JP4026273B2 - Material for organic electroluminescence device and organic electroluminescence device using the same - Google Patents
Material for organic electroluminescence device and organic electroluminescence device using the same Download PDFInfo
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- JP4026273B2 JP4026273B2 JP09717499A JP9717499A JP4026273B2 JP 4026273 B2 JP4026273 B2 JP 4026273B2 JP 09717499 A JP09717499 A JP 09717499A JP 9717499 A JP9717499 A JP 9717499A JP 4026273 B2 JP4026273 B2 JP 4026273B2
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- light emitting
- organic
- emitting layer
- substituted
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- 239000000463 material Substances 0.000 title claims description 76
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- 239000007924 injection Substances 0.000 claims description 50
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- 125000003277 amino group Chemical group 0.000 claims description 6
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- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 125000002192 heptalenyl group Chemical group 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
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- COLNWNFTWHPORY-UHFFFAOYSA-M lithium;8-hydroxyquinoline-2-carboxylate Chemical compound [Li+].C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1 COLNWNFTWHPORY-UHFFFAOYSA-M 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
- 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- YERRTOUSFSZICJ-UHFFFAOYSA-N methyl 2-amino-2-(4-bromophenyl)acetate Chemical compound COC(=O)C(N)C1=CC=C(Br)C=C1 YERRTOUSFSZICJ-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound 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
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 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
- 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
- 239000003208 petroleum Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 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
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer 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
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005581 pyrene 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
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical class C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- KWQNQSDKCINQQP-UHFFFAOYSA-K tri(quinolin-8-yloxy)gallane Chemical compound C1=CN=C2C(O[Ga](OC=3C4=NC=CC=C4C=CC=3)OC=3C4=NC=CC=C4C=CC=3)=CC=CC2=C1 KWQNQSDKCINQQP-UHFFFAOYSA-K 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- CATVHUNBFWPEKR-UHFFFAOYSA-N triphenylen-1-ol Chemical group C1=CC=CC2=C3C(O)=CC=CC3=C(C=CC=C3)C3=C21 CATVHUNBFWPEKR-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 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
- CJGUQZGGEUNPFQ-UHFFFAOYSA-L zinc;2-(1,3-benzothiazol-2-yl)phenolate Chemical compound [Zn+2].[O-]C1=CC=CC=C1C1=NC2=CC=CC=C2S1.[O-]C1=CC=CC=C1C1=NC2=CC=CC=C2S1 CJGUQZGGEUNPFQ-UHFFFAOYSA-L 0.000 description 1
- BRODZLXTYKNNPW-UHFFFAOYSA-L zinc;2-(benzotriazol-2-yl)phenolate Chemical compound [Zn+2].[O-]C1=CC=CC=C1N1N=C2C=CC=CC2=N1.[O-]C1=CC=CC=C1N1N=C2C=CC=CC2=N1 BRODZLXTYKNNPW-UHFFFAOYSA-L 0.000 description 1
- NVCBVYYESHBQKS-UHFFFAOYSA-L zinc;2-carboxyquinolin-8-olate Chemical compound [Zn+2].C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1.C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1 NVCBVYYESHBQKS-UHFFFAOYSA-L 0.000 description 1
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）素子用発光材料および高輝度の発光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素子は、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、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）。この方法は、金属キレート錯体を発光層、アミン系化合物を正孔注入層に使用して、高輝度の緑色発光を得ており、６〜７Ｖの直流電圧で輝度は数１０００ｃｄ／ｍ2、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。
【０００４】
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、繰り返し使用時の安定性に劣るという大きな問題を持っている。これは、例えば、トリス（８−ヒドロキシキノリナート）アルミニウム錯体等の金属キレート錯体が、電界発光時に化学的に不安定であり、陰極との密着性も悪く、短時間の発光で大きく劣化していた。以上の理由により、高い発光輝度、発光効率を持ち、繰り返し使用時での安定性の優れた有機ＥＬ素子の開発のために、優れた発光能力を有し、耐久性のある発光材料の開発が望まれている。
【０００５】
【発明が解決しようとする課題】
本発明は、発光輝度が高く、繰り返し使用時での安定性の優れた有機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］で示される有機ＥＬ素子用材料を使用した有機ＥＬ素子の発光輝度および発光効率が高く、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を成すに至った。
【０００６】
【課題を解決するための手段】
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 用発光材料に関する。
一般式［１］
【０００７】
【化２】
［式中、Ｂはホウ素原子を表し、Ａは、炭素数１０〜４０個からなる２価の縮合芳香環基、または、少なくとも１つの炭素数１０〜４０個からなる縮合芳香環を含む芳香環構造単位２〜１０個が直接連結した２価の基を表す。Ａｒ1〜Ａｒ4は、それぞれ独立に、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単環基、置換もしくは未置換の縮合多環基を表し、Ａｒ1とＡ ｒ2とは、またはＡｒ3とＡｒ4とは、互いに結合して一体となっても良い。ただし、下記一般式［２］で表されるボラン誘導体である場合を除く。］
一般式［２］
【化４】
【０００９】
また本発明は、Ａｒ1〜Ａｒ4が置換もしくは未置換の単環アリール基であることを特徴とする上記有機エレクトロルミネッセンス素子用材料である。
また本発明は、一対の電極間に発光層または発光層を含む複数層の有機化合物薄膜を形成してなる有機エレクトロルミネッセンス素子において、いずれかの層が、上記有機エレクトロルミネッセンス素子用材料を単独もしくは混合物として含有することを特徴とする有機エレクトロルミネッセンス素子である。
また本発明は、一対の電極間に発光層または発光層を含む複数層の有機化合物薄膜を形成してなる有機エレクトロルミネッセンス素子において、発光層が上記有機エレクトロルミネッセンス素子用材料を単独もしくは混合物として含有することを特徴とする有機エレクトロルミネッセンス素子である。
【００１０】
また本発明は、一対の電極間に発光層または発光層を含む複数層の有機化合物薄膜を形成してなる有機エレクトロルミネッセンス素子において、電子注入層が上記有機エレクトロルミネッセンス素子用材料を単独もしくは混合物として含有することを特徴とする有機エレクトロルミネッセンス素子である。
さらに本発明は、陽極と発光層との間に正孔注入層を形成することを特徴とする上記有機エレクトロルミネッセンス素子である。
また本発明は、正孔注入層が、アリールアミン誘導体、フタロシアニン化合物、およびトリフェニレン誘導体からなる群から選ばれる少なくとも１種を含有する層であることを特徴とする上記有機エレクトロルミネッセンス素子である。
【００１１】
【発明の実施の形態】
本発明における一般式［１］で示される化合物のＡは、炭素数１０〜４０個からなる２価の縮合芳香環基、または、少なくとも１つの炭素数１０〜４０個からなる縮合芳香環を含む芳香環構造単位２〜１０個が直接連結した２価の基を表す。置換もしくは未置換の２価の縮合芳香環基の具体例としては、ナフタレン、アントラセン、フェナントレン、フルオレン、ピレン、クリセン、ナフタセン、ペリレン、アズレン、フルオレノン、アントラキノン、ジベンゾスベレノン、テトラシアノキノジメタン、コロネン、ルビセン、デカシクレン等の置換もしくは未置換の縮合芳香族環の２価の残基が挙げられる。
【００１４】
芳香環構造単位は、アルキル基などで置換されていても良い。また，ホウ素と結合する部位は，芳香環構造単位であることが好ましい．
【００１５】
具体的には、２個以上の芳香環構造単位が直接結合した例としては、ビナフチルの骨格を有する２価の残基が挙げられる。
【００１７】
Ａは、炭素数１０〜４０個からなる２価の縮合芳香環基、または、少なくとも１つの炭素数１０〜４０個からなる縮合芳香環を含む芳香環構造単位２〜１０個が直接連結した２価の基である。その具体例は、ナフタレン、アントラセン、フェナントレン、フルオレン、ピレン、クリセン、ナフタセン、ペンタセン、ペリレン、アズレン、コロネン、ルビセン、デカシクレン、１，１−ビナフタレン、９，９−ビアントラセン等がある。
【００１８】
以下に、本発明の一般式［１］の化合物のＡの構造の代表例を、表１に具体的に例示するが、本発明は、この代表例に限定されるものではない。
【００１９】
【表１】
【表１】
【表１】
【表１】
本発明における一般式［１］で示される化合物のＡｒ1〜Ａｒ4は、それぞれ独立に、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単環基、置換もしくは未置換の縮合多環基を表す。Ａｒ1〜Ａｒ4の具体例は、置換もしくは未置換のアルキル基としては、置換もしくは未置換のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基、２−フェニルイソプロピル基、トリクロロメチル基、トリフルオロメチル基、ベンジル基、α−フェノキシベンジル基、α，α−ジメチルベンジル基、α，α−メチルフェニルベンジル基、α，α−ジトリフルオロメチルベンジル基、トリフェニルメチル基、α−ベンジルオキシベンジル基等の炭素数１〜３０のアルキル基の置換基がある。
【００３０】
置換もしくは未置換の単環基としては、単環シクロアルキル基、単環アリール基、単環複素環基等がある。単環シクロアルキル基としては、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等の炭素数４〜８のシクロアルキル基がある。単環アリール基としては、フェニル基がある。単環複素環基としては、チエニル基、チオフェニル基、フリル基、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジニル基、ピラジニル基、ピリミジニル基、ピリダジニル基、トリアジニル基、トリアゾリル基、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。
【００３１】
置換もしくは未置換の縮合多環基としては、縮合多環アリール基、縮合多環複素環基、縮合多環シクロアルキル基等がある。縮合多環アリール基としては、ナフチル基、アントラニル基、フェナントレニル基、フルオレニル基、アセナフチル基、アズレニル基、ヘプタレニル基、アセナフチレニル基、ピレニル基、ペリレニル基、トリフェニレル基等がある。
【００３２】
縮合多環複素環基としては、インドリル基、キノリル基、イソキノリル基、フタラジニル基、キノキサリニル基、キナゾリニル基、カルバゾリル基、アクリジニル基、フェナジニル基、フルフリル基、イソチアゾリル基、イソキサゾリル基、フラザニル基、フェノキサジニル基、ベンゾチアゾリル基、ベンゾオキサゾリル基、ベンズイミダゾリル、ベンゾトリアゾリル基、プラニル基等がある。その他の縮合多環基として、１−テトラリル基、２−テトラリル基、テトラヒドロキノリル基等がある。
【００３３】
Ａｒ1とＡｒ2とは、または、Ａｒ3とＡｒ4とは、互いに結合して一体となっても良く、ピロリジン環、ジオキソラン環、ピラゾリジン環、ピペリジン環、ジオキサン環、モルフォリン環、ピペラジン環、トリチアン環等および上記芳香族複素環が結合されて形成される。
【００３４】
ＡないしはＡｒ1〜Ａｒ4の有する置換基の具体例は、ハロゲン原子としては弗素、塩素、臭素、ヨウ素、置換もしくは未置換のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基、２−フェニルイソプロピル基、トリクロロメチル基、トリフルオロメチル基、ベンジル基、α−フェノキシベンジル基、α，α−ジメチルベンジル基、α，α−メチルフェニルベンジル基、α，α−ジトリフルオロメチルベンジル基、トリフェニルメチル基、α−ベンジルオキシベンジル基等がある。置換もしくは未置換のアルコキシル基としては、メトキシ基、エトキシ基、プロポキシ基、ｎ−ブトキシ基、ｔ−ブトキシ基、ｎ−オクチルオキシ基、ｔ−オクチルオキシ基、１，１，１−テトラフルオロエトキシ基、フェノキシ基、ベンジルオキシ基、オクチルフェノキシ基等がある。置換もしくは未置換のアリール基としては、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、４−エチルフェニル基、ビフェニル基、４−メチルビフェニル基、４−エチルビフェニル基、４−シクロヘキシルビフェニル基ターフェニル基、３，５−ジクロロフェニル基、ナフチル基、５−メチルナフチル基、アントリル基、ピレニル基等がある。置換もしくは未置換のアミノ基としては、アミノ基、ジメチルアミノ基、ジエチルアミノ基、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、ジベンジルアミノ基等がある。また、隣接する置換基同士で、それぞれ互いに結合して、置換もしくは未置換の、シクロペンテン環、シクロヘキセン環、フェニル環、ナフタレン環、アントラセン環、ピレン環、フルオレン環、フラン環、チオフェン環、ピロール環、オキサゾール環、チアゾール環、イミダゾール環、ピリジン環、ピラジン環、ピロリン環、ピラゾリン環、インドール環、キノリン環、キノキサリン環、キサンテン環、カルバゾール環、アクリジン環、フェナントロリン環等を新たに形成しても良い。
【００３５】
以下に、本発明の一般式［１］の化合物のホウ素原子の外側の基（一般式［１］における、Ａｒ1〜Ａｒ4）の代表例を、表２に具体的に例示するが、本発明は、この代表例に限定されるものではない。
【００３６】
【表２】
本発明における化合物はホウ素原子を導入することにより、ガラス転移点や融点が高くなる。このため、電界発光時における有機層中、有機層間もしくは、有機層と金属電極間で発生するジュール熱に対する耐性（耐熱性）が向上するので、有機ＥＬ素子材料として使用した場合、高い発光輝度を示し、長時間発光させる際にも有利である。
【００４０】
本発明の一般式［１］で示される化合物の一般的な合成方法を以下に示す。一般式［１］のＡに当たる２価の残基のリチウム化合物と、Ａｒ1およびＡｒ2、もしくはＡｒ3およびＡｒ4と、フッ素とを有するホウ素誘導体を、テトラヒドルフラン溶媒中で反応させて、一般式［１］の化合物を合成することができ る。一般式［１］のＡに当たる２価の残基のリチウム化合物に代えて当該残基のナトリウム化合物から合成できるものもある。溶媒は、ジエチルエーテル、石油エーテル、またはヘキサンがある。以上の合成法は一例であり、特に限定されるものではない。
【００４１】
以下に、本発明の一般式［１］の化合物の代表例を、表３に具体的に例示するが、本発明は、この代表例に限定されるものではない。
【００４２】
【表３】
【表３】
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場発光性にも優れている。また、金属電極からの優れた電子注入性および電子輸送性を併せて持ち合わせているので、発光材料として有効に使用することができ、更には、他の正孔輸送性材料、電子輸送性材料もしくはドーピング材料を使用してもさしつかえない。
【００５０】
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、正孔注入材料もしくは電子注入材料を含有しても良い。しかしながら、本発明の発光材料は、極めて高い発光量子効率、高い正孔輸送能力および電子輸送能力を併せ持ち、均一な薄膜を形成することができるので、本発明の発光材料のみで発光層を形成することも可能である。多層型は、（陽極／正孔注入帯域／発光層／陰極）、（陽極／発光層／電子注入帯域／陰極）、（陽極／正孔注入帯域／発光層／電子注入帯域／陰極）の多層構成で積層した有機ＥＬ素子がある。一般式［１］の化合物は、高い発光特性を持ち、正孔注入性、正孔輸送特性および電子注入性、電子輸送特性をもっているので、発光材料として発光層に使用できる。
【００５１】
発光層には、必要があれば、本発明の一般式［１］の化合物に加えて、さらなる公知の発光材料、ドーピング材料、正孔注入材料や電子注入材料を使用することもできる。有機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。必要があれば、発光材料、ドーピング材料、正孔注入材料や電子注入材料を組み合わせて使用することが出来る。また、ドーピング材料により、発光輝度や発光効率の向上、赤色や青色の発光を得ることもできる。また、正孔注入帯域、発光層、電子注入帯域は、それぞれ二層以上の層構成により形成されても良い。その際には、正孔注入帯域の場合、電極から正孔を注入する層を正孔注入層、正孔注入層から正孔を受け取り発光層まで正孔を輸送する層を正孔輸送層と呼ぶ。同様に、電子注入帯域の場合、電極から電子を注入する層を電子注入層、電子注入層から電子を受け取り発光層まで電子を輸送する層を電子輸送層と呼ぶ。これらの各層は、材料のエネルギー準位、耐熱性、有機層もしくは金属電極との密着性等の各要因により選択されて使用される。
【００５２】
一般式［１］の化合物と共に発光層に使用できる発光材料または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、ベンゾキノリン金属錯体、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、ルブレンおよび色素レーザー用や増白用の蛍光色素等があるが、これらに限定されるものではない。
【００５３】
一般式［１］の化合物および共に発光層に使用できる上記の化合物の発光層中での存在比率はどれが主成分であってもよい。つまり、上記の化合物および本発明における化合物のそれぞれの組み合わせにより、本発明における化合物は発光層を形成する主材料にも他の主材料中へのドーピンク材料にも成り得る。
【００５４】
正孔注入材料としては、正孔を輸送する能力を持ち、陽極からの正孔注入効果、発光層または発光材料に対して優れた正孔注入効果を有し、発光層で生成した励起子の電子注入帯域または電子注入材料への移動を防止し、かつ薄膜形成能力の優れた化合物が挙げられる。具体的には、フタロシアニン誘導体、ナフタロシアニン誘導体、ポルフィリン誘導体、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、イミダゾールチオン、ピラゾリン、ピラゾロン、テトラヒドロイミダゾール、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。
【００５５】
本発明の有機ＥＬ素子において使用できる正孔注入材料の中で、さらに効果的な正孔注入材料は、アリールアミン誘導体、フタロシアニン化合物ないしは トリフェニレン誘導体である。アリールアミン誘導体の具体例としては、トリフェニルアミン、トリトリルアミン、トリルジフェニルアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ジ−ｍ−トリル−４，４’−ビフェニルジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ（ｐ−トリル）−ｐ−フェニレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ−ｐ−トリル−４，４’−ビフェニルジアミン、Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ジ（１−ナフチル）−４，４’−ビフェニルジアミン、Ｎ，Ｎ’−ジ（４−ｎ−ブチルフェニル）−Ｎ，Ｎ’−ジ−ｐ−トリル−９，１０−フェナントレンジアミン、４，４’，４”−トリス（Ｎ−フェニル−Ｎ−ｍ−トリルアミノ）トリフェニルアミン、１，１−ビス［４−（ジ−ｐ−トリルアミノ）フェニル］シクロヘキサン等、もしくはこれらの芳香族三級アミン骨格を有したオリゴマーもしくはポリマー等があるが、これらに限定されるものではない。
【００５６】
フタロシアニン（Ｐｃ）化合物の具体例としては、Ｈ2Ｐｃ、ＣｕＰｃ、Ｃ ｏＰｃ、ＮｉＰｃ、ＺｎＰｃ、ＰｄＰｃ、ＦｅＰｃ、ＭｎＰｃ、ＣｌＡｌＰｃ、ＣｌＧａＰｃ、ＣｌＩｎＰｃ、ＣｌＳｎＰｃ、Ｃｌ2ＳｉＰｃ、（ＨＯ）Ａ ｌＰｃ、（ＨＯ）ＧａＰｃ、ＶＯＰｃ、ＴｉＯＰｃ、ＭｏＯＰｃ、ＧａＰｃ−Ｏ−ＧａＰｃ等のフタロシアニン誘導体およびナフタロシアニン誘導体等があるが、これらに限定されるものではない。
【００５７】
トリフェニレン誘導体の具体例としては、ヘキサメトキシトリフェニレン、ヘキサエトキシトリフェニレン、ヘキサヘキシルオキシトリフェニレン、ヘキサベンジルオキシトリフェニレン、トリメチレンジオキシトリフェニレン、トリエチレンジオキシトリフェニレンなどのヘキサアルコキシトリフェニレン類、ヘキサフェノキシトリフェニレン、ヘキサナフチルオキシトリフェニレン、ヘキサビフェニリルオキシトリフェニレン、トリフェニレンジオキシトリフェニレンなどのヘキサアリールオキシトリフェニレン類、ヘキサアセトキシトリフェニレン、ヘキサベンゾイルオキシトリフェニレンなどのヘキサアシロキシトリフェニレン類等があるが、これらに限定されるものではない。
【００５８】
電子注入材料としては、電子を輸送する能力を持ち、陰極からの正孔注入効果、発光層または発光材料に対して優れた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帯域への移動を防止し、かつ薄膜形成能力の優れた化合物が挙げられる。例えば、フルオレノン、アントラキノジメタン、ジフェノキノン、チオピランジオキシド、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、ペリレンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等とそれらの誘導体があるが、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することにより増感させることもできる。
【００５９】
本発明の有機ＥＬ素子において、さらに効果的な電子注入材料は、金属錯体化合物もしくは含窒素五員環誘導体である。具体的には、金属錯体化合物としては、８−ヒドロキシキノリナートリチウム、ビス（８−ヒドロキシキノリナート）亜鉛、ビス（８−ヒドロキシキノリナート）銅、ビス（８−ヒドロキシキノリナート）マンガン、トリス（８−ヒドロキシキノリナート）アルミニウム、トリス（２−メチル−８−ヒドロキシキノリナート）アルミニウム、トリス（８−ヒドロキシキノリナート）ガリウム、ビス（１０−ヒドロキシベンゾ［ｈ］キノリナート）ベリリウム、ビス（１０−ヒドロキシベンゾ［ｈ］キノリナート）亜鉛、ビス（２−メチル−８−ヒドロキシキノリナート）クロロガリウム、ビス（２−メチル−８−ヒドロキシキノリナート）（ｏ−クレゾラート）ガリウム、ビス（２−メチル−８−ヒドロキシキノリナート）（１−ナフトラート）アルミニウム、ビス（２−メチル−８−ヒドロキシキノリナート）（２−ナフトラート）ガリウム、ビス（２−メチル−８−ヒドロキシキノリナート）フェノラートガリウム、ビス（ｏ−（２−ベンゾオキサゾリル）フェノラート）亜鉛、ビス（ｏ−（２−ベンゾチアゾリル）フェノラート）亜鉛、ビス（ｏ−（２−ベンゾトリアゾリル）フェノラート）亜鉛等があるが、これらに限定されるものではない。
【００６０】
また、含窒素五員誘導体としては、オキサゾール、チアゾール、オキサジアゾール、チアジアゾールもしくはトリアゾール誘導体が好ましい。具体的には、２，５−ビス（１−フェニル）−１，３，４−オキサゾール、ジメチルＰＯＰＯＰ、２，５−ビス（１−フェニル）−１，３，４−チアゾール、２，５−ビス（１−フェニル）−１，３，４−オキサジアゾール、２−（４’−ｔｅｒｔ−ブチルフェニル）−５−(４”−ビフェニル)−１，３，４−オキサジアゾール、２，５−ビス（１−ナフチル）−１，３，４−オキサジアゾール、１，４−ビス［２−(５−フェニルオキサジアゾリル)］ベンゼン、１，４−ビス［２−(５−フェニルオキサジアゾリル)−４−ｔｅｒｔ−ブチルベンゼン］、２−（４’−ｔｅｒｔ−ブチルフェニル）−５−(４”−ビフェニル)−１，３，４−チアジアゾール、２，５−ビス（１−ナフチル）−１，３，４−チアジアゾール、１，４−ビス［２−(５−フェニルチアジアゾリル)］ベンゼン、２−（４’−ｔｅｒｔ−ブチルフェニル）−５−(４”−ビフェニル)−１，３，４−トリアゾール、２，５−ビス（１−ナフチル）−１，３，４−トリアゾール、１，４−ビス［２−(５−フェニルトリアゾリル)］ベンゼン等があるが、これらに限定されるものではない。
【００６１】
本有機ＥＬ素子においては、発光層中に、一般式［１］化合物の他に、発光材料、ドーピング材料、正孔注入材料および電子注入材料の少なくとも１種が同一層に含有されてもよい。また、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、樹脂等により素子全体を保護することも可能である。
【００６２】
有機ＥＬ素子の陽極に使用される導電性材料としては、４ｅＶより大きな仕事関数を持つものが適しており、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基板に使用される酸化スズ、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。
【００６３】
陰極に使用される導電性物質としては、４ｅＶより小さな仕事関数を持つものが適しており、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、アルミニウム等およびそれらの合金が用いられるが、これらに限定されるものではない。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、蒸着源の温度、雰囲気、真空度等により制御され、適切な比率に選択される。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。
【００６４】
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にすることが望ましい。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が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、透明性を有するもの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、ポリエチレンテレフテレート板、ポリエーテルサルフォン板、ポリプロピレン板等の透明樹脂があげられる。
【００６５】
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、プラズマ、イオンプレーティ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、フローコーティ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、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。
【００６６】
湿式成膜法の場合、各層を形成する材料を、エタノール、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させ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、いずれの有機薄膜層においても、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。使用の可能な樹脂としては、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およびそれらの共重合体、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。
【００６７】
以上のように、有機ＥＬ素子の発光層に本発明の化合物を用いることにより、発光効率、最大発光輝度等の有機ＥＬ素子特性を改良することができた。また、この素子は熱や電流に対して非常に安定であり、さらには低い駆動電圧で実用的に使用可能の発光輝度が得られるため、従来まで大きな問題であった劣化も大幅に低下させることができた。
【００６８】
本発明の有機ＥＬ素子は、壁掛けテレビ等のフラットパネルディスプレイや、平面発光体として、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等へ応用が考えられ、その工業的価値は非常に大きい。
【００６９】
本発明の材料は、有機ＥＬ素子、電子写真感光体、光電変換素子、太陽電池、イメージセンサー等の分野においても使用できる。
【００７０】
【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。
参考合成例
下記化合物（２）の合成方法
アルゴン気流下、テトラヒドロフラン５０部、９，１０−ジリチウムアントラセン６部を加え、−５０℃に冷却下、ジメシチルフルオロボロンのジエチルエーテル溶液５０部を入れ、２４時間攪拌した。その後、溶媒を除き、得られた個体を希塩酸で処理し、目的物をエーテルで抽出した。これを濃縮し、シリカゲルを用いたカラムクロマトグラフィーにより精製して粉末３部を得た。分子量分析、赤外線吸収スペクトルの結果、化合物（２）であることを確認した。
【化５】
実施例３
洗浄したＩＴＯ電極付きガラス板上に、表３の化合物（３）を塩化メチレンに溶解させ、スピンコーティング法により膜厚５０ｎｍの発光層を得た。次い で、ビス（２−メチル−８−ヒドロキシキノリナート）（２−ナフトラート）ガリウムを真空蒸着して膜厚１０ｎｍの電子注入層を作成し、その上に、マグネシウムとアルミニウムを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。発光層および電子注入層は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１００（ｃｄ／ｍ2）、最高輝度６０００（ｃｄ／ｍ2）、発光効率０．５（ｌｍ／Ｗ）の発光が得られた。
【００７５】
実施例９〜１１、１７〜２０
洗浄したＩＴＯ電極付きガラス板上に表４の正孔注入材料のうちの１種を真空蒸着して、膜厚３０ｎｍの正孔注入層を得た。次いで、表３の発光材料のうちの１種を真空蒸着して膜厚３０ｎｍ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。各層は１０-6Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。各素子に使用した材料とこの素子の発光特性を表５に示す。本実施例の有機ＥＬ素子は、全て最高輝度４０００（ｃｄ／ｍ2）以上の輝度特性を有していた。
【００７６】
【表４】
【表５】
実施例２２
洗浄したＩＴＯ電極付きガラス板上に、銅フタロシアニンを真空蒸着して、膜厚２５ｎｍの第一正孔注入層を得た。さらに、正孔注入材料（Ｈ−２）を真空蒸着して、膜厚５ｎｍの第二正孔注入層を得た。次いで、発光材料として化合物（３）を真空蒸着して膜厚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１５０ｎｍの電極を形成して有機ＥＬ素子を得た。この素子は、直流電圧５Ｖで７１０（ｃｄ／ｍ2）、最高輝度 ９０００（ｃｄ／ｍ2）、発光効率１．０（ｌｍ／Ｗ）の発光が得られた。
【００８４】
実施例２３
洗浄したＩＴＯ電極付きガラス板上に、表４の化合物（Ｈ−８）真空蒸着して、膜厚２５ｎｍの第一正孔注入層を得た。さらに、正孔注入材料（Ｈ−５）を真空蒸着して、膜厚５ｎｍの第二正孔注入層を得た。次いで、発光材料として化合物（３）を真空蒸着して膜厚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１５０ｎｍの電極を形成して有機ＥＬ素子を得た。この素子は、直流電圧５Ｖで６５０（ｃｄ／ｍ2）、最高 輝度８０００（ｃｄ／ｍ2）、発光効率０．９（ｌｍ／Ｗ）の発光が得られた 。
【００８７】
実施例２６
発光層として、表３の化合物（３）とＮ，Ｎ’−ジメチルキナクリドンを１００：１の重量比で蒸着した膜厚３０ｎｍの発光層を使用する以外は、実施例５と同様の方法で有機ＥＬ素子を作製した。この素子は、直流電圧５Ｖで６００（ｃｄ／ｍ2）、最高輝度５００００（ｃｄ／ｍ2）、発光効率５．２（ｌｍ／Ｗ）の発光が得られた。
【００８８】
本実施例で示された有機ＥＬ素子は、発光輝度として５０００（ｃｄ／ｍ2 ）以上であり、全て高い発光効率を得ることができた。本実施例で示された有機ＥＬ素子について、３（ｍＡ／ｃｍ2）で連続発光させたところ、１０００ 時間以上安定な発光を観測することができ、ダークスポットもほとんど観察されなかった。本発明の有機ＥＬ素子材料を発光材料として使用した有機ＥＬ素子は、発光材料の蛍光量子効率が極めて高いので、この発光材料を使用した素子においては、低電流印可領域での高輝度発光が可能になり、また、発光層中で一般式［１］の化合物に加えてドーピング材料を使用することにより、最大発光輝度、最大発光効率を向上させることができた。さらには、一般式［１］の化合物に、蛍光色の異なるドーピング材料を添加することによって、異なる発光色の発光素子を得ることができた。
【００８９】
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。
【００９０】
【発明の効果】
本発明の有機ＥＬ素子材料を発光材料として使用した有機ＥＬ素子は、従来に比べて高い発光効率で高輝度の発光を示し、長寿命の有機ＥＬ素子を得るこ とができた。以上により本発明で示した化合物を、有機ＥＬ素子の少なくとも一層に使用すること、および、本発明の素子構成により形成された有機ＥＬ素子は、高輝度、高発光効率、長寿命の有機ＥＬ素子を容易に作製することが可能となった。[0001]
[Industrial application fields]
The present invention relates to a light-emitting material for organic electroluminescence (EL) elements and a high-luminance light-emitting element used for flat light sources and displays.
[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 element 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, holes are injected from the anode side, the electrons recombine with holes in the light emitting layer, and the energy level starts from the conduction band. It is a phenomenon in which energy is released as light when returning 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, organic EL devices in which thin films containing organic compounds with high fluorescence quantum efficiency that emit light at a low voltage of 10 V or less have been reported and attracted attention (Applied Physics Letters, Vol. 51, page 913). 1987). This method uses a metal chelate complex as a light emitting layer and an amine compound as a hole injection layer to obtain a high luminance green light emission. The luminance is several thousand cd / m 2 at a direct current voltage of 6 to 7 V, maximum. The luminous efficiency is 1.5 lm / W, which is close to the practical range.
[0004]
However, the organic EL devices up to now have improved light emission intensity due to the improvement of the structure, but do not yet have sufficient light emission luminance. Moreover, it has a big problem that it is inferior in stability during repeated use. This is because, for example, metal chelate complexes such as tris (8-hydroxyquinolinate) aluminum complex are chemically unstable during electroluminescence, poor adhesion to the cathode, and greatly deteriorated in a short time of light emission. It was. For the above reasons, in order to develop an organic EL device having high luminous brightness and luminous efficiency and excellent stability during repeated use, the development of a light-emitting material with excellent luminous ability and durability has been developed. It is desired.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide an organic EL device having high emission luminance and excellent stability in repeated use. As a result of intensive studies by the present inventors, the organic EL device using the organic EL device material represented by the general formula [1] has high emission luminance and light emission efficiency, and excellent stability during repeated use. As a result, the present invention has been accomplished.
[0006]
[Means for Solving the Problems]
The present invention relates to a light emitting material for an organic electroluminescence element represented by the following general formula [1].
General formula [1]
[0007]
[Chemical 2]
[In the formula, B represents a boron atom, and A represents a divalent condensed aromatic ring group having 10 to 40 carbon atoms, or an aromatic ring containing at least one condensed aromatic ring having 10 to 40 carbon atoms. It represents a divalent group in which 2 to 10 structural units are directly connected. Ar 1 to Ar 4 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted monocyclic group, a substituted or unsubstituted condensed polycyclic group, and Ar 1 and Ar 2 are Ar 3 and Ar 4 may be combined with each other. However, the case where it is a borane derivative represented by the following general formula [2] is excluded. ]
General formula [2]
[Formula 4]
[0009]
The present invention is also the above-described material for an organic electroluminescence device, wherein Ar 1 to Ar 4 are substituted or unsubstituted monocyclic aryl groups.
Further, the present invention provides an organic electroluminescence device comprising a light emitting layer or a plurality of organic compound thin films including a light emitting layer between a pair of electrodes, wherein any one of the layers is the above organic electroluminescent device material. It is an organic electroluminescent element characterized by containing as a mixture.
Further, the present invention provides an organic electroluminescent device comprising a light emitting layer or a plurality of organic compound thin film containing a light emitting layer between a pair of electrodes, wherein the light emitting layer contains the above organic electroluminescent device material alone or as a mixture. It is an organic electroluminescent element characterized by doing.
[0010]
Further, the present invention provides an organic electroluminescent device comprising a light emitting layer or a plurality of organic compound thin film containing a light emitting layer between a pair of electrodes, wherein the electron injecting layer is a single or mixture of the above organic electroluminescent device materials. It is an organic electroluminescent element characterized by containing.
Furthermore, the present invention is the above organic electroluminescence device, wherein a hole injection layer is formed between the anode and the light emitting layer.
The present invention is also the above organic electroluminescence device, wherein the hole injection layer is a layer containing at least one selected from the group consisting of arylamine derivatives, phthalocyanine compounds, and triphenylene derivatives.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
A of the compound represented by the general formula [1] in the present invention includes a divalent condensed aromatic ring group having 10 to 40 carbon atoms, or at least one condensed aromatic ring having 10 to 40 carbon atoms. It represents a divalent group in which 2 to 10 aromatic ring structural units are directly connected. Specific examples of the substituted or unsubstituted divalent fused aromatic ring group include naphthalene, anthracene, phenanthrene, fluorene, pyrene, chrysene, naphthacene, perylene, azulene, fluorenone, anthraquinone, dibenzosuberenone, tetracyanoquinodimethane, Examples thereof include divalent residues of substituted or unsubstituted condensed aromatic rings such as coronene, rubicene, and decacyclene.
[0014]
The aromatic ring structural unit may be substituted with an alkyl group or the like. Moreover, it is preferable that the site | part couple | bonded with boron is an aromatic ring structural unit.
[0015]
Specifically, two or more aromatic rings structural units Examples bound directly, divalent residue having a skeleton of binaphthy Le.
[0017]
A is a divalent condensed aromatic ring group having 10 to 40 carbon atoms, or 2 to 10 aromatic ring structural units each having at least one condensed aromatic ring having 10 to 40 carbon atoms directly connected to each other. Is a valent group. Specific examples thereof include naphthalene, anthracene, phenanthrene, fluorene, pyrene, chrysene, naphthacene, pentacene, perylene, azulene, coronene, rubicene, decacyclene, 1,1-binaphthalene, 9,9-bianthracene and the like.
[0018]
Hereinafter, typical examples of the structure of A of the compound of the general formula [1] of the present invention are specifically illustrated in Table 1, but the present invention is not limited to these representative examples.
[0019]
[Table 1]
[Table 1]
[Table 1]
[Table 1]
Ar 1 to Ar 4 in the compound represented by the general formula [1] in the present invention are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted monocyclic group, a substituted or unsubstituted condensed polycyclic group. Represents. Specific examples of Ar 1 to Ar 4 include a substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, or a tert-butyl group. Group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α, α-dimethylbenzyl group, α , Α-methylphenylbenzyl group, α, α-ditrifluoromethylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group and the like.
[0030]
Examples of the substituted or unsubstituted monocyclic group include a monocyclic cycloalkyl group, a monocyclic aryl group, and a monocyclic heterocyclic group. Examples of the monocyclic cycloalkyl group include cycloalkyl groups having 4 to 8 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. A monocyclic aryl group includes a phenyl group. Monocyclic heterocyclic groups include thienyl, thiophenyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, triazolyl, oxazolyl, thiazolyl, There are oxadiazolyl group, thiadiazolyl group, imidadiazolyl group and the like.
[0031]
Examples of the substituted or unsubstituted condensed polycyclic group include a condensed polycyclic aryl group, a condensed polycyclic heterocyclic group, and a condensed polycyclic cycloalkyl group. Examples of the condensed polycyclic aryl group include a naphthyl group, anthranyl group, phenanthrenyl group, fluorenyl group, acenaphthyl group, azulenyl group, heptalenyl group, acenaphthylenyl group, pyrenyl group, perylenyl group, and triphenylyl group.
[0032]
The condensed polycyclic heterocyclic group includes indolyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, phenoxazinyl group Benzothiazolyl group, benzoxazolyl group, benzimidazolyl, benzotriazolyl group, pranyl group and the like. Examples of other condensed polycyclic groups include 1-tetralyl group, 2-tetralyl group, tetrahydroquinolyl group and the like.
[0033]
Ar 1 and Ar 2 , or Ar 3 and Ar 4 may be combined to form a pyrrolidine ring, dioxolane ring, pyrazolidine ring, piperidine ring, dioxane ring, morpholine ring, piperazine ring , A trithiane ring, etc. and the above aromatic heterocycle are formed.
[0034]
Specific examples of the substituent of A or Ar 1 to Ar 4 include fluorine, chlorine, bromine, iodine as a halogen atom, methyl group, ethyl group, propyl group, butyl group as substituted or unsubstituted alkyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, 2-phenylisopropyl group, trichloromethyl group, trifluoromethyl group, benzyl group, α-phenoxybenzyl group, α , Α-dimethylbenzyl group, α, α-methylphenylbenzyl group, α, α-ditrifluoromethylbenzyl group, triphenylmethyl group, α-benzyloxybenzyl group and the like. Examples of the substituted or unsubstituted alkoxyl group include methoxy group, ethoxy group, propoxy group, n-butoxy group, t-butoxy group, n-octyloxy group, t-octyloxy group, 1,1,1-tetrafluoroethoxy Group, phenoxy group, benzyloxy group, octylphenoxy group and the like. Examples of substituted or unsubstituted aryl groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, biphenyl, 4-methylbiphenyl, 4-ethylbiphenyl. Group, 4-cyclohexylbiphenyl group terphenyl group, 3,5-dichlorophenyl group, naphthyl group, 5-methylnaphthyl group, anthryl group, pyrenyl group and the like. Examples of the substituted or unsubstituted amino group include an amino group, a dimethylamino group, a diethylamino group, a phenylmethylamino group, a diphenylamino group, a ditolylamino group, and a dibenzylamino group. Further, adjacent substituents are bonded to each other, and are substituted or unsubstituted, cyclopentene ring, cyclohexene ring, phenyl ring, naphthalene ring, anthracene ring, pyrene ring, fluorene ring, furan ring, thiophene ring, pyrrole ring. , Oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyrazine ring, pyrroline ring, pyrazoline ring, indole ring, quinoline ring, quinoxaline ring, xanthene ring, carbazole ring, acridine ring, phenanthroline ring, etc. good.
[0035]
Specific examples of groups outside the boron atom of the compound of the general formula [1] of the present invention (Ar 1 to Ar 4 in the general formula [1]) are specifically exemplified in Table 2, The invention is not limited to this representative example.
[0036]
[Table 2]
The compound in the present invention has a high glass transition point and melting point by introducing boron atoms. For this reason, resistance to Joule heat (heat resistance) generated in the organic layer during organic electroluminescence, between the organic layers or between the organic layer and the metal electrode is improved. This is also advantageous when emitting light for a long time.
[0040]
A general synthesis method of the compound represented by the general formula [1] of the present invention is shown below. A lithium compound having a divalent residue corresponding to A of the general formula [1], Ar 1 and Ar 2 , or Ar 3 and Ar 4 and a boron derivative having fluorine are reacted in a tetrahydrofuran solvent; A compound of the general formula [1] can be synthesized. Some compounds can be synthesized from the sodium compound of the residue instead of the lithium compound of the divalent residue corresponding to A in the general formula [1]. The solvent is diethyl ether, petroleum ether, or hexane. The above synthesis method is an example and is not particularly limited.
[0041]
Hereinafter, representative examples of the compound of the general formula [1] of the present invention are specifically illustrated in Table 3, but the present invention is not limited to these representative examples.
[0042]
[Table 3]
[Table 3]
The compound represented by the general formula [1] of the present invention is a compound having strong fluorescence in the solid state and excellent in electroluminescence. In addition, since it has excellent electron injecting property and electron transporting property from the metal electrode, it can be used effectively as a light emitting material, and further, other hole transporting material, electron transporting material or Doping materials can be used.
[0050]
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 may further contain a hole injecting material or an electron injecting material in order to transport holes injected from the anode or electrons injected from the cathode to the light emitting material. However, since the light emitting material of the present invention has extremely high emission quantum efficiency, high hole transport ability and electron transport ability and can form a uniform thin film, the light emitting layer is formed only by the light emitting material of the present invention. It is also possible. The multi-layer type includes (anode / hole injection band / light emitting layer / cathode), (anode / light emitting layer / electron injection band / cathode), and (anode / hole injection band / light emitting layer / electron injection band / cathode). There are organic EL elements stacked in a configuration. The compound of the general formula [1] has high light emission properties and has hole injection properties, hole transport properties, electron injection properties, and electron transport properties, and therefore can be used as a light emitting material in a light emitting layer.
[0051]
If necessary, in addition to the compound of the general formula [1] of the present invention, further known light emitting materials, doping materials, hole injection materials, and electron injection materials can be used for the light emitting layer. 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 injection material, and an electron injection material can be used in combination. Further, by using a doping material, it is possible to improve light emission luminance and light emission efficiency and to obtain red and blue light emission. Moreover, the hole injection zone, the light emitting layer, and the electron injection zone may each be formed with a layer configuration of two or more layers. In that case, in the case of the hole injection zone, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection zone, a layer for injecting electrons from an electrode is referred to as an electron injection layer, and a layer for receiving electrons from the electron injection layer and transporting electrons to a light emitting layer is referred to as an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or metal electrode.
[0052]
Examples of the light-emitting material or doping material that can be used in the light-emitting layer together with the compound of the general formula [1] include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenyl Butadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole , Pyran, thiopyran, polymethine, merocyanine, imidazole chelating oxinoid compound, quinacridone, rubre However, the present invention is not limited to these.
[0053]
Any of the abundance ratios of the compound of the general formula [1] and the above-mentioned compound that can be used in the light emitting layer in the light emitting layer may be the main component. That is, by the combination of the above-described compound and the compound in the present invention, the compound in the present invention can be a main material for forming a light emitting layer or a dopink material in another main material.
[0054]
As a hole injection material, it has the ability to transport holes, has a hole injection effect from the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and excitons generated in the light emitting layer. Examples thereof include compounds that prevent movement to an electron injection zone or an electron injection material and have an excellent thin film forming ability. Specifically, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyaryl Alkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, etc., and their derivatives, and polymer materials such as polyvinyl carbazole, polysilane, conductive polymer, etc. However, it is not limited to these.
[0055]
Among the hole injection materials that can be used in the organic EL device of the present invention, more effective hole injection materials are arylamine derivatives, phthalocyanine compounds, or triphenylene derivatives. Specific examples of the arylamine derivative include triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N′-di-m-tolyl-4,4′-biphenyldiamine, N, N, N ', N'-tetra (p-tolyl) -p-phenylenediamine, N, N, N', N'-tetra-p-tolyl-4,4'-biphenyldiamine, N, N'-diphenyl-N, N′-di (1-naphthyl) -4,4′-biphenyldiamine, N, N′-di (4-n-butylphenyl) -N, N′-di-p-tolyl-9,10-phenanthrenediamine 4,4 ′, 4 ″ -tris (N-phenyl-Nm-tolylamino) triphenylamine, 1,1-bis [4- (di-p-tolylamino) phenyl] cyclohexane, etc., or aromatics thereof Tertiary amine skeleton There are oligomers or polymers, etc., but is not limited thereto.
[0056]
Specific examples of the phthalocyanine (Pc) compound include H 2 Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl 2 SiPc, (HO) AlPc, (HO) ) There are, but are not limited to, phthalocyanine derivatives and naphthalocyanine derivatives such as GaPc, VOPc, TiOPc, MoOPc, and GaPc-O-GaPc.
[0057]
Specific examples of triphenylene derivatives include hexaalkoxytriphenylenes such as hexamethoxytriphenylene, hexaethoxytriphenylene, hexahexyloxytriphenylene, hexabenzyloxytriphenylene, trimethylenedioxytriphenylene, triethylenedioxytriphenylene, hexaphenoxytriphenylene, hexanaphthyl. Examples include, but are not limited to, hexaaryloxytriphenylenes such as oxytriphenylene, hexabiphenylyloxytriphenylene, and triphenylenedioxytriphenylene, and hexaacyloxytriphenylenes such as hexaacetoxytriphenylene and hexabenzoyloxytriphenylene.
[0058]
As an electron injection material, it has the ability to transport electrons, has a hole injection effect from the cathode, and an excellent electron injection effect for the light-emitting layer or light-emitting material, and hole injection of excitons generated in the light-emitting layer Examples thereof include compounds that prevent migration to the zone and have an excellent thin film forming ability. For example, there are fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and their derivatives. However, it is not limited to these. Further, it can be sensitized by adding an electron accepting substance to the hole injecting material and an electron donating substance to the electron injecting material.
[0059]
In the organic EL device of the present invention, a more effective electron injection material is a metal complex compound or a nitrogen-containing five-membered ring derivative. Specifically, as the metal complex compound, 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinate) zinc, bis (8-hydroxyquinolinate) copper, bis (8-hydroxyquinolinate) manganese , Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium Bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-hydroxyquinolinato) chlorogallium, bis (2-methyl-8-hydroxyquinolinato) (o-cresolate) gallium, Bis (2-methyl-8-hydroxyquinolinate) (1-naphthlar ) Aluminum, bis (2-methyl-8-hydroxyquinolinato) (2-naphtholato) gallium, bis (2-methyl-8-hydroxyquinolinato) phenolate gallium, bis (o- (2-benzoxazolyl) (L) phenolate) zinc, bis (o- (2-benzothiazolyl) phenolate) zinc, bis (o- (2-benzotriazolyl) phenolate) zinc, and the like, but are not limited thereto.
[0060]
Further, as the nitrogen-containing five-membered derivative, an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative is preferable. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5- Bis (1-phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-oxadiazole, 2, 5-bis (1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyl) Oxadiazolyl) -4-tert-butylbenzene], 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-thiadiazole, 2,5-bis (1- Naphthyl) -1,3,4-thiadiazole, 1,4-bis [2- (5- Benzyl thiadiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1, Examples include, but are not limited to, 3,4-triazole and 1,4-bis [2- (5-phenyltriazolyl)] benzene.
[0061]
In the organic EL device, in the light emitting layer, in addition to the compound of the general formula [1], at least one of a light emitting material, a doping material, a hole injection material, and an electron injection material may be contained in the same layer. 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 is provided on the surface of the device, or the entire device is protected by silicon oil, resin, etc. Is also possible.
[0062]
As a conductive material used for an anode of an organic EL element, a material having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, etc. Further, alloys thereof, metals such as tin oxide and indium oxide used for ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used.
[0063]
As the conductive material used for the cathode, those having a work function smaller than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, and alloys thereof are used. However, it is not limited to these. 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 temperature of the vapor deposition source, the atmosphere, the degree of vacuum, etc., and is selected to an appropriate ratio. If necessary, the anode and the cathode may be formed of two or more layers.
[0064]
In the organic EL element, in order to efficiently emit light, it is desirable that at least one of the elements be sufficiently transparent in the light emission wavelength region of the element. The substrate is also preferably transparent. The transparent electrode is set using the above-described conductive material so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering. The electrode on the light emitting surface preferably has a light transmittance of 10% or more. The substrate is not limited as long as it has mechanical and thermal strength and has transparency. For example, a glass substrate, a polyethylene plate, a polyethylene terephthalate plate, a polyethersulfone plate, Examples thereof include a transparent resin such as a polypropylene plate.
[0065]
For the formation of each layer of the organic EL device according to the present invention, any of dry film forming methods such as vacuum deposition, sputtering, plasma, ion plating, etc. and wet film forming methods such as spin coating, dipping, and flow coating is applied. be able to. The film thickness is not particularly limited, but must 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.
[0066]
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 ethanol, chloroform, tetrahydrofuran, dioxane or the like to form a thin film, and any solvent may be used. In any organic thin film layer, an appropriate resin or additive may be used for improving film formability and preventing pinholes in the film. Usable resins include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
[0067]
As described above, by using the compound of the present invention in the light emitting layer of the organic EL device, the organic EL device characteristics such as the light emission efficiency and the maximum light emission luminance can be improved. In addition, this element is extremely stable against heat and current, and can be used for light emission brightness that can be used practically at a low driving voltage, so that the degradation that has been a major problem until now is greatly reduced. I was able to.
[0068]
The organic EL device of the present invention can be applied to flat panel displays such as wall-mounted TVs, flat light emitters, light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights. The industrial value is very large.
[0069]
The material of the present invention can also be used in the fields of organic EL devices, electrophotographic photoreceptors, photoelectric conversion devices, solar cells, image sensors and the like.
[0070]
【Example】
Hereinafter, the present invention will be described in more detail based on examples.
Reference synthesis example
The following compounds synthesis method Under a stream of argon (2), tetrahydrofuran 50 parts 9,10-lithium anthracene 6 parts was added, under cooling to -50 ° C., placed in diethyl ether solution of 50 parts of di-mesityl fluoro boron, 24 Stir for hours. Thereafter, the solvent was removed, the obtained solid was treated with dilute hydrochloric acid, and the target product was extracted with ether. This was concentrated and purified by column chromatography using silica gel to obtain 3 parts of powder. As a result of molecular weight analysis and infrared absorption spectrum, it was confirmed to be compound (2).
[Chemical formula 5]
Example 3
On the washed glass plate with an ITO electrode, the compound (3) in Table 3 was dissolved in methylene chloride, and a light emitting layer having a thickness of 50 nm was obtained by a spin coating method. Next, bis (2-methyl-8-hydroxyquinolinate) (2-naphtholate) gallium was vacuum-deposited to form an electron injection layer having a thickness of 10 nm, on which magnesium and aluminum were added 10: 1. An electrode having a film thickness of 100 nm was formed from the alloy mixed in the above to obtain an organic EL device. The light emitting layer and the electron injection layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device emitted light of 100 (cd / m 2 ), a maximum luminance of 6000 (cd / m 2 ), and a luminous efficiency of 0.5 (lm / W) at a DC voltage of 5V.
[0075]
Examples 9-11, 17-20
One of the hole injection materials shown in Table 4 was vacuum-deposited on the cleaned glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 30 nm. Next, one of the light emitting materials shown in Table 3 is vacuum-deposited to form a light emitting layer having a thickness of 30 nm, and an alloy in which magnesium and silver are mixed at a ratio of 10: 1 is formed on the light emitting layer. An electrode was formed to obtain an organic EL element. Each layer was deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. Table 5 shows the materials used for each element and the light emission characteristics of the element. All the organic EL elements of this example had a luminance characteristic of a maximum luminance of 4000 (cd / m 2 ) or more.
[0076]
[Table 4]
[Table 5]
Example 22
Copper phthalocyanine was vacuum-deposited on the washed glass plate with an ITO electrode to obtain a first hole injection layer having a thickness of 25 nm. Further, a hole injection material (H-2) was vacuum-deposited to obtain a second hole injection layer having a thickness of 5 nm. Subsequently, the compound (3) was vacuum-deposited as a light emitting material to obtain a light emitting layer having a thickness of 20 nm. On top of that, 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. This device emitted light of 710 (cd / m 2 ), a maximum luminance of 9000 (cd / m 2 ), and a luminous efficiency of 1.0 (lm / W) at a DC voltage of 5V.
[0084]
Example 23
On the washed glass plate with an ITO electrode, the compound (H-8) in Table 4 was vacuum-deposited to obtain a first hole injection layer having a film thickness of 25 nm. Further, a hole injection material (H-5) was vacuum deposited to obtain a second hole injection layer having a thickness of 5 nm. Subsequently, the compound (3) was vacuum-deposited as a light emitting material to obtain a light emitting layer having a thickness of 20 nm. On top of that, 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 emitted light of 650 (cd / m 2 ), a maximum luminance of 8000 (cd / m 2 ), and a luminous efficiency of 0.9 (lm / W) at a DC voltage of 5V.
[0087]
Example 26
The organic layer was prepared in the same manner as in Example 5 except that the light emitting layer was a 30 nm thick light emitting layer in which the compound (3) in Table 3 and N, N′-dimethylquinacridone were deposited at a weight ratio of 100: 1. An EL element was produced. This device emitted light of 600 (cd / m 2 ), a maximum luminance of 50000 (cd / m 2 ), and a luminous efficiency of 5.2 (lm / W) at a DC voltage of 5V.
[0088]
The organic EL elements shown in this example had a light emission luminance of 5000 (cd / m 2 ) or higher, and all were able to obtain high light emission efficiency. When the organic EL device shown in this example was allowed to emit light continuously at 3 (mA / cm 2 ), stable light emission could be observed for 1000 hours or more, and dark spots were hardly observed. The organic EL element using the organic EL element material of the present invention as a light emitting material has a very high fluorescence quantum efficiency of the light emitting material. Therefore, an element using this light emitting material can emit light with high brightness in a low current application region. In addition, by using a doping material in addition to the compound of the general formula [1] in the light emitting layer, it was possible to improve the maximum light emission luminance and the maximum light emission efficiency. Furthermore, by adding doping materials having different fluorescent colors to the compound of the general formula [1], light emitting elements having different emission colors could be obtained.
[0089]
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.
[0090]
【The invention's effect】
The organic EL element using the organic EL element material of the present invention as a light emitting material showed high luminance emission with higher luminous efficiency than the conventional one, and was able to obtain a long-life organic EL element. As described above, the use of the compound shown in the present invention in at least one layer of the organic EL element, and the organic EL element formed by the element configuration of the present invention is an organic EL element having high luminance, high luminous efficiency, and long life. Can be easily produced.
Claims (7)
一般式［１］
一般式［２］
General formula [1]
General formula [2]
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| JP4804661B2 (en) * | 2001-07-11 | 2011-11-02 | コニカミノルタホールディングス株式会社 | Organic electroluminescence device |
| JP4374842B2 (en) * | 2001-11-09 | 2009-12-02 | コニカミノルタホールディングス株式会社 | Organic electroluminescence element and display device |
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| US6835473B2 (en) * | 2001-12-06 | 2004-12-28 | Konica Corporation | Organic electroluminescence element and display |
| KR101102102B1 (en) | 2003-05-08 | 2012-01-18 | 오스람 옵토 세미컨덕터스 게엠베하 | Non-conjugated polymeric perarylated boranes, use thereof as organically semiconductor transmitters and/or transport materials, methods for producing same and uses thereof |
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| KR101378047B1 (en) * | 2006-06-15 | 2014-03-27 | 도레이 카부시키가이샤 | Material for light-emitting device, and light-emitting device |
| KR20100118258A (en) * | 2009-04-28 | 2010-11-05 | 다우어드밴스드디스플레이머티리얼 유한회사 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| JP5379179B2 (en) * | 2011-03-17 | 2013-12-25 | コニカミノルタ株式会社 | Organic electroluminescence element and display device |
| JP5129359B2 (en) * | 2011-03-17 | 2013-01-30 | コニカミノルタホールディングス株式会社 | Organic electroluminescence element and display device |
| WO2016017514A1 (en) * | 2014-07-31 | 2016-02-04 | コニカミノルタ株式会社 | Organic electroluminescent element, light-emitting thin film, display device, and lighting device |
| KR102322013B1 (en) | 2014-12-12 | 2021-11-05 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| KR102328676B1 (en) | 2014-12-24 | 2021-11-19 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| KR102314468B1 (en) | 2014-12-30 | 2021-10-20 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| KR102360091B1 (en) * | 2014-12-31 | 2022-02-09 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
| US11730053B2 (en) | 2015-05-06 | 2023-08-15 | Samsung Display Co., Ltd. | Organic light-emitting device |
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1999
- 1999-04-05 JP JP09717499A patent/JP4026273B2/en not_active Expired - Fee Related
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