JP4136352B2 - Organic light emitting device - Google Patents
Organic light emitting device Download PDFInfo
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- JP4136352B2 JP4136352B2 JP2001306084A JP2001306084A JP4136352B2 JP 4136352 B2 JP4136352 B2 JP 4136352B2 JP 2001306084 A JP2001306084 A JP 2001306084A JP 2001306084 A JP2001306084 A JP 2001306084A JP 4136352 B2 JP4136352 B2 JP 4136352B2
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- 150000001875 compounds Chemical class 0.000 claims description 47
- 125000000623 heterocyclic group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、有機発光素子に関し、詳しくは有機化合物を含む薄膜に電界を印加することにより光を放出する素子に関する。
【０００２】
【従来の技術】
有機発光素子は、陽極と陰極間に蛍光性有機化合物を含む薄膜を挟持させて、各電極から電子およびホール（正孔）を注入することにより、蛍光性化合物の励起子を生成させ、この励起子が基底状態にもどる際に放射される光を利用する素子である。
【０００３】
１９８７年コダック社の研究（Ａｐｐｌ．Ｐｈｙｓ．Ｌｅｔｔ．５１，９１３（１９８７））では、陽極にＩＴＯ、陰極にマグネシウム銀の合金をそれぞれ用い、電子輸送材料および発光材料としてアルミニウムキノリノール錯体を用い、ホール輸送材料にトリフェニルアミン誘導体を用いた機能分離型２層構成の素子で、１０Ｖ程度の印加電圧において１０００ｃｄ／ｍ2程度の発光が報告されている。関連の特許としては，米国特許４，５３９，５０７号，米国特許４，７２０，４３２号，米国特許４，８８５，２１１号等が挙げられる。
【０００４】
また、蛍光性有機化合物の種類を変えることにより、紫外から赤外までの発光が可能であり、最近では様々な化合物の研究が活発に行われている。例えば、米国特許５，１５１，６２９号，米国特許５，４０９，７８３号，米国特許５，３８２，４７７号，特開平２−２４７２７８号公報，特開平３−２５５１９０号公報，特開平５−２０２３５６号公報，特開平９−２０２８７８号公報，特開平９−２２７５７６号公報等に記載されている。
【０００５】
さらに、上記のような低分子材料を用いた有機発光素子の他にも、共役系高分子を用いた有機発光素子が、ケンブリッジ大学のグループ（Ｎａｔｕｒｅ，３４７，５３９（１９９０））により報告されている。この報告ではポリフェニレンビニレン（ＰＰＶ）を塗工系で成膜することにより、単層で発光を確認している。共役系高分子を用いた有機発光素子の関連特許としては、米国特許５，２４７，１９０号、米国特許５，５１４，８７８号、米国特許５，６７２，６７８号、特開平４−１４５１９２号公報、特開平５−２４７４６０号公報等が挙げられる。
【０００６】
このように有機発光素子における最近の進歩は著しく、その特徴は低印加電圧で高輝度、発光波長の多様性、高速応答性、薄型、軽量の発光デバイス化が可能であることから、広汎な用途への可能性を示唆している。
【０００７】
しかしながら、現状では更なる高輝度の光出力あるいは高変換効率が必要である。また、長時間の使用による経時変化や酸素を含む雰囲気気体や湿気などによる劣化等の耐久性の面で未だ多くの問題がある。さらにはフルカラーディスプレイ等への応用を考えた場合、色純度の良い青、緑、赤の発光が必要となるが、この問題に関してもまだ十分に解決されておらず、特に赤色発光が充分ではない。
【０００８】
一方、スピロ化合物が特異な立体構造を有し、その特異的な材料物性から有機機能性材料として注目されている（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１１０，５６８７，１９８８）。スピロ化合物を有機発光素子に用いた例（特開平７−２７８５３７号公報）があるが、電子輸送層や発光層として十分な発光特性は得られていない。
【０００９】
【発明が解決しようとする課題】
本発明は、このような従来技術の問題点を解決するためになされたものであり、極めて高効率で高輝度、高寿命の光出力を有する有機発光素子を提供することを目的とする。
【００１０】
また、発光波長に多様性があり、種々の発光色相を呈するが、特に、燈色、赤色などの発光色相を呈するとともに、極めて耐久性のある有機発光素子を提供することを目的とする。
【００１１】
さらには、製造が容易でかつ比較的安価に作成可能な有機発光素子を提供することを目的とする。
【００１２】
【課題を解決するための手段】
即ち、本発明の有機発光素子は、陽極及び陰極からなる一対の電極と、該一対の電極間に挟持された一または複数の有機化合物を含む層を少なくとも有する有機発光素子において、前記有機化合物を含む層の少なくとも一層が下記一般式［Ｉ］で示される化合物の少なくとも一種を含有することを特徴とする。
【００１３】
【化４】
（式中、Ｋ1、Ｋ2、Ｋ3およびＫ4は、置換あるいは無置換の芳香環または複素環を表わし、Ｋ1、Ｋ2、Ｋ3およびＫ4の少なくとも１つは窒素原子を少なくとも１つ含む複素環を表わす。Ｋ1、Ｋ2、Ｋ3およびＫ4は、同じであっても異なっていてもよい。
【００１５】
Ｌ1、Ｌ2、Ｌ3およびＬ4は、水素原子、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、アルコキシル基、ニトロ基、置換あるいは無置換のアミノ基または下記一般式［Ｘ］、［ＸＩＩ］あるいは［ＸＩＩ］の構造式からなる基を表わす。Ｌ1、Ｌ2、Ｌ3およびＬ4は、同じであっても異なっていてもよい。）
【００１６】
【化５】
（式中、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13、Ｒ14およびＲ15は、水素原子、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基またはニトロ基を表わし、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13、Ｒ14およびＲ15は、同じであっても異なっていてもよい。
【００１８】
Ｘ1、Ｘ2、Ｘ3、Ｙ1、Ｙ2およびＹ3は、窒素原子あるいはＣ−Ｒ16を表わし、Ｘ1、Ｘ2、Ｘ3、Ｙ1、Ｙ2およびＹ3は同じであっても異なっていてもよい。
【００１９】
Ｚ1、Ｚ2およびＺ3は、−Ｏ−、−Ｓ−、−ＮＲ17−、−Ｓｉ（Ｒ18）Ｒ19−、−Ｃ（Ｒ20）Ｒ21−、−ＣＨ＝ＣＨ−あるいは−ＣＨ＝Ｎ−を表わし、Ｚ1、Ｚ2およびＺ3は、同じであっても異なっていてもよい。
【００２０】
Ｒ17、Ｒ20およびＲ21は、水素原子、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基または置換あるいは無置換の複素環基を表わす。Ｒ20およびＲ21は、同じであっても異なっていてもよい。
【００２１】
Ｒ18およびＲ19は、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基または置換あるいは無置換の複素環基を表わし、Ｒ18およびＲ19は同じであっても異なっていてもよい。
【００２２】
ｌは０または１、ｍは０または１〜３０の整数、ｎは０または１〜３０の整数、ｍ＋ｎは０または１〜３０の整数、ｐは０または１、ｑは０または１〜３０の整数、ｒは１〜３０の整数を表わす。）
【００２３】
本発明の有機発光素子においては、前記一般式［Ｉ］で示される化合物が、下記一般式［ＩＩ］、［ＩＩＩ］、［ＩＶ］、［Ｖ］、［ＶＩ］、［ＶＩＩ］、［ＶＩＩＩ］または［ＩＸ］で示される化合物であることが好ましい。
【００２４】
【化６】
（式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、水素原子、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、アルコキシル基、ニトロ基または置換あるいは無置換のアミノ基を表わし、Ｒ1、Ｒ2、Ｒ3およびＲ4は、同じであっても異なっていてもよい。）
【００２６】
また、前記Ｌ1、Ｌ2、Ｌ3およびＬ4の少なくとも一つが、前記一般式［Ｘ］〜［ＸＩＩ］の構造式からなる基から選択される基であることが、ガラス転移点が高くなり有機発光素子としての安定性が向上する点で好ましい。
【００２７】
更に、少なくとも電子注入層、電子輸送層または発光層が、前記一般式［Ｉ］で示される化合物を含有することが好ましい。
【００２８】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【００２９】
まず、上記一般式［Ｉ］〜［ＸＩＩ］における置換基の具体例を以下に示す。
【００３０】
アルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｔｅｒ−ブチル基、オクチル基などが挙げられる。
【００３１】
アラルキル基としては、ベンジル基、フェネチル基などが挙げられる。
【００３２】
アリール基としては、フェニル基、ビフェニル基、ターフェニル基、ナフチル基、アントラリル基、フェナントリル基、フルオレニル基などが挙げられる。
【００３３】
複素環基としては、チエニル基、ピロリル基、イミダジル基、フリル基、ピリジル基、インドリル基、キノリル基、カルバゾリル基などが挙げられる。
【００３４】
アルコキシル基としては、メトキシル基、エトキシル基、プロポキシル基、フェノキシル基などが挙げられる。
【００３５】
アミノ基としては、ジメチルアミノ基、ジエチルアミノ基、ジベンジルアミノ基、ジフェニルアミノ基などが挙げられる。
【００３６】
上記置換基が有してもよい置換基としては、メチル基、エチル基、プロピル基などのアルキル基、ベンジル基、フェネチル基などのアラルキル基、フェニル基、ナフチル基、アントラリル基などのアリール基、チエニル基、ピロリル基、ピリジル基、キノリル基などの複素環基、ジメチルアミノ基、ジエチルアミノ基、ジベンジルアミノ基、ジフェニルアミノ基などのアミノ基が挙げられる。
【００３７】
また、一般式［Ｘ］〜［ＸＩＩ］で示される置換基としては、以下に示すようなものが挙げられる。
【００３８】
【化７】
【化８】
以下、一般式［Ｉ］で示されるスピロシロール化合物の代表例を挙げるが、本発明はこれらに限定されるものではない。尚、表１〜８における置換基１〜１４は、以下に示す置換基である。また、表１〜８のＲ1〜Ｒ4の欄における括弧内の数字は、置換位置を表す。
【００４１】
【化９】
【化１０】
【表１】
【化１１】
【表２】
【化１２】
【表３】
【化１３】
【表４】
【化１４】
【表５】
【化１５】
【表６】
【化１６】
【表７】
【化１７】
【表８】
次に、本発明の有機発光素子について図面に沿って説明する。
【００５９】
図１は本発明の有機発光素子の一例を示す断面図である。図１は基板１上に陽極２、発光層３及び陰極４を順次設けた構成のものである。ここで使用する発光素子はそれ自体でホール輸送能、エレクトロン輸送能及び発光性の性能を単一で有している場合や、それぞれの特性を有する化合物を混ぜて使う場合に有用である。
【００６０】
図２は本発明の有機発光素子における他の例を示す断面図である。図２は基板１上に陽極２、ホール輸送層５、電子輸送層６及び陰極４を順次設けた構成のものである。この場合、発光物質はホール輸送性かあるいは電子輸送性のいずれかあるいは両方の機能を有している材料をそれぞれの層に用い、発光性の無い単なるホール輸送物質あるいは電子輸送物質と組み合わせて用いる場合に有用である。また、この場合、発光層３はホール輸送層５あるいは電子輸送層６のいずれかから成る。
【００６１】
図３は本発明の有機発光素子における他の例を示す断面図である。図３は基板１上に陽極２、ホール輸送層５、発光層３，電子輸送層６及び陰極４を順次設けた構成のものである。これはキャリヤ輸送と発光の機能を分離したものであり、ホール輸送性、電子輸送性、発光性の各特性を有した化合物と適時組み合わせて用いられ極めて材料選択の自由度が増すとともに、発光波長を異にする種々の化合物が使用できるため、発光色相の多様化が可能になる。さらに、中央の発光層３に各キャリヤあるいは励起子を有効に閉じこめて発光効率の向上を図ることも可能になる。
【００６２】
図４は本発明の有機発光素子における他の例を示す断面図である。図４は基板１上に陽極２、ホール輸送層５，電子輸送層６、電子注入層７及び陰極４を順次設けた構成のものである。これは陰極４から電子輸送層６へ電子を効率よく注入させるために電子注入層７を設けたもので、陰極４からの電子注入と電子輸送の機能を分離したものである。
【００６３】
ただし、図１〜４はあくまでごく基本的な素子構成であり、本発明の化合物を用いた有機発光素子の構成はこれらに限定されるものではない。例えば、電極と有機層界面に絶縁性層を設ける、接着層あるいは干渉層を設ける、ホール輸送層がイオン化ポテンシャルの異なる２層から構成されるなど多様な層構成をとることができる。
【００６４】
本発明に用いられる一般式［Ｉ］で示される化合物は、従来の化合物に比べ、電子注入性、電子輸送性、発光性および耐久性の優れた化合物であり、図１〜図４のいずれの形態をも使用することができる。
【００６５】
特に、本発明の一般式［Ｉ］で示される化合物を用いた有機層は、電子注入層、電子輸送層および発光層として有用であり、また真空蒸着法や溶液塗布法などによって形成した層は結晶化などが起こりにくく、経時安定性に優れている。
【００６６】
本発明の有機発光素子においては、一般式［Ｉ］で示される化合物を真空蒸着法や溶液塗布法により陽極２及び陰極４の間に形成する。その有機層の厚みは１０μｍより薄く、好ましくは０．５μｍ以下、より好ましくは０．０１〜０．５μｍの厚みに薄膜化することが好ましい。
【００６７】
本発明においては、電子注入層、電子輸送層および発光層の構成成分として一般式［Ｉ］で示される化合物を好適に用いるものであるが、これまで知られているホール輸送性化合物、発光性化合物、あるいは電子輸送性化合物等を必要に応じて一緒に使用することもできる。
【００６８】
以下にこれらの化合物例を挙げる。
【００６９】
【化１８】
【化１９】
【化２０】
【化２１】
【化２２】
【化２３】
本発明の有機発光素子において、一般式［Ｉ］で示される化合物を含有する層およびその他の有機化合物を含む層は、一般には真空蒸着法あるいは、適当な溶媒に溶解させて塗布法により薄膜を形成する。特に塗布法で成膜する場合は、適当な結着樹脂と組み合わせて膜を形成することもできる。
【００７６】
上記結着樹脂としては広範囲な結着性樹脂より選択でき、たとえばポリビニルカルバゾール樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアリレート樹脂、ポリスチレン樹脂、アクリル樹脂、メタクリル樹脂、ブチラール樹脂、ポリビニルアセタール樹脂、ジアリルフタレート樹脂、フェノール樹脂、エポキシ樹脂、シリコーン樹脂、ポリスルホン樹脂、尿素樹脂等が挙げられるが、これらに限定されるものではない。また、これらは単独または共重合体ポリマーとして１種または２種以上混合してもよい。
【００７７】
陽極材料としては仕事関数がなるべく大きなものがよく、例えば、金、白金、ニッケル、パラジウム、コバルト、セレン、バナジウム等の金属単体あるいはこれらの合金、酸化錫、酸化亜鉛、酸化錫インジウム（ＩＴＯ），酸化亜鉛インジウム等の金属酸化物が使用できる。また、ポリアニリン、ポリピロール、ポリチオフェン、ポリフェニレンスルフィド等の導電性ポリマーも使用できる。これらの電極物質は単独で用いてもよく、複数併用することもできる。
【００７８】
一方、陰極材料としては仕事関数の小さなものがよく、リチウム、ナトリウム、カリウム、カルシウム、マグネシウム、アルミニウム、インジウム、銀、鉛、錫、クロム等の金属単体あるいは複数の合金として用いることができる。酸化錫インジウム（ＩＴＯ）等の金属酸化物の利用も可能である。また、陰極は一層構成でもよく、多層構成をとることもできる。
【００７９】
本発明で用いる基板としては、特に限定するものではないが、金属製基板、セラミックス製基板等の不透明性基板、ガラス、石英、プラスチックシート等の透明性基板が用いられる。また、基板にカラーフィルター膜、蛍光色変換フィルター膜、誘電体反射膜などを用いて発色光をコントロールする事も可能である。
【００８０】
なお、作成した素子に対して、酸素や水分等との接触を防止する目的で保護層あるいは封止層を設けることもできる。保護層としては、ダイヤモンド薄膜、金属酸化物、金属窒化物等の無機材料膜、フッソ樹脂、ポリパラキシレン、ポリエチレン、シリコーン樹脂、ポリスチレン樹脂等の高分子膜、さらには、光硬化性樹脂等が挙げられる。また、ガラス、気体不透過性フィルム、金属などをカバーし、適当な封止樹脂により素子自体をパッケージングすることもできる。
【００８１】
【実施例】
以下に実施例により本発明をさらに具体的に説明していくが、本発明はこれらに限定されるものではない。
【００８２】
［実施例１］
図２に示す構造の素子を作成した。
【００８３】
基板１としてのガラス基板上に陽極２としての酸化錫インジウム（ＩＴＯ）をスパッタ法にて１２０ｎｍの膜厚で成膜したものを透明導電性支持基板として用いた。これをアセトン、イソプロピルアルコール（ＩＰＡ）で順次超音波洗浄し、ＩＰＡで煮沸洗浄、乾燥をした。さらに、ＵＶ／オゾン洗浄したものを透明導電性支持基板として使用した。
【００８４】
透明導電性支持基板上に下記構造式で示される化合物を真空蒸着法により７０ｎｍの膜厚で成膜し、ホール輸送層５を形成した。さらに例示化合物Ｎｏ．１で示される化合物を真空蒸着法により７０ｎｍの膜厚で成膜し、電子輸送層６を形成した。蒸着時の真空度は１．０×１０-4ｐａ、成膜速度は０．２〜０．３ｎｍ／ｓｅｃの条件で成膜した。
【００８５】
【化２４】
次に、アルミニウムとリチウム（リチウム濃度１原子％）からなる蒸着材料を用いて、上記有機層の上に、真空蒸着法により厚さ１５０ｎｍの金属層膜（陰極４）を形成した。蒸着時の真空度は１．０×１０-4Ｐａ、成膜速度は１．０〜１．２ｎｍ／ｓｅｃの条件で成膜した。
【００８７】
この様にして得られた素子に、ＩＴＯ電極を正極、Ａｌ−Ｌｉ電極を負極にして、８Ｖの直流電圧を印加すると８．０ｍＡ／ｃｍ2の電流密度で電流が素子に流れ、５６０ｃｄ／ｍ2の輝度で赤色の発光が観測された。
【００８８】
さらに、窒素雰囲気下で電流密度を７．０ｍＡ／ｃｍ2に保ち１００時間電圧を印加したところ、初期輝度５１０ｃｄ／ｍ2から１００時間後４８５ｃｄ／ｍ2と輝度劣化は小さかった。
【００８９】
［実施例２〜１７、比較例１〜２］
例示化合物Ｎｏ．１に代えて、表９に示す化合物を用いた他は実施例１と同様に素子を作成し、同様な評価を行った。結果を表９に示す。
【００９０】
尚、比較化合物Ｎｏ．１は、下記構造式で示される化合物である（特開平７−２７８５３７号公報に記載）。
【００９１】
【化２５】
また、比較化合物Ｎｏ．２は、下記構造式で示される化合物である（特開平９−８７６１６号公報に記載）。
【００９３】
【化２６】
【表９】
［実施例１８］
図２に示す構造の素子を作成した。
【００９６】
実施例１と同様に、透明導電性支持基板上にホール輸送層５を形成した。
【００９７】
さらに例示化合物Ｎｏ．２で示される化合物およびアルミニウムトリスキノリノール（重量比１：２０）を真空蒸着法により７０ｎｍの膜厚で成膜し、電子輸送層６を形成した。蒸着時の真空度は１．０×１０-4Ｐａ、成膜速度は０．２〜０．３ｎｍ／ｓｅｃの条件で成膜した。
【００９８】
次に、実施例１と同様に、陰極４を形成した。
【００９９】
この様にして得られた素子に、ＩＴＯ電極を正極、Ａｌ−Ｌｉ電極を負極にして、８Ｖの直流電圧を印加すると８．５ｍＡ／ｃｍ2の電流密度で電流が素子に流れ、８００ｃｄ／ｍ2の輝度で橙色の発光が観測された。
【０１００】
さらに、窒素雰囲気下で電流密度を７．０ｍＡ／ｃｍ2に保ち１００時間電圧を印加したところ、初期輝度６２０ｃｄ／ｍ2から１００時間後５９０ｃｄ／ｍ2と輝度劣化は小さかった。
【０１０１】
［実施例１９〜２８、比較例３〜４］
例示化合物Ｎｏ．２に代えて、表１０に示す化合物を用いた他は実施例１８と同様に素子を作成し、同様な評価を行った。結果を表１０に示す。
【０１０２】
【表１０】
［実施例２９］
図３に示す構造の素子を作成した。
【０１０４】
実施例１と同様に、透明導電性支持基板上にホール輸送層５を形成した。
【０１０５】
次に、アルミニウムトリスキノリノールを真空蒸着法により３０ｎｍの膜厚で成膜し、発光層３を形成した。さらに例示化合物Ｎｏ．４で示される化合物を真空蒸着法により５０ｎｍの膜厚で成膜し、電子輸送層６を形成した。蒸着時の真空度は１．０×１０-4Ｐａ、成膜速度は０．２〜０．３ｎｍ／ｓｅｃの条件で成膜した。
【０１０６】
次に、実施例１と同様に、陰極４を形成した。
【０１０７】
この様にして得られた素子に、ＩＴＯ電極を正極、Ａｌ−Ｌｉ電極を負極にして、１０Ｖの直流電圧を印加すると１１．０ｍＡ／ｃｍ2の電流密度で電流が素子に流れ、１０５０ｃｄ／ｍ2の輝度で黄色の発光が観測された。
【０１０８】
さらに、窒素雰囲気下で電流密度を１０．０ｍＡ／ｃｍ2に保ち１００時間電圧を印加したところ、初期輝度９９８０ｃｄ／ｍ2から１００時間後９３０ｃｄ／ｍ2と輝度劣化は小さかった。
【０１０９】
［実施例３０〜３９、比較例５〜６］
例示化合物Ｎｏ．４に代えて、表１１に示す化合物を用いた他は実施例２９と同様に素子を作成し、同様な評価を行った。結果を表１１に示す。
【０１１０】
【表１１】
［実施例４０］
図１に示す構造の素子を作成した。
【０１１２】
実施例１で用いた透明導電性支持基板上に、例示化合物Ｎｏ．１で示される化合物を０．０５０ｇおよびポリ−Ｎ−ビニルカルバゾール（重量平均分子量＝６３，０００）１．００ｇをクロロホルム８０ｍｌに溶解した溶液を、スピンコート法（回転数＝２０００ｒｐｍ）により１２０ｎｍの膜厚に成膜し、発光層３を形成した。
【０１１３】
次に、実施例１と同様に、陰極４を形成した。
【０１１４】
この様にして得られた素子に、ＩＴＯ電極を正極、Ａｌ−Ｌｉ電極を負極にして、１０Ｖの直流電圧を印加すると９．０ｍＡ／ｃｍ2の電流密度で電流が素子に流れ、４１０ｃｄ／ｍ2の輝度で橙色の発光が観測された。
【０１１５】
［比較例１０］
例示化合物Ｎｏ．１に代えて、比較化合物Ｎｏ．２を用いた他は実施例４０と同様に素子を作成し、同様に１０Ｖの直流電圧を印加すると９．０ｍＡ／ｃｍ2の電流密度で電流が素子に流れ、３０ｃｄ／ｍ2の輝度で黄緑色の発光が観測された。
【０１１６】
【発明の効果】
本発明の一般式［Ｉ］で示されるスピロシロール化合物を用いた有機発光素子は、低い印加電圧で高輝度な発光が得られ、耐久性にも優れている。
【０１１７】
特に、本発明の一般式［Ｉ］で示されるスピロシロール化合物を用いた有機層は、電子輸送層や発光層として優れている。
【０１１８】
さらに、素子の作成も真空蒸着あるいはキャスティング法等を用いて作成可能であり、比較的安価で大面積の素子を容易に作成できる。
【図面の簡単な説明】
【図１】本発明における有機発光素子の一例を示す断面図である。
【図２】本発明における有機発光素子の他の例を示す断面図である。
【図３】本発明における有機発光素子の他の例を示す断面図である。
【図４】本発明における有機発光素子の他の例を示す断面図である。
【符号の説明】
１ 基板
２ 陽極
３ 発光層
４ 陰極
５ ホール輸送層
６ 電子輸送層
７ 電子注入層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic light-emitting device, and more particularly to a device that emits light by applying an electric field to a thin film containing an organic compound.
[0002]
[Prior art]
An organic light-emitting element generates an exciton of a fluorescent compound by interposing a thin film containing a fluorescent organic compound between an anode and a cathode, and injecting electrons and holes from each electrode. It is an element that utilizes light emitted when the child returns to the ground state.
[0003]
In a study of Kodak Company in 1987 (Appl. Phys. Lett. 51, 913 (1987)), ITO was used for the anode and magnesium-silver alloy for the cathode, and an aluminum quinolinol complex was used as the electron transport material and the light emitting material. It is reported that the device has a function separation type two-layer structure using a triphenylamine derivative as a transport material, and emits light of about 1000 cd / m 2 at an applied voltage of about 10V. Related patents include US Pat. No. 4,539,507, US Pat. No. 4,720,432, US Pat. No. 4,885,211 and the like.
[0004]
In addition, by changing the type of the fluorescent organic compound, light emission from ultraviolet to infrared is possible, and recently, various compounds have been actively researched. For example, US Pat. No. 5,151,629, US Pat. No. 5,409,783, US Pat. No. 5,382,477, JP-A-2-247278, JP-A-3-255190, JP-A-5-202356. No. 9, JP-A-9-202878, JP-A-9-227576, and the like.
[0005]
In addition to organic light-emitting elements using low molecular materials as described above, organic light-emitting elements using conjugated polymers have been reported by a group of Cambridge University (Nature, 347, 539 (1990)). Yes. In this report, light emission was confirmed in a single layer by forming a film of polyphenylene vinylene (PPV) in a coating system. Related patents for organic light emitting devices using conjugated polymers include US Pat. No. 5,247,190, US Pat. No. 5,514,878, US Pat. No. 5,672,678, and Japanese Patent Laid-Open No. 4-145192. JP, 5-247460, A, etc. are mentioned.
[0006]
As described above, recent advances in organic light-emitting devices are remarkable, and their features are high brightness, variety of emission wavelengths, high-speed response, low profile, and light-emitting devices with low applied voltage. Suggests the possibility to.
[0007]
However, under the present circumstances, light output with higher brightness or higher conversion efficiency is required. In addition, there are still many problems in terms of durability, such as changes over time due to long-term use and deterioration due to atmospheric gas containing oxygen or moisture. Furthermore, when considering application to full-color displays, blue, green, and red light emission with good color purity is required. However, this problem has not been sufficiently solved, and red light emission is not particularly sufficient. .
[0008]
On the other hand, spiro compounds have a specific three-dimensional structure and are attracting attention as organic functional materials due to their specific material properties (J. Am. Chem. Soc., 110 , 5687, 1988). There is an example (Japanese Patent Laid-Open No. 7-278537) in which a spiro compound is used in an organic light emitting device, but sufficient light emitting characteristics as an electron transport layer and a light emitting layer are not obtained.
[0009]
[Problems to be solved by the invention]
The present invention has been made to solve such problems of the prior art, and an object of the present invention is to provide an organic light emitting device having an extremely high efficiency, high luminance, and long life light output.
[0010]
Another object of the present invention is to provide an organic light-emitting element that has a variety of emission wavelengths and exhibits various emission hues, and in particular, has an emission hue such as amber and red and is extremely durable.
[0011]
It is another object of the present invention to provide an organic light emitting device that can be easily manufactured and can be produced at a relatively low cost.
[0012]
[Means for Solving the Problems]
That is, the organic light-emitting device of the present invention is an organic light-emitting device having at least a layer containing a pair of electrodes composed of an anode and a cathode and one or more organic compounds sandwiched between the pair of electrodes. At least one of the containing layers contains at least one compound represented by the following general formula [I].
[0013]
[Formula 4]
(Wherein K 1 , K 2 , K 3 and K 4 represent a substituted or unsubstituted aromatic ring or heterocyclic ring, and at least one of K 1 , K 2 , K 3 and K 4 represents at least a nitrogen atom. 1 represents a heterocyclic ring containing 1. K 1 , K 2 , K 3 and K 4 may be the same or different.
[0015]
L 1 , L 2 , L 3 and L 4 are each a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, an alkoxyl group, a nitro group, It represents a substituted or unsubstituted amino group or a group having the structural formula of the following general formula [X], [XII] or [XII]. L 1 , L 2 , L 3 and L 4 may be the same or different. )
[0016]
[Chemical formula 5]
Wherein R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl. Represents a group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a nitro group, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 may be the same or different.
[0018]
X 1 , X 2 , X 3 , Y 1 , Y 2 and Y 3 represent a nitrogen atom or C—R 16 , and X 1 , X 2 , X 3 , Y 1 , Y 2 and Y 3 are the same. Or different.
[0019]
Z 1 , Z 2 and Z 3 are —O—, —S—, —NR 17 —, —Si (R 18 ) R 19 —, —C (R 20 ) R 21 —, —CH═CH— or — Represents CH═N—, and Z 1 , Z 2 and Z 3 may be the same or different.
[0020]
R 17 , R 20 and R 21 represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R 20 and R 21 may be the same or different.
[0021]
R 18 and R 19 represent an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R 18 and R 19 are the same or different. May be.
[0022]
l is 0 or 1, m is 0 or an integer of 1 to 30, n is an integer of 0 or 1 to 30, m + n is an integer of 0 or 1 to 30, p is 0 or 1, q is 0 or 1 to 30 An integer, r represents an integer of 1-30. )
[0023]
In the organic light-emitting device of the present invention, the compound represented by the general formula [I] is represented by the following general formulas [II], [III], [IV], [V], [VI], [VII], [VIII]. Or a compound represented by [IX].
[0024]
[Chemical 6]
Wherein R 1 , R 2 , R 3 and R 4 are a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxyl group. Represents a nitro group or a substituted or unsubstituted amino group, and R 1 , R 2 , R 3 and R 4 may be the same or different.)
[0026]
Further, at least one of L 1 , L 2 , L 3 and L 4 is a group selected from the group consisting of the structural formulas of the general formulas [X] to [XII], so that the glass transition point is high. It is preferable in terms of improving the stability as an organic light emitting device.
[0027]
Furthermore, it is preferable that at least the electron injection layer, the electron transport layer, or the light emitting layer contains the compound represented by the general formula [I].
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0029]
First, specific examples of the substituents in the general formulas [I] to [XII] are shown below.
[0030]
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a ter-butyl group, and an octyl group.
[0031]
Examples of the aralkyl group include a benzyl group and a phenethyl group.
[0032]
Examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a fluorenyl group.
[0033]
Examples of the heterocyclic group include a thienyl group, a pyrrolyl group, an imidazolyl group, a furyl group, a pyridyl group, an indolyl group, a quinolyl group, and a carbazolyl group.
[0034]
Examples of the alkoxyl group include a methoxyl group, an ethoxyl group, a propoxyl group, and a phenoxyl group.
[0035]
Examples of the amino group include a dimethylamino group, a diethylamino group, a dibenzylamino group, and a diphenylamino group.
[0036]
Examples of the substituent that the substituent may have include an alkyl group such as a methyl group, an ethyl group, and a propyl group, an aralkyl group such as a benzyl group and a phenethyl group, an aryl group such as a phenyl group, a naphthyl group, and an anthryl group, Examples thereof include heterocyclic groups such as thienyl group, pyrrolyl group, pyridyl group and quinolyl group, and amino groups such as dimethylamino group, diethylamino group, dibenzylamino group and diphenylamino group.
[0037]
Examples of the substituent represented by the general formulas [X] to [XII] include those shown below.
[0038]
[Chemical 7]
[Chemical 8]
Hereinafter, typical examples of the spirosilol compound represented by the general formula [I] are listed, but the present invention is not limited thereto. In addition, the substituents 1-14 in Tables 1-8 are the substituents shown below. The numbers in parentheses in the columns R 1 to R 4 in Tables 1 to 8 represent substitution positions.
[0041]
[Chemical 9]
[Chemical Formula 10]
[Table 1]
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[Table 2]
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[Table 3]
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[Table 4]
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[Table 5]
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[Table 6]
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[Table 7]
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[Table 8]
Next, the organic light emitting device of the present invention will be described with reference to the drawings.
[0059]
FIG. 1 is a cross-sectional view showing an example of the organic light emitting device of the present invention. FIG. 1 shows a structure in which an anode 2, a light emitting layer 3 and a cathode 4 are sequentially provided on a substrate 1. The light-emitting element used here is useful when it has a single hole transport ability, electron transport ability, and light-emitting performance, or when a compound having each characteristic is mixed.
[0060]
FIG. 2 is a cross-sectional view showing another example of the organic light emitting device of the present invention. FIG. 2 shows a configuration in which an anode 2, a hole transport layer 5, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, the luminescent material is a material having either or both of a hole transporting property and an electron transporting property, and is used in combination with a mere hole transporting material or electron transporting material having no light emitting property. Useful in cases. In this case, the light emitting layer 3 includes either the hole transport layer 5 or the electron transport layer 6.
[0061]
FIG. 3 is a cross-sectional view showing another example of the organic light emitting device of the present invention. FIG. 3 shows a structure in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. This is a separation of carrier transport and light emission functions. It is used in combination with compounds having hole transport properties, electron transport properties, and light emission properties in a timely manner. Since various compounds having different values can be used, it is possible to diversify the emission hue. Further, it is possible to effectively confine each carrier or exciton in the central light emitting layer 3 to improve the light emission efficiency.
[0062]
FIG. 4 is a cross-sectional view showing another example of the organic light emitting device of the present invention. FIG. 4 shows a structure in which an anode 2, a hole transport layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 4 are sequentially provided on a substrate 1. In this structure, an electron injection layer 7 is provided in order to efficiently inject electrons from the cathode 4 to the electron transport layer 6, and the functions of electron injection from the cathode 4 and electron transport are separated.
[0063]
However, FIGS. 1-4 are very basic element structures to the last, and the structure of the organic light emitting element using the compound of this invention is not limited to these. For example, various layer configurations such as providing an insulating layer at the interface between the electrode and the organic layer, providing an adhesive layer or interference layer, and the hole transporting layer are composed of two layers having different ionization potentials can be employed.
[0064]
The compound represented by the general formula [I] used in the present invention is a compound excellent in electron injecting property, electron transporting property, light emitting property and durability as compared with conventional compounds. Forms can also be used.
[0065]
In particular, the organic layer using the compound represented by the general formula [I] of the present invention is useful as an electron injection layer, an electron transport layer, and a light emitting layer, and a layer formed by a vacuum deposition method or a solution coating method is used. Crystallization is unlikely to occur and the stability over time is excellent.
[0066]
In the organic light emitting device of the present invention, the compound represented by the general formula [I] is formed between the anode 2 and the cathode 4 by a vacuum deposition method or a solution coating method. The thickness of the organic layer is less than 10 μm, preferably 0.5 μm or less, more preferably 0.01 to 0.5 μm.
[0067]
In the present invention, the compound represented by the general formula [I] is preferably used as a component of the electron injection layer, the electron transport layer, and the light emitting layer. A compound, an electron transporting compound, or the like can be used together as necessary.
[0068]
Examples of these compounds are given below.
[0069]
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In the organic light-emitting device of the present invention, the layer containing the compound represented by the general formula [I] and the layer containing another organic compound are generally formed into a thin film by a vacuum deposition method or a coating method by dissolving in a suitable solvent. Form. In particular, when a film is formed by a coating method, the film can be formed in combination with an appropriate binder resin.
[0076]
The binder resin can be selected from a wide range of binder resins, such as polyvinyl carbazole resin, polycarbonate resin, polyester resin, polyarylate resin, polystyrene resin, acrylic resin, methacrylic resin, butyral resin, polyvinyl acetal resin, diallyl phthalate resin. , Phenol resin, epoxy resin, silicone resin, polysulfone resin, urea resin and the like, but are not limited thereto. Moreover, you may mix these 1 type, or 2 or more types as a single or copolymer polymer.
[0077]
As the anode material, a material having a work function as large as possible is good. For example, simple metals such as gold, platinum, nickel, palladium, cobalt, selenium, vanadium or alloys thereof, tin oxide, zinc oxide, indium tin oxide (ITO), A metal oxide such as zinc indium oxide can be used. In addition, conductive polymers such as polyaniline, polypyrrole, polythiophene, and polyphenylene sulfide can also be used. These electrode materials may be used alone or in combination.
[0078]
On the other hand, the cathode material preferably has a small work function, and can be used as a single metal or a plurality of alloys such as lithium, sodium, potassium, calcium, magnesium, aluminum, indium, silver, lead, tin, and chromium. A metal oxide such as indium tin oxide (ITO) can also be used. Further, the cathode may have a single layer structure or a multilayer structure.
[0079]
Although it does not specifically limit as a board | substrate used by this invention, Transparent substrates, such as opaque board | substrates, such as a metal board | substrate and a ceramic board | substrate, glass, quartz, a plastic sheet, are used. It is also possible to control the color light by using a color filter film, a fluorescent color conversion filter film, a dielectric reflection film, or the like on the substrate.
[0080]
Note that a protective layer or a sealing layer can be provided on the prepared element for the purpose of preventing contact with oxygen or moisture. Examples of protective layers include diamond thin films, inorganic material films such as metal oxides and metal nitrides, polymer films such as fluorine resins, polyparaxylene, polyethylene, silicone resins, and polystyrene resins, and photocurable resins. Can be mentioned. Further, it is possible to cover glass, a gas impermeable film, a metal, etc., and to package the element itself with an appropriate sealing resin.
[0081]
【Example】
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
[0082]
[Example 1]
An element having the structure shown in FIG. 2 was produced.
[0083]
What formed indium tin oxide (ITO) as the anode 2 with the film thickness of 120 nm on the glass substrate as the board | substrate 1 by the sputtering method was used as a transparent conductive support substrate. This was ultrasonically washed successively with acetone and isopropyl alcohol (IPA), boiled and washed with IPA, and dried. Furthermore, what was UV / ozone cleaned was used as a transparent conductive support substrate.
[0084]
A compound represented by the following structural formula was formed into a film with a thickness of 70 nm on the transparent conductive support substrate by a vacuum vapor deposition method to form a hole transport layer 5. Furthermore, Exemplified Compound No. The compound shown by 1 was formed into a film with a film thickness of 70 nm by a vacuum evaporation method, and the electron transport layer 6 was formed. The degree of vacuum during vapor deposition was 1.0 × 10 −4 pa, and the film formation rate was 0.2 to 0.3 nm / sec.
[0085]
Embedded image
Next, a metal layer film (cathode 4) having a thickness of 150 nm was formed on the organic layer by a vacuum vapor deposition method using a vapor deposition material composed of aluminum and lithium (lithium concentration: 1 atomic%). The degree of vacuum at the time of vapor deposition was 1.0 × 10 −4 Pa, and the film formation rate was 1.0 to 1.2 nm / sec.
[0087]
When a direct current voltage of 8 V is applied to the device obtained in this manner with an ITO electrode as a positive electrode and an Al-Li electrode as a negative electrode, a current flows through the device at a current density of 8.0 mA / cm 2 560 cd / m. Red light emission was observed at a luminance of 2 .
[0088]
Further, when a voltage was applied for 100 hours with the current density kept to 7.0 mA / cm 2 in a nitrogen atmosphere, after the initial luminance 510 cd / m 2 100 hours 485cd / m 2 and luminance degradation was small.
[0089]
[Examples 2-17, Comparative Examples 1-2]
Exemplified Compound No. A device was prepared in the same manner as in Example 1 except that the compounds shown in Table 9 were used in place of 1, and the same evaluation was performed. The results are shown in Table 9.
[0090]
In addition, comparative compound No. 1 is a compound represented by the following structural formula (described in JP-A-7-278537).
[0091]
Embedded image
Comparative compound No. 2 is a compound represented by the following structural formula (described in JP-A-9-87616).
[0093]
Embedded image
[Table 9]
[Example 18]
An element having the structure shown in FIG. 2 was produced.
[0096]
In the same manner as in Example 1, a hole transport layer 5 was formed on a transparent conductive support substrate.
[0097]
Furthermore, Exemplified Compound No. The compound shown by 2 and aluminum triskinolinol (weight ratio 1:20) were formed into a film with a film thickness of 70 nm by the vacuum evaporation method, and the electron carrying layer 6 was formed. The degree of vacuum at the time of vapor deposition was 1.0 × 10 −4 Pa, and the film formation rate was 0.2 to 0.3 nm / sec.
[0098]
Next, a cathode 4 was formed in the same manner as in Example 1.
[0099]
When a direct current voltage of 8 V was applied to the device thus obtained with an ITO electrode as a positive electrode and an Al—Li electrode as a negative electrode, a current flowed to the device at a current density of 8.5 mA / cm 2 , resulting in 800 cd / m. An orange luminescence with a brightness of 2 was observed.
[0100]
Further, when a voltage was applied for 100 hours with the current density kept to 7.0 mA / cm 2 in a nitrogen atmosphere, after the initial luminance 620 cd / m 2 100 hours 590cd / m 2 and luminance degradation was small.
[0101]
[Examples 19 to 28, Comparative Examples 3 to 4]
Exemplified Compound No. A device was prepared in the same manner as in Example 18 except that the compounds shown in Table 10 were used instead of 2, and the same evaluation was performed. The results are shown in Table 10.
[0102]
[Table 10]
[Example 29]
An element having the structure shown in FIG. 3 was prepared.
[0104]
In the same manner as in Example 1, a hole transport layer 5 was formed on a transparent conductive support substrate.
[0105]
Next, aluminum triskinolinol was formed into a film with a thickness of 30 nm by a vacuum evaporation method, and the light emitting layer 3 was formed. Furthermore, Exemplified Compound No. The compound represented by 4 was formed into a film with a thickness of 50 nm by a vacuum evaporation method, and the electron transport layer 6 was formed. The degree of vacuum at the time of vapor deposition was 1.0 × 10 −4 Pa, and the film formation rate was 0.2 to 0.3 nm / sec.
[0106]
Next, a cathode 4 was formed in the same manner as in Example 1.
[0107]
When a direct current voltage of 10 V was applied to the device thus obtained with the ITO electrode as the positive electrode and the Al-Li electrode as the negative electrode, a current flowed through the device at a current density of 11.0 mA / cm 2 , and 1050 cd / m. Yellow luminescence was observed at a luminance of 2 .
[0108]
Furthermore, when a voltage was applied for 100 hours while maintaining the current density at 10.0 mA / cm 2 in a nitrogen atmosphere, the luminance deterioration was small, from the initial luminance of 9980 cd / m 2 to 930 cd / m 2 after 100 hours.
[0109]
[Examples 30 to 39, Comparative Examples 5 to 6]
Exemplified Compound No. A device was prepared in the same manner as in Example 29 except that the compounds shown in Table 11 were used in place of 4, and the same evaluation was performed. The results are shown in Table 11.
[0110]
[Table 11]
[Example 40]
An element having the structure shown in FIG. 1 was prepared.
[0112]
On the transparent conductive support substrate used in Example 1, Exemplified Compound No. A solution obtained by dissolving 0.050 g of the compound represented by 1 and 1.00 g of poly-N-vinylcarbazole (weight average molecular weight = 63,000) in 80 ml of chloroform was converted into a 120 nm film by spin coating (rotation speed = 2000 rpm). The light emitting layer 3 was formed by forming a thick film.
[0113]
Next, a cathode 4 was formed in the same manner as in Example 1.
[0114]
When a DC voltage of 10 V was applied to the device obtained in this manner with the ITO electrode as the positive electrode and the Al-Li electrode as the negative electrode, a current flowed through the device at a current density of 9.0 mA / cm 2 , and 410 cd / m Orange emission was observed at a luminance of 2 .
[0115]
[Comparative Example 10]
Exemplified Compound No. In place of Comparative Compound No. 1 A device was prepared in the same manner as in Example 40 except that 2 was used. Similarly, when a DC voltage of 10 V was applied, a current flowed through the device at a current density of 9.0 mA / cm 2 , and a yellow color with a luminance of 30 cd / m 2. Green luminescence was observed.
[0116]
【The invention's effect】
The organic light-emitting device using the spirosilol compound represented by the general formula [I] of the present invention can emit light with high luminance at a low applied voltage and has excellent durability.
[0117]
In particular, the organic layer using the spirosilol compound represented by the general formula [I] of the present invention is excellent as an electron transport layer or a light emitting layer.
[0118]
Furthermore, the device can be formed using vacuum deposition, casting method, or the like, so that a device having a relatively large area can be easily manufactured.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of an organic light emitting device in the present invention.
FIG. 2 is a cross-sectional view showing another example of the organic light emitting device according to the present invention.
FIG. 3 is a cross-sectional view showing another example of the organic light emitting device according to the present invention.
FIG. 4 is a cross-sectional view showing another example of the organic light emitting device in the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Light emitting layer 4 Cathode 5 Hole transport layer 6 Electron transport layer 7 Electron injection layer
Claims (4)
Ｌ1、Ｌ2、Ｌ3およびＬ4は、水素原子、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基、置換あるいは無置換の複素環基、アルコキシル基、ニトロ基、置換あるいは無置換のアミノ基または下記一般式［Ｘ］、［ＸＩＩ］あるいは［ＸＩＩ］の構造式からなる基を表わす。Ｌ1、Ｌ2、Ｌ3およびＬ4は、同じであっても異なっていてもよい。）
Ｘ1、Ｘ2、Ｘ3、Ｙ1、Ｙ2およびＹ3は、窒素原子あるいはＣ−Ｒ16を表わし、Ｘ1、Ｘ2、Ｘ3、Ｙ1、Ｙ2およびＹ3は同じであっても異なっていてもよい。
Ｚ1、Ｚ2およびＺ3は、−Ｏ−、−Ｓ−、−ＮＲ17−、−Ｓｉ（Ｒ18）Ｒ19−、−Ｃ（Ｒ20）Ｒ21−、−ＣＨ＝ＣＨ−あるいは−ＣＨ＝Ｎ−を表わし、Ｚ1、Ｚ2およびＺ3は、同じであっても異なっていてもよい。
Ｒ17、Ｒ20およびＲ21は、水素原子、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基または置換あるいは無置換の複素環基を表わす。Ｒ20およびＲ21は、同じであっても異なっていてもよい。
Ｒ18およびＲ19は、アルキル基、置換あるいは無置換のアラルキル基、置換あるいは無置換のアリール基または置換あるいは無置換の複素環基を表わし、Ｒ18およびＲ19は同じであっても異なっていてもよい。
ｌは０または１、ｍは０または１〜３０の整数、ｎは０または１〜３０の整数、ｍ＋ｎは０または１〜３０の整数、ｐは０または１、ｑは０または１〜３０の整数、ｒは１〜３０の整数を表わす。）In an organic light-emitting element having at least one layer including an anode and a cathode and one or more organic compound layers sandwiched between the pair of electrodes, at least one of the organic compound layers is represented by the following general formula [ An organic light-emitting device comprising at least one of the compounds represented by I].
L 1 , L 2 , L 3 and L 4 are each a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, an alkoxyl group, a nitro group, It represents a substituted or unsubstituted amino group or a group having the structural formula of the following general formula [X], [XII] or [XII]. L 1 , L 2 , L 3 and L 4 may be the same or different. )
X 1 , X 2 , X 3 , Y 1 , Y 2 and Y 3 represent a nitrogen atom or C—R 16 , and X 1 , X 2 , X 3 , Y 1 , Y 2 and Y 3 are the same. Or different.
Z 1 , Z 2 and Z 3 are —O—, —S—, —NR 17 —, —Si (R 18 ) R 19 —, —C (R 20 ) R 21 —, —CH═CH— or — Represents CH═N—, and Z 1 , Z 2 and Z 3 may be the same or different.
R 17 , R 20 and R 21 represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R 20 and R 21 may be the same or different.
R 18 and R 19 represent an alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R 18 and R 19 are the same or different. May be.
l is 0 or 1, m is 0 or an integer of 1 to 30, n is an integer of 0 or 1 to 30, m + n is an integer of 0 or 1 to 30, p is 0 or 1, q is 0 or 1 to 30 An integer, r represents an integer of 1-30. )
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001306084A JP4136352B2 (en) | 2001-10-02 | 2001-10-02 | Organic light emitting device |
| PCT/JP2002/008803 WO2003020847A1 (en) | 2001-09-03 | 2002-08-30 | Organic luminescence device |
| US10/385,461 US6916555B2 (en) | 2001-09-03 | 2003-03-12 | Organic luminescence device |
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| JP2001306084A JP4136352B2 (en) | 2001-10-02 | 2001-10-02 | Organic light emitting device |
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| JP4136352B2 true JP4136352B2 (en) | 2008-08-20 |
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| JP5847605B2 (en) * | 2011-08-22 | 2016-01-27 | 住友化学株式会社 | Silole derivative and organic electronic device comprising silole derivative |
| CN111087416B (en) | 2018-10-24 | 2024-05-14 | 北京夏禾科技有限公司 | Silicon-containing electron transport materials and their applications |
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