JP3562652B2 - Organic electroluminescence device - Google Patents

Organic electroluminescence device Download PDF

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JP3562652B2
JP3562652B2 JP31361892A JP31361892A JP3562652B2 JP 3562652 B2 JP3562652 B2 JP 3562652B2 JP 31361892 A JP31361892 A JP 31361892A JP 31361892 A JP31361892 A JP 31361892A JP 3562652 B2 JP3562652 B2 JP 3562652B2
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light emitting
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JPH05331459A (en
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仁 仲田
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Pioneer Corp
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Pioneer Corp
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Priority to US08/037,454 priority patent/US5393614A/en
Priority to EP19930302459 priority patent/EP0564224B1/en
Priority to DE1993610982 priority patent/DE69310982T2/en
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【０００１】
【産業上の利用分野】
本発明はエレクトロルミネッセンス素子に関し、特に陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子に関する。
【０００２】
【従来の技術】
この種の有機エレクトロルミネッセンス素子として、図１に示すように、陰極である金属電極１と陽極である透明電極２との間に、互いに積層された有機蛍光体薄膜（発光層）３及び有機正孔輸送層４が配された２層構造のものが知れている。また、図２に示すように、金属電極１と透明電極２との間に互いに積層された有機電子輸送層５、発光層３及び有機正孔輸送層４が配された３層構造のものも知れている。ここで、有機正孔輸送層４は陽極から正孔を注入させ易くする機能と電子をブロックする機能とを有し、有機電子輸送層５は陰極から電子を注入させ易くする機能を有している。
【０００３】
これら有機エレクトロルミネッセンス素子において、透明電極２の外側にはガラス基板６が配されている。金属電極１から注入された電子と透明電極２から注入された正孔との再結合によって、励起子が生じ、この励起子が放射失活する過程で光を放ち、この光が透明電極２及びガラス板６を介して外部に放出される。
【０００４】
【発明が解決しようとする課題】
しかしながら、比較的高い輝度で発光が得られる有機エレクトロルミネッセンス素子であっても、輝度について充分満足なものではなかった。
本発明は、上述した従来の要望を満たすべくなされたものであって、有機蛍光体を効率良く高輝度にて発光させることができる有機エレクトロルミネッセンス素子を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明によるエレクトロルミネッセンス素子は、陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層は、前記発光層とは組成が異なりかつ前記発光層に接する下記化学式１で示されるフェナントロリン誘導体
【０００６】
【化１】

Figure 0003562652
【０００７】
（化学式１中、Ｒ1〜Ｒ8は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からなることを特徴とする。本発明によるエレクトロルミネッセンス素子は、陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層は、前記発光層とは組成が異なりかつ前記発光層に接する下記化学式８３で示される１，７−フェナントロリン誘導体
【０００８】
【化８３】
Figure 0003562652
【０００９】
（化学式８３中、Ｒ1〜Ｒ8は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からなることを特徴とする。本発明によるエレクトロルミネッセンス素子は、陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層は、前記発光層とは組成が異なりかつ前記発光層に接する下記化学式８４で示される４，７−フェナントロリン誘導体
【００１０】
【化８４】
Figure 0003562652
【００１１】
（化学式８４中、Ｒ1〜Ｒ8は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からなることを特徴とする。本発明によるエレクトロルミネッセンス素子は、陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層は、前記発光層とは組成が異なりかつ前記発光層に接する下記化学式８７で示されるジベンゾフェナントロリンのジヒドロ体を骨格とするフェナントロリン誘導体
【００１２】
【化８７】
Figure 0003562652
【００１３】
（化学式８７中、Ｒ１〜Ｒ１０は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からなることを特徴とする。
【００１４】
【作用】
本発明によれば、効率良く高輝度で発光させることができる有機エレクトロルミネッセンス素子が得られる。
【００１５】
【実施例】
以下、本発明を図に基づいて詳細に説明する。
本発明の有機エレクトロルミネッセンス素子は、図２に示した構造の有機エレクトロルミネッセンス素子と同様であって、図２に示すように、一対の金属陰極１と透明陽極２との間に電子輸送層５、発光層３及び正孔輸送層４を順に成膜した構造を有する。この場合、電極１，２については一方が透明であればよい。例えば陰極１には、アルミニウム、マグネシウム、インジウム、銀又は各々の合金等の仕事関数が小さな金属からなり厚さが約 １００〜５０００Å程度のものを用い得る。また、例えば陽極２には、インジウムすず酸化物（以下、ＩＴＯともいう）等の仕事関数の大きな導電性材料からなり厚さが１０００〜３０００Å程度で、又は金で厚さが ８００〜１５００Å程度のものを用い得る。なお、金を電極材料として用いた場合には、電極は半透明の状態となる。
【００１６】
図２に示すように有機正孔輸送層４には、例えば下記化学式２のトリフェニルアミン誘導体、更に下記化学式３〜１３のＣＴＭ（Ｃａｒｒｉｅｒ Ｔｒａｎｓｐｏｒｔ Ｍａｔｅｒｉａｌｓ）として知られる化合物を用い得る。
【００１７】
【化２】
Figure 0003562652
【００１８】
【化３】
Figure 0003562652
【００１９】
【化４】
Figure 0003562652
【００２０】
【化５】
Figure 0003562652
【００２１】
【化６】
Figure 0003562652
【００２２】
【化７】
Figure 0003562652
【００２３】
【化８】
Figure 0003562652
【００２４】
【化９】
Figure 0003562652
【００２５】
【化１０】
Figure 0003562652
【００２６】
【化１１】
Figure 0003562652
【００２７】
【化１２】
Figure 0003562652
【００２８】
【化１３】
Figure 0003562652
【００２９】
図２に示すように発光層３としては、下記化学式１４〜１６及び８５で示されるテトラフェニルブタジエン化合物を含む蛍光体薄膜が好ましく用いられる。
【００３０】
【化１４】
Figure 0003562652
【００３１】
【化１５】
Figure 0003562652
【００３２】
【化１６】
Figure 0003562652
【００３３】
【化８５】
Figure 0003562652
【００３４】
また、発光層３としては、さらに記化学式１７〜２５の化合物も用いられる。これらの発光層３の膜厚は１μｍ以下に設定される。
【００３５】
【化１７】
Figure 0003562652
【００３６】
【化１８】
Figure 0003562652
【００３７】
【化１９】
Figure 0003562652
【００３８】
【化２０】
Figure 0003562652
【００３９】
【化２１】
Figure 0003562652
【００４０】
【化２２】
Figure 0003562652
【００４１】
【化２３】
Figure 0003562652
【００４２】
【化２４】
Figure 0003562652
【００４３】
【化２５】
Figure 0003562652
【００４４】
図２に示すように電子輸送層５としては、化学式１で示される一般式の化合物が用いられる。
【００４５】
【化１】
Figure 0003562652
【００４６】
（化学式１中、Ｒ１〜Ｒ８は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）から形成される。
以下、本発明で用いられるフェナントロリン誘導体の具体例を化学式２６〜８２に示すが、本発明はこれに限定されるものではない。
【００４７】
【化２６】
Figure 0003562652
【００４８】
【化２７】
Figure 0003562652
【００４９】
【化２８】
Figure 0003562652
【００５０】
【化２９】
Figure 0003562652
【００５１】
【化３０】
Figure 0003562652
【００５２】
【化３１】
Figure 0003562652
【００５３】
【化３２】
Figure 0003562652
【００５４】
【化３３】
Figure 0003562652
【００５５】
【化３４】
Figure 0003562652
【００５６】
【化３５】
Figure 0003562652
【００５７】
【化３６】
Figure 0003562652
【００５８】
【化３７】
Figure 0003562652
【００５９】
【化３８】
Figure 0003562652
【００６０】
【化３９】
Figure 0003562652
【００６１】
【化４０】
Figure 0003562652
【００６２】
【化４１】
Figure 0003562652
【００６３】
【化４２】
Figure 0003562652
【００６４】
【化４３】
Figure 0003562652
【００６５】
【化４４】
Figure 0003562652
【００６６】
【化４５】
Figure 0003562652
【００６７】
【化４６】
Figure 0003562652
【００６８】
【化４７】
Figure 0003562652
【００６９】
【化４８】
Figure 0003562652
【００７０】
【化４９】
Figure 0003562652
【００７１】
【化５０】
Figure 0003562652
【００７２】
【化５１】
Figure 0003562652
【００７３】
【化５２】
Figure 0003562652
【００７４】
【化５３】
Figure 0003562652
【００７５】
【化５４】
Figure 0003562652
【００７６】
【化５５】
Figure 0003562652
【００７７】
【化５６】
Figure 0003562652
【００７８】
【化５７】
Figure 0003562652
【００７９】
【化５８】
Figure 0003562652
【００８０】
【化５９】
Figure 0003562652
【００８１】
【化６０】
Figure 0003562652
【００８２】
【化６１】
Figure 0003562652
【００８３】
【化６２】
Figure 0003562652
【００８４】
【化６３】
Figure 0003562652
【００８５】
【化６４】
Figure 0003562652
【００８６】
【化６５】
Figure 0003562652
【００８７】
【化６６】
Figure 0003562652
【００８８】
【化６７】
Figure 0003562652
【００８９】
【化６８】
Figure 0003562652
【００９０】
【化６９】
Figure 0003562652
【００９１】
【化７０】
Figure 0003562652
【００９２】
【化７１】
Figure 0003562652
【００９３】
【化７２】
Figure 0003562652
【００９４】
【化７３】
Figure 0003562652
【００９５】
【化７４】
Figure 0003562652
【００９６】
【化７５】
Figure 0003562652
【００９７】
【化７６】
Figure 0003562652
【００９８】
【化７７】
Figure 0003562652
【００９９】
【化７８】
Figure 0003562652
【０１００】
【化７９】
Figure 0003562652
【０１０１】
【化８０】
Figure 0003562652
【０１０２】
【化８１】
Figure 0003562652
【０１０３】
【化８２】
Figure 0003562652
【０１０４】
また、上記実施例では、有機エレクトロルミネッセンス素子における電子輸送層５は、上記化学式１で示される１，１０−フェナントロリンを骨格とする誘導体から形成されているが、下記化学式８３又は８４で示される１，７−フェナントロリン又は４，７−フェナントロリンを骨格とするフェナントロリン誘導体から形成された薄膜でもよい。
【０１０５】
【化８３】
Figure 0003562652
【０１０６】
【化８４】
Figure 0003562652
【０１０７】
化学式８３及び８４中、Ｒ１〜Ｒ８は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす。
さらにまた、１，７−フェナントロリン又は４，７−フェナントロリンを骨格とするフェナントロリン誘導体の他に、有機エレクトロルミネッセンス素子における電子輸送層５は、下記化学式８７で示されるジベンゾフェナントロリンのジヒドロ体を骨格とするフェナントロリン誘導体から形成された薄膜でもよい。
【０１０８】
【化８７】
Figure 0003562652
【０１０９】
化学式８７中、Ｒ１〜Ｒ１０は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす。ジベンゾフェナントロリンのジヒドロ体の誘導体の具体例を化学式８８〜９１に示すが、本発明はこれに限定されるものではない。
【０１１０】
【化８８】
Figure 0003562652
【０１１１】
【化８９】
Figure 0003562652
【０１１２】
【化９０】
Figure 0003562652
【０１１３】
【化９１】
Figure 0003562652
【０１１４】
［実施例１］
膜厚１５００ÅのＩＴＯの薄膜が形成されたガラス基板を、エタノール中で５分間超音波洗浄した後、風乾した。このガラス基板上に、化学式２で示される化合物
【０１１５】
【化２】
Figure 0003562652
【０１１６】
をタンタル製ボートから蒸着速度３Å／秒で ５００Åの膜厚に成膜し、正孔輸送層を形成した。蒸着時の真空度は５×１０−６Ｔｏｒｒであった。
次に、この正孔輸送層上に発光物質として化学式１５で示されるテトラフェニルブタジエン誘導体
【０１１７】
【化１５】
Figure 0003562652
【０１１８】
を蒸着速度４Å／秒で ２００Åの膜厚に成膜し、発光層を形成した。
次に、この発光層上に化学式３９で示されるフェナントロリン化合物
【０１１９】
【化３９】
Figure 0003562652
【０１２０】
を蒸着速度３Å／秒で ５００Åの膜厚に成膜し、電子輸送層を形成した。
最後に、この電子輸送層上に膜厚１５００ÅのＭｇ−Ａｇ合金の金属層を各々別のボートからＭｇを蒸着速度１０Å／秒で、Ａｇを蒸着速度１Å／秒で成膜し、電極層を形成して、有機エレクトロルミネッセンス素子を作成した。
この様にして作成した有機エレクトロルミネッセンス素子のＩＴＯ薄膜を陽極、Ｍｇ−Ａｇ合金層を陰極として電圧を印加したところ、５Ｖで輝度２５ｃｄ／ｍ２の青色発光を得た。このときの発光効率は０．７ ｌｍ／Ｗであった。
【０１２１】
［実施例２］
電子輸送層に化学式４０で示されるフェナントロリン化合物を用いた以外は、実施例１と同様な方法で有機エレクトロルミネッセンス素子を作成した。
【０１２２】
【化４０】
Figure 0003562652
【０１２３】
この素子のＩＴＯ薄膜を陽極、Ｍｇ−Ａｇ合金層を陰極として電圧を印加したところ、１２Ｖで輝度４７ｃｄ／ｍ２の青色発光を得た。このときの発光効率は０．３ ｌｍ／Ｗであった。
［実施例３］
発光層に化学式１４で示されるテトラフェニルブタジエン誘導体を用いた以外は実施例１と同様な方法で有機エレクトロルミネッセンス素子を作成した。
【０１２４】
【化１４】
Figure 0003562652
【０１２５】
この素子のＩＴＯ薄膜を陽極、Ｍｇ−Ａｇ合金層を陰極として電圧を印加したところ、７Ｖで輝度７２ｃｄ／ｍ２の青色発光を得た。このときの発光効率は０．４ ｌｍ／Ｗであった。
［実施例４］
発光層に化学式８５で示される１，１，４，４−テトラフェニル−１，３−ブタジエンを用いた以外は、実施例１と同様な方法で有機エレクトロルミネッセンス素子を作成した。
【０１２６】
【化８５】
Figure 0003562652
【０１２７】
この素子のＩＴＯ薄膜を陽極、Ｍｇ−Ａｇ合金層を陰極として電圧を印加したところ、６Ｖで輝度６３ｃｄ／ｍ２の青色発光を得た。このときの発光効率は１．５ｌｍ／Ｗであった。さらに、この素子に１３Ｖの電圧を印加すると、輝度５８００ｃｄ／ｍ２の青色発光が得られた。
［実施例５］
電子輸送層上の陰極として膜厚８００ÅのＬｉ濃度０．２ｗｔ％のＡｌ−Ｌｉ合金の金属層を蒸着速度１０Å／秒で形成た以外は実施例４と同様な方法で有機エレクトロルミネッセンス素子を作成した。
【０１２８】
この素子のＩＴＯ薄膜を陽極、Ａｌ−Ｌｉ合金層を陰極として電圧を印加したところ、５Ｖで輝度８２ｃｄ／ｍ２の青色発光を得た。このときの発光効率は２．４ ｌｍ／Ｗであった。さらに、この素子に１２Ｖの電圧を印加すると、輝度９７００ｃｄ／ｍ２の青色発光が得られた。
［比較例１］
電子輸送層を形成しない以外は実施例１と同様な方法で比較例１の有機エレクトロルミネッセンス素子を作成した。
【０１２９】
この素子のＩＴＯ薄膜を陽極、Ｍｇ−Ａｇ合金層を陽極として電圧を印加したところ１２Ｖで輝度２４ｃｄ／ｍ２の発光を得た。このときの発光効率は０．０２ ｌｍ／Ｗで、実施例に比べ１桁小さいものであった。
［実施例６］
実施例４の有機エレクトロルミネッセンス素子を真空中で輝度４０ｃｄ／ｍ２で発光させ一定電流値で保持したところ輝度の半減期は４時間４５分であった。
【０１３０】
［比較例２］
従来から電子輸送材料として最も優れているもののひとつとされている化学式８６で示されるｔ−Ｂｕ−ＰＢＤ｛２−（４´−ｔｅｒｔ−ｂｕｔｙｌｐｈｅｎｙｌ）−５−（４´´−ｂｉｐｈｅｎｙｌ）−１，３，４−ｏｘａｄｉａｚｏｌｅ｝を電子輸送層として用いた以外は、実施例４と同様な方法で比較例２の有機エレクトロルミネッセンス素子を作成した。
【０１３１】
【化８６】
Figure 0003562652
【０１３２】
この素子のＩＴＯ薄膜を陽極、Ｍｇ−Ａｇ合金層を陽極として電圧を印加したところ７Ｖで輝度２９ｃｄ／ｍ２、発光効率１．４ ｌｍ／Ｗの青色発光を得たが、この素子に１３Ｖの電圧印加した時には輝度１３００ｃｄ／ｍ２の発光しか得られなかった。これは、実施例４に比べ四分の一以下の最大輝度である。
さらにこの素子を真空中で輝度４０ｃｄ／ｍ２で発光させ一定電流値で保持したところ輝度の半減期は４分であり、図３に示すように実施例６に比して著しく短かった。
【０１３３】
［実施例７］
電子輸送層に化学式４０で示されるフェナントロリン化合物を用いた以外は、実施例４と同様な方法で有機エレクトロルミネッセンス素子を作成した。
【０１３４】
【化４０】
Figure 0003562652
【０１３５】
この素子を真空中で発光させ一定電流値で保持したところ、初期輝度２００ｃｄ／ｍ２の青色発光からの輝度の半減期は４時間４５分であり、初期輝度４０ｃｄ／ｍ２の青色発光からの輝度の半減期は３５時間であり、初期輝度１０ｃｄ／ｍ２の青色発光からの輝度の半減期は１００時間であり、この素子は比較例２に比して輝度の半減期が著しく延びた。
【０１３６】
［実施例８］
電子輸送層に化学式８８で示されるジベンゾフェナントロリンのジヒドロ体の誘導体を用いた以外は、実施例１と同様な方法で有機エレクトロルミネッセンス素子を作成した。
【０１３７】
【化８８】
Figure 0003562652
【０１３８】
この素子を真空中で初期輝度４０ｃｄ／ｍ２で青色発光させ一定電流値で保持したところ、輝度の半減期は３３時間であり、比較例２に比して輝度の半減期が著しく延びた。
【０１３９】
【発明の効果】
以上説明したように、本発明による有機エレクトロルミネッセンス素子においては、有機化合物からなり互いに積層された電子輸送層、発光層及び正孔輸送層が陰極及び陽極間に配された構成の有機エレクトロルミネッセンス素子であって、電子輸送層が上記のフェナントロリン誘導体を含む薄膜からなるので、効率良く高輝度で長期間に亘って発光させることができる。
【図面の簡単な説明】
【図１】有機エレクトロルミネッセンス素子の概略構造図である。
【図２】有機エレクトロルミネッセンス素子の概略構造図である。
【図３】実施例６及び比較例２の有機エレクトロルミネッセンス素子の輝度の経時変化を示すグラフである。
【符号の説明】
１ 金属電極（陰極）
２ 透明電極（陽極）
３ 発光層
４ 有機正孔輸送層
５ 有機電子輸送層
６ ガラス基板[0001]
[Industrial applications]
The present invention relates to an electroluminescent device, and more particularly, to an organic electroluminescent device in which an anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an electron transport layer made of an organic compound, and a cathode are sequentially stacked.
[0002]
[Prior art]
As this type of organic electroluminescent device, as shown in FIG. 1, an organic phosphor thin film (light emitting layer) 3 and an organic positive electrode layer laminated together between a metal electrode 1 as a cathode and a transparent electrode 2 as an anode. A two-layer structure having a hole transport layer 4 is known. As shown in FIG. 2, a three-layer structure in which an organic electron transporting layer 5, a light emitting layer 3, and an organic hole transporting layer 4 are laminated between a metal electrode 1 and a transparent electrode 2 is also available. Is known. Here, the organic hole transport layer 4 has a function of facilitating injection of holes from the anode and a function of blocking electrons, and the organic electron transport layer 5 has a function of facilitating injection of electrons from the cathode. I have.
[0003]
In these organic electroluminescent elements, a glass substrate 6 is arranged outside the transparent electrode 2. The recombination of the electrons injected from the metal electrode 1 and the holes injected from the transparent electrode 2 generates excitons, and emits light in the process of radiation deactivation of the excitons, and this light is It is released to the outside via the glass plate 6.
[0004]
[Problems to be solved by the invention]
However, even an organic electroluminescence device capable of emitting light with relatively high luminance has not been sufficiently satisfactory in luminance.
The present invention has been made to satisfy the above-described conventional needs, and has as its object to provide an organic electroluminescence device capable of efficiently emitting an organic phosphor with high luminance.
[0005]
[Means for Solving the Problems]
The electroluminescent device according to the present invention is an organic electroluminescent device in which an anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an electron transport layer made of an organic compound, and a cathode are stacked in this order. The transport layer has a composition different from that of the light emitting layer and is in contact with the light emitting layer, and is a phenanthroline derivative represented by the following chemical formula 1.
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Figure 0003562652
[0007]
(In Chemical Formula 1, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. ). The electroluminescent device according to the present invention is an organic electroluminescent device in which an anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an electron transport layer made of an organic compound, and a cathode are stacked in this order. The transport layer has a different composition from the light emitting layer and is in contact with the light emitting layer, and is a 1,7-phenanthroline derivative represented by the following chemical formula 83.
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Figure 0003562652
[0009]
(In Chemical Formula 83, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. ). The electroluminescent device according to the present invention is an organic electroluminescent device in which an anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an electron transport layer made of an organic compound, and a cathode are stacked in this order. The transport layer has a composition different from that of the light emitting layer and is in contact with the light emitting layer, and is a 4,7-phenanthroline derivative represented by the following chemical formula 84:
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Figure 0003562652
[0011]
(In the chemical formula 84, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. ). The electroluminescent device according to the present invention is an organic electroluminescent device in which an anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an electron transport layer made of an organic compound, and a cathode are stacked in this order. The transport layer has a composition different from that of the light emitting layer and is in contact with the light emitting layer, and is a phenanthroline derivative having a skeleton of a dihydro form of dibenzophenanthroline represented by the following chemical formula 87.
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Figure 0003562652
[0013]
(In Chemical Formula 87, R 1 to R 10 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. ).
[0014]
[Action]
According to the present invention, an organic electroluminescence element capable of efficiently emitting light with high luminance can be obtained.
[0015]
【Example】
Hereinafter, the present invention will be described in detail with reference to the drawings.
The organic electroluminescent device of the present invention is the same as the organic electroluminescent device having the structure shown in FIG. 2, and has an electron transport layer 5 between a pair of metal cathodes 1 and a transparent anode 2 as shown in FIG. , A light emitting layer 3 and a hole transport layer 4 in this order. In this case, one of the electrodes 1 and 2 only needs to be transparent. For example, the cathode 1 may be made of a metal having a small work function, such as aluminum, magnesium, indium, silver, or an alloy thereof, and having a thickness of about 100 to 5000 °. Further, for example, the anode 2 is made of a conductive material having a large work function such as indium tin oxide (hereinafter also referred to as ITO) and has a thickness of about 1000 to 3000 ° or gold of about 800 to 1500 °. Can be used. When gold is used as an electrode material, the electrode is in a translucent state.
[0016]
As shown in FIG. 2, for example, a triphenylamine derivative represented by the following chemical formula 2 and a compound known as CTM (Carrier Transport Materials) represented by the following chemical formulas 3 to 13 can be used for the organic hole transport layer 4.
[0017]
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Figure 0003562652
[0018]
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Figure 0003562652
[0019]
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Figure 0003562652
[0020]
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Figure 0003562652
[0021]
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Figure 0003562652
[0022]
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Figure 0003562652
[0023]
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Figure 0003562652
[0024]
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[0025]
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[0026]
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[0027]
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Figure 0003562652
[0028]
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Figure 0003562652
[0029]
As shown in FIG. 2, as the light emitting layer 3, a phosphor thin film containing a tetraphenylbutadiene compound represented by the following chemical formulas 14 to 16 and 85 is preferably used.
[0030]
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Figure 0003562652
[0031]
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Figure 0003562652
[0032]
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Figure 0003562652
[0033]
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Figure 0003562652
[0034]
Further, as the light emitting layer 3, compounds of the above formulas 17 to 25 are also used. The thickness of these light emitting layers 3 is set to 1 μm or less.
[0035]
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Figure 0003562652
[0036]
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[0037]
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[0038]
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[0039]
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[0040]
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[0041]
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[0042]
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[0043]
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[0044]
As shown in FIG. 2, as the electron transporting layer 5, a compound represented by the general formula 1 is used.
[0045]
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Figure 0003562652
[0046]
(In Chemical Formula 1, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. ).
Hereinafter, specific examples of the phenanthroline derivative used in the present invention are shown in Chemical Formulas 26 to 82, but the present invention is not limited thereto.
[0047]
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[0048]
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[0049]
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[0050]
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[0051]
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[0052]
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[0053]
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[0054]
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[0055]
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[0056]
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[0057]
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[0058]
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[0059]
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[0060]
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[0061]
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[0062]
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[0063]
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[0064]
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[0065]
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[0066]
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[0067]
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[0068]
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[0069]
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[0070]
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[0071]
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[0072]
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[0073]
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[0074]
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[0075]
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[0076]
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[0077]
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[0078]
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[0079]
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[0080]
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[0081]
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[0082]
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[0083]
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[0084]
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[0085]
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[0086]
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[0087]
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[0088]
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[0089]
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[0090]
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[0091]
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[0092]
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[0093]
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[0094]
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[0095]
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[0096]
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[0097]
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[0098]
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[0099]
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[0100]
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[0101]
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[0102]
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[0103]
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Figure 0003562652
[0104]
In the above embodiment, the electron transport layer 5 in the organic electroluminescence device is formed from the derivative having the skeleton of 1,10-phenanthroline represented by the above chemical formula 1, but the electron transport layer 5 represented by the following chemical formula 83 or 84 is used. A thin film formed from a phenanthroline derivative having a skeleton of 4,7-phenanthroline or 4,7-phenanthroline may be used.
[0105]
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Figure 0003562652
[0106]
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Figure 0003562652
[0107]
In Chemical Formulas 83 and 84, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or Represents a hydroxyl group.
Furthermore, in addition to the phenanthroline derivative having 1,7-phenanthroline or 4,7-phenanthroline as a skeleton, the electron transport layer 5 in the organic electroluminescence device has a dihydro dibenzophenanthroline represented by the following chemical formula 87 as a skeleton. A thin film formed from a phenanthroline derivative may be used.
[0108]
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Figure 0003562652
[0109]
In Chemical Formula 87, R 1 to R 10 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. Express. Specific examples of the dihydro derivative of dibenzophenanthroline are shown in Chemical Formulas 88 to 91, but the present invention is not limited thereto.
[0110]
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Figure 0003562652
[0111]
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[0112]
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[0113]
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[0114]
[Example 1]
The glass substrate on which a thin film of ITO having a thickness of 1500 ° was formed was ultrasonically washed in ethanol for 5 minutes, and then air-dried. On this glass substrate, a compound represented by the chemical formula 2
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Figure 0003562652
[0116]
Was deposited from a tantalum boat at a deposition rate of 3 ° / sec to a film thickness of 500 ° to form a hole transport layer. The degree of vacuum at the time of vapor deposition was 5 × 10 −6 Torr.
Next, a tetraphenylbutadiene derivative represented by the chemical formula 15 as a light emitting substance is formed on the hole transport layer.
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Figure 0003562652
[0118]
Was formed at a deposition rate of 4 ° / sec to a thickness of 200 ° to form a light emitting layer.
Next, a phenanthroline compound represented by the chemical formula 39 was formed on the light emitting layer.
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Figure 0003562652
[0120]
Was formed into a film having a thickness of 500 ° at a deposition rate of 3 ° / sec to form an electron transport layer.
Finally, a 1500-.ANG.-thick Mg-Ag alloy metal layer was formed on the electron transport layer from a separate boat by depositing Mg at a deposition rate of 10 DEG / sec and Ag at a deposition rate of 1 DEG / sec. The organic electroluminescent device was formed.
When a voltage was applied using the ITO thin film of the organic electroluminescent element thus prepared as an anode and the Mg-Ag alloy layer as a cathode, blue light emission with a luminance of 25 cd / m 2 at 5 V was obtained. The luminous efficiency at this time was 0.7 lm / W.
[0121]
[Example 2]
An organic electroluminescent device was prepared in the same manner as in Example 1, except that the phenanthroline compound represented by the chemical formula 40 was used for the electron transport layer.
[0122]
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Figure 0003562652
[0123]
When voltage was applied using the ITO thin film of the device as an anode and the Mg-Ag alloy layer as a cathode, blue light emission with a luminance of 47 cd / m 2 at 12 V was obtained. The luminous efficiency at this time was 0.3 lm / W.
[Example 3]
An organic electroluminescent device was prepared in the same manner as in Example 1, except that the tetraphenylbutadiene derivative represented by Chemical Formula 14 was used for the light emitting layer.
[0124]
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Figure 0003562652
[0125]
When voltage was applied using the ITO thin film of the device as an anode and the Mg-Ag alloy layer as a cathode, blue light emission with a luminance of 72 cd / m 2 at 7 V was obtained. The luminous efficiency at this time was 0.4 lm / W.
[Example 4]
An organic electroluminescent device was prepared in the same manner as in Example 1, except that 1,1,4,4-tetraphenyl-1,3-butadiene represented by Chemical Formula 85 was used for the light emitting layer.
[0126]
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Figure 0003562652
[0127]
When voltage was applied using the ITO thin film of the device as an anode and the Mg-Ag alloy layer as a cathode, blue light emission with a luminance of 63 cd / m 2 at 6 V was obtained. The luminous efficiency at this time was 1.5 lm / W. When a voltage of 13 V was applied to this device, blue light emission with a luminance of 5800 cd / m 2 was obtained.
[Example 5]
An organic electroluminescent device was prepared in the same manner as in Example 4, except that a metal layer of an Al—Li alloy having a thickness of 800% and a Li concentration of 0.2 wt% was formed at a deposition rate of 10 ° / sec as a cathode on the electron transport layer. did.
[0128]
When voltage was applied using the ITO thin film of the device as an anode and the Al-Li alloy layer as a cathode, blue light emission with a luminance of 82 cd / m 2 was obtained at 5 V. The luminous efficiency at this time was 2.4 lm / W. Further, when a voltage of 12 V was applied to this element, blue light emission with a luminance of 9700 cd / m 2 was obtained.
[Comparative Example 1]
An organic electroluminescent device of Comparative Example 1 was prepared in the same manner as in Example 1 except that the electron transport layer was not formed.
[0129]
When voltage was applied using the ITO thin film as the anode and the Mg-Ag alloy layer as the anode, light emission of 24 cd / m 2 at 12 V was obtained. At this time, the luminous efficiency was 0.02 lm / W, which was one digit smaller than that of the example.
[Example 6]
When the organic electroluminescent device of Example 4 emitted light at a luminance of 40 cd / m 2 in vacuum and was kept at a constant current value, the half-life of the luminance was 4 hours and 45 minutes.
[0130]
[Comparative Example 2]
T-Bu-PBD ｛2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1, represented by chemical formula 86, which has conventionally been regarded as one of the most excellent electron transport materials. An organic electroluminescent device of Comparative Example 2 was produced in the same manner as in Example 4, except that 3,4-oxadazole * was used as the electron transporting layer.
[0131]
Embedded image
Figure 0003562652
[0132]
When voltage was applied using the ITO thin film of the device as an anode and the Mg-Ag alloy layer as an anode, blue light emission with a luminance of 29 cd / m 2 and a luminous efficiency of 1.4 lm / W was obtained at 7 V. When voltage was applied, only light emission with a luminance of 1300 cd / m 2 was obtained. This is a maximum luminance of one-fourth or less as compared with the fourth embodiment.
Further, when this device was made to emit light at a luminance of 40 cd / m 2 in a vacuum and kept at a constant current value, the half-life of the luminance was 4 minutes, which was significantly shorter than that of Example 6 as shown in FIG.
[0133]
[Example 7]
An organic electroluminescence device was prepared in the same manner as in Example 4, except that the phenanthroline compound represented by the chemical formula 40 was used for the electron transport layer.
[0134]
Embedded image
Figure 0003562652
[0135]
When this device was made to emit light in a vacuum and kept at a constant current value, the half-life of the luminance from blue light emission with an initial luminance of 200 cd / m 2 was 4 hours and 45 minutes, and the half life from the blue light emission with an initial luminance of 40 cd / m 2 was The half-life of the luminance was 35 hours, and the half-life of the luminance from blue light emission having an initial luminance of 10 cd / m 2 was 100 hours. The half-life of the luminance of this device was significantly increased as compared with Comparative Example 2.
[0136]
Example 8
An organic electroluminescent device was prepared in the same manner as in Example 1 except that a dihydrophenbenzophenanthroline derivative represented by the chemical formula 88 was used for the electron transport layer.
[0137]
Embedded image
Figure 0003562652
[0138]
When this device was made to emit blue light at an initial luminance of 40 cd / m 2 in a vacuum and kept at a constant current value, the half-life of the luminance was 33 hours, and the half-life of the luminance was significantly extended as compared with Comparative Example 2.
[0139]
【The invention's effect】
As described above, in the organic electroluminescent device according to the present invention, an organic electroluminescent device having a configuration in which an electron transport layer, a light emitting layer, and a hole transport layer, which are made of an organic compound and are stacked on each other, is disposed between a cathode and an anode. In addition, since the electron transport layer is formed of a thin film containing the phenanthroline derivative, light can be efficiently emitted with high luminance for a long period of time.
[Brief description of the drawings]
FIG. 1 is a schematic structural diagram of an organic electroluminescence element.
FIG. 2 is a schematic structural view of an organic electroluminescence element.
FIG. 3 is a graph showing a change over time in luminance of the organic electroluminescence devices of Example 6 and Comparative Example 2.
[Explanation of symbols]
1 metal electrode (cathode)
2 Transparent electrode (anode)
3 light emitting layer 4 organic hole transport layer 5 organic electron transport layer 6 glass substrate

Claims (4)

陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層は、前記発光層とは組成が異なりかつ前記発光層に接する下記化学式１で示されるフェナントロリン誘導体
Figure 0003562652
（化学式１中、Ｒ1〜Ｒ8は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からな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。An anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an organic electroluminescent element in which an electron transport layer made of an organic compound and a cathode are sequentially stacked, wherein the electron transport layer has the light emitting layer and Is a phenanthroline derivative represented by the following chemical formula 1 having a different composition and in contact with the light emitting layer:
Figure 0003562652
 (In Chemical Formula 1, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. Wherein the organic electroluminescent device comprises: 陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層は、前記発光層とは組成が異なりかつ前記発光層に接する下記化学式８３で示される１，７−フェナントロリン誘導体
Figure 0003562652
（化学式８３中、Ｒ1〜Ｒ8は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からな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。An anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an organic electroluminescent element in which an electron transport layer made of an organic compound and a cathode are sequentially stacked, wherein the electron transport layer has the light emitting layer and Is a 1,7-phenanthroline derivative having a different composition and in contact with the light emitting layer, represented by the following chemical formula 83:
Figure 0003562652
 (In Chemical Formula 83, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. Wherein the organic electroluminescent device comprises: 陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層は、前記発光層とは組成が異なりかつ前記発光層に接する下記化学式８４で示される４，７−フェナントロリン誘導体
Figure 0003562652
（化学式８４中、Ｒ1〜Ｒ8は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からな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。An anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an organic electroluminescent element in which an electron transport layer made of an organic compound and a cathode are sequentially stacked, wherein the electron transport layer has the light emitting layer and Is a 4,7-phenanthroline derivative having a different composition and in contact with the light emitting layer, represented by the following chemical formula 84:
Figure 0003562652
 (In the chemical formula 84, R 1 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. Wherein the organic electroluminescent device comprises: 陽極、有機化合物からなる正孔輸送層、有機化合物からなる発光層、有機化合物からなる電子輸送層及び陰極が順に積層された有機エレクトロルミネッセンス素子であって、前記電子輸送層が化学式８７で示されるジベンゾフェナントロリンのジヒドロ体を骨格とするフェナントロリン誘導体
Figure 0003562652
（化学式８７中、Ｒ1〜Ｒ10は、それぞれ独立に、水素原子、置換もしくは非置換アルキル基、置換もしくは非置換アリール基、置換もしくは非置換アミノ基、ハロゲン原子、ニトロ基、シアノ基又は水酸基を表わす）からな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。An organic electroluminescent device in which an anode, a hole transport layer made of an organic compound, a light emitting layer made of an organic compound, an electron transport layer made of an organic compound, and a cathode are sequentially stacked, wherein the electron transport layer is represented by a chemical formula 87. Phenanthroline derivatives based on the dihydro form of dibenzophenanthroline
Figure 0003562652
 (In formula 87, R 1 to R 10 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a halogen atom, a nitro group, a cyano group, or a hydroxyl group. Wherein the organic electroluminescent device comprises:
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