JP3663892B2 - Organic electroluminescent device material and organic electroluminescent device using the same - Google Patents
Organic electroluminescent device material and organic electroluminescent device using the same Download PDFInfo
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- JP3663892B2 JP3663892B2 JP05630498A JP5630498A JP3663892B2 JP 3663892 B2 JP3663892 B2 JP 3663892B2 JP 05630498 A JP05630498 A JP 05630498A JP 5630498 A JP5630498 A JP 5630498A JP 3663892 B2 JP3663892 B2 JP 3663892B2
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- 239000000463 material Substances 0.000 title claims description 54
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- 125000005110 aryl thio group Chemical group 0.000 claims description 4
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- 125000000753 cycloalkyl group Chemical group 0.000 description 2
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- NDMVXIYCFFFPLE-UHFFFAOYSA-N anthracene-9,10-diamine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=C(N)C2=C1 NDMVXIYCFFFPLE-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
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- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical group C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 1
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- QRQHCGWCUVLPSQ-UHFFFAOYSA-N bis(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C(C=C1)=CC=C1C1=CC=CC=C1 QRQHCGWCUVLPSQ-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 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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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 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
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 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
- 238000007598 dipping method Methods 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000000434 field desorption mass spectrometry Methods 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
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 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
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- NBGMRMDAEWWFIR-UHFFFAOYSA-N imidazole-2-thione Chemical compound S=C1N=CC=N1 NBGMRMDAEWWFIR-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 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
- 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
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000011133 lead 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
- 238000004519 manufacturing process Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 239000000203 mixture Substances 0.000 description 1
- JULPEDSLKXGZKK-UHFFFAOYSA-N n,n-dimethyl-1h-imidazole-5-carboxamide Chemical group CN(C)C(=O)C1=CN=CN1 JULPEDSLKXGZKK-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- WSRHMJYUEZHUCM-UHFFFAOYSA-N perylene-1,2,3,4-tetracarboxylic acid Chemical class C=12C3=CC=CC2=CC=CC=1C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C2=C1C3=CC=C2C(=O)O WSRHMJYUEZHUCM-UHFFFAOYSA-N 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
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- ARFWEVQMYYLLPJ-UHFFFAOYSA-N phenanthrene-1,2-diamine Chemical compound C1=CC=C2C3=CC=C(N)C(N)=C3C=CC2=C1 ARFWEVQMYYLLPJ-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=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
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 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
- 125000000719 pyrrolidinyl 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
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux 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
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
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- NZFNXWQNBYZDAQ-UHFFFAOYSA-N thioridazine hydrochloride Chemical compound Cl.C12=CC(SC)=CC=C2SC2=CC=CC=C2N1CCC1CCCCN1C NZFNXWQNBYZDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 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
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- 238000002834 transmittance Methods 0.000 description 1
- 125000004784 trichloromethoxy group Chemical group ClC(O*)(Cl)Cl 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
- 125000005580 triphenylene group Chemical group 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001771 vacuum deposition 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は平面光源や表示に使用される有機エレクトロルミネッセンス（ＥＬ）素子に関するものである。
【０００２】
【従来の技術】
有機物質を使用したＥＬ素子は、固体発光型の安価な大面積フルカラー表示素子としての用途が有望視され、多くの開発が行われている。一般にＥＬは、発光層および該層をはさんだ一対の対向電極から構成されている。
発光は、両電極間に電界が印加されると、陰極側から電子が注入され、陽極側から正孔が注入される。さらに、この電子が発光層において正孔と再結合し、エネルギー準位が伝導帯から価電子帯に戻る際にエネルギーを光として放出する現象である。
【０００３】
従来の有機ＥＬ素子は、無機ＥＬ素子に比べて駆動電圧が高く、発光輝度や発光効率も低かった。また、特性劣化も著しく実用化には至っていなかった。
近年、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ＥＬ素子が報告され、関心を集めている（アプライド・フィジクス・レターズ、５１巻、９１３ページ、１９８７年参照）。
この方法では、金属キレート錯体を蛍光体層、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１００ｃｄ／ｍ2 、最大発光効率は１．５ｌｍ／Ｗを達成して、実用領域に近い性能を持っている。しかしながら、現在までの有機ＥＬ素子は、構成の改善により発光強度は改良されているが、未だ充分な発光輝度は有していない。また、寿命が高々１０００時間程度という大きな問題を持っている。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、発光効率が高く、寿命が長い有機ＥＬ素子の提供にある。本発明者らが鋭意検討した結果、一般式［１］で示される化合物の有機ＥＬ素子材料を少なくとも一層に使用した有機ＥＬ素子の発光効率が高く、繰り返し使用時での安定性も優れていることを見いだし本発明に至った。
【０００５】
【課題を解決するための手段】
即ち、本発明は、下記一般式［１］で示される有機エレクトロルミネッセンス素子材料である。
一般式［１］
【０００６】
【化２】
［ただし、式中 n1 〜 n4 は 0〜 3の整数を表す（ただし、n1+n2+n3+n4 = 4 〜 8である。）。Ｒ1 〜Ｒ4 はそれぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、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コキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、置換もしくは未置換の単環基、置換もしくは未置換の縮合多環基、置換もしくは未置換のアミノ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基を表す。］
【０００８】
更に本発明は、一対の電極間に発光層を含む複数層の有機化合物薄膜を形成した有機エレクトロルミネッセンス素子において、少なくとも一層が上記記載の有機エレクトロルミネッセンス素子材料を含有する層である有機エレクトロルミネッセンス素子である。
【０００９】
更に本発明は、一対の電極間に発光層を含む複数層の有機化合物薄膜を形成した有機エレクトロルミネッセンス素子において、発光層が上記記載の有機エレクトロルミネッセンス素子材料を含有する層である有機エレクトロルミネッセンス素子である。
【００１０】
【発明実施の形態】
【００１１】
本発明の一般式［１］で表される化合物のＲ1 〜Ｒ4 はそれぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、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コキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換の単環基、置換もしくは未置換の縮合多環基、置換もしくは未置換のアミノ基、置換もしくは未置換のアルキルアミノ基、置換もしくは未置換のアリールアミノ基である。
【００１２】
本発明における一般式［１］で表される化合物のＲ1 〜Ｒ4 のハロゲン原子の具体例としては、塩素、臭素、ヨウ素、フッ素があり、アルキル基の具体例としては、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、ヘプチル基、オクチル基、ステアリル基、トリクロロメチル基等があり、シクロアルキルの具体例としては、シクロペンタン環、シクロヘキサン環等がある。
【００１３】
本発明における一般式［１］で表される化合物のＲ1 〜Ｒ4 のアルコキシ基の具体例としては、メトキシ基、エトキシ基、ｎ−ブトキシ基、ｔｅｒｔ−ブトキシ基、トリクロロメトキシ基、トリフルオロエトキシ基、ペンタフルオロプロポキシ基、２，２，３，３−テトラフルオロプロポキシ基、１，１，１，３，３，３−ヘキサフルオロ−２−プロポキシ基、６−（パーフルオロエチル）ヘキシルオキシ基等があり、アリールオキシ基の具体例としては、フェノキシ基、ｐ−ニトロフェノキシ基、ｐ−ｔｅｒｔ−ブチルフェノキシ基、３−フルオロフェノキシ基、ペンタフルオロフェニル基、３−トリフルオロメチルフェノキシ基等がある。
【００１４】
本発明における一般式［１］で表される化合物のＲ1 〜Ｒ4 のアルキルチオ基の具体例としては、メチルチオ基、エチルチオ基、ｔｅｒｔ−ブチルチオ基、ヘキシルチオ基、オクチルチオ基、トリフルオロメチルチオ基等があり、アリールチオ基の具体例としては、フェニルチオ基、ｐ−ニトロフェニルチオ基、ｐ−ｔｅｒｔ−ブチルフェニルチオ基、３−フルオロフェニルチオ基、ペンタフルオロフェニルチオ基、３−トリフルオロメチルフェニルチオ基等がある。
【００１５】
本発明における一般式［１］で表される化合物のＲ1 〜Ｒ4 の単環基の具体例としては、フェニル基、チオニル基、チオフェニル基、フラニル基、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、オキサゾリル基、チアゾリル基、オキサジアゾリル基、チアジアゾリル基、イミダジアゾリル基等がある。
【００１６】
本発明における一般式［１］で表される化合物のＲ1 〜Ｒ4 の縮合多環基の具体例としては、ナフチル基、アントリル基、フェナントリル基、フルオレニル基、ピレニル基、インドール基、プリン基、キノリン基、イソキノリン基、シノリン基、キノキサリン基、ベンゾキノリン基、フルオレノン基、カルバゾール基、オキサゾール基、オキサジアゾール基、チアゾール基、チアジアゾール基、トリアゾール基、イミダゾール基、ベンゾオキサゾール基、ベンゾチアゾール基、ベンゾトリアゾール基、ベンゾイミダゾール基、ビスベンゾオキサゾール基、ビスベンゾチアゾール基、ビスベンゾイミダゾール基、アントロン基、ジベンゾフラン基、ジベンゾチオフェン基、アントラキノン基、アクリドン基、フェノチアジン基、ピロリジン基、ジオキサン基、モルフォリン基等がある。
【００１７】
本発明における一般式［１］で表される化合物のＲ1 〜Ｒ4 のアミノ基の具体例としては、アミノ基、ビス（アセトキシメチル）アミノ基、ビス（アセトキシエチル）アミノ基、ビスアセトキシプロピル）アミノ基、ビス（アセトキシブチル）アミノ基等があり、アルキルアミノ基の具体例としてはエチルアミノ基、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、ベンジルアミノ基ジベンジルアミノ基等があり、アリールアミノ基の具体例としては、フェニルアミノ基、（３−メチルフェニル）アミノ基、（４−メチルフェニル）アミノ基等があり、フェニルアミノ基の具体例としては、フェニルアミノ基、フェニルメチルアミノ基、ジフェニルアミノ基、ジトリルアミノ基、ジビフェニルアミノ基、ジ（４−メチルビフェニル）アミノ基、ジ（３−メチルフェニル）アミノ基、ジ（４−メチルフェニル）アミノ基、ナフチルフェニルアミノ基、ビス［４−（α，α’−ジメチルベンジル）フェニル］アミノ基等がある。
【００１８】
一般式［１］で表される化合物のフェニル環ないしはフェニレン環上の水素原子は、他の置換基に置換されても構わない。有する置換基の種類としては、Ｒ1 〜Ｒ4 と同様のものが挙げられる。
【００１９】
本発明において、一般式［１］で表される化合物は例えば次のような方法で合成することが出来る。四塩化チタン存在下で下記一般式［２］と一般式［３］をテトラヒドロフラン中で加熱することによって得ることが出来る。
一般式［２］
【００２０】
【化３】
一般式［３］
【００２２】
【化４】
［式中 n1 〜 n4 、Ｒ1 〜Ｒ4 は前記と同じである。］
【００２４】
本発明の化合物の代表例を表１に具体的に例示するが、本発明は以下の代表例に限定されるものではない。
【００２５】
【表１】
一般式［１］で表される化合物は、１分子中にオレフィン部位（＞Ｃ＝Ｃ＜）を有している。このオレフィン部位の幾何異性体により、一般式［１］で表される化合物はシス体、トランス体の組み合わせがあるが本発明の化合物はそのいずれであってもよく、混合したものであってもよい。
【００３９】
有機ＥＬ素子は、陽極と陰極間に一層もしくは多層の有機薄膜を形成した素子である。一層型の場合、陽極と陰極との間に発光層を設けている。発光層は、発光材料を含有し、それに加えて陽極から注入した正孔もしくは陰極から注入した電子を発光材料まで輸送させるために正孔注入材料、正孔輸送材料もしくは電子注入材料、電子輸送材料を含有しても良い。電子注入材料とは陰極から電子を注入されうる能力を持つ材料であり、電子輸送材料とは注入された電子を発光層へ輸送する能力を持つ材料である。正孔注入材料とは、陽極から正孔を注入されうる能力を持つ材料であり、正孔輸送材料とは、注入された正孔を発光層へ輸送する能力を持つ材料である。多層型は、（陽極／正孔注入層／発光層／陰極）、（陽極／正孔注入層／正孔輸送層／発光層／陰極）、（陽極／発光層／電子注入層／陰極）、（陽極／発光層／電子輸送層／電子注入層／陰極）、（陽極／正孔注入層／発光層／電子注入層／陰極）、（陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／電子注入層／陰極）の多層構成で積層した有機ＥＬ素子がある。多層型の正孔輸送層および電子輸送層は複数の層からなってもよい。本発明の一般式［１］で示される化合物は、固体状態において強い蛍光を持つ化合物であり電界発光性に優れているので、発光材料として発光層内で使用することができる。また、一般式［１］の化合物は、発光層内においてドーピング材料として発光層中にて最適の割合でドーピングすることにより、高い発光効率および発光波長の最適な選択が可能である。
【００４０】
発光層のホスト材料に、ドーピング材料（ゲスト材料）として一般式［１］の化合物を使用して、発光輝度が高い有機ＥＬ素子を得ることもできる。一般式［１］の化合物は、発光層内において、ホスト材料に対して０．００１重量％〜５０重量％の範囲で含有されていることが望ましく、更には０．０１重量％〜１０重量％の範囲が効果的である。
【００４１】
一般式［１］の化合物と併せて使用できるホスト材料としては、キノリン金属錯体、オキサジアゾール、ベンゾチアゾール金属錯体、ベンゾオキサゾール金属錯体、ベンゾイミダゾール金属錯体、トリアゾール、イミダゾール、オキサゾール、オキサジアゾール、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フルオレノン、ジアミノアントラセン型トリフェニルアミン、ジアミノフェナントレン型トリフェニルアミン、アントラキノジメタン、ジフェノキノン、チアジアゾール、テトラゾール、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、トリフェニレン、アントロン等とそれらの誘導体、および、ポリビニルカルバゾール、ポリシラン等の導電性高分子の高分子材料等がある。
【００４２】
逆に、一般式［１］の化合物をホスト材料として、他のドーピング材料を使用して発光色を変化させることも可能である。一般式［１］と共に使用されるドーピング材料としては、アントラセン、ナフタレン、フェナントレン、ピレン、テトラセン、コロネン、クリセン、フルオレセイン、ペリレン、フタロペリレン、ナフタロペリレン、ペリノン、フタロペリノン、ナフタロペリノン、ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、オキサジアゾール、アルダジン、ビスベンゾキサゾリン、ビススチリル、ピラジン、シクロペンタジエン、キノリン金属錯体、アミノキノリン金属錯体、イミン、ジフェニルエチレン、ビニルアントラセン、ジアミノカルバゾール、ピラン、チオピラン、ポリメチン、メロシアニン、イミダゾールキレート化オキシノイド化合物、キナクリドン、ルブレン等およびそれらの誘導体があるが、これらに限定されるものではない。
【００４３】
発光層には、発光材料およびドーピング材料に加えて、必要があれば正孔注入材料や電子注入材料を使用することもできる。
【００４４】
有機ＥＬ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、必要があれば、発光材料、ドーピング材料、キャリア注入を行う正孔注入材料や電子注入材料を二種類以上組み合わせて使用することも出来る。また、正孔注入層、発光層、電子注入層は、それぞれ二層以上の層構成により形成されても良く、正孔もしくは電子が効率よく電極から注入され、層中で輸送される素子構造が選択される。
【００４５】
有機ＥＬ素子の陽極に使用される導電性材料は、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、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材料は、４ｅＶ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、カルシウム、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。合金としては、マグネシウム／銀、マグネシウム／インジウム、リチウム／アルミニウム等が代表例として挙げられるが、これらに限定されるものではない。合金の比率は、加熱の温度、雰囲気、真空度により制御され適切な比率が選択される。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。
【００４６】
有機ＥＬ素子では、効率良く発光させるために、少なくとも一方は素子の発光波長領域において充分透明であることが望ましい。また、基板も透明であることが望ましい。透明電極は、上記の導電性材料を使用して、蒸着やスパッタリング等の方法で所定の透光性を確保するように設定する。発光面の電極は、光透過率を１０％以上にすることが望ましい。
基板は、機械的、熱的強度を有し、透明であれば限定されるものではないが、例示すると、ガラス基板、ポリエチレン板、ポリエーテルサルフォン板、ポリプロピレン板等の透明性樹脂があげられる。
【００４７】
本発明に係わる有機ＥＬ素子の各層の形成は、真空蒸着、スパッタリング等の乾式成膜法やスピンコーティング、ディッピング等の湿式成膜法のいずれの方法を適用することができる。膜厚は特に限定されるものではないが、各層は適切な膜厚に設定する必要がある。膜厚が厚すぎると、一定の光出力を得るために大きな印加電圧が必要になり効率が悪くなる。膜厚が薄すぎるとピンホール等が発生して、電界を印加しても充分な発光輝度が得られない。通常の膜厚は５ｎｍから１０μｍの範囲が適しているが、１０ｎｍから０．２μｍの範囲がさらに好ましい。
【００４８】
湿式成膜法の場合、各層を形成する材料を、クロロホルム、テトラヒドロフラン、ジオキサン等の適切な溶媒に溶解または分散して薄膜を形成するが、その溶媒はいずれであっても良い。また、いずれの薄膜においても、成膜性向上、膜のピンホール防止等のため適切な樹脂や添加剤を使用しても良い。
このような樹脂としては、ポリスチレン、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、ポリウレタン、ポリスルフォン、ポリメチルメタクリレート、ポリメチルアクリレート、セルロース等の絶縁性樹脂、ポリ−Ｎ−ビニルカルバゾール、ポリシラン等の光導電性樹脂、ポリチオフェン、ポリピロール等の導電性樹脂を挙げることができる。また、添加剤としては、酸化防止剤、紫外線吸収剤、可塑剤等を挙げることができる。
【００４９】
正孔注入材料としては、正孔を注入する能力を持ち、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層または電子注入材料への移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。具体的には、フタロシアニン系化合物、ナフタロシアニン系化合物、ポルフィリン系化合物、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、オキサゾール、オキサジアゾール、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。
【００５０】
電子注入材料としては、電子を注入する能力を持ち、発光層または発光材料に対して優れた電子注入効果を有し、発光層で生成した励起子の正孔注入層または正孔注入材料への移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。例えば、キノリン金属錯体、オキサジアゾール、ベンゾチアゾール金属錯体、ベンゾオキサゾール金属錯体、ベンゾイミダゾール金属錯体、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、オキサジアゾール、チアジアゾール、テトラゾール、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があるが、これらに限定されるものではない。また、正孔注入材料に電子受容物質を、電子注入材料に電子供与性物質を添加して増感させることもできる。
【００５１】
本発明により得られた有機ＥＬ素子の、温度、湿度、雰囲気等に対する安定性の向上のために、素子の表面に保護層を設けたり、シリコンオイル等を封入して素子全体を保護することも可能である。
【００５２】
【実施例】
以下、本発明を実施例に基づきさらに詳細に説明する。
【００５３】
化合物（１）の合成方法
ＴＨＦ７０ｍｌをフラスコに入れアイスバスにより冷却し、四塩化チタン１. ５ｍｌを滴下した。その後、４, ４’- ジフェニルベンゾフェノン３ｇをフラスコ中に投入し、亜鉛粉末１. ７５ｇを少しずつ加えた。すべて加えた後フラスコを加熱し、還流下５時間反応を行った。反応終了後、水を加え、クロロホルムで抽出した。クロロホルムを除き再結晶した後、昇華精製した。ＮＭＲ、ＦＤ−ＭＳ、ＩＲによって化合物の生成を確認した。
【００５４】
実施例１
洗浄したＩＴＯ電極付きガラス板上に、Ｎ，Ｎ' ―（３―メチルフェニル）―Ｎ，Ｎ' ―ジフェニル―１，１―ビフェニル- ４，４―ジアミン（ＴＰＤ）を真空蒸着して、膜厚２０ｎｍの正孔注入層を得た。次いで、化合物（１）を蒸着し膜厚４０ｎｍの発光層を作成し、トリス（８−ヒドロキシキノリン）アルミニウム錯体（Ａｌｑ３）を蒸着し、膜厚３０ｎｍの電子注入層を得た。その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１００ｎｍの電極を形成して有機ＥＬ素子を得た。正孔注入層および発光層は１０-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は直流電圧５Ｖで発光輝度１００ｃｄ／ｍ2 、最大発光輝度３２０００ｃｄ／ｍ2 、５Ｖの時の発光効率５. ０ｌｍ／Ｗの青緑色発光が得られた。次に３ｍＡ／ｃｍ2 の電流密度で、この素子を連続して発光させた寿命試験の結果、初期輝度の１／２以上の発光が１００００時間以上保持された。
【００５５】
実施例２〜３９
発光層に、化合物（１）に換え、表２で示した化合物を使用する以外は実施例１と同様の方法で有機ＥＬ素子を作製した。この素子は表２に示す発光特性を示した。
【００５６】
【表２】
実施例４０
洗浄したＩＴＯ電極付きガラス板上に化合物（３１）を真空蒸着して膜厚１００ｎｍの発光層を作成し、その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１５０ｎｍの膜厚の電極を形成して有機ＥＬ素子を得た。発光層および陰極は、１０-6Ｔｏｒｒの真空中で基板温度室温の条件下で蒸着した。この素子は直流電圧５Ｖで発光輝度３０ｃｄ／ｍ2 、最大発光輝度２２００ｃｄ／ｍ2 、５Ｖの時の発光効率０．５ｌｍ／Ｗの青緑色発光が得られた。次に３ｍＡ／ｃｍ2 の電流密度で、この素子を連続して発光させた寿命試験の結果、初期輝度の１／２以上の発光が５０００時間以上保持された。
【００５９】
実施例４１
洗浄したＩＴＯ電極付きガラス板上に、化合物（３２）を蒸着し膜厚８０ｎｍの正孔注入層を作成し、次いで、Ａｌｑ３を蒸着し、膜厚２０ｎｍの発光層を得た。その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１００ｎｍの電極を形成して有機ＥＬ素子を得た。正孔注入層および発光層は１０-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は直流電圧５Ｖで発光輝度８０ｃｄ／ｍ2 、最大発光輝度８０００ｃｄ／ｍ2 、５Ｖの時の発光効率１．０ｌｍ／Ｗの発光が得られた。次に３ｍＡ／ｃｍ2 の電流密度で、この素子を連続して発光させた寿命試験の結果、初期輝度の１／２以上の発光が３０００時間以上保持された。
【００６０】
実施例４２
洗浄したＩＴＯ電極付きガラス板上に、ＴＰＤを蒸着して膜厚５０ｎｍの正孔注入層を作製し、次いで、Ａｌｑ３を蒸着し、膜厚２０ｎｍの発光層を得た。化合物（２９）を蒸着し膜厚６０ｎｍの電子注入層を作成し、その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１００ｎｍの電極を形成して有機ＥＬ素子を得た。正孔注入層および発光層は１０-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は直流電圧５Ｖで発光輝度９０ｃｄ／ｍ2 、最大発光輝度６０００ｃｄ／ｍ2 、５Ｖの時の発光効率１．２ｌｍ／Ｗの発光が得られた。次に３ｍＡ／ｃｍ2 の電流密度で、この素子を連続して発光させた寿命試験の結果、初期輝度の１／２以上の発光が３０００時間以上保持された。
【００６１】
実施例４３
洗浄したＩＴＯ電極付きガラス板上に、ＴＰＤを真空蒸着して、膜厚２０ｎｍの正孔注入層を得た。次いで、Ｎ，Ｎ' ―（４―メチルフェニル）―Ｎ，Ｎ' ―（４−ｎ−ブチルフェニル）―フェナントレン―９，１０―ジアミンと化合物（２）とを１００：１の重量比で蒸着し膜厚４０ｎｍの発光層を作成し、Ａｌｑ３を蒸着し、膜厚１０ｎｍの電子注入層を得た。その上に、アルミニウムとリチウムを２５：１で混合した合金で膜厚１００ｎｍの電極を形成して有機ＥＬ素子を得た。正孔注入層および発光層は１０-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は直流電圧５Ｖで発光輝度１２０ｃｄ／ｍ2 、最大発光輝度１４０００ｃｄ／ｍ2 、５Ｖの時の発光効率２．８ｌｍ／Ｗの発光が得られた。次に３ｍＡ／ｃｍ2 の電流密度で、この素子を連続して発光させた寿命試験の結果、初期輝度の１／２以上の発光が１００００時間以上保持された。
【００６２】
実施例４４
洗浄したＩＴＯ電極付きガラス板上に、ＴＰＤを真空蒸着して、膜厚２０ｎｍの正孔注入層を得た。次いで、化合物（１）とルブレンとを１００：１の重量比で蒸着し膜厚４０ｎｍの発光層を作成し、Ａｌｑ３を蒸着し、膜厚１０ｎｍの電子注入層を得た。その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１００ｎｍの電極を形成して有機ＥＬ素子を得た。正孔注入層および発光層は１０-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は直流電圧５Ｖで発光輝度１４０ｃｄ／ｍ2 、最大発光輝度１４０００ｃｄ／ｍ2 、５Ｖの時の発光効率２．８ｌｍ／Ｗの黄色発光が得られた。次に３ｍＡ／ｃｍ2 の電流密度で、この素子を連続して発光させた寿命試験の結果、初期輝度の１／２以上の発光が１００００時間以上保持された。
【００６３】
実施例４５〜４８
発光層に、ドーピング化合物として表３で示した化合物を使用する以外は実施例４４と同様の方法で有機ＥＬ素子を作製した。この素子は表３に示す発光特性を示した。
【００６４】
【表３】
実施例４９
洗浄したＩＴＯ電極付きガラス板上に、４、４’、４”−トリス［Ｎ−（３−メチルフェニル）−Ｎ−フェニルアミノ］トリフェニルアミンを真空蒸着して、膜厚４０ｎｍの正孔注入層を得た。次いで、４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル（α−ＮＰＤ）を真空蒸着して、膜厚１０ｎｍの第二正孔注入層を得た。さらに、化合物（１）を真空蒸着して、膜厚３０ｎｍの発光層を作成し、さらにビス（２−メチル−８−ヒドロキシキノリナト）（１−フェノラート）ガリウム錯体を真空蒸着して膜厚３０ｎｍの電子注入層を作成し、その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１５０ｎｍの電極を形成して、有機ＥＬ素子を得た。正孔注入層および発光層は１０- 6 Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は、直流電圧５Ｖで発光輝度１２０（ｃｄ／ｍ2 ）、最大発光輝度３４０００（ｃｄ／ｍ2 ）、発光効率５．０（ｌｍ／Ｗ）の青緑色発光が得られた。
【００６６】
実施例５０〜６７
発光層に、化合物（１）に換え、表４で示した化合物を使用する以外は実施例４９と同様の方法で有機ＥＬ素子を作製した。この素子は表４に示す発光特性を示した。
【００６７】
【表４】
洗浄したＩＴＯ電極付きガラス板上に、化合物（１４）、トリス（８−ヒドロキシキノリン）アルミニウム錯体、ＴＰＤ、ポリカーボネート樹脂（ＰＣ−Ａ）を３：２：３：８の重量比でテトラヒドロフランに溶解させ、スピンコーティング法により膜厚１００ｎｍの発光層を得た。その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１５０ｎｍの電極を形成し有機ＥＬ素子を得た。この素子は直流電圧５Ｖで発光輝度１２ｃｄ／ｍ2 、最大発光輝度３１００ｃｄ／ｍ2 、５Ｖの時の発光効率０．５ｌｍ／Ｗの発光が得られた。次に３ｍＡ／ｃｍ2 の電流密度で、この素子を連続して発光させた寿命試験の結果、初期輝度の１／２以上の発光が３０００時間以上保持された。
【００６９】
本発明の有機ＥＬ素子は発光効率、発光輝度の向上と長寿命化を達成するものであり、併せて使用される発光材料、ドーピング材料、正孔注入材料、電子注入材料、増感剤、樹脂、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。
【００７０】
【発明の効果】
本発明により、従来に比べて高発光効率、高輝度であり、長寿命の有機ＥＬ素子を得ることができた。[0001]
[Industrial application fields]
The present invention relates to an organic electroluminescence (EL) element used for a planar light source and display.
[0002]
[Prior art]
An EL element using an organic substance is considered to be promising for use as an inexpensive large-area full-color display element of a solid light emitting type, and many developments have been made. In general, an EL is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer.
In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Furthermore, this electron is recombined with holes in the light emitting layer, and energy is emitted as light when the energy level returns from the conduction band to the valence band.
[0003]
Conventional organic EL elements have a higher driving voltage and lower light emission luminance and light emission efficiency than inorganic EL elements. Further, the characteristic deterioration has been remarkably not put into practical use.
In recent years, an organic EL device in which a thin film containing an organic compound having a high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported and attracted attention (Applied Physics Letters, Vol. 51, page 913). 1987).
In this method, a metal chelate complex is used as a phosphor layer and an amine compound is used as a hole injection layer to obtain high luminance green light emission. The luminance is 100 cd / m 2 at a direct current voltage of 6 to 7 V, maximum The luminous efficiency is 1.5 lm / W, and the performance is close to the practical range. However, the organic EL elements up to now have improved light emission intensity due to the improvement of the structure, but do not yet have sufficient light emission luminance. In addition, there is a serious problem that the lifetime is at most about 1000 hours.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an organic EL device having high luminous efficiency and a long lifetime. As a result of intensive studies by the present inventors, the organic EL element using at least one layer of the organic EL element material of the compound represented by the general formula [1] has high luminous efficiency and excellent stability during repeated use. As a result, the present invention has been achieved.
[0005]
[Means for Solving the Problems]
That is, the present invention is an organic electroluminescence element material represented by the following general formula [1].
General formula [1]
[0006]
[Chemical formula 2]
[Wherein n1 to n4 represent an integer of 0 to 3 (where n1 + n2 + n3 + n4 = 4 to 8). R 1 to R 4 are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Substituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted monocyclic group, substituted or unsubstituted condensed polycyclic group, substituted or unsubstituted amino group, substituted or unsubstituted alkylamino group, substituted Alternatively, it represents an unsubstituted arylamino group. ]
[0008]
Furthermore, the present invention relates to an organic electroluminescence device in which a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, wherein at least one layer is a layer containing the organic electroluminescence device material described above. It is.
[0009]
Furthermore, the present invention provides an organic electroluminescence device in which a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, wherein the light emitting layer is a layer containing the above-described organic electroluminescence device material. It is.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
[0011]
R 1 to R 4 of the compound represented by the general formula [1] of the present invention are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group. Group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted monocyclic group, substituted or unsubstituted A condensed polycyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylamino group, and a substituted or unsubstituted arylamino group.
[0012]
Specific examples of the halogen atom represented by R 1 to R 4 in the compound represented by the general formula [1] in the present invention include chlorine, bromine, iodine and fluorine. Specific examples of the alkyl group include a methyl group, ethyl Group, propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, and the like. Specific examples of cycloalkyl include cyclopentane. Ring, cyclohexane ring and the like.
[0013]
Specific examples of the alkoxy group of R 1 to R 4 of the compound represented by the general formula [1] in the present invention include a methoxy group, an ethoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, and a trifluoro group. Ethoxy group, pentafluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 1,1,1,3,3,3-hexafluoro-2-propoxy group, 6- (perfluoroethyl) hexyloxy Specific examples of the aryloxy group include phenoxy group, p-nitrophenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy group, pentafluorophenyl group, 3-trifluoromethylphenoxy group, and the like. There is.
[0014]
Specific examples of the alkylthio group of R 1 to R 4 of the compound represented by the general formula [1] in the present invention include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group, a trifluoromethylthio group, and the like. Specific examples of the arylthio group include phenylthio group, p-nitrophenylthio group, p-tert-butylphenylthio group, 3-fluorophenylthio group, pentafluorophenylthio group, 3-trifluoromethylphenylthio group. There are groups.
[0015]
Specific examples of R 1 to R 4 monocyclic groups of the compound represented by the general formula [1] in the present invention include phenyl group, thionyl group, thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, Examples include pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, oxazolyl group, thiazolyl group, oxadiazolyl group, thiadiazolyl group, and imidadiazolyl group.
[0016]
Specific examples of the condensed polycyclic group of R 1 to R 4 of the compound represented by the general formula [1] in the present invention include naphthyl group, anthryl group, phenanthryl group, fluorenyl group, pyrenyl group, indole group, purine group. , Quinoline group, isoquinoline group, sinoline group, quinoxaline group, benzoquinoline group, fluorenone group, carbazole group, oxazole group, oxadiazole group, thiazole group, thiadiazole group, triazole group, imidazole group, benzoxazole group, benzothiazole group Benzotriazole group, benzimidazole group, bisbenzoxazole group, bisbenzothiazole group, bisbenzoimidazole group, anthrone group, dibenzofuran group, dibenzothiophene group, anthraquinone group, acridone group, phenothiazine group, pyrrolidine group, Oxane group, a morpholine group.
[0017]
Specific examples of the amino group represented by R 1 to R 4 of the compound represented by the general formula [1] in the present invention include an amino group, a bis (acetoxymethyl) amino group, a bis (acetoxyethyl) amino group, and bisacetoxypropyl. ) Amino group, bis (acetoxybutyl) amino group and the like, and specific examples of alkylamino group include ethylamino group, diethylamino group, dipropylamino group, dibutylamino group, benzylamino group dibenzylamino group, Specific examples of the arylamino group include a phenylamino group, (3-methylphenyl) amino group, and (4-methylphenyl) amino group. Specific examples of the phenylamino group include a phenylamino group, phenylmethylamino. Group, diphenylamino group, ditolylamino group, dibiphenylamino group, di (4-methylbiphenyl) ) Amino group, di (3-methylphenyl) amino group, di (4-methylphenyl) amino group, naphthylphenylamino group, bis [4- (alpha,. Alpha .'- dimethylbenzyl) phenyl] is an amino group.
[0018]
The hydrogen atom on the phenyl ring or phenylene ring of the compound represented by the general formula [1] may be substituted with another substituent. The types of substituents with are the same as those for R 1 to R 4.
[0019]
In the present invention, the compound represented by the general formula [1] can be synthesized, for example, by the following method. The following general formulas [2] and [3] can be obtained by heating in tetrahydrofuran in the presence of titanium tetrachloride.
General formula [2]
[0020]
[Chemical 3]
General formula [3]
[0022]
[Formula 4]
[Wherein n1 ~ n4, R 1 ~R 4 are as defined above. ]
[0024]
Although the representative example of the compound of this invention is specifically illustrated in Table 1, this invention is not limited to the following representative examples.
[0025]
[Table 1]
The compound represented by the general formula [1] has an olefin moiety (> C = C <) in one molecule. Depending on the geometric isomer of the olefin moiety, the compound represented by the general formula [1] has a combination of a cis isomer and a trans isomer, but the compound of the present invention may be either of them or a mixture thereof. Good.
[0039]
An organic EL element is an element in which a single-layer or multilayer organic thin film is formed between an anode and a cathode. In the case of the single layer type, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material, and in addition to that, a hole injecting material, a hole transporting material or an electron injecting material, and an electron transporting material for transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. May be contained. The electron injection material is a material having the ability to inject electrons from the cathode, and the electron transport material is a material having the ability to transport the injected electrons to the light emitting layer. The hole injection material is a material having the ability to inject holes from the anode, and the hole transport material is a material having the ability to transport the injected holes to the light emitting layer. The multilayer type includes (anode / hole injection layer / light emitting layer / cathode), (anode / hole injection layer / hole transport layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), (Anode / light emitting layer / electron transport layer / electron injection layer / cathode), (anode / hole injection layer / light emitting layer / electron injection layer / cathode), (anode / hole injection layer / hole transport layer / light emitting layer) There are organic EL elements laminated in a multilayer structure of / electron transport layer / electron injection layer / cathode). The multilayer hole transport layer and the electron transport layer may be composed of a plurality of layers. Since the compound represented by the general formula [1] of the present invention is a compound having strong fluorescence in a solid state and excellent in electroluminescence, it can be used as a light emitting material in a light emitting layer. In addition, the compound of the general formula [1] can be optimally selected for high light emission efficiency and light emission wavelength by doping the light emitting layer as a doping material at an optimum ratio in the light emitting layer.
[0040]
An organic EL device having high emission luminance can be obtained by using the compound of the general formula [1] as a doping material (guest material) for the host material of the light emitting layer. The compound of the general formula [1] is desirably contained in the light emitting layer in the range of 0.001% by weight to 50% by weight with respect to the host material, and further 0.01% by weight to 10% by weight. The range of is effective.
[0041]
Host materials that can be used in combination with the compound of the general formula [1] include quinoline metal complex, oxadiazole, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, triazole, imidazole, oxazole, oxadiazole, Stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine fluorenone, diaminoanthracene type triphenylamine, diaminophenanthrene type triphenylamine, anthraquinodimethane, diphenoquinone, thiadiazole, tetrazole, perylene Tetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, triphenylene, anthrone, and their derivatives, and polyvinylcarba Lumpur, polymeric materials such conductive polymers polysilane.
[0042]
On the contrary, it is also possible to change the emission color by using the compound of the general formula [1] as a host material and using other doping materials. The doping materials used together with the general formula [1] include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin. , Oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelation Oxinoid compounds, quinacridone, rubrene, etc. and their derivatives, but are not limited to these Not.
[0043]
In addition to the light emitting material and the doping material, if necessary, a hole injection material or an electron injection material can be used for the light emitting layer.
[0044]
By making the organic EL element have a multi-layer structure, it is possible to prevent a decrease in luminance and lifetime due to quenching. If necessary, a light emitting material, a doping material, a hole injecting material for injecting carriers, and an electron injecting material can be used in combination. In addition, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed of two or more layers, and there is an element structure in which holes or electrons are efficiently injected from the electrode and transported in the layer. Selected.
[0045]
The conductive material used for the anode of the organic EL element is preferably one having a work function larger than 4 eV, such as carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, and the like. These alloys, ITO substrates, metal oxides such as tin oxide and indium oxide called NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used.
A conductive material used for the cathode is preferably one having a work function smaller than 4 eV, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, and alloys thereof are used. Examples of alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the heating temperature, atmosphere, and degree of vacuum, and an appropriate ratio is selected. If necessary, the anode and the cathode may be formed of two or more layers.
[0046]
In the organic EL element, in order to emit light efficiently, it is desirable that at least one of the elements is sufficiently transparent in the light emission wavelength region of the element. The substrate is also preferably transparent. The transparent electrode is set so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering using the conductive material. The electrode on the light emitting surface preferably has a light transmittance of 10% or more.
The substrate has mechanical and thermal strength and is not limited as long as it is transparent. Examples thereof include transparent resins such as a glass substrate, a polyethylene plate, a polyethersulfone plate, and a polypropylene plate. .
[0047]
Formation of each layer of the organic EL device according to the present invention can be performed by any of dry film forming methods such as vacuum deposition and sputtering and wet film forming methods such as spin coating and dipping. The film thickness is not particularly limited, but each layer needs to be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.
[0048]
In the case of the wet film-forming method, the material for forming each layer is dissolved or dispersed in an appropriate solvent such as chloroform, tetrahydrofuran, dioxane or the like to form a thin film, and any solvent may be used. In any thin film, an appropriate resin or additive may be used in order to improve film formability and prevent pinholes in the film.
Examples of such resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and photoconductivity such as poly-N-vinylcarbazole and polysilane. Examples thereof include conductive resins such as conductive resins, polythiophene, and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
[0049]
As a hole injection material, it has the ability to inject holes, has an excellent hole injection effect for the light emitting layer or light emitting material, and excitons generated in the light emitting layer to the electron injection layer or electron injection material And a compound having an excellent ability to form a thin film. Specifically, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, poly Aryl alkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and their derivatives, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers However, it is not limited to these.
[0050]
As an electron injection material, it has the ability to inject electrons, has an excellent electron injection effect for the light emitting layer or the light emitting material, and excitons generated in the light emitting layer are injected into the hole injection layer or the hole injection material. Examples thereof include compounds that prevent migration and have excellent thin film forming ability. For example, quinoline metal complex, oxadiazole, benzothiazole metal complex, benzoxazole metal complex, benzimidazole metal complex, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxadiazole, thiadiazole, tetrazole, perylenetetracarboxylic Acids, fluorenylidene methane, anthraquinodimethane, anthrone and the like and derivatives thereof are not limited thereto. Further, sensitization can be performed by adding an electron accepting substance to the hole injecting material and an electron donating substance to the electron injecting material.
[0051]
In order to improve the stability of the organic EL device obtained by the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer may be provided on the surface of the device, or silicon oil or the like may be sealed to protect the entire device. Is possible.
[0052]
【Example】
Hereinafter, the present invention will be described in more detail based on examples.
[0053]
Method of synthesizing compound (1) 70 ml of THF was placed in a flask and cooled with an ice bath, and 1.5 ml of titanium tetrachloride was added dropwise. Thereafter, 3 g of 4,4′-diphenylbenzophenone was put into the flask, and 1.75 g of zinc powder was added little by little. After all was added, the flask was heated and reacted under reflux for 5 hours. After completion of the reaction, water was added and extracted with chloroform. Sublimation purification was carried out after recrystallization after removing chloroform. Formation of the compound was confirmed by NMR, FD-MS, and IR.
[0054]
Example 1
N, N '-(3-methylphenyl) -N, N'-diphenyl-1,1-biphenyl-4,4-diamine (TPD) is vacuum-deposited on the cleaned glass plate with an ITO electrode to form a film. A hole injection layer having a thickness of 20 nm was obtained. Subsequently, the compound (1) was vapor-deposited to prepare a light-emitting layer having a thickness of 40 nm, and tris (8-hydroxyquinoline) aluminum complex (Alq3) was vapor-deposited to obtain an electron injection layer having a thickness of 30 nm. On top of that, an electrode having a thickness of 100 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device emission luminance 100 cd / m 2 at a direct current voltage 5V, emission at the maximum emission luminance 32000cd / m 2, 5V efficiency 5. blue green light 0lm / W was obtained. Next, as a result of a life test in which the device was continuously emitted at a current density of 3 mA / cm 2 , emission of 1/2 or more of the initial luminance was maintained for 10,000 hours or more.
[0055]
Examples 2-39
An organic EL device was produced in the same manner as in Example 1 except that the compound shown in Table 2 was used instead of the compound (1) in the light emitting layer. This device exhibited the light emission characteristics shown in Table 2.
[0056]
[Table 2]
Example 40
A compound (31) is vacuum-deposited on a cleaned glass plate with an ITO electrode to form a light-emitting layer having a thickness of 100 nm, and an alloy in which magnesium and silver are mixed at a ratio of 10: 1 is formed thereon with a film thickness of 150 nm. The electrode was formed to obtain an organic EL device. The light emitting layer and the cathode were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. The device produced blue-green light emission with a direct-current voltage of 5 V, an emission luminance of 30 cd / m 2 , a maximum emission luminance of 2200 cd / m 2 , and an emission efficiency of 0.5 lm / W at 5 V. Next, as a result of a life test in which this element was continuously emitted at a current density of 3 mA / cm 2 , emission of 1/2 or more of the initial luminance was maintained for 5000 hours or more.
[0059]
Example 41
On the washed glass plate with an ITO electrode, the compound (32) was vapor-deposited to form a hole injection layer with a thickness of 80 nm, and then Alq3 was vapor-deposited to obtain a light-emitting layer with a thickness of 20 nm. On top of that, an electrode having a thickness of 100 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device emission luminance 80 cd / m 2 at a direct current voltage 5V, emission of luminous efficiency 1.0lm / W at the maximum emission luminance 8000cd / m 2, 5V is obtained. Next, as a result of a life test in which this element was continuously emitted at a current density of 3 mA / cm 2 , emission of 1/2 or more of the initial luminance was maintained for 3000 hours or more.
[0060]
Example 42
On the washed glass plate with an ITO electrode, TPD was vapor-deposited to produce a hole injection layer with a thickness of 50 nm, and then Alq3 was vapor-deposited to obtain a light-emitting layer with a thickness of 20 nm. A compound (29) was deposited to form an electron injection layer having a thickness of 60 nm, and an electrode having a thickness of 100 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device was capable of emitting light with an emission efficiency of 1.2 lm / W when the direct current voltage was 5 V, the emission luminance was 90 cd / m 2 , the maximum emission luminance was 6000 cd / m 2 , and 5 V. Next, as a result of a life test in which this element was continuously emitted at a current density of 3 mA / cm 2 , emission of 1/2 or more of the initial luminance was maintained for 3000 hours or more.
[0061]
Example 43
TPD was vacuum-deposited on the washed glass plate with the ITO electrode to obtain a 20 nm-thick hole injection layer. Next, N, N ′-(4-methylphenyl) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine and compound (2) were deposited in a weight ratio of 100: 1. Then, a light emitting layer having a film thickness of 40 nm was prepared, and Alq3 was deposited to obtain an electron injection layer having a film thickness of 10 nm. On top of that, an electrode having a thickness of 100 nm was formed from an alloy in which aluminum and lithium were mixed at a ratio of 25: 1 to obtain an organic EL element. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. The device produced light emission with a direct current voltage of 5 V and an emission luminance of 120 cd / m 2 , a maximum emission luminance of 14000 cd / m 2 , and an emission efficiency of 2.8 lm / W at 5 V. Next, as a result of a life test in which the device was continuously emitted at a current density of 3 mA / cm 2 , emission of 1/2 or more of the initial luminance was maintained for 10,000 hours or more.
[0062]
Example 44
TPD was vacuum-deposited on the washed glass plate with the ITO electrode to obtain a 20 nm-thick hole injection layer. Subsequently, the compound (1) and rubrene were vapor-deposited at a weight ratio of 100: 1 to prepare a light-emitting layer having a film thickness of 40 nm, and Alq3 was vapor-deposited to obtain an electron injection layer having a film thickness of 10 nm. On top of that, an electrode having a thickness of 100 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device produced yellow light emission with a direct current voltage of 5 V and a light emission luminance of 140 cd / m 2 , a maximum light emission luminance of 14000 cd / m 2 , and a light emission efficiency of 2.8 lm / W at 5 V. Next, as a result of a life test in which the device was continuously emitted at a current density of 3 mA / cm 2 , emission of 1/2 or more of the initial luminance was maintained for 10,000 hours or more.
[0063]
Examples 45-48
An organic EL device was produced in the same manner as in Example 44, except that the compound shown in Table 3 was used as the doping compound for the light emitting layer. This device exhibited the light emission characteristics shown in Table 3.
[0064]
[Table 3]
Example 49
4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine is vacuum-deposited on a cleaned glass plate with an ITO electrode to inject holes with a thickness of 40 nm. Next, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum-deposited to form a second hole injection layer having a thickness of 10 nm. Further, the compound (1) was vacuum-deposited to prepare a light-emitting layer having a film thickness of 30 nm, and further a bis (2-methyl-8-hydroxyquinolinato) (1-phenolate) gallium complex was vacuum-deposited. An electron injection layer having a thickness of 30 nm was prepared, and an electrode having a thickness of 150 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL device. layer 10 - of 6 Torr in vacuum, group Was deposited under the conditions of temperature room. This device, blue light emission luminance 120 at a direct current voltage 5V (cd / m 2), the maximum emission luminance 34000 (cd / m 2), luminous efficiency 5.0 (lm / W) Green emission was obtained.
[0066]
Examples 50-67
An organic EL device was produced in the same manner as in Example 49 except that the compound shown in Table 4 was used instead of the compound (1) in the light emitting layer. This device exhibited the light emission characteristics shown in Table 4.
[0067]
[Table 4]
Compound (14), tris (8-hydroxyquinoline) aluminum complex, TPD, and polycarbonate resin (PC-A) are dissolved in tetrahydrofuran at a weight ratio of 3: 2: 3: 8 on a cleaned glass plate with an ITO electrode. A light emitting layer having a thickness of 100 nm was obtained by spin coating. On top of this, an electrode having a thickness of 150 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL element. This device emission luminance 12 cd / m 2 at a direct current voltage 5V, emission of luminous efficiency 0.5lm / W at the maximum emission luminance 3100cd / m 2, 5V is obtained. Next, as a result of a life test in which the device was continuously emitted at a current density of 3 mA / cm 2 , emission of 1/2 or more of the initial luminance was maintained for 3000 hours or more.
[0069]
The organic EL device of the present invention achieves improvement in light emission efficiency, light emission luminance and long life, and is used together with light emitting materials, doping materials, hole injection materials, electron injection materials, sensitizers, resins. The electrode material and the element manufacturing method are not limited.
[0070]
【The invention's effect】
According to the present invention, it was possible to obtain an organic EL device having higher luminous efficiency and higher luminance than the conventional one and having a long lifetime.
Claims (3)
一般式［１］
General formula [1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP05630498A JP3663892B2 (en) | 1998-03-09 | 1998-03-09 | Organic electroluminescent device material and organic electroluminescent device using the same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP05630498A JP3663892B2 (en) | 1998-03-09 | 1998-03-09 | Organic electroluminescent device material and organic electroluminescent device using the same |
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| JPH11260551A JPH11260551A (en) | 1999-09-24 |
| JP3663892B2 true JP3663892B2 (en) | 2005-06-22 |
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| US7029764B2 (en) * | 2003-01-24 | 2006-04-18 | Ritdisplay Corporation | Organic electroluminescent material and electroluminescent device by using the same |
| EP2008992A4 (en) * | 2006-04-18 | 2011-03-09 | Idemitsu Kosan Co | Aromatic amine derivative and organic electroluminescent device using the same |
| US8829783B2 (en) | 2007-06-18 | 2014-09-09 | Idemitsu Kosan Co., Ltd. | Trinaphthyl monoamine or derivative thereof, organic electroluminescent device using the same, and organic electroluminescent material-containing solution |
| KR101084675B1 (en) * | 2008-07-04 | 2011-11-22 | 주식회사 엘지화학 | Radial-shaped liquid crystal compound and optical film and liquid crystal display device comprising the same |
| WO2010047335A1 (en) * | 2008-10-21 | 2010-04-29 | 国立大学法人京都大学 | Benzene compound |
| WO2011106990A1 (en) * | 2010-03-01 | 2011-09-09 | The Hong Kong University Of Science And Technology | Light emitting tetraphenylene derivatives, its method for preparation and light emitting device using the same derivatives |
| JP5934570B2 (en) * | 2012-05-07 | 2016-06-15 | 株式会社カネカ | Luminescent material and organic EL device |
| CN104557552B (en) * | 2013-10-22 | 2016-08-31 | 中国科学院理化技术研究所 | Star-shaped tetraphenylethylene derivative molecular glass, positive photoresist coating and application thereof |
| CN107141190A (en) * | 2017-06-12 | 2017-09-08 | 宁波大学 | A kind of gathering induced luminescence material and preparation method thereof |
| EP3470398B1 (en) * | 2017-10-13 | 2022-05-04 | Novaled GmbH | Organic electronic device comprising an organic semiconductor layer |
| KR102477550B1 (en) * | 2020-07-09 | 2022-12-15 | 연세대학교 산학협력단 | Ferroelectric Luminescent Self-Assembly compound and organic electronic device comprising the same |
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