経験的分子軌道法計算により判明した。しかしながら、その他にも、スタナシクロペンタジエン環あるいはゲルマシクロペンタジエン環の構造等が電子輸送性に効果を与えていると考えている。
【００１２】
本発明は、下記化３で表されるシクロペンタジエン誘導体の少なくとも１種を正孔阻止層の成分として用いることを特徴とする電界発光素子である。
【００１３】
【化３】
［式中、ＡはＧｅもしくはＳｎであり；Ｘ及びＹは、それぞれ独立に炭素数１から６までの飽和若しくは不飽和の炭化水素基、アルコキシ基、アルケニルオキシ基、アルキニルオキシ基、ヒドロキシ基、置換若しくは無置換のアリール基、または置換若しくは無置換のヘテロ環であり、ＸとＹが結合して飽和若しくは不飽和の環を形成してもよく；Ｒ１〜Ｒ４は、それぞれ独立に水素、ハロゲン、置換もしくは無置換の炭素数１から６までのアルキル基、アルコキシ基、アリールオキシ基、パーフルオロアルキル基、パーフルオロアルコキシ基、アミノ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アゾ基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、スルフィニル基、スルフォニル基、スルファニル基、シリル基、カルバモイル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基、ニトロ基、ホルミル基、ニトロソ基、ホルミルオキシ基、イソシアノ基、シアネート基、イソシアネート基、チオシアネート基、イソチオシアネート基、またはシアノ基であり、これらの基が隣接した場合には隣接した基同士が結合して置換若しくは無置換の環を形成してもよい。］
【００１５】
前記化３で表されるシクロペンタジエン誘導体は、そのうちの少なくとも１種を電界発光素子の電荷輸送層として用いることもでき、または、そのうちの少なくとも１種を電界発光素子の発光層の成分として用いることもできる。
【００１６】
本発明について以下に詳述する。
本発明で用いられるシクロペンタジエン誘導体は、例えば、以下の製造法により得ることができる。すなわち、下記化４
【００１７】
【化４】
［式中、Ｒ1及びＲ2は、それぞれ独立に水素、ハロゲン、置換もしくは無置換の炭素数１から６までのアルキル基、アルコキシ基、アリールオキシ基、パーフルオロアルキル基、パーフルオロアルコキシ基、アミノ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アゾ基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、スルフィニル基、スルフォニル基、スルファニル基、シリル基、カルバモイル基、アリール基、ヘテロ環基、アルケニル基、アルキニル基、ニトロ基、ホルミル基、ニトロソ基、ホルミルオキシ基、イソシアノ基、シアネート基、イソシアネート基、チオシアネート基、イソチオシアネート基もしくはシアノ基又は隣接した場合には置換若しくは無置換の環が縮合した構造である。］で表されるアセチレン誘導体にアルカリ金属あるいはその錯体を反応させ、続いて一般式化５
【００１９】
【化５】
［式中、Ａは、ゲルマニウム若しくは錫を示し、Ｘ及びＹは、それぞれ独立に炭素数１から６までの飽和若しくは不飽和の炭化水素基、アルコキシ基、アルケニルオキシ基、アルキニルオキシ基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環を示すか、ＸとＹが結合して飽和または不飽和の環を形成している。］で表される塩化物を作用させることによって、目的のシクロペンタジエン誘導体が得られる。
【００２１】
ここで用いられるアセチレン誘導体には、アルカリ金属若しくはその錯体とアセチレンとの反応を阻害しにくいものを置換基として有するものを好適に用いることができる。置換基として特に好ましくはアルカリ金属若しくはその錯体に対して不活性なものである。用いられるアルカリ金属若しくはその錯体としては、例えば、リチウム、ナトリウム、カリウム、リチウムナフタレニド、ナトリウムナフタレニド、カリウムナフタレニド、リチウム４，４’−ジターシャリーブチル−２，２’−ビフェニリドあるいはリチウム（Ｎ、Ｎ−ジメチルアミノ）ナフタレニドなどがあげられる。用いられる溶媒としては、アルカリ金属あるいはアルカリ金属錯体に不活性なものなら特に制限はなく、通常、エーテルあるいはテトラヒドロフランなどのエーテル系の溶媒が用いられる。この一連の反応は、不活性気流中で行うことが好ましく、窒素若しくはアルゴンガスが使われる。反応は、ＮＭＲあるいはクロマトグラフィー等の一般的な分析手段により反応を追跡し、反応の終点を決定すればよい。
【００２２】
本発明で用いられる化合物において、シクロペンタジエン環にベンゼン環が縮合している場合には、上記製造法とは異なる方法が用いられる。これまでに知られている公知の方法を用いることができるが、例えば以下の方法を例示することができる。すなわち、下記化６
【００２３】
【化６】
［式中、Ｘは、塩素、臭素若しくはヨウ素を表し、Ｒ1からＲ8は、それぞれ独立に炭素数１から６までの飽和若しくは不飽和の炭化水素基、アルコキシ基、アルケニルオキシ基、アルキニルオキシ基、フッ素、水素、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環、シアノ基、隣接している場合には、飽和または不飽和の環を形成している。］で表される２，２’−ジハロゲノビフェニル誘導体にアルカリ金属、アルカリ土類金属あるいはアルカリ金属錯体を作用させ、これに下記化７
【００２５】
【化７】
［式中、Ａは、ゲルマニウム若しくは錫を示し、Ｘ及びＹは、それぞれ独立に炭素数１から６までの飽和若しくは不飽和の炭化水素基、アルコキシ基、アルケニルオキシ基、アルキニルオキシ基、置換若しくは無置換のアリール基、置換あるいは無置換のヘテロ環を示すか、ＸとＹが結合して飽和または不飽和の環を形成している。］で表されるジクロロゲルマニウム誘導体若しくはジクロロスタナン誘導体を反応させることによって、本発明で用いられるシクロペンタジエン誘導体を得ることができる。ここで用いられる金属としては、リチウム、ナトリウム、マグネシウムあるいはカリウム等があげられ、金属錯体としては、ノルマルブチルリチウム、ターシャリーブチルリチウムあるいはフェニルリチウム等があげられる。用いられる２，２’−ジハロゲノビフェニル誘導体の置換基としては、アルカリ金属、アルカリ土類金属あるいはアルカリ金属錯体に、この反応条件下不活性なものなら特に制限はない。アルカリ金属、アルカリ土類金属あるいはアルカリ金属錯体を作用させる時の反応温度についても特に制限はなく、通常、０℃以下で行われる。ただし、反応性の高いシアノ基などの置換基が存在している時には低い温度が好ましく、通常、−７０℃以下で行われる。用いられる反応溶媒としては、アルカリ金属、アルカリ土類金属あるいはアルカリ金属錯体に不活性なものなら特に制限はなく、通常、エーテルあるいはテトラヒドロフランなどのエーテル系の溶媒が用いられる。
【００２７】
このようにして得られた本発明で用いられるシクロペンタジエン誘導体のヘテロ元素上に付く置換基としては、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、シクロペンチル基、あるいはターシャリーブチル基などのアルキル基、ビニル基、アリル基、ブテニル基あるいはスチリル基などのアルケニル基、エチニル基、プロパギル基あるいはフェニルアセチニル基などのアルキニル基、メトキシ基、エトキシ基、イソプロポキシ基あるいはターシャリーブトキシ基などのアルコキシ基、ビニルオキシ基あるいはアリルオキシ基などのアルケニルオキシ基、エチニルオキシ基あるいはフェニルアセチルオキシ基などのアルキニルオキシ基、フェニル基、ナフチル基、アントラセニル基、ビフェニル基、トルイル基、ピレニル基、ペリレニル基、アニシル基、ターフェニル基あるいはフェナンスレニル基等のアリール基、ヒドロフリル基、ヒドロピレニル基、ジオキサニル基、チエニル基、フリル基、オキサゾリル基、オキサジアゾリル基、チアゾリル基、チアジアゾリル基、アクリジニル基、キノリル基、キノキサロイル基、フェナンスロリル基、ベンゾチエニル基、ベンゾチアゾリル基、インドリル基、ゲルマシクロペンタジエニル基あるいはピリジル基等のヘテロ環等があげられる。さらに、これらの置換基がお互いに任意の場所で結合してスピロ環を形成していても良い。
【００２８】
シクロペンタジエン環の炭素上に付く置換基としては、水素、フッ素あるいは塩素等のハロゲン、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、シクロペンチル基、あるいはターシャリーブチル基などのアルキル基、ビニル基、アリル基、ブテニル基あるいはスチリル基などのアルケニル基、エチニル基、プロパギル基あるいはフェニルアセチニル基などのアルキニル基、メトキシ基、エトキシ基、イソプロポキシ基あるいはターシャリーブトキシ基などのアルコキシ基、ビニルオキシ基あるいはアリルオキシ基などのアルケニルオキシ基、エチニルオキシ基あるいはフェニルアセチルオキシ基などのアルキニルオキシ基、フェノキシ基、ナフトキシ基、ビフェニルオキシ基あるいはピレニルオキシ基などのアリールオキシ基、トリフルオロメチル基、トリフルオロメトキシ基あるいはペンタフルオロエトキシ基などのパーフルオロ基、ジメチルアミノ基、ジエチルアミノ基あるいはジフェニルアミノ基などのアミノ基、アセチル基あるいはベンゾイル基などのケトン、アセトキシ基あるいはベンゾイルオキシ基などのエステル基、メトキシカルボニル基、エトキシカルボニル基あるいはフェノキシカルボニル基などのエステル基、メチルスルフィニル基あるいはフェニルスルフィニル基などのスルフィニル基、トリメチルシリル基、ジメチルターシャリーブチルシリル基、トリメトキシシリル基あるいはトリフェニルシリル基などのシリル基、フェニル基、ビフェニル基、ターフェニル基、ナフチル基、アントラセニル基、ピレニル基、トルイル基、アニシル基、フルオロフェニル基、ジフェニルアミノフェニル基、ジメチルアミノフェニル基、ジエチルアミノフェニル基あるいはフェナンスレニル基などのアリール基、チエニル基、フリル基、ゲルマシクロペンタジエニル基、オキサゾリル基、オキサジアゾリル基、チアゾリル基、チアジアゾリル基、アクリジニル基、キノリル基、キノキサロイル基、フェナンスロリル基、ベンゾチエニル基、ベンゾチアゾリル基、インドリル基、カルバゾリル基、ピリジル基、ピロリル基、ベンゾオキサゾリル基、ピリミジル基あるいはイミダゾリル基等のヘテロ環、ニトロ基、ホルミル基、ニトロソ基、ホルミルオキシ基、イソシアノ基、シアネート基、イソシアネート基、チオシアネート基、イソチオシアネート基あるいはシアノ基等があげられる。さらに、これらの置換基がお互いに任意の場所で結合して環を形成していても良い。
これらの置換基の導入方法は、シクロペンタジエン環の形成前に導入しても良いし、シクロペンタジエン環形成後に導入しても良い。
【００２９】
本発明で用いられるシクロペンタジエン誘導体例として以下のものを例示することができる。
１，１ージメチルー２，３，４，５ーテトラフェニルゲルマシクロペンタジエン
１，１ージエチルー２，３，４，５ーテトラキス（２ーメチルフェニル）ゲルマシクロペンタジエン
１，１ージイソプロピルー２，３，４，５ーテトラキス（３ーメチルフェニル）ゲルマシクロペンタジエン
１−エチル−１ーメチルー２，３，４，５ーテトラキス（４ーメチルフェニル）ゲルマシクロペンタジエン
１，１ージターシャリーブチルー２，３，４，５ーテトラキス（２ーエチルフェニル）ゲルマシクロペンタジエン
１，１ージフェニルー２，３，４，５ーテトラキス（３ーエチルフェニル）ゲルマシクロペンタジエン
１ーメチル−１−フェニルー２，３，４，５ーテトラキス（４ーエチルフェニル）ゲルマシクロペンタジエン
【００３０】
１−フェニル−１−ターシャリーブチルー２，３，４，５ーテトラキス（３ーターシャリーブチルフェニル）ゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（３ーメチルフェニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージ（４−トルイル）ー２，５ービス（４ーメチルフェニル）ー３，４ージフェニルゲルマシクロペンタジエン
１ーゲルマシクロヘキサン−１−スピロー２’，５’ージ（２ービフェニル）ー３’，４’ージフェニル−１’−ゲルマシクロペンタジエン
１ーゲルマシクロペンタン−１−スピロー２’，５’ージ（３ービフェニル）ー３’，４’ージフェニル−１’−ゲルマシクロペンタジエン
９−ゲルマフルオレン−９−スピロ−２’，５’ージ（４ービフェニル）ー３’，４’ージフェニル−１’−ゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（２ートリフルオロメチルフェニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（３ーフルオロフェニル）ー３，４ージフェニルゲルマシクロペンタジエン
【００３１】
１，２ービス（１ーメチルー２，５ービス（３ーメトキシフェニル）ー３、４ージフェニルゲルマシクロペンタジエニル）エタン
１，１ージメチルー２，５ービス（４ーシアノフェニル）ー３，４ージフェニルスタナシクロペンタジエン
１，１ージメチルー２，５ービス｛２ー（２ーベンゾオキサゾリル）フェニル｝ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス｛３ー（２ーベンゾチエニル）フェニル｝ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス｛４ー（２ーベンゾフリル）フェニル｝ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス｛２ー（２ーベンゾチアゾリル）フェニル｝ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス｛３ー（２ーベンゾイミダゾリル）フェニル｝ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス｛４ー（２ーインドリル）フェニル｝ー３，４ージフェニルゲルマシクロペンタジエン
【００３２】
１，１ージメチルー２，５ービス｛３ー（５ーメトキシー２ーベンゾチアゾリル）フェニル｝ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ージ（１ーナフチル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ージ（２ーメチルー１ーナフチル）ー３，４ージフェニルスタナシクロペンタジエン
１，１ージメトキシー２，５ージ（２ーナフチル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ージ（２ーベンゾチエニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（３ーメチルー２ーベンゾチエニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（３ーフェニルー２ーベンゾチエニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（２ーメチルー３ーベンゾチエニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ージ（２ーベンゾチアゾリル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ージ（２ーベンゾオキサゾリル）ー３，４ージフェニルゲルマシクロペンタジエン
【００３３】
１，１ージメチルー２，５ービス（５ーメチルー２ーベンゾオキサゾリル）ー３，４ージフェニルスタナシクロペンタジエン
１，１ージメチルー２，５ービス（５ーフェニルー２ーベンゾチアジアゾリル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ージ（３ーベンゾフラニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（３，４ージフルオロフェニル）ー３，４ージフェニルゲルマシクロペンタジエン
１，１ージメチルー２，５ービス（３，４，５ートリフルオロフェニル）ー３，４ージフェニルスタナシクロペンタジエン
１，１ージメチルー２，５ービス（２，３，４，５，６ーペンタフルオロフェニル）ー３，４ージフェニルゲルマシクロペンタジエン
５，５’−ジブロモ−１，１，１’，１’−テトラエチル−３，３’，４，４’−テトラフェニル−２，２’−ビゲルモール
５，５’−ジメチル−１，１，１’，１’−テトラエチル−３，３’，４，４’−テトラフェニル−２，２’−ビスタノール
５，５’’’−ジブロモ−１，１，１’，１’，１’’，１’’，１’’’，１’’’−オクタエチル−３，３’，３’’，３’’’，４，４’，４’’，４’’’−オクタフェニル−２，２’：５’，２’’：５’’，２’’’−クォーターゲルモール
９，９’−ゲルマスピロビフルオレン
９，９’−スタナスピロビフルオレン
９，９−ジフェニル−９−スタナフルオレン
９，９−ジナフチル−９−ゲルマフルオレン
【００３４】
本発明のＥＬ素子の構成は、各種の態様があるが、基本的には一対の電極（陽極と陰極）間に、前記シクロペンタジエン誘導体を挟持した構成とし、これに必要に応じて、正孔輸送材料、発光材料および電子輸送材料を加えるか、別の層として積層すればよい。
【００３５】
具体例としては、陽極／シクロペンタジエン誘導体層／陰極、陽極／正孔輸送層／シクロペンタジエン誘導体層／陰極、陽極／正孔輸送層／発光層／シクロペンタジエン誘導体層／陰極、陽極／正孔輸送材料＋発光材料＋シクロペンタジエン誘導体層／陰極などが挙げられる。他のシクロペンタジエン誘導体の特殊な使用法として、正孔阻止材料への適用がある。正孔阻止材料とは、電子と正孔の２つの電荷のうち電子のみを輸送し、正孔を伝達しない若しくは伝達し難い材料のことである。本発明で用いられるシクロペンタジエン誘導体は、電子を優先的若しくは選択的に輸送するので、本発明の有機ＥＬ素子の他の具体例として、陽極／正孔輸送層／シクロペンタジエン誘導体層／電子輸送層／陰極等があげられる。この場合、発光するのは、正孔輸送層あるいはシクロペンタジエン誘導体層になる。特に、このような正孔阻止の効果を出すシクロペンタジエン誘導体としては、発光波長の短いものがあげられる。例えば、９，９’−ゲルマスピロビフルオレン等があげられる。この９，９’−ゲルマスピロビフルオレンを正孔阻止層に、ＴＰＤを正孔輸送層に、８−ヒドロキシキノリンアルミニウム（以下Ａｌｑと略記する。）を電子輸送層に用いた素子においては、その発光は、ＴＰＤの発光に由来する紫色のものしか見られず、非常に優れた正孔阻止能を有する。このようにＴＰＤが発光する素子としては、キドら（Kido, et. al.Science,267,1332(1995)）によるトリアゾール誘導体を用いた素子があるが完全ではなかった。さらに特殊な例として、本発明で用いられるシクロペンタジエン誘導体層を発光層若しくは電子輸送性発光層として使用できる。この場合の素子の構成は、陽極／正孔輸送層／（シクロペンタジエン誘導体＋電子輸送材料）層／陰極等があげられる。
【００３６】
本発明の素子は、いずれも基板に支持されていることが好ましく、該基板に付いては特に制限はなく、従来ＥＬ素子に慣用されているもの、例えばガラス、透明プラスチック、導電性高分子あるいは石英などから成るものを用いることができる。
【００３７】
本発明で使用される各層は、例えば蒸着法、塗布法等の公知の方法によって、薄膜化する事により形成することができる。
このようにして形成された各層の薄膜の厚みについては特に制限はなく、適宜状況に応じて選ぶことができるが、通常２ｎｍないし５０００ｎｍの範囲で選定される。
【００３８】
本発明のＥＬ素子における陽極として、仕事関数の大きい（４ｅＶ以上）金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具体例としてはＡｕなどの金属、ＣｕＩ、ＳｎＯ2、ＺｎＯ、ＩＴＯ（酸化インジウム）などの誘電性透明材料が挙げられる。陽極は、これらの電極物質を蒸着やスパッタリングなどの方法により、薄膜を形成させることにより作製することができる。この電極より発光を取り出す場合には、透過率を１０％より大きくすることが望ましく、また、電極としてのシート抵抗は数百Ω／square以下が好ましい。膜厚は材料にもよるが、好ましくは１０ｎｍないし１μｍ、より好ましくは１０〜２００ｎｍの範囲である。
【００３９】
陰極としては、仕事関数の小さい（４．３ｅＶ以下）金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、カルシウム、マグネシウム、リチウム、アルミニウム、マグネシウム合金、リチウム合金、アルミニウム合金、アルミニウム／リチウム混合物、マグネシウム／銀混合物、インジウムなどが挙げられる。陰極は、これらの電極物質を蒸着やスパッタリングなどの方法により、薄膜を形成させることにより、作製することができる。また、電極としてのシート抵抗は数百Ω／square以下が好ましく、好ましくは１０ｎｍないし１μｍ、より好ましくは５０〜２００ｎｍの範囲である。
【００４０】
本発明の有機ＥＬ素子の構成は、前記したように各種の態様があるが、正孔輸送層を設けると発光効率が向上する。
正孔輸送層に用いられる正孔輸送材料としては、電界を与えられた２個の電極間に配置されて陽極から正孔が注入された場合、該正孔を適切に発光層へ伝達しうる化合物であって、例えば、１０4〜１０6Ｖ／ｃｍの電界印加時に、少なくとも１０-6ｃｍ2／Ｖ・秒以上の正孔移動度をもつものが好適である。正孔輸送材料として用いる材料はこのような性質を有する物であれば特に制限はなく、従来、光導電材料において、正孔の電荷輸送材として慣用されているものやＥＬ素子の正孔輸送層に使用される公知のものの中から任意のものを選択して用いることができる。
【００４１】
正孔輸送材料としては、例えばカルバゾール誘導体（Ｎーフェニルカルバゾール、ポリビニルカルバゾールなど。）、トリアリールアミン誘導体（ＴＰＤ、芳香族第３級アミンを主鎖あるいは側鎖に持つポリマー、１，１−ビス（４−ジ−ｐ−トリルアミノフェニル）シクロヘキサン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ジナフチル−４，４’−ジアミノビフェニルなど。）、フタロシアニン誘導体（無金属、銅フタロシアニンなど）、ポリシランなどがあげられる。本発明の有機ＥＬ素子における電子を輸送する層において、複数の電子輸送材料を使用する場合は、ゲルマシクロペンタジエン誘導体ばかりでなく、他の電子輸送材料を用いても良い。このような電子輸送材料について特に制限はなく、従来公知の化合物の中から任意のものを選択して用いる事ができる。電子輸送材料の好ましい例としては、下記化８
【化８】
【００４２】
【化９】
【化１０】
などの化合物（ジャーナル・アプライド・フィジックス(J.Apply.Phys.),27,269(1988)などに記載のもの。）や、オキサジアゾール誘導体（ジャパニーズ・ジャーナル・オブ・アプライド・フィジックス（Jpn.J.Appl.Phys.）,27,L713(1988)、アプライドフィジックスレター(Appl.Phys.Lett.),55,1489(1989)に記載のもの）、チオフェン誘導体（特開平４−２１２２８６号公報などに記載のもの。）、トリアゾール誘導体（ジャパニーズ ジャーナル オブ アプライド フィジックス（Jpn.J.Appl.Phys.),32,L917(1993)などに記載のもの。）、チアジアゾール誘導体（第４３回高分子学会予稿集、IIIＰ１ａ００７などに記載のもの。）、オキシン誘導体の金属錯体（電子情報通信学会技術研究報告、92(311),43(1992)などに記載のもの）、キノキサリン誘導体のポリマー（ジャパニーズ ジャーナル オブ アプライド フィジックス（Jpn.J.Appl.Phys.）,33,L250(1994)などに記載のもの。）、フェナントロリン誘導体（第４３回高分子討論会予稿集、１４Ｊ０７などに記載のもの）などを挙げることができる。
【００４５】
本発明に用いる発光材料には、高分子学会編 高分子機能材料シリーズ”光機能材料”、共立出版(1991)、P236 に記載されているような昼光蛍光材料、蛍光増白剤、レーザー色素、有機シンチレータ、各種の蛍光分析試薬などの公知の発光材料を用いることができるが、具体的には、アントラセン、フェナントレン、ピレン、クリセン、ペリレン、コロネン、ルブレン、キナクリドンなどの多環縮合化合物、クオーターフェニルなどのオリゴフェニレン系化合物、１，４−ビス（２−メチルスチリル）ベンゼン、１，４−ビス（４−メチルスチリル）ベンゼン、１，４−ビス（４−メチル−５−フェニル−２−オキザゾリル）ベンゼン、１，４−ビス（５−フェニル−２−オキサゾリル）ベンゼン、２，５−ビス（５−タシャリー−ブチル−２−ベンズオキサゾリル）チオフェン、１，４−ジフェニル−１，３−ブタジエン、１，６−ジフェニル−１，３，５−ヘキサトリエン、１，１，４，４−テトラフェニル−１，３，−ブタジエンなどの液体シンチレーション用シンチレータ、特開昭63-264692 号公報記載のオキシン誘導体の金属錯体、クマリン染料、ジシアノメチレンピラン染料、ジシアノメチレンチオピラン染料、ポリメチン染料、オキソベンズアントラセン染料、キサンテン染料、カルボスチリル染料およびペリレン染料、独国特許2534713 公報に記載のオキサジン系化合物、第４０回応用物理学関係連合講演会講演予稿集、1146(1993)に記載のスチルベン誘導体および特開平4-363891号公報記載のオキサジアゾール系化合物が好ましい。また、本発明のシクロペンタジエン誘導体を用いても良い。
【００４６】
本発明の有機ＥＬ素子は従来行われている方法により作製することができる。以下に本発明に好適な方法のを例示する。
【００４７】
陽極／該シクロペンタジエン誘導体層／陰極からなるＥＬ素子を以下のようにして作製することができる。まず適当な基板上に、所望の電極物質、例えば陽極用物質からなる薄膜を、１μｍ以下、好ましくは１０〜２００ｎｍの範囲の膜厚になるように、蒸着やスパッタリングなどの方法により形成させ、陽極を作製したのち、この上にシクロペンタジエン誘導体の薄膜を形成させる。薄膜化の方法としては、例えば、浸漬塗工法、スピンコート法、キャスト法、蒸着法等があるが、より均質な膜が得られやすく、より不純物が混ざり難くかつピンホールが生成しにくいなどの点から蒸着法がより好ましい。
【００４８】
次に、このシクロペンタジエン誘導体層の形成後、その上に陰極用物質からなる薄膜を、１μｍ以下、例えば蒸着やスパッタリング等の方法により形成させ、陰極を設けることにより、所望の有機ＥＬ素子を得ることができる。なお、この有機ＥＬ素子の作製においては、作製順序を逆にして、陰極、該シクロペンタジエン誘導体層、陽極の順に作製することも可能である。
このようにして得られたＥＬ素子に直流電圧を印加すると、発光が透明または半透明の電極側より観測できる。さらに、交流電圧を印加することによっても発光する。なお印加する交流の波形は任意でよい。
【００４９】
【実施例】
以下に実施例にて本発明を具体的に説明するが、本発明は下記の実施例に限定されるものではない。
【００５０】
実施例１
２５ｍｍ×７５ｍｍ×１．１ｍｍのガラス基板上にＩＴＯを蒸着法にて５０ｎｍの厚さで製膜したもの（東京三容真空（株）製）を透明支持基板とした。
この透明支持基板を市販の蒸着装置（真空機工（株）製）の基板ホルダーに固定し、石英製のるつぼにＴＰＤをいれ、さらに別のるつぼに１，１−ジメチル−２，３，４，５−テトラフェニルゲルマシクロペンタジエン（以下ＴＰＧと略記する。）を入れて真空槽を１×１０-4Ｐａまで減圧した。
こののち、ＴＰＤ入りのるつぼを加熱し、膜厚５０ｎｍになるようにＴＰＤを蒸着したのち、さらにこの上に、ＴＰＧ入りのるつぼを加熱して、膜厚５０ｎｍになるようにＴＰＧを蒸着した。蒸着速度は０．１〜０．２ｎｍ／秒であった。その後真空槽を２×１０-4Ｐａまで減圧たのち、グラファイト性のるつぼを用い、マグネシウムを１．２〜２．４ｎｍ／秒の蒸着速度で、同時にさらに別のるつぼから銀を０．１〜０．２ｎｍ／秒の蒸着速度で蒸着し、発光層の上にマグネシウムと銀の混合金属電極の対向電極とし、素子を形成した。
ＩＴＯ電極を陽極、マグネシウムと銀の混合電極を陰極として、得られた素子に、直流電圧を印加すると電流が流れ、緑色の発光を得た。
【００５１】
実施例２
ＴＰＧを９，９’−スタナスピロビフルオレンに代えた以外は実施例１と同様な方法で素子を作成した。得られた素子に、直流電圧を印加すると電流が流れ、青紫色の発光を得た。
【００５２】
実施例３
ＴＰＧを９，９’−ゲルマスピロビフルオレンに代えた以外は実施例１と同様な方法で素子を作成した。得られた素子に、直流電圧１７Ｖを印加すると約５０ｍＡ／ｃｍ2の電流が流れ、約１００ｃｄ／ｍ2の青色の発光を得た。
【００５３】
実施例４
ＴＰＧを１，１ージエチルー２，３，４，５ーテトラフェニルスタナシクロペンタジエンに代えた以外は実施例１と同様な方法で素子を作成した。得られた素子に、直流電圧を印加すると電流が流れ、緑色の発光を得た。
【００５４】
実施例５
実施例１で用いた透明支持基板を蒸着装置の基板ホルダーに固定し、石英製のるつぼにＴＰＤ、別のるつぼに９，９’−ゲルマスピロビフルオレン、さらに別のるつぼに４，４’−ビス（２，２−ジフェニルビニル）ビフェニル（以下ＤＰＶＢｉと略記する）を入れて真空槽を１×１０-4Ｐａまで減圧した。
まず、ＴＰＤ入りのるつぼを加熱し、膜厚５０ｎｍになるようにＴＰＤを蒸着した。この上に、ＤＰＶＢｉ入りのるつぼを加熱して膜厚２０ｎｍになるようにＤＰＶＢｉを蒸着し、さらに、この上に９，９’−スピロビゲルマフルオレン入りのるつぼを加熱して膜厚３０ｎｍになるように蒸着した。蒸着速度は０．１〜０．２ｎｍ／秒であった。
その後真空槽を２×１０-4Ｐａまで減圧したのち、グラファイト性のるつぼから、マグネシウムを１．２〜２．４ｎｍ／秒の蒸着速度で、同時にもう一方のるつぼから銀を０．１〜０．２ｎｍ／秒の蒸着速度で蒸着し、マグネシウムと銀の混合金属電極を発光層の上に２００ｎｍ積層蒸着し対向電極とし、素子を形成した。
ＩＴＯ電極を陽極、マグネシウムと銀の混合電極を陰極として、得られた素子に、直流電圧を印加すると電流が流れ青色の発光を得た。発光スペクトルはＤＰＶＢｉの蒸着膜の蛍光スペクトルと一致した。
【００５５】
実施例６
ＤＰＶＢｉをＡｌｑ代えた以外は実施例５と同様な方法で素子を作成した。得られた素子に、直流電圧を印加すると電流が流れ緑色の発光を得た。
【００５６】
実施例７
実施例１で用いた透明支持基板を蒸着装置の基板ホルダーに固定し、石英製のるつぼにＴＰＤ、別のるつぼにＴＰＧ、さらにもう１つのるつぼにナイルレッドを入れて真空槽を１×１０-4Ｐａまで減圧した。
ＴＰＤ入りのるつぼを加熱し、膜厚５０ｎｍになるようにＴＰＤを蒸着した。この上に、ＴＰＧとナイルレッドのるつぼを共に加熱して膜厚５０ｎｍになるように蒸着した。ＴＰＧの蒸着速度は０．１〜０．２ｎｍ／秒であり、ナイルレッドのそれはＴＰＧの１００分の１であった。
その後真空槽を２×１０-4Ｐａまで減圧したのち、グラファイト性のるつぼから、マグネシウムを１．２〜２．４ｎｍ／秒の蒸着速度で、同時にもう一方のるつぼから銀を０．１〜０．２ｎｍ／秒の蒸着速度で蒸着し、マグネシウムと銀の混合金属電極を発光層の上に２００ｎｍ積層蒸着し、対向電極とし素子を作製した。
ＩＴＯ電極を陽極、マグネシウムと銀の混合電極を陰極として、得られた素子に、直流電圧印加すると電流が流れの赤橙色の発光を得た。
【００５７】
実施例８
実施例１で用いた透明支持基板を市販のスピンナー（協栄セミコンダクター（株）製）に固定し、ポリビニルカルバゾール５０重量部、９，９’−ゲルマスピロビフルオレン５０重量部を１，２−ジクロロエタンに溶解したものを５０００ｒｐｍで塗布した。その後、この基板を１０-1Ｐａの減圧下５０℃にて乾燥後、蒸着装置の基板ホルダーに固定した。
その後真空槽を２×１０-4Ｐａまで減圧したのち、グラファイト性のるつぼから、マグネシウムを１．２〜２．４ｎｍ／秒の蒸着速度で、同時にもう一方のるつぼから銀を０．１〜０．２ｎｍ／秒の蒸着速度で蒸着し、マグネシウムと銀の混合金属電極を発光層の上に２００ｎｍ積層蒸着し、対向電極とし、素子を形成した。
ＩＴＯ電極を陽極、マグネシウムと銀の混合電極を陰極として、得られた素子に、直流電圧を印加すると電流が流れ、紫色の発光を得た。
【００５８】
実施例９
ポリビニルカルバゾール５０重量部、９，９’−ゲルマスピロビフルオレン５０重量部の１，２−ジクロロエタン溶液に代えて、ポリビニルカルバゾール５０重量部、９，９’−ゲルマスピロビフルオレン５０重量部、クマリン６（ＫＯＤＡＫ社製）１重量部の１，２−ジクロロエタン溶液を用いた以外は実施例８に同様な方法で素子を作成した。得られた素子に、直流電圧を印加すると電流が流れ緑色の発光を得た。
【００５９】
実施例１０
クマリン６をペリレンに代えた以外は実施例９と同様な方法で素子を作成した。得られた素子に、直流電圧を印加すると電流が流れ青色の発光を得た。
【００６０】
実施例１１
クマリン６をナイルレッドに代えた以外は実施例９と同様な方法で素子を作成した。得られた素子に、直流電圧を印加すると電流が流れ橙色の発光を得た。
【００６１】
実施例１２
ＤＰＶＢｉを９，９’−ゲルマスピロビフルオレンに、９，９’−ゲルマスピロビフルオレンをＡｌｑに代えた以外は実施例５と同様の方法で素子を作成した。得られた素子に、直流電圧を１０Ｖ印加すると約３００ｍＡ／ｃｍ２の電流 が流れ、約１７００ｃｄ／ｍ２の紫色の発光を得た。発光スペクトルは、ＴＰＤ 蒸着膜の蛍光スペクトルとほぼ一致し、発光波長は４０５ｎｍであった。
【００６２】
実施例１３
実施例１で用いた透明支持基板を蒸着装置の基板ホルダーに固定し、石英製のるつぼにＴＰＤ４０重量部、９，９’−ゲルマスピロビフルオレン６０重量部及びクマリン６を１重量部入れて真空槽を１×１０-4Ｐａまで減圧した。
このるつぼを加熱し、膜厚１００ｎｍになるように蒸着した。蒸着速度は１〜１．２ｎｍ／秒であった。
その後真空槽を２×１０-4Ｐａまで減圧してから、グラファイト性のるつぼから、マグネシウムを１．２〜２．４ｎｍ／秒の蒸着速度で、同時にもう一方のるつぼから銀を０．１〜０．２ｎｍ／秒の蒸着速度で蒸着し、マグネシウムと銀の混合金属電極を発光層の上に２００ｎｍ積層蒸着し、対向電極とし、素子を形成した。
ＩＴＯ電極を陽極、マグネシウムと銀の混合電極を陰極として、得られた素子に、直流電圧を印加すると電流が流れ緑色の発光を得た。
【００６３】
【発明の効果】
本発明のシクロペンタジエン誘導体を電子輸送材料として用いた有機電界発光素子は、従来の電子輸送材料を使用した素子よりも電子輸送性に優れ、低電圧で高輝度な発光することができる。これらを用いることにより、フルカラーのフラットパネルディスプレー等の発光素子が作成できる。
【化７】
BACKGROUND OF THE INVENTION
The present invention relates to an electroluminescent (ELECTROLUMINESCENCE, hereinafter abbreviated as EL) device, and more particularly to an organic EL device using a cyclopentadiene derivative.
[0002]
[Prior art]
In recent years, organic EL elements have attracted attention as candidates for unprecedented high-brightness flat displays, and their research and development have been activated. The organic EL element has a structure in which an organic light emitting layer is sandwiched between two electrodes, and holes injected from the anode and electrons injected from the cathode recombine in the light emitting layer to emit light. Organic materials used include low-molecular materials and high-molecular materials, and both are known to provide high-brightness organic EL elements.
[0003]
There are two types of such organic EL elements. One is the addition of a fluorescent dye published by CWTang et al. In the charge transport layer (J. Appl. Phys., 65, 3610 (1989)). One uses a fluorescent dye alone (for example, an element described in Japanese Journal of the Applied Physics (Jpn. J. Appl. Phys.), 27, L269 (1988)). In the latter element, the luminous efficiency is improved when the fluorescent dye is laminated with a hole transport layer that transports only holes that are one of electric charges and / or an electron transport layer that transports only electrons. It is shown.
[0004]
As for the hole transport material used for the organic EL element, although a wide variety of materials are known centering on triphenylamine derivatives, few are known about the electron transport material. An existing electron transport material is an existing hole transport material such as N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diaminobiphenyl (hereinafter abbreviated as TPD). However, when used in an organic EL device, the performance was limited by the electron transport material used, and sufficient device characteristics could not be extracted.
[0005]
Specific examples of conventional electron transport materials include metal complexes of oxine derivatives (described in JP-A-59-194393), 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1 3,4-oxadiazole (hereinafter abbreviated as PBD) and the like are known. The former can drive the organic EL element at a relatively low voltage, but it is not yet sufficient, and since its own light emission is green, it is not practical for a full color display. As an example of using the latter as an electron transport layer, the organic EL device described in Japanese Journal of the Applied Physics (Jpn.J.Appl.Phys.), 27, L269 (1988) can be cited, but crystallization is likely to occur. It has been pointed out that the stability of the thin film is poor.
[0006]
In order to solve this problem, a compound having a plurality of oxadiazole rings (Journal of Chemical Society of Japan, 11, 1540 (1991), JP-A-6-145658, JP-A-6-92947, JP-A-5-152072, JP-A-5-202011) And those described in Japanese Patent Application Laid-Open No. 6-136359, etc.) have been developed, but these have not had practically sufficient properties such as high driving voltage. Further, it has been reported that dimerization of a quinoxaline derivative (JP-A-6-207169) can increase the molecular weight and improve the stability of the thin film, but the driving voltage is still high and not sufficient for practical use.
[0007]
Cyclopentadiene derivatives (Appl. Phys. Lett.,56, 799 (1990), 1,2,3,4,5-pentacyclopentadiene) have been reported, but a device having high efficiency and high light emission has not been obtained.
[0008]
As described above, the electron transport material used in the conventional organic EL element is inferior in electron transport ability and insufficient in full color display, thin film stability, drive voltage, light emission efficiency, and the like. It is necessary to increase the efficiency of the organic EL element by using an excellent material, and it is considered that first of all, it is necessary to have an excellent electron transport capability.
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide an organic EL device having a low voltage and high luminous efficiency.
[0010]
[Means for Solving the Problems]
As a result of intensive investigations to solve the above-mentioned problems of conventional organic EL devices, the present inventors have achieved low voltage and high luminous efficiency by using stanacyclopentadiene rings or germanacyclopentadiene ring derivatives. As a result, the present invention was completed.
[0011]
As a result of various studies conducted by the present inventors on the reason why a stanacyclopentadiene ring or a germanacyclopentadiene ring is suitable as an organic EL device, it is the least unoccupied compared to the corresponding cyclopentadiene ring, thiophene ring, pyrrole ring or furan ring. Semi-empirical molecular orbital calculation revealed that the structure has a low molecular orbital and easily accepts electrons. However, in addition, it is considered that the structure of the stanacyclopentadiene ring or the germanacyclopentadiene ring has an effect on the electron transport property.
[0012]
The present invention relates to a cyclopentadiene derivative represented by the following chemical formula 3Using at least one of the above as a component of the hole blocking layerElectroluminescent deviceIs.
[0013]
[Chemical Formula 3]
[Wherein A is Ge or Sn;X and Y are each independently a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, a substituted or unsubstituted aryl group,OrSubstituted or unsubstituted heterocycleAndX and Y combine to saturateYoungForms an unsaturated ringMay be;R1~ R4Are each independently hydrogen, halogen, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl Group, alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, Aryl group, heterocyclic group, alkenyl group, alkynyl group, nitro group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group,AlsoIs a cyano groupAnd these groups areIf adjacentAdjacent groups join togetherSubstituted or unsubstituted ringMay form. ]
[0015]
Of the cyclopentadiene derivatives represented by Chemical Formula 3, at least one of them can be used as a charge transport layer of an electroluminescent device, or at least one of them can be used as a component of a light emitting layer of an electroluminescent device. You can also.
[0016]
The present invention is described in detail below.
The cyclopentadiene derivative used in the present invention can be obtained, for example, by the following production method. That is,
[0017]
[Formula 4]
[Wherein R1And R2Are each independently hydrogen, halogen, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, alkoxy group, aryloxy group, perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl Group, alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfinyl group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, Aryl group, heterocyclic group, alkenyl group, alkynyl group, nitro group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group Ku is a structure substituted or the unsubstituted rings are condensed is when a cyano group or adjacent. ] Is reacted with an alkali metal or a complex thereof, followed by general formula 5
[0019]
[Chemical formula 5]
[Wherein, A represents germanium or tin, and X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a substituted or It represents an unsubstituted aryl group, a substituted or unsubstituted heterocycle, or X and Y are bonded to form a saturated or unsaturated ring. The target cyclopentadiene derivative is obtained by allowing the chloride represented by
[0021]
As the acetylene derivative used here, a derivative having a substituent that hardly inhibits the reaction between an alkali metal or a complex thereof and acetylene can be preferably used. The substituent is particularly preferably inert to an alkali metal or a complex thereof. Examples of the alkali metal or complex thereof used include lithium, sodium, potassium, lithium naphthalenide, sodium naphthalenide, potassium naphthalenide, lithium 4,4′-ditertiary butyl-2,2′-biphenylide or And lithium (N, N-dimethylamino) naphthalenide. The solvent used is not particularly limited as long as it is inactive to an alkali metal or an alkali metal complex, and usually an ether solvent such as ether or tetrahydrofuran is used. This series of reactions is preferably performed in an inert gas stream, and nitrogen or argon gas is used. The reaction may be traced by a general analytical means such as NMR or chromatography to determine the end point of the reaction.
[0022]
In the compound used in the present invention, when a benzene ring is condensed to a cyclopentadiene ring, a method different from the above production method is used. Known methods that have been known so far can be used. For example, the following methods can be exemplified. That is,
[0023]
[Chemical 6]
[Wherein X represents chlorine, bromine or iodine;1To R8Each independently represents a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, fluorine, hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group. When adjacent to a ring, a cyano group, a saturated or unsaturated ring is formed. An alkali metal, alkaline earth metal or alkali metal complex is allowed to act on the 2,2′-dihalogenobiphenyl derivative represented by the following formula:
[0025]
[Chemical 7]
[Wherein, A represents germanium or tin, and X and Y each independently represent a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a substituted or It represents an unsubstituted aryl group, a substituted or unsubstituted heterocycle, or X and Y are bonded to form a saturated or unsaturated ring. The cyclopentadiene derivative used in the present invention can be obtained by reacting a dichlorogermanium derivative or a dichlorostannane derivative represented by the formula: Examples of the metal used here include lithium, sodium, magnesium, and potassium, and examples of the metal complex include normal butyl lithium, tertiary butyl lithium, and phenyl lithium. The substituent of the 2,2'-dihalogenobiphenyl derivative used is not particularly limited as long as it is inert to the alkali metal, alkaline earth metal or alkali metal complex under the reaction conditions. There is no particular limitation on the reaction temperature when the alkali metal, alkaline earth metal or alkali metal complex is allowed to act, and the reaction is usually carried out at 0 ° C. or lower. However, when a substituent such as a highly reactive cyano group is present, a low temperature is preferred, and it is usually carried out at -70 ° C or lower. The reaction solvent used is not particularly limited as long as it is inert to alkali metals, alkaline earth metals, or alkali metal complexes, and usually ether solvents such as ether or tetrahydrofuran are used.
[0027]
Substituents attached to the hetero elements of the cyclopentadiene derivative used in the present invention thus obtained include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, cyclopentyl group, and tertiary butyl group. Group, vinyl group, allyl group, butenyl group such as butenyl group or styryl group, alkynyl group such as ethynyl group, propargyl group or phenylacetylin group, alkoxy such as methoxy group, ethoxy group, isopropoxy group or tertiary butoxy group Group, alkenyloxy group such as vinyloxy group or allyloxy group, alkynyloxy group such as ethynyloxy group or phenylacetyloxy group, phenyl group, naphthyl group, anthracenyl group, biphenyl group, toluyl group, pyrenyl group, Aryl groups such as lilenyl group, anisyl group, terphenyl group or phenanthrenyl group, hydrofuryl group, hydropyrenyl group, dioxanyl group, thienyl group, furyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, acridinyl group, quinolyl group, Heterocycles such as a quinoxaloyl group, a phenanthrolyl group, a benzothienyl group, a benzothiazolyl group, an indolyl group, a germacyclopentadienyl group, or a pyridyl group. Further, these substituents may be bonded to each other at an arbitrary position to form a spiro ring.
[0028]
Substituents on the carbon of the cyclopentadiene ring include hydrogen, halogen such as fluorine or chlorine, methyl group, ethyl group, normal propyl group, isopropyl group, cyclopentyl group, or alkyl group such as tertiary butyl group, vinyl group Alkenyl group such as allyl group, butenyl group or styryl group, alkynyl group such as ethynyl group, propargyl group or phenylacetylin group, alkoxy group such as methoxy group, ethoxy group, isopropoxy group or tertiary butoxy group, vinyloxy group Or an alkenyloxy group such as an allyloxy group, an alkynyloxy group such as an ethynyloxy group or a phenylacetyloxy group, an aryloxy group such as a phenoxy group, a naphthoxy group, a biphenyloxy group or a pyrenyloxy group Perfluoro group such as trifluoromethyl group, trifluoromethoxy group or pentafluoroethoxy group, amino group such as dimethylamino group, diethylamino group or diphenylamino group, ketone such as acetyl group or benzoyl group, acetoxy group or benzoyloxy group Ester group such as methoxycarbonyl group, ethoxycarbonyl group or phenoxycarbonyl group, sulfinyl group such as methylsulfinyl group or phenylsulfinyl group, trimethylsilyl group, dimethyl tertiary butylsilyl group, trimethoxysilyl group or triphenyl Silyl group such as silyl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, pyrenyl group, toluyl group, anisyl group, Aryl group such as fluorophenyl group, diphenylaminophenyl group, dimethylaminophenyl group, diethylaminophenyl group or phenanthrenyl group, thienyl group, furyl group, germacyclopentadienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, acridinyl Group, quinolyl group, quinoxaloyl group, phenanthrolyl group, benzothienyl group, benzothiazolyl group, indolyl group, carbazolyl group, pyridyl group, pyrrolyl group, benzoxazolyl group, pyrimidyl group or imidazolyl group, heterocycle, nitro group, formyl Group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, thiocyanate group, isothiocyanate group or cyano group. Further, these substituents may be bonded to each other at any place to form a ring.
These substituents may be introduced before the formation of the cyclopentadiene ring or after the formation of the cyclopentadiene ring.
[0029]
The following can be illustrated as an example of a cyclopentadiene derivative used in the present invention.
1,1-dimethyl-2,3,4,5-tetraphenylgermacyclopentadiene
1,1-diethyl-2,3,4,5-tetrakis (2-methylphenyl) germacyclopentadiene
1,1-diisopropyl-2,3,4,5-tetrakis (3-methylphenyl) germacyclopentadiene
1-ethyl-1-methyl-2,3,4,5-tetrakis (4-methylphenyl) germacyclopentadiene
1,1-ditertiary butyl-2,3,4,5-tetrakis (2-ethylphenyl) germacyclopentadiene
1,1-diphenyl-2,3,4,5-tetrakis (3-ethylphenyl) germacyclopentadiene
1-methyl-1-phenyl-2,3,4,5-tetrakis (4-ethylphenyl) germacyclopentadiene
[0030]
1-phenyl-1-tertiarybutyl-2,3,4,5-tetrakis (3-tertiarybutylphenyl) germacyclopentadiene
1,1-dimethyl-2,5-bis (3-methylphenyl) -3,4-diphenylgermacyclopentadiene
1,1-di (4-toluyl) -2,5-bis (4-methylphenyl) -3,4-diphenylgermacyclopentadiene
1-germacyclohexane-1-spiro 2 ', 5'-di (2-biphenyl) -3', 4'-diphenyl-1'-germacyclopentadiene
1-germacyclopentane-1-spiro 2 ', 5'-di (3-biphenyl) -3', 4'-diphenyl-1'-germacyclopentadiene
9-germafluorene-9-spiro-2 ', 5'-di (4-biphenyl) -3', 4'-diphenyl-1'-germacyclopentadiene
1,1-dimethyl-2,5-bis (2-trifluoromethylphenyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis (3-fluorophenyl) -3,4-diphenylgermacyclopentadiene
[0031]
1,2-bis (1-methyl-2,5-bis (3-methoxyphenyl) -3,4-diphenylgermacyclopentadienyl) ethane
1,1-dimethyl-2,5-bis (4-cyanophenyl) -3,4-diphenylstanacyclopentadiene
1,1-dimethyl-2,5-bis {2- (2-benzoxazolyl) phenyl} -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis {3- (2-benzothienyl) phenyl} -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis {4- (2-benzofuryl) phenyl} -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis {2- (2-benzothiazolyl) phenyl} -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis {3- (2-benzimidazolyl) phenyl} -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis {4- (2-indolyl) phenyl} -3,4-diphenylgermacyclopentadiene
[0032]
1,1-dimethyl-2,5-bis {3- (5-methoxy-2-benzothiazolyl) phenyl} -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-di (1-naphthyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-di (2-methyl-1-naphthyl) -3,4-diphenylstanacyclopentadiene
1,1-dimethoxy-2,5-di (2-naphthyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-di (2-benzothienyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis (3-methyl-2-benzothienyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis (3-phenyl-2-benzothienyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis (2-methyl-3-benzothienyl) -3,4-diphenylgermacyclopentadiene
1,1-Dimethyl-2,5-di (2-benzothiazolyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-di (2-benzoxazolyl) -3,4-diphenylgermacyclopentadiene
[0033]
1,1-Dimethyl-2,5-bis (5-methyl-2-benzoxazolyl) -3,4-diphenylstanacyclopentadiene
1,1-Dimethyl-2,5-bis (5-phenyl-2-benzothiadiazolyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-di (3-benzofuranyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis (3,4-difluorophenyl) -3,4-diphenylgermacyclopentadiene
1,1-dimethyl-2,5-bis (3,4,5-trifluorophenyl) -3,4-diphenylstanacyclopentadiene
1,1-dimethyl-2,5-bis (2,3,4,5,6-pentafluorophenyl) -3,4-diphenylgermacyclopentadiene
5,5'-dibromo-1,1,1 ', 1'-tetraethyl-3,3', 4,4'-tetraphenyl-2,2'-bigermol
5,5'-dimethyl-1,1,1 ', 1'-tetraethyl-3,3', 4,4'-tetraphenyl-2,2'-vistanol
5,5 ′ ″-dibromo-1,1,1 ′, 1 ′, 1 ″, 1 ″, 1 ′ ″, 1 ′ ″-octaethyl-3,3 ′, 3 ″, 3 ′ '', 4,4 ', 4' ', 4' ''-octaphenyl-2,2 ': 5', 2 '': 5 '', 2 '' '-quarter gel mall
9,9'-germaspirobifluorene
9,9'-stanaspirobifluorene
9,9-diphenyl-9-stanafluorene
9,9-Dinaphthyl-9-germafluorene
[0034]
There are various configurations for the EL element of the present invention. Basically, the cyclopentadiene derivative is sandwiched between a pair of electrodes (anode and cathode). A transport material, a light-emitting material, and an electron transport material may be added or stacked as separate layers.
[0035]
Specific examples include anode / cyclopentadiene derivative layer / cathode, anode / hole transport layer / cyclopentadiene derivative layer / cathode, anode / hole transport layer / light emitting layer / cyclopentadiene derivative layer / cathode, anode / hole transport. Examples include material + light emitting material + cyclopentadiene derivative layer / cathode. Another special use of cyclopentadiene derivatives is application to hole blocking materials. The hole blocking material is a material that transports only electrons out of two charges of electrons and holes and does not transmit or hardly transmit holes. Since the cyclopentadiene derivative used in the present invention transports electrons preferentially or selectively, other specific examples of the organic EL device of the present invention include an anode / hole transport layer / cyclopentadiene derivative layer / electron transport layer. / Cathode etc. In this case, light is emitted from the hole transport layer or the cyclopentadiene derivative layer. In particular, examples of the cyclopentadiene derivative exhibiting such hole blocking effect include those having a short emission wavelength. For example, 9,9'-germaspirobifluorene and the like can be mentioned. In an element using 9,9′-germaspirobifluorene as a hole blocking layer, TPD as a hole transport layer, and 8-hydroxyquinoline aluminum (hereinafter abbreviated as Alq) as an electron transport layer, The emission is only purple due to the emission of TPD, and has a very good hole blocking ability. As a device for emitting TPD as described above, there is a device using a triazole derivative by Kido et al. (Kido, et. Al. Science, 267, 1332 (1995)), but it is not perfect. As a more specific example, the cyclopentadiene derivative layer used in the present invention can be used as a light emitting layer or an electron transporting light emitting layer. The structure of the element in this case includes anode / hole transport layer / (cyclopentadiene derivative + electron transport material) layer / cathode.
[0036]
Any of the elements of the present invention is preferably supported by a substrate, and the substrate is not particularly limited, and those conventionally used for EL elements such as glass, transparent plastic, conductive polymer, or the like Those made of quartz or the like can be used.
[0037]
Each layer used in the present invention can be formed by thinning it by a known method such as vapor deposition or coating.
The thickness of the thin film of each layer formed in this way is not particularly limited and can be appropriately selected according to the situation, but is usually selected in the range of 2 nm to 5000 nm.
[0038]
As the anode in the EL element of the present invention, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, CuI, and SnO.2, ZnO, ITO (indium oxide), and other dielectric transparent materials. The anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. When light emission is extracted from this electrode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the electrode is preferably several hundred Ω / square or less. Although the film thickness depends on the material, it is preferably in the range of 10 nm to 1 μm, more preferably 10 to 200 nm.
[0039]
As the cathode, a material using a metal, an alloy, an electrically conductive compound, and a mixture thereof having a low work function (4.3 eV or less) as an electrode material is used. Specific examples of such electrode materials include calcium, magnesium, lithium, aluminum, magnesium alloy, lithium alloy, aluminum alloy, aluminum / lithium mixture, magnesium / silver mixture, indium and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as an electrode is preferably several hundred Ω / square or less, preferably 10 nm to 1 μm, more preferably 50 to 200 nm.
[0040]
The configuration of the organic EL device of the present invention has various modes as described above. However, when a hole transport layer is provided, the light emission efficiency is improved.
The hole transport material used for the hole transport layer can be appropriately transferred to the light emitting layer when holes are injected from the anode placed between two electrodes to which an electric field is applied. A compound, for example 10Four-106When an electric field of V / cm is applied, at least 10-6cm2Those having a hole mobility of / V · sec or more are preferable. The material used as the hole transport material is not particularly limited as long as it has such properties. Conventionally, a photoconductive material commonly used as a hole charge transport material or a hole transport layer of an EL element is used. An arbitrary one can be selected and used from known ones used in the above.
[0041]
Examples of the hole transport material include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), triarylamine derivatives (TPD, polymers having aromatic tertiary amines in the main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, etc.), phthalocyanine derivatives (metal free, copper phthalocyanine, etc.), polysilane Etc. In the case of using a plurality of electron transport materials in the layer for transporting electrons in the organic EL device of the present invention, not only the germanacyclopentadiene derivative but also other electron transport materials may be used. There is no restriction | limiting in particular about such an electron transport material, Arbitrary things can be selected and used from a conventionally well-known compound. Preferred examples of the electron transport material include8
[Chemical 8]
[0042]
[Chemical 9]
Embedded image
Such as compounds described in Journal Applied Physics (J.Apply. Phys.), 27,269 (1988), and oxadiazole derivatives (Japanese Journal of Applied Physics (Jpn.J. Appl. Phys.), 27, L713 (1988), Applied Physics Letter (Appl. Phys. Lett.), 55, 1489 (1989)), thiophene derivatives (described in JP-A-4-212286, etc.) ), Triazole derivatives (described in Japanese Journal of Applied Physics (Jpn.J.Appl.Phys.), 32, L917 (1993), etc.), thiadiazole derivatives (43th Polymer Society Proceedings, IIIP1a007, etc.), metal complexes of oxine derivatives (described in IEICE Technical Report, 92 (311), 43 (1992), etc.), quinoxaline derivative polymers (Japanese -Null of Applied Physics (described in Jpn.J.Appl.Phys.), 33, L250 (1994), etc.), phenanthroline derivatives (described in the 43rd Annual Meeting of the Polymeric Debate, 14J07, etc.), etc. Can be mentioned.
[0045]
Luminescent materials used in the present invention include daylight fluorescent materials, fluorescent brighteners, laser dyes as described in Polymer Functional Materials Series “Functional Functional Materials”, Kyoritsu Shuppan (1991), P236. In addition, known luminescent materials such as organic scintillators and various fluorescent analysis reagents can be used. Specifically, polycyclic condensed compounds such as anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene, and quinacridone, and quarters can be used. Oligophenylene compounds such as phenyl, 1,4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-methyl-5-phenyl-2-) Oxazolyl) benzene, 1,4-bis (5-phenyl-2-oxazolyl) benzene, 2,5-bis (5-tert-butyl-2-butyl) Benzoxazolyl) thiophene, 1,4-diphenyl-1,3-butadiene, 1,6-diphenyl-1,3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3,- Scintillators for liquid scintillation such as butadiene, metal complexes of oxine derivatives described in JP-A-63-264692, coumarin dyes, dicyanomethylenepyran dyes, dicyanomethylenethiopyran dyes, polymethine dyes, oxobenzanthracene dyes, xanthene dyes, carbo Styryl dyes and perylene dyes, oxazine compounds described in German Patent 2534713, Proceedings of the 40th Joint Conference on Applied Physics, Stilbene Derivatives described in 1146 (1993), and JP-A-4-363891 Of these, oxadiazole compounds are preferred. Further, the cyclopentadiene derivative of the present invention may be used.
[0046]
The organic EL device of the present invention can be produced by a conventional method. The method suitable for the present invention will be exemplified below.
[0047]
An EL element comprising an anode / the cyclopentadiene derivative layer / cathode can be produced as follows. First, a thin film made of a desired electrode material, for example, an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 10 to 200 nm. After that, a thin film of a cyclopentadiene derivative is formed thereon. Examples of the thinning method include a dip coating method, a spin coating method, a casting method, and a vapor deposition method, but a more uniform film is easily obtained, impurities are less likely to be mixed, and pinholes are not easily generated. From the viewpoint, the vapor deposition method is more preferable.
[0048]
Next, after forming the cyclopentadiene derivative layer, a thin film made of a cathode material is formed thereon by a method of 1 μm or less, for example, by vapor deposition or sputtering, and a cathode is provided to obtain a desired organic EL device. be able to. In the production of this organic EL element, the production order can be reversed, and the cathode, the cyclopentadiene derivative layer, and the anode can be produced in this order.
When a DC voltage is applied to the EL element thus obtained, light emission can be observed from the transparent or translucent electrode side. Furthermore, it emits light when an AC voltage is applied. The applied AC waveform may be arbitrary.
[0049]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
[0050]
Example 1
A transparent support substrate was formed by depositing ITO with a thickness of 50 nm on a glass substrate of 25 mm × 75 mm × 1.1 mm by a vapor deposition method (manufactured by Tokyo Sanyo Vacuum Co., Ltd.).
This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.), TPD is placed in a quartz crucible, and 1,1-dimethyl-2,3,4, 5-Tetraphenylgermacyclopentadiene (hereinafter abbreviated as TPG) is added and the vacuum chamber is 1 × 10.-FourThe pressure was reduced to Pa.
Thereafter, the crucible containing TPD was heated to deposit TPD so as to have a film thickness of 50 nm, and further, the crucible containing TPG was further heated to deposit TPG so as to have a film thickness of 50 nm. The deposition rate was 0.1 to 0.2 nm / second. Then vacuum the tank 2 × 10-FourAfter reducing the pressure to Pa, using a graphite crucible, magnesium is deposited at a deposition rate of 1.2 to 2.4 nm / second, and silver is further deposited at a deposition rate of 0.1 to 0.2 nm / second from another crucible. Vapor deposition was performed to form a device on the light emitting layer as a counter electrode of a mixed metal electrode of magnesium and silver.
When a direct current voltage was applied to the resulting device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, a current flowed and green light emission was obtained.
[0051]
Example 2
A device was prepared in the same manner as in Example 1 except that TPG was replaced with 9,9'-stanaspirobifluorene. When a DC voltage was applied to the obtained device, a current flowed, and blue-violet light emission was obtained.
[0052]
Example 3
A device was prepared in the same manner as in Example 1 except that TPG was replaced with 9,9'-germaspirobifluorene. When a DC voltage of 17 V is applied to the obtained device, it is about 50 mA / cm.2Current of about 100 cd / m2Blue light emission was obtained.
[0053]
Example 4
A device was prepared in the same manner as in Example 1 except that TPG was replaced with 1,1-diethyl-2,3,4,5-tetraphenylstanacyclopentadiene. When a DC voltage was applied to the obtained device, a current flowed and green light emission was obtained.
[0054]
Example 5
The transparent support substrate used in Example 1 was fixed to the substrate holder of the vapor deposition apparatus, TPD was put in a quartz crucible, 9,9'-germaspirobifluorene was put in another crucible, and 4,4'- was put in another crucible. Bis (2,2-diphenylvinyl) biphenyl (hereinafter abbreviated as DPVBi) is added and the vacuum chamber is 1 × 10-FourThe pressure was reduced to Pa.
First, the crucible containing TPD was heated to deposit TPD so as to have a film thickness of 50 nm. On top of this, DPVBi is deposited to a thickness of 20 nm by heating the crucible containing DPVBi, and further, the crucible containing 9,9′-spirobigermafluorene is heated to a thickness of 30 nm. Evaporated as follows. The deposition rate was 0.1 to 0.2 nm / second.
Then vacuum the tank 2 × 10-FourAfter depressurizing to Pa, magnesium is deposited at a deposition rate of 1.2 to 2.4 nm / sec from a graphite crucible, and at the same time, silver is deposited at a deposition rate of 0.1 to 0.2 nm / sec from the other crucible. Then, a mixed metal electrode of magnesium and silver was laminated and deposited to a thickness of 200 nm on the light emitting layer to form a counter electrode, thereby forming an element.
When a direct current voltage was applied to the resulting device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, a current flowed and blue light emission was obtained. The emission spectrum coincided with the fluorescence spectrum of the deposited film of DPVBi.
[0055]
Example 6
A device was prepared in the same manner as in Example 5 except that DPVBi was replaced with Alq. When a DC voltage was applied to the resulting device, a current flowed and green light emission was obtained.
[0056]
Example 7
The transparent support substrate used in Example 1 is fixed to the substrate holder of the vapor deposition apparatus, TPD is put in a quartz crucible, TPG is put in another crucible, and Nile Red is put in another crucible, and the vacuum chamber is 1 × 10.-FourThe pressure was reduced to Pa.
The crucible containing TPD was heated to deposit TPD so as to have a film thickness of 50 nm. On top of this, both TPG and Nile Red crucibles were heated and evaporated to a thickness of 50 nm. The deposition rate of TPG was 0.1 to 0.2 nm / second, and that of Nile Red was 1/100 of that of TPG.
Then vacuum the tank 2 × 10-FourAfter depressurizing to Pa, magnesium is deposited at a deposition rate of 1.2 to 2.4 nm / sec from a graphite crucible, and at the same time, silver is deposited at a deposition rate of 0.1 to 0.2 nm / sec from the other crucible. Then, a mixed metal electrode of magnesium and silver was laminated and deposited on the light emitting layer to a thickness of 200 nm to produce a device as a counter electrode.
When a direct current voltage was applied to the resulting device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, red-orange light emission with current flowing was obtained.
[0057]
Example 8
The transparent support substrate used in Example 1 was fixed to a commercially available spinner (manufactured by Kyoei Semiconductor Co., Ltd.), and 50 parts by weight of polyvinylcarbazole and 50 parts by weight of 9,9′-germaspirobifluorene were added to 1,2-dichloroethane. What was dissolved in was applied at 5000 rpm. Then, this substrate is-1After drying at 50 ° C. under reduced pressure of Pa, it was fixed to a substrate holder of a vapor deposition apparatus.
Then vacuum the tank 2 × 10-FourAfter depressurizing to Pa, magnesium is deposited from a crucible crucible at a deposition rate of 1.2 to 2.4 nm / sec, and at the same time silver is deposited from the other crucible at a deposition rate of 0.1 to 0.2 nm / sec. Then, a mixed metal electrode of magnesium and silver was laminated and deposited on the light emitting layer to a thickness of 200 nm to form a counter electrode, thereby forming an element.
When a direct current voltage was applied to the resulting device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, a current flowed and purple light emission was obtained.
[0058]
Example 9
Instead of 1,2-dichloroethane solution of 50 parts by weight of polyvinyl carbazole and 50 parts by weight of 9,9'-germaspirobifluorene, 50 parts by weight of polyvinylcarbazole, 50 parts by weight of 9,9'-germaspirobifluorene, coumarin 6 A device was prepared in the same manner as in Example 8 except that 1 part by weight of a 1,2-dichloroethane solution (manufactured by KODAK) was used. When a DC voltage was applied to the resulting device, a current flowed and green light emission was obtained.
[0059]
Example 10
A device was prepared in the same manner as in Example 9 except that coumarin 6 was replaced with perylene. When a DC voltage was applied to the obtained device, a current flowed and blue light emission was obtained.
[0060]
Example 11
A device was prepared in the same manner as in Example 9 except that Coumarin 6 was replaced with Nile Red. When a DC voltage was applied to the resulting device, a current flowed and orange light emission was obtained.
[0061]
Example 12
Example except that DPVBi was replaced with 9,9'-germaspirobifluorene and 9,9'-germaspirobifluorene was replaced with Alq5A device was prepared in the same manner as described above. When a DC voltage of 10 V is applied to the obtained device, it is about 300 mA / cm.2Current of about 1700 cd / m2A purple luminescence was obtained. The emission spectrum almost coincided with the fluorescence spectrum of the TPD vapor deposition film, and the emission wavelength was 405 nm.
[0062]
Example 13
The transparent support substrate used in Example 1 was fixed to the substrate holder of the vapor deposition apparatus, and 40 parts by weight of TPD, 60 parts by weight of 9,9′-germaspirobifluorene and 1 part by weight of coumarin 6 were placed in a quartz crucible and vacuumed. 1 × 10 tank-FourThe pressure was reduced to Pa.
This crucible was heated and evaporated to a film thickness of 100 nm. The deposition rate was 1-1.2 nm / second.
Then vacuum the tank 2 × 10-FourAfter depressurizing to Pa, from a graphite crucible, magnesium is deposited at a deposition rate of 1.2 to 2.4 nm / second, and at the same time, silver is deposited from the other crucible at a deposition rate of 0.1 to 0.2 nm / second. Vapor deposition was performed, and a mixed metal electrode of magnesium and silver was deposited on the light emitting layer in a thickness of 200 nm to form a counter electrode, thereby forming an element.
When a direct current voltage was applied to the resulting device using an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, a current flowed and green light emission was obtained.
[0063]
【The invention's effect】
An organic electroluminescent device using the cyclopentadiene derivative of the present invention as an electron transporting material is superior in electron transporting property to a device using a conventional electron transporting material, and can emit light with low voltage and high luminance. By using these, a light emitting element such as a full-color flat panel display can be produced.
[Chemical 7]
Claims (2)
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| JP18865396A JP3755196B2 (en) | 1996-06-28 | 1996-06-28 | Electroluminescent device using cyclopentadiene derivative |
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| Application Number | Priority Date | Filing Date | Title |
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| JP18865396A JP3755196B2 (en) | 1996-06-28 | 1996-06-28 | Electroluminescent device using cyclopentadiene derivative |
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| KR102658368B1 (en) | 2016-12-09 | 2024-04-18 | 삼성디스플레이 주식회사 | Condensed compound and organic light emitting device comprising the same |
| KR102738038B1 (en) | 2017-01-06 | 2024-12-06 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light-emitting device comprising the same |
| KR102504130B1 (en) | 2017-05-23 | 2023-02-28 | 삼성디스플레이 주식회사 | Condensed compound and organic light emitting device comprising the same |
| KR102536248B1 (en) | 2017-06-21 | 2023-05-25 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light emitting device comprising the same |
| KR102415376B1 (en) | 2017-08-04 | 2022-07-01 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| KR102414108B1 (en) | 2017-08-08 | 2022-06-29 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light-emitting device comprising the same |
| KR102552271B1 (en) | 2017-10-27 | 2023-07-07 | 삼성디스플레이 주식회사 | Condensed compound and organic light emitting device comprising the same |
| KR20190049958A (en) | 2017-10-30 | 2019-05-10 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| KR102571084B1 (en) | 2017-10-31 | 2023-08-28 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light-emitting device comprising the same |
| KR102630642B1 (en) | 2018-02-09 | 2024-01-30 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light emitting device comprising the same |
| KR102536246B1 (en) | 2018-03-23 | 2023-05-25 | 삼성디스플레이 주식회사 | Heterocyclic compound and organic light emitting device comprising the same |
-
1996
- 1996-06-28 JP JP18865396A patent/JP3755196B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12538702B2 (en) | 2016-12-13 | 2026-01-27 | Samsung Display Co., Ltd. | Condensed cyclic compound and organic electroluminescence device including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1017860A (en) | 1998-01-20 |
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