JP3950556B2 - Luminescent organic / inorganic composite material and manufacturing method thereof - Google Patents

Description

【００６０】
）、ＤＣＭ１（4-Dicyanmethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran、式：
【００６１】
【化２】

【００６２】
）、ＤＣＭ２（4-Dicyanmethylene-2-methyl-6-(octahydroquinolizine[c,d]styryl)-4H-pyran、式：
【００６３】
【化３】

【００６４】
）、ルブレン（Rubrene、式：
【００６５】
【化４】

【００６６】
）、キナクリドン誘導体（Quinacridone derivatives、式：
【００６７】
【化５】

【００６８】
）等の１種以上があげられる。
【００６９】
前記有機ポリマーと無機ポリマーは、それぞれの前駆体を混合し同時にポリマー化させて製造したものであってもよく、また、無機ポリマーを作製した後にその空孔内に有機ポリマーを含浸させる方法で有機ポリマーと無機ポリマーとを混在させたものであってもよい。それぞれに電荷輸送剤、蛍光発光性化合物あるいは分子などを加えておいてもよい。
【００７０】
製造された発光型有機・無機複合材料において、有機ポリマーと無機ポリマーとはナノメートルのオーダーで構造制御されていることが好ましい。
【００７１】
本発明の有機・無機複合材料は、一方の面が透明電極に接し、他方の面には金属電極が施されている。
【００７２】
前記透明電極は、仕事関数が大きな酸化インジュウム錫（ＩＴＯ）、酸化錫（ＳｎＯ₂）、酸化インジュウム（ＩｎＯ_ｘ）等の内から形成されていることが好ましく、金属電極は、仕事関数が小さなアルミニウム、アルミニウムリチウム合金、アルミニウムマグネシウム合金、マグネシウム、マグネシウム銀合金、マグネシウムインジュウム合金等の内の少なくとも一つから形成されていることが好ましい。
【００７３】
透明電極や金属電極は、双方が直接蒸着により形成されていてもよく、透明電極を施したガラス基板上で有機・無機複合材料を作製した後、金属電極が直接蒸着により形成されていてもよい。
【００７４】
本発明の有機・無機複合材料と透明電極および金属電極とを接触させ、透明電極をアノード電極（陰極）とし、金属電極をカソード電極（陽極）とし、電界を印加することにより、本発明の複合材料は発光する。また、透明電極をアノード電極（陰極）とし、金属電極をカソード電極（陽極）とし、それぞれにリード線を取り付けた後に、透明電極側を透明のガラスあるいはプラスチックで覆い、金属電極側をプラスチック等の絶縁物で覆った後に、材料端面をエポキシ樹脂等の封止樹脂で封止し、外部からの劣化因子となる不純物の侵入を防ぎ、長時間安定に電界を印加することにより発光させることができる。
【００７５】
本発明を、本発明の発光型有機・無機複合材料の模式図である図１にしたがって説明する。
【００７６】
本発明は、図１に示されるような、厚みが０．５〜１．５ミクロン、さらには０．９〜１．４ミクロン、たとえば１ミクロン程度で、現行の有機ＥＬ材料に比べて、発光性分子が充分の量で存在し、高輝度発光を余裕を持って行えるようにした発光型有機・無機複合材料である。なお、図１において、３は透明電極、４は金属電極、５は発光型有機・無機複合材料、６は透明電極の透明カバー、７は金属電極のカバー、８は封止樹脂、９はリード線である。
【００７７】
本発明における無機ポリマーとしては、たとえばゾルゲル法によるポーラスな細孔の多い材料が用いられる。たとえばこの細孔部に有機ポリマーを含浸させることにより、本発明の発光型有機・無機複合材料が製造される。無機部と有機部との界面は密着した状態にある。この様な、有機・無機複合材料に電荷輸送剤、ドーパント発光剤を必要に応じて入れることにより、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。電荷輸送剤の濃度は、正負の両電荷共に材料全体に対して１５〜４０ｗｔ％、さらには２５ｗｔ％程度が好ましい。なお、有機ポリマー部に正電荷輸送剤（負電荷輸送剤）が２５ｗｔ％、無機ポリマー部に負電荷輸送剤（正電荷輸送剤）が２５ｗｔ％含まれ、全体の５０ｗｔ％を電荷輸送剤がしめることになるのが最も好ましい。
【００７８】
上記の有機・無機複合材料は常圧下で作製でき、超高真空条件を必要としない。よって、大面積の発光材料が作れる。また、発光時にでる熱の放逸も無機材料部で行えるので、安定に長時間効率よく発光させることができる。
【００７９】
また、有機材料の柔軟性と無機材料の剛直性とを相乗的に合わせ持った加工性に優れた材料が得られる。
【００８０】
本発明の複合材料自身は、たとえば１ミクロン程度の厚みにされるが、その内部は図２（本発明の発光型有機・無機複合材料の内部構造と電荷の移動を表わす模式図、図中の１は有機ポリマー部、２は無機ポリマー部を示す）に示されるように、ナノメータオーダで制御されているので、電荷再結合とそのエキシトンエネルギーによる発光性分子の励起を効率よく行うことができる。よって、印加電界も、従来の有機ＥＬ材料および無機ＥＬ材料に対して用いられてきた１００万ボルト／ｃｍより低くできる。さらに、電極から離れたところで、エキシトンにより発光性分子が励起されるので、発光性分子からの発光効率も大きくなる。また、本発明の材料は１ミクロン程度の厚みにされるため、発光成分の分子数が多くなり、高輝度発光を余裕を持って行える。即ち、従来法のように高電圧を印加しなくとも、高輝度発光が行えるようになる。その結果駆動寿命も長くなる。
【００８１】
また、本発明の複合材料自身は１ミクロン程度の厚みであるために、ピンホールが生成しなくなり、電極間での導通が無くなり、発光輝度の面内の均一性が良くなると共に、電界発光素子としての寿命が長くなる。
【００８２】
本発明の有機・無機複合材料は、正電荷輸送剤と負電荷輸送剤とが別々に無機部（無機ポリマー部）と有機部（有機ポリマー部）のどちらかに含まれている有機・無機複合材料であってもよく、無機部と有機部の少なくともどちらか一方に正電荷輸送剤と負電荷輸送剤の両方ともが含まれている有機・無機複合材料であってもよい。
【００８３】
正電荷輸送剤と負電荷輸送剤とが別々に無機部と有機部のどちらかに含まれている場合には、各電荷は有機・無機界面で再結合を行うまでは効率よく移動できる。それは、無機部と有機部とが共に、数ナノメータから数十ナノメータのサイズから成っているので、各電荷は途中でトラップされずに、効率よく有機・無機界面にまで到達するからである。有機・無機界面までの距離も各材料部は蛇行した、編み目構造であるので、界面までの距離もせいぜい百ナノメータ程度になる。そのために、各電荷は材料の厚み１ミクロン程度をも移動する必要は無く、有機部と無機部の材料界面に到達でき、無機部と有機部との界面でのみ効率よく再結合する。さらに、発光性分子のエキシトンによる励起にとって不利となる電極近傍でのエキシトンの失活が抑えられる。さらに、無機部と有機部の接触界面は従来の平面構造でなく、曲面構造であるので、接触面積は広くなり、正電荷と負電荷との再結合の確率が一段と高くなり効率よくなる。
【００８４】
無機ポリマーあるいは有機ポリマーのどちらか一方に、正電荷輸送剤と負電荷輸送剤とを同時に含ませた場合も、材料の厚みが１ミクロン程度も有るために、正電荷輸送剤と負電荷輸送剤とが同時に含まれたとしても、正負の各電荷は対向する別々の電極から注入されるために、両電荷は対向方向に移動して行き、両電極とは離れた所で再結合し、電極近傍でのエキシトンの失活が抑えられ、エキシトンによる発光性分子を効率よく励起し、高効率な電界発光が達成される。発光性分子としては、電荷輸送剤自身がその役割を担う場合と、電荷輸送剤の発光波長以外の光を発光させたいときには、その波長を蛍光波長とする蛍光発光性化合物あるいは分子をドーパントとして添加する場合とがある。因って、蛍光発光性化合物あるいは分子は必ずしも、添加されるわけではない。添加される場合には、種々の波長の発光が可能となる。なお、有機部と無機部のどの部分も、蛇行しながら、それぞれ両電極と接している構造をしている。
【００８５】
各電極は有機・無機複合材料表面を研磨後に直接蒸着する。このため、本発明の有機・無機複合材料と透明電極と金属電極の両電極との接触が密になり、電荷注入効率が上がる。
【００８６】
本発明では、各電極は、図１、図２及び図３（本発明の発光型有機・無機複合材料の研磨後の表面状態の模式図）に示されるように、無機部と有機部の双方に接触させる。しかし、たとえば無機部に正電荷輸送剤が含まれており、有機部には、負電荷輸送剤が含まれている場合には、無機部には仕事関数の大きいＩＴＯ電極のみから正電荷が注入される。また、有機部には仕事関数の小さな金属電極のみから負電荷が注入される。各電荷輸送剤が含まれる材料部が逆の場合には（無機部に負電荷輸送剤、有機部に正電荷輸送剤が含まれる場合）、無機部には金属電極からのみ、負電荷が注入される。有機部にはＩＴＯ電極のみから正電荷が注入される。この様に、各電極は、選択的に正か負の電荷を無機部あるいは有機部に注入する。即ち、各材料部（有機部と無機部）はそこに含まれる電荷輸送剤の性質により、正電荷か負電荷のどちらかのみが選択的に注入される。また、無機部と有機部との比率、あるいは、正電荷輸送剤と負電荷輸送剤の比率を最適に選び（電荷輸送剤の種類によりこの比率は変化するかも知れないが）、注入される正電荷と負電荷とのバランスを最適化させる。最適に選ぶのは、正電荷と負電荷の注入量が、できうる限り等しくなるようにするためである。その結果、正電荷と負電荷との再結合とエキシトン形成が高効率化できる。また、電極から離れたところでホールとエレクトロンが再結合できるので、電極近傍でのエキシトンの失活を抑えられ、発光効率が増す。以上のようにして、高効率、高輝度、長寿命駆動、および大面積の電界発光材料を提供することができる。
【００８７】
なお、有機部にポリビニルカルバゾール（ＰＶＫ）の様なホール輸送性のあるポリマーが含まれていても、アルミノキノリニウム（ＡｌＱ₃）の様な電子輸送剤をＰＶＫに対して５０ｗｔ％以上にまで含むようにすれば、電子輸送を行わせることが可能になる。ＰＶＫにホール輸送剤を含ませれば、いよいよホール輸送能が増大する。
【００８８】
有機ポリマーか無機ポリマーかのどちらか一方に正負の両電荷輸送剤が含まれる場合には、ＩＴＯ電極から正電荷が、対向電極である金属電極から負電荷が、それぞれ両電荷輸送剤を含む同一の材料部に注入される。しかし、これら両電荷は１ミクロン程度の厚みの材料内を対向して移動するため、電極面から離れた材料内部で両電荷が再結合し、エキシトンを生成し、発光性分子を効率よく励起し発光させる。
【００８９】
本発明の有機・無機複合材料では加工性の良さから表面研磨が行える。その結果、表面は無機部と有機部とが明確に区別されて存在する。即ち、密着した状態で分離している（図３）。そのために、透明電極と金属電極の両電極は、それぞれ選択的にホールとエレクトロンとを無機部と有機部とに注入することができる。厚みのコントロールもでき、表面の平滑性も得られる。その結果、電極材料が均一に密着され、電荷注入の効率が良くなる。
【００９０】
以上のように本発明の有機・無機複合材料では、電界印加により、効率よく正負の両電荷が注入され、それらは、また、効率よく再結合しエキシトンを形成し、そのエネルギーで発光性分子を励起し、電界発光が効率よく起こる。また、厚みも１ミクロン程度の薄さであるが、従来の有機ＥＬ材料よりも１０倍厚く、ピンホールの生成が無く、発光輝度が材料面内で均一であり、駆動動作寿命を長くしてくれる。また、有機材料を含んでいるため、材料の加工性に優れ、無機材料を含んでいるために、材料の光学特性にも優れる。また、無機材料は発光時の発熱を放逸してくれるために、材料の駆動動作寿命が延びる。
【００９１】
【実施例】
つぎに、本発明を実施例にもとづいて説明するが、本発明はこれらに限定されるものではない。
【００９２】
実施例１
無機ポリマーの前駆体としてテトラエトキシシラン、有機ポリマーの前駆体としてビニルカルバゾールを用いる。テトラエトキシシラン（ＴＥＯＳ）１０ｇと負電荷輸送剤ＡｌＱ₃ １．５ｇとを２．５ｇのエタノールに溶かして溶液とし、該溶液に硝酸水溶液を加えてｐＨ５．０に調製し、この液をテフロンシャーレ中に入れ、加水分解・重縮合法によりゲル化させて、熱処理（９０℃、２０時間）を行い、ＡｌＱ₃を含んだＳｉＯ₂の無機ガラス（直径が１５ｃｍ）を得た。このガラスは１５ナノメートルの空孔を有していた（窒素吸着実験とＢＥＴ法により測定）。また、空孔率（空孔の体積比）は５８％であった。このガラスを、ビニルカルバゾール３ｇと２，２′−アゾビスイソブチロニトリル１ｍｇおよび正電荷輸送剤ＴＰＤ １．５ｇを含むテトラヒドロフラン（ＴＨＦ）溶液中に入れ、上記のＳｉＯ₂の無機ガラス中でビニルカルバゾールの重合を起こさせた。なお、前記ＴＨＦ溶液は全て消費された。その結果、上記のＡｌＱ₃を含んだＳｉＯ₂の無機ガラス中に、ＴＰＤを含んだポリビニルカルバゾールを有機ポリマー部として含む有機・無機複合材料を得た。得られた有機・無機複合材料の厚みは１．３マイクロメータであり、バフ研磨等の研磨を行い、厚みが１．１マイクロメータの光学特性が優れた有機・無機複合材料が得られた。得られた複合材料の一面に、透明な導電性の酸化インジュウム錫（ＩＴＯ）を直流スパッター法で蒸着させ、アノード電極を形成した。ＩＴＯの表面抵抗が２０Ω／□になるようにした。次に、前記複合材料の他方の面に、ＡｌとＬｉの合金（Ａｌ／Ｌｉ＝１０／１）を３０ｎｍの厚みで蒸着し、カソード電極を形成した。両電極に銅リード線を導電性ペーストで取り付けた。以上のようにして得られた複合材料のＩＴＯ電極面を透明アクリル板で覆い、Ａｌ／Ｌｉ電極面を、ポリプロピレン樹脂板で覆い、それらの全端面をエポキシ樹脂で封止した。この電極を取り付けた複合材料のＩＴＯ電極をプラス電位に、Ａｌ／Ｌｉ電極をマイナス電位に成るように、直流電圧を印加した。その結果、図４に示されるような、印加電圧・発光輝度特性を示した。即ち、印加電圧３０ボルト（Ｖ）から約０．１ｃｄ／ｍ²の発光が始まった。印加電圧を上げて行くに連れ、発光輝度は上昇し、印加電圧が７０Ｖで５００ｃｄ／ｍ²の発光、印加電圧が１００Ｖで２５００ｃｄ／ｍ²の発光が達成された。この発光は、発光波長中心が５４５ｎｍで、発光波長半値幅が約１００ｎｍの黄緑色の発光である。発光波長特性は、印加電圧に因らず同一の特性を示す。次に、前記電極を取り付けた複合材料への印加電圧を７０Ｖに固定して、発光させ続けたところ、初期の５００ｃｄ／ｍ²の発光が半減するのは、５０００時間が経ってからであった。この様に、本実施例では、高輝度の発光が長時間に亘って持続し、各種面発光型表示機器等に利用できることが分かった。なお、現状の５００ｃｄ／ｍ²の発光が半減するのは良いものであっても１０００時間程度である（参照文献：Ｈｏｓｏｋａｗａ他、Ｓｙｎｔｈ．Ｍｅｔ．，９１，（１９９７）ｐ．３）。
【００９３】
実施例２
無機ポリマーの前駆体としてテトラエトキシシラン、有機ポリマーの前駆体としてビニルカルバゾールを用いる。テトラエトキシシラン（ＴＥＯＳ）１０ｇと正電荷輸送剤ＴＰＤ １．５ｇとを２．５ｇのエタノールに溶かして溶液とし、該溶液に硝酸水溶液を加えてｐＨ５．０に調製し、この液をテフロンシャーレ中に入れ、加水分解・重縮合法によりゲル化させて、熱処理（９０℃、２０時間）を行いＴＰＤを含んだＳｉＯ₂の無機ガラス（直径が１５ｃｍ）を得た。このガラスは１４ナノメートルの空孔を有していた（窒素吸着実験とＢＥＴ法により測定）。また、空孔率（空孔の体積比）は５９％であった。このガラスを、ビニルカルバゾール３ｇと２，２′−アゾビスイソブチロニトリル１ｍｇおよび負電荷輸送剤ＡｌＱ₃を１．５ｇを含むテトラヒドロフラン溶液中に入れ、上記のＳｉＯ₂の無機ガラス中でビニルカルバゾールの重合を起こさせた。なお、前記ＴＨＦ溶液は全て消費された。その結果、上記のＴＰＤを含んだＳｉＯ₂の無機ガラス中に、ＡｌＱ₃を含んだポリビニルカルバゾールを有機ポリマー部として含む有機・無機複合材料を得た。得られた有機・無機複合材料の厚みは１．２マイクロメータであり、バフ研磨等の研磨を行い、厚みが１．１マイクロメータの光学特性が優れた有機・無機複合材料を得た。得られた複合材料の一面に、透明な導電性の酸化インジュウム錫（ＩＴＯ）を直流スパッター法で蒸着させ、アノード電極を形成した。ＩＴＯの表面抵抗が２０Ω／□になるようにした。次に、前記複合材料の他方の面に、ＡｌとＬｉの合金（Ａｌ／Ｌｉ＝１０／１）を３０ｎｍの厚みで蒸着し、カソード電極を形成した。両電極に銅リード線を導電性ペーストで取り付けた。以上のようにして得られた複合材料のＩＴＯ電極面を透明硝子板で覆い、Ａｌ／Ｌｉ電極面を、ＡＢＳ樹脂で覆い、それらの全端面をエポキシ樹脂で封止した。この電極を取り付けた複合材料のＩＴＯ電極をプラス電位に、Ａｌ／Ｌｉ電極をマイナス電位に成るように、直流電圧を印加した。その結果、図４と類似の、電圧・発光特性を示した。即ち、印加電圧２８ボルト（Ｖ）から約０．１ｃｄ／ｍ²の発光が始まった。印加電圧を上げて行くに連れ、発光輝度は上昇し、印加電圧が７３Ｖで５００ｃｄ／ｍ²の発光、印加電圧が１００Ｖで２３００ｃｄ／ｍ²の発光が達成された。この発光は、発光波長中心が５４７ｎｍで、発光波長半値幅が約１００ｎｍの黄緑色の発光である。発光波長特性は、印加電圧に因らず同一の特性を示す。次に、前記電極を取り付けた複合材料に印加電圧を７３Ｖに固定して、発光させ続けたところ、初期の５００ｃｄ／ｍ²の発光が半減するのは、５０００時間が経ってからであった。この様に、本実施例では、高輝度の発光が長時間に亘って持続し、各種面発光型表示機器等に利用できることが分かった。なお、現状の５００ｃｄ／ｍ²の発光が半減するのは良いものであっても１０００時間程度である（参照文献：Ｈｏｓｏｋａｗａ他、Ｓｙｎｔｈ．Ｍｅｔ．，９１，（１９９７）ｐ．３）。
【００９４】
実施例３
無機ポリマーの前駆体としてテトラエトキシシラン、有機ポリマーの前駆体としてビニルカルバゾールを用いる。テトラエトキシシラン（ＴＥＯＳ）１０ｇと負電荷輸送剤ＡｌＱ₃を１．５ｇと蛍光発光性分子（発光性色素）ＤＣＭ２を１５ｍｇとを２．５ｇのエタノールに溶かして溶液とし、該溶液に硝酸水溶液を加えてｐＨ５．０に調製し、この液をテフロンシャーレ中に入れ、加水分解・重縮合法によりゲル化させて、熱処理（９０℃、２０時間）を行いＡｌＱ₃と蛍光発光性分子ＤＣＭ２を含んだＳｉＯ₂の無機ガラス（直径が１５ｃｍ）を得た。このガラスは１５ナノメートルの空孔を有していた（窒素吸着実験とＢＥＴ法により測定）。また、空孔率（空孔の体積比）は５８％であった。このガラスを、ビニルカルバゾール３ｇと２，２′−アゾビスイソブチロニトリル１ｍｇおよび正電荷輸送剤ＴＰＤ １．５ｇを含むテトラヒドロフラン溶液中に入れ、上記のＳｉＯ₂の無機ガラス中でビニルカルバゾールの重合を起こさせた。なお、前記ＴＨＦ溶液は全て消費された。その結果、上記のＡｌＱ₃とＤＣＭ２とを含んだＳｉＯ₂の無機ガラス中に、ＴＰＤを含んだポリビニルカルバゾールを有機ポリマー部として含む有機・無機複合材料を得た。得られた有機・無機複合材料の厚みは１．３マイクロメータであり、バフ研磨等の研磨を行い、厚みが１．１マイクロメータの光学特性が優れた有機・無機複合材料が得られた。得られた複合材料の一面に、透明な導電性の酸化インジュウム錫（ＩＴＯ）を直流スパッター法で蒸着させ、アノード電極を形成した。ＩＴＯの表面抵抗が２０Ω／□になるようにした。次に、前記複合材料の他方の面に、ＡｌとＬｉの合金（Ａｌ／Ｌｉ＝１０／１）を３０ｎｍの厚みで蒸着し、カソード電極を形成した。両電極に銅リード線を導電性ペーストで取り付けた。以上のようにして得られた複合材料のＩＴＯ電極面を透明アクリル板で覆い、Ａｌ／Ｌｉ電極面を、ＡＢＳ樹脂で覆い、それらの全端面をエポキシ樹脂で封止した。この電極を取り付けた複合材料のＩＴＯ電極をプラス電位に、Ａｌ／Ｌｉ電極をマイナス電位に成るように、直流電圧を印加した。その結果、図４と類似の、電圧・発光特性を示した。即ち、印加電圧３５ボルト（Ｖ）から約０．１ｃｄ／ｍ²の発光が始まった。印加電圧を上げて行くに連れ、発光輝度は上昇し、印加電圧が７５Ｖで５００ｃｄ／ｍ²の発光、印加電圧が１００Ｖで２０００ｃｄ／ｍ²の発光が達成された。この発光は、発光波長中心が６３０ｎｍで、発光波長半値幅が約７０ｎｍの赤色の発光である。発光波長特性は、印加電圧に因らず同一の特性を示す。次に、前記電極を取り付けた複合材料に印加電圧を７５Ｖに固定して、発光させ続けたところ、初期の５００ｃｄ／ｍ²の発光が半減するのは、３０００時間が経ってからであった。この様に、本実施例では、高輝度の発光が長時間に亘って持続し、各種面発光型表示機器等に利用できることが分かった。なお、現状の５００ｃｄ／ｍ²の発光が半減するのは良いものであっても１０００時間程度である（参照文献：Ｈｏｓｏｋａｗａ他、Ｓｙｎｔｈ．Ｍｅｔ．，９１，（１９９７）ｐ．３）。
【００９５】
実施例４
無機ポリマーの前駆体としてテトラエトキシシラン、有機ポリマーの前駆体としてビニルカルバゾールを用いる。テトラエトキシシラン（ＴＥＯＳ）１０ｇと負電荷輸送剤ＡｌＱ₃を１．５ｇと正電荷輸送剤ＴＰＤ １．５ｇとを２．５ｇのエタノールに溶かして溶液とし、該溶液に硝酸水溶液を加えてｐＨ５．０に調製し、この液をテフロンシャーレ中に入れ、加水分解・重縮合法によりゲル化させて、熱処理（９０℃、２０時間）を行いＡｌＱ₃とＴＰＤとを含んだＳｉＯ₂の無機ガラス（直径が１５ｃｍ）を得た。このガラスは１５ナノメートルの空孔を有していた（窒素吸着実験とＢＥＴ法により測定）。また、空孔率（空孔の体積比）は５８％であった。このガラスを、ビニルカルバゾール３ｇと２，２′−アゾビスイソブチロニトリル１ｍｇおよび正電荷輸送剤ＴＰＤ １．５ｇを含むテトラヒドロフラン溶液中に入れ、上記のＳｉＯ₂の無機ガラス中でビニルカルバゾールの重合を起こさせた。なお、前記ＴＨＦ溶液は全て消費された。その結果、上記のＡｌＱ₃とＴＰＤとを含んだＳｉＯ₂の無機ガラス中に、ＴＰＤを含んだポリビニルカルバゾールを有機ポリマー部として含む有機・無機複合材料を得た。得られた有機・無機複合材料の厚みは１．３マイクロメータであり、バフ研磨等の研磨を行い、厚みが１．１マイクロメータの光学特性が優れた有機・無機複合材料が得られた。得られた複合材料の一面に、透明な導電性の酸化インジュウム錫（ＩＴＯ）を直流スパッター法で蒸着させ、アノード電極を形成した。ＩＴＯの表面抵抗が２０Ω／□になるようにした。次に、前記複合材料の他方の面に、ＭｇとＡｇの合金（Ｍｇ／Ａｇ＝９／１）を５０ｎｍの厚みで蒸着し、カソード電極を形成した。両電極に銅リード線を導電性ペーストで取り付けた。以上のようにして得られた複合材料のＩＴＯ電極面を透明アクリル板で覆い、Ｍｇ／Ａｇ電極面を、ポリプロピレン樹脂板で覆い、それらの全端面をエポキシ樹脂で封止した。この電極を取り付けた複合材料のＩＴＯ電極をプラス電位に、Ｍｇ／Ａｇ電極をマイナス電位に成るように、直流電圧を印加した。その結果、図４と類似の、電圧・発光特性を示した。即ち、印加電圧４０ボルト（Ｖ）から約０．１ｃｄ／ｍ²の発光が始まった。印加電圧を上げて行くに連れ、発光輝度は上昇し、印加電圧が８０Ｖで５００ｃｄ／ｍ²の発光、印加電圧が１００Ｖで２３００ｃｄ／ｍ²の発光が達成された。この発光は、発光波長中心が５４０ｎｍで、発光波長半値幅が約８０ｎｍの黄緑色の発光である。発光波長特性は、印加電圧に因らず同一の特性を示す。次に、前記電極を取り付けた複合材料に印加電圧を８０Ｖに固定して、発光させ続けたところ、初期の５００ｃｄ／ｍ²の発光が半減するのは、４０００時間が経ってからであった。この様に、本実施例では、高輝度の発光が長時間に亘って持続し、各種面発光型表示機器等に利用できることが分かった。なお、現状の５００ｃｄ／ｍ²の発光が半減するのは良いものであっても１０００時間程度である（参照文献：Ｈｏｓｏｋａｗａ他、Ｓｙｎｔｈ．Ｍｅｔ．，９１，（１９９７）ｐ．３）。
【００９６】
実施例５
無機ポリマーの前駆体としてテトラエトキシシラン、有機ポリマーの前駆体としてメチルメタアクリレート（ＭＭＡ）を用いる。テトラエトキシシラン（ＴＥＯＳ）１０ｇと負電荷輸送剤ＡｌＱ₃を１．５ｇとを２．５ｇのエタノールに溶かして溶液とし、該溶液に硝酸水溶液を加えてｐＨ５．０に調製し、この液をＩＴＯ電極を蒸着させたガラス基板上に塗布し、加水分解・重縮合法によりゲル化させて、熱処理（９０℃、２０時間）を行いＡｌＱ₃を含んだＳｉＯ₂の無機ガラス（直径が１５ｃｍ）を得た。このガラスは１５ナノメートルの空孔を有していた（窒素吸着実験とＢＥＴ法により測定）。また、空孔率（空孔の体積比）は５８％であった。このガラスを、メチルメタアクリレート（ＭＭＡ）２．８ｇと２，２′−アゾビスイソブチロニトリル１ｍｇおよび正電荷輸送剤ＴＰＤ １．５ｇを含むテトラヒドロフラン溶液中に入れ、上記のＳｉＯ₂の無機ガラス中でＭＭＡの重合を起こさせた。なお、前記ＴＨＦ溶液は全て消費された。その結果、上記のＡｌＱ₃を含んだＳｉＯ₂の無機ガラス中に、ＴＰＤを含んだポリメチルメタアクリレート（ＰＭＭＡ）を有機ポリマー部として含む有機・無機複合材料を得た。得られた有機・無機複合材料の厚みは１．３マイクロメータであった。ＩＴＯガラス基板上の有機・無機複合材料をバフ研磨等の研磨を行い、厚みが１．１マイクロメータの光学特性が優れた有機・無機複合材料が得られた。得られた複合材料のＩＴＯガラス基板の反対面に、ＡｌとＬｉの合金（Ａｌ／Ｌｉ＝１０／１）を３０ｎｍの厚みで蒸着し、カソード電極を形成した。両電極に銅リード線を導電性ペーストで取り付けた。以上のようにして得られた複合材料のＡｌ／Ｌｉ電極面を、ポリプロピレン樹脂板で覆い、それらの全端面をエポキシ樹脂で封止した。この電極を取り付けた複合材料のＩＴＯ電極をプラス電位に、Ａｌ／Ｌｉ電極をマイナス電位に成るように、直流電圧を印加した。その結果、図４と類似の、電圧・発光特性を示した。即ち、印加電圧４５ボルト（Ｖ）から約０．１ｃｄ／ｍ²の発光が始まった。印加電圧を上げて行くに連れ、発光輝度は上昇し、印加電圧が７０Ｖで４００ｃｄ／ｍ²の発光、印加電圧が１００Ｖで２０００ｃｄ／ｍ²の発光が達成された。この発光は、発光波長中心が５４５ｎｍで、発光波長半値幅が約１００ｎｍの黄緑色の発光である。発光波長特性は、印加電圧に因らず同一の特性を示す。次に、前記電極を取り付けた複合材料に印加電圧を７０Ｖに固定して、発光させ続けたところ、初期の４００ｃｄ／ｍ²の発光が半減するのは、４０００時間が経ってからであった。この様に、本実施例では、高輝度の発光が長時間に亘って持続し、各種面発光型表示機器等に利用できることが分かった。なお、現状の５００ｃｄ／ｍ²の発光が半減するのは良いものであっても１０００時間程度である（参照文献：Ｈｏｓｏｋａｗａ他、Ｓｙｎｔｈ．Ｍｅｔ．，９１，（１９９７）ｐ．３）。
【００９７】
実施例６
無機ポリマーの前駆体としてテトラエトキシシラン、有機ポリマーの前駆体としてビニルカルバゾールを用いる。テトラエトキシシラン（ＴＥＯＳ）を１０ｇとＡｌＱ₃を１．５ｇ、さらに、ビニルカルバゾール３ｇとα−ＮＰＤを１．５ｇと２，２′−アゾビスイソブチロニトリルを１ｍｇとを５ｇのエタノールと５ｇのテトラヒドロフラン混合溶液に溶かした。上記溶液に硝酸水溶液を加えてｐＨ５．０に調製し、この液をテフロンシャーレ中に入れ、加水分解・重縮合法によるＴＥＯＳのゲル化とビニルカルバゾールの重合を起こさせた。その結果、相溶性の関係でＡｌＱ₃の大半と一部のα−ＮＰＤとを含んだＳｉＯ₂を無機ポリマー部とし、α−ＮＰＤの大半と一部のＡｌＱ₃とを含んだポリビニルカルバゾールを有機ポリマー部とする有機・無機複合材料（ＴＨＦで有機部を溶出させたものは１８ナノメートルの空孔を有しており（窒素吸着実験とＢＥＴ法により測定）、空孔率は５７％であった）を得た。得られた有機・無機複合材料の厚みは１．３マイクロメータであり、バフ研磨等の研磨を行い、厚みが１．１マイクロメータの光学特性が優れた有機・無機複合材料が得られた。得られた複合材料の一面に、透明な導電性の酸化インジュウム錫（ＩＴＯ）を直流スパッター法で蒸着させ、アノード電極を形成した。ＩＴＯの表面抵抗が２０Ω／□になるようにした。次に、前記複合材料の他方の面に、ＡｌとＬｉの合金（Ａｌ／Ｌｉ＝１０／１）を３０ｎｍの厚みで蒸着し、カソード電極を形成した。両電極に銅リード線を導電性ペーストで取り付けた。以上のようにして得られた複合材料のＩＴＯ電極面を透明硝子板で覆い、Ａｌ／Ｌｉ電極面を、ポリプロピレン樹脂板で覆い、それらの全端面をエポキシ樹脂で封止した。この電極を取り付けた複合材料のＩＴＯ電極をプラス電位に、Ａｌ／Ｌｉ電極をマイナス電位に成るように、直流電圧を印加した。その結果、図４と類似の、電圧・発光特性を示した。即ち、印加電圧４５ボルト（Ｖ）から約０．１ｃｄ／ｍ²の発光が始まった。印加電圧を上げて行くに連れ、発光輝度は上昇し、印加電圧が７０Ｖで４００ｃｄ／ｍ²の発光、印加電圧が１００Ｖで２０００ｃｄ／ｍ²の発光が達成された。この発光は、発光波長中心が５４５ｎｍで、発光波長半値幅が約１００ｎｍの黄緑色の発光である。発光波長特性は、印加電圧に因らず同一の特性を示す。次に、前記電極を取り付けた複合材料に印加電圧を７０Ｖに固定して、発光させ続けたところ、初期の４００ｃｄ／ｍ²の発光が半減するのは、４０００時間が経ってからであった。この様に、本実施例では、高輝度の発光が長時間に亘って持続し、各種面発光型表示機器等に利用できることが分かった。なお、現状の５００ｃｄ／ｍ²の発光が半減するのは良いものであっても１０００時間程度である（参照文献：Ｈｏｓｏｋａｗａ他、Ｓｙｎｔｈ．Ｍｅｔ．，９１，（１９９７）ｐ．３）。
【００９８】
実施例７
無機ポリマーの前駆体としてテトラエトキシジルコニア、有機ポリマーの前駆体としてビニルカルバゾールを用いる。テトラエトキシジルコニア（ＴＥＯＺｒ）６ｇと負電荷輸送剤ＢｅＱ₂を１．５ｇとを３．５ｇのエタノールに溶かして溶液とし、該溶液に硝酸水溶液を加えてｐＨ５．０に調製し、この液をテフロンシャーレ中に入れ、加水分解・重縮合法によりゲル化させて、熱処理（１００℃、２０時間）を行いＢｅＱ₂を含んだＺｒＯ₂の無機ガラス（直径が１５ｃｍ）を得た。このガラスは１３ナノメートルの空孔を有していた（窒素吸着実験とＢＥＴ法により測定）。また、空孔率（空孔の体積比）は５５％であった。このガラスを、ポリビニルカルバゾール３ｇと正電荷輸送剤ｍ−ＭＴＤＡＴＡ １．９ｇを含むテトラヒドロフラン溶液中に入れ、テトラヒドロフランを蒸発除去した。その結果、上記のＢｅＱ₂を含んだＺｒＯ₂の無機ガラス中に、ｍ−ＭＴＤＡＴＡを含んだポリビニルカルバゾールを有機ポリマー部として含む有機・無機複合材料を得た。得られた有機・無機複合材料の厚みは１．３マイクロメータであり、バフ研磨等の研磨を行い、厚みが１．１マイクロメータの光学特性が優れた有機・無機複合材料が得られた。得られた複合材料の一面に、透明な導電性の酸化インジュウム錫（ＩＴＯ）を直流スパッター法で蒸着させ、アノード電極を形成した。ＩＴＯの表面抵抗が２０Ω／□になるようにした。次に、前記複合材料の他方の面に、ＡｌとＬｉの合金（Ａｌ／Ｌｉ＝１０／１）を３０ｎｍの厚みで蒸着し、カソード電極を形成した。両電極に銅リード線を導電性ペーストで取り付けた。以上のようにして得られた複合材料のＩＴＯ電極面を透明アクリル板で覆い、Ａｌ／Ｌｉ電極面を、ＡＢＳ樹脂で覆い、それらの全端面をエポキシ樹脂で封止した。この電極を取り付けた複合材料のＩＴＯ電極をプラス電位に、Ａｌ／Ｌｉ電極をマイナス電位に成るように、直流電圧を印加した。その結果、図（４）と類似の、電圧・発光特性を示した。即ち、印加電圧３０ボルト（Ｖ）から約０．１ｃｄ／ｍ²の発光が始まった。印加電圧を上げて行くに連れ、発光輝度は上昇し、印加電圧が７８Ｖで４５０ｃｄ／ｍ²の発光、印加電圧が１００Ｖで２１００ｃｄ／ｍ²の発光が達成された。この発光は、発光波長中心が５１６ｎｍで、発光波長半値幅が約８０ｎｍの緑色の発光である。発光波長特性は、印加電圧に因らず同一の特性を示す。次に、前記電極を取り付けた複合材料に印加電圧を７８Ｖに固定して、発光させ続けたところ、初期の４５０ｃｄ／ｍ²の発光が半減するのは、５５００時間が経ってからであった。この様に、本実施例では、高輝度の発光が長時間に亘って持続し、各種面発光型表示機器等に利用できることが分かった。なお、現状の５００ｃｄ／ｍ²の発光が半減するのは良いものであっても１０００時間程度である（参照文献：Ｈｏｓｏｋａｗａ他、Ｓｙｎｔｈ．Ｍｅｔ．，９１，（１９９７）ｐ．３）。
【００９９】
【発明の効果】
請求項１の発明によれば、有機ポリマーと無機ポリマーとの両成分から成り、ポーラスな無機ポリマーの空孔部に有機ポリマーが含まれており、有機ポリマーは正電荷輸送能を有し、無機ポリマーは負電荷輸送能を有し、０．５〜１．５ミクロンの厚みを有することを特長とする発光型有機・無機複合材料であるため、厚みが１ミクロン程度で電圧印加時に劣化が起りにくく、有機エレクトロンルミネッセンス材料に比べて、発光分子が充分な量で存在し、高輝度発光を余裕を持って行えるエレクトロルミネッセンス材料を提供することができる。即ち、従来法では印加電圧を高めることにより高輝度発光を実現させていたが、本発明では、従来法のように高電圧を印加しなくとも高輝度発光を行えるようになる。また、発光時に出る熱の放逸も無機部で行えるので、安定に長時間効率よく発光させることができる。その結果、高輝度発光の駆動条件下でも材料の長寿命化が達成できる。また、無機ポリマーと有機ポリマーとの界面は密着した状態にあり、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。さらに有機ポリマーの柔軟性と無機ポリマーの剛直性とを相乗的に合わせ持ち加工性に優れる。
【０１００】
請求項２の発明によれば、有機ポリマーと無機ポリマーとの両成分から成り、ポーラスな無機ポリマーの空孔部に有機ポリマーが含まれており、有機ポリマーは正電荷輸送剤を有し、無機ポリマーは負電荷輸送剤を有し、０．５〜１．５ミクロンの厚みを有することを特長とする発光型有機・無機複合材料であるため、厚みが１ミクロン程度で電圧印加時に劣化が起こりにくく、有機エレクトロンルミネッセンス材料に比べて、発光分子が充分な量で存在し、高輝度発光を余裕を持って行えるエレクトロルミネッセンス材料を提供することができる。即ち、従来法では印加電圧を高めることにより高輝度発光を実現させていたが、本発明では、従来法のように高電圧を印加しなくとも高輝度発光を行えるようになる。また、発光時に出る熱の放逸も無機部で行えるので、安定に長時間効率よく発光させることができる。その結果、高輝度発光の駆動条件下でも材料の長寿命化が達成できる。また、無機ポリマーと有機ポリマーとの界面は密着した状態にあり、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。さらに有機ポリマーの柔軟性と無機ポリマーの剛直性とを相乗的に合わせ持ち加工性に優れる。
【０１０１】
請求項３の発明によれば、有機ポリマーと無機ポリマーとの両成分から成り、ポーラスな無機ポリマーの空孔部に有機ポリマーが含まれており、有機ポリマーは負電荷輸送能を有し、無機ポリマーは正電荷輸送能を有し、０．５〜１．５ミクロンの厚みを有することを特長とする発光型有機・無機複合材料であるため、厚みが１ミクロン程度で電圧印加時に劣化が起こりにくく、有機エレクトロンルミネッセンス材料に比べて、発光分子が充分な量で存在し、高輝度発光を余裕を持って行えるエレクトロルミネッセンス材料を提供することができる。即ち、従来法では印加電圧を高めることにより高輝度発光を実現させていたが、本発明では、従来法のように高電圧を印加しなくとも高輝度発光を行えるようになる。また、発光時に出る熱の放逸も無機部で行えるので、安定に長時間効率よく発光させることができる。その結果、高輝度発光の駆動条件下でも材料の長寿命化が達成できる。また、無機ポリマーと有機ポリマーとの界面は密着した状態にあり、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。さらに有機ポリマーの柔軟性と無機ポリマーの剛直性とを相乗的に合わせ持ち加工性に優れる。
【０１０２】
請求項４の発明によれば、有機ポリマーと無機ポリマーとの両成分から成り、ポーラスな無機ポリマーの空孔部に有機ポリマーが含まれており、有機ポリマーは負電荷輸送剤を有し、無機ポリマーは正電荷輸送剤を有し、０．５〜１．５ミクロンの厚みを有することを特長とする発光型有機・無機複合材料であるため、厚みが１ミクロン程度で電圧印加時に劣化が起こりにくく、有機エレクトロンルミネッセンス材料に比べて、発光分子が充分な量で存在し、高輝度発光を余裕を持って行えるエレクトロルミネッセンス材料を提供することができる。即ち、従来法では印加電圧を高めることにより高輝度発光を実現させていたが、本発明では、従来法のように高電圧を印加しなくとも高輝度発光を行えるようになる。また、発光時に出る熱の放逸も無機部で行えるので、安定に長時間効率よく発光させることができる。その結果、高輝度発光の駆動条件下でも材料の長寿命化が達成できる。また、無機ポリマーと有機ポリマーとの界面は密着した状態にあり、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。さらに有機ポリマーの柔軟性と無機ポリマーの剛直性とを相乗的に合わせ持ち加工性に優れる。
【０１０３】
請求項５の発明によれば、有機ポリマーと無機ポリマーとの両成分から成り、ポーラスな無機ポリマーの空孔部に有機ポリマーが含まれており、有機ポリマーと無機ポリマーの少なくとも一方が、正電荷輸送能および負電荷輸送能の双方を有し、０．５〜１．５ミクロンの厚みを有することを特長とする発光型有機・無機複合材料であるため、厚みが１ミクロン程度で電圧印加時に劣化が起こりにくく、有機エレクトロンルミネッセンス材料に比べて、発光分子が充分な量で存在し、高輝度発光を余裕を持って行えるエレクトロルミネッセンス材料を提供することができる。即ち、従来法では印加電圧を高めることにより高輝度発光を実現させていたが、本発明では、従来法のように高電圧を印加しなくとも高輝度発光を行えるようになる。また、発光時に出る熱の放逸も無機部で行えるので、安定に長時間効率よく発光させることができる。その結果、高輝度発光の駆動条件下でも材料の長寿命化が達成できる。また、無機ポリマーと有機ポリマーとの界面は密着した状態にあり、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。さらに有機ポリマーの柔軟性と無機ポリマーの剛直性とを相乗的に合わせ持ち加工性に優れる。
【０１０４】
請求項６の発明によれば、有機ポリマーと無機ポリマーとの両成分から成り、ポーラスな無機ポリマーの空孔部に有機ポリマーが含まれており、有機ポリマーと無機ポリマーの少なくとも一方が、正電荷輸送剤および負電荷輸送剤の双方を有し、０．５〜１．５ミクロンの厚みを有することを特長とする発光型有機・無機複合材料であるため、厚みが１ミクロン程度で電圧印加時に劣化が起こりにくく、有機エレクトロンルミネッセンス材料に比べて、発光分子が充分な量で存在し、高輝度発光を余裕を持って行えるエレクトロルミネッセンス材料を提供することができる。即ち、従来法では印加電圧を高めることにより高輝度発光を実現させていたが、本発明では、従来法のように高電圧を印加しなくとも高輝度発光を行えるようになる。また、発光時に出る熱の放逸も無機部で行えるので、安定に長時間効率よく発光させることができる。その結果、高輝度発光の駆動条件下でも材料の長寿命化が達成できる。また、無機ポリマーと有機ポリマーとの界面は密着した状態にあり、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。さらに有機ポリマーの柔軟性と無機ポリマーの剛直性とを相乗的に合わせ持ち加工性に優れる。
【０１０５】
請求項７の発明によれば、正電荷輸送剤として、ＴＰＤ（Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ビス（３−メチルフェニル）−［１，１′−ビフェニル］−４，４′−ジアミン）、α−ＮＰＤ（Ｎ，Ｎ′-ジフェニル−Ｎ，Ｎ′-ビス（α−ナフチル）−[１，１′−ビフェニル]−４，４′−ジアミン：４，４′−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニル−アミノ]ビフェニル）、Ｃｚ−ＴＰＤ（４，４′−ビス（９−カルバゾリル）−１，１′−ビフェニル）、ＰＴＣＤＡ（３，４，９，１０−ペリレンテトラカルボキシリック ジアンハイドライド）、ＣｕＰｃ（銅フタロシアニン）、ＺｎＴＰＰ（亜鉛（II）５，１０，１５，２０−テトラフェニルポルフィリン）、ＰＯ−ＴＰＤ（４，４′−ビス（１０−フェノキサジニル）ビフェニル）、ＰＴ−ＴＰＤ（４，４′−ビス（１０−フェノチアジニル）ビフェニル）、ＤＰＢＩ（４，４′−（２，２−ジフェニルビニレン）−１，１′−ビフェニル）、ＤＴＶＢＩ（４，４′−（２，２−ジ-パラメチルフェニルビニレン)-１，１′−ビフェニル）、ｍ−ＭＴＤＡＴＡ（４，４′，４″−トリス(３−メチルフェニルフェニルアミノ)トリフェニルアミン）、ＨＤＲＺ（４−ビフェニルアミノフェニル−ビフェニルヒドラゾン）、Ｒｕ（II）錯体（ルテニウム（II）錯体）の内の少なくとも一つを用いることを特長とする請求項２、４または６記載の発光型有機・無機複合材料であるため、請求項２、４または６記載の発光型有機・無機複合材料における高輝度・高効率・長寿命のエレクトロルミネッセンス材料の特性をさらに改善することができる。
【０１０６】
請求項８の発明によれば、負電荷輸送剤として、ＡｌＱ₃（トリス（８−ヒドロキシ−キノリノ）アルミニウム）、ＢｅＱ₂（ビス（８−ヒドロキシ−キノリノ）ベリリウム）、Ｚｎ（ＢＯＺ）₂（亜鉛−ビス−ベンゾキサゾール）、Ｚｎ（ＢＴＺ）₂（亜鉛−ビス−ベンゾチアゾール）、Ｅｕ（ＤＢＭ）₃（Ｐｈｅｎ）（トリス（１，３−ジフェニル−１，３−プロパンジオノ）（モノフェナントロリン）ユーロピウム（III））、Ｂｕｔｙｌ−ＰＢＤ（２−ビフェニル−５−（パラ−ｔｅｒ−ブチルフェニル)−１，３，４−オキサジアゾール）、ＴＡＺ（１−フェニル−２−ビフェニル−５−パラ−ｔｅｒ−ブチルフェニル−１，３，４−トリアゾール）の内の少なくとも一つを用いることを特長とする請求項２、４または６記載の発光型有機・無機複合材料であるため、請求項２、４または６記載の発光型有機・無機複合材料における高輝度・高効率・長寿命のエレクトロルミネッセンス材料の特性をさらに改善することができる。
【０１０７】
請求項９の発明によれば、蛍光発光性化合物あるいは分子を、ドーパントとして、有機ポリマー部及び無機ポリマー部の少なくとも一方に含むことを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料における高輝度・高効率・長寿命のエレクトロルミネッセンス材料の特性をさらに改善することができる。すなわち、電荷輸送剤の発光波長以外の光を発光させるときには、発光性分子として、発光させたい波長を蛍光波長とする蛍光発光性化合物あるいは分子をドーパントとして添加することができ、種々の波長の光を発光する発光材料を提供することができる。
【０１０８】
請求項１０の発明によれば、蛍光発光性化合物あるいは分子が発光性色素であることを特長とする請求項９記載の発光型有機・無機複合材料であるため、請求項９の発光型有機・無機複合材料における高輝度・高効率・長寿命のエレクトロルミネッセンス材料の特性をさらに改善することができる。
【０１０９】
請求項１１の発明によれば、発光性色素がクマリン５４０、ＤＣＭ１、ＤＣＭ２、ルブレン、キナクリドン誘導体の内の少なくとも一つであることを特長とする請求項１０記載の発光型有機・無機複合材料であるため、請求項１０の発光型有機・無機複合材料における高輝度・高効率・長寿命のエレクトロルミネッセンス材料の特性をさらに改善することができる。
【０１１０】
請求項１２の発明によれば、有機ポリマーが導電性ポリマーであることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料における有機部がＰＶＫの様な正電荷輸送能のあるポリマーであっても、アルミノキノリニウム（ＡｌＱ₃）の様な負電荷輸送剤をＰＶＫに対して５０ｗｔ％以上にまで含むようにすれば、負電荷輸送が行われることが可能になり、ＰＶＫに正電荷輸送剤を含ませれば、いよいよ正電荷輸送能が増大する。
【０１１１】
請求項１３の発明によれば、導電性ポリマーとして、ポリビニルカルバゾール、ポリビニルフェロセン、ポリビニルピラゾリン、ポリパラフェニレンビニレン、ポリパラフェニレン、ポリチオフェンの内の少なくとも一つの導電性ポリマーを用いることを特長とする請求項１２記載の発光型有機・無機複合材料であるため、請求項１２記載の発光型有機・無機複合材料における負電荷輸送能や正電荷輸送能をさらに改善することができる。
【０１１２】
請求項１４の発明によれば、有機ポリマーがアクリレート系ポリマーであることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合型材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料における透明性が高くなり、光の透過性を改善することができる。
【０１１３】
請求項１５の発明によれば、アクリレート系ポリマーが、ポリメタアクリレート、ポリアルキルメタアクリレート、ポリヒドロキシメタアクリレート、ポリヒドロキシアルキルメタアクリレートの内の少なくとも一つのアクリレート系ポリマーであることを特長とする請求項１４記載の発光型有機・無機複合材料であるため、請求項１４記載の発光型有機・無機複合材料における特性をさらに改善することができる。
【０１１４】
請求項１６の発明によれば、無機ポリマーが金属アルコキシドを前駆体とし、加水分解・重縮合反応させた高分子であることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料におけるポーラスな細孔の多い無機部を常圧下で超高真空条件を必要としないで容易に製造することができる。この結果、大面積の発光型有機・無機複合材料を作ることができる。
【０１１５】
請求項１７の発明によれば、金属アルコキシドが、アルコキシシラン、アルコキシチタン、アルコキシジルコニアの内の少なくとも一つの金属アルコキシドであることを特長とする請求項１６記載の発光型有機・無機複合材料であるため、請求項１６記載の発光型有機・無機複合材料におけるポーラスな細孔の多い無機部をさらに容易に製造することができる。
【０１１６】
請求項１８の発明によれば、有機ポリマーと無機ポリマーとして、それぞれの前駆体を混合し同時にポリマー化させた有機ポリマーと無機ポリマーとを用いることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料におけるポーラスな細孔の多い無機部を常圧下で超高真空条件を必要としないで容易に製造することができ、かつ、無機部と有機部との界面が密着した状態のものにすることができる。この結果、大面積の発光型有機・無機複合材料を作ることができる。この様な、有機・無機複合材料に電荷輸送剤、発光剤を入れることにより、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。
【０１１７】
請求項１９の発明によれば、無機ポリマーを作製した後にその空孔内に有機ポリマーを含浸させる方法で有機ポリマーと無機ポリマーとを混在させることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料における無機部と有機部との界面を密着した状態にすることができる。この様な、有機・無機複合材料に電荷輸送剤、発光剤を入れることにより、高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。
【０１１８】
請求項２０の発明によれば、有機ポリマーと無機ポリマーとがナノメートルのオーダーで構造制御されることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料において生成したホールとエレクトロンとが途中でトラップされずに、効率よく有機・無機界面にまで到達することができる。界面までの距離も各材料部は蛇行した、編み目構造であるので、有機・無機界面までの距離もせいぜい百ナノメータ程度になる。そのために、材料の厚み１ミクロン程度を移動する必要は無く、有機部と無機部の界面に到達することができ、無機部と有機部との界面でのみ効率よく再結合する。さらに、発光性分子のエキシトンによる励起にとって不利となる電極近傍でのエキシトンの失活が抑えられる。さらに、無機部と有機部の接触界面は従来の平面構造でなく、曲面構造であるので、接触面積は広くなり、正電荷と負電荷との再結合の確率が一段と効率よくなる。電荷再結合とそのエキシトンエネルギーによる発光性分子の励起を効率よく行えるので、印加電界は、従来の無機エレクトロルミネッセンス材料及び有機エレクトロルミネッセンス材料に用いられている印加電界１００万ボルト／ｃｍ以下にすることができる。さらに、電極から離れたところで、発光性分子が励起されるので、発光分子からの発光効率も大きくなる。正電荷輸送剤と負電荷輸送剤とが別々に無機部と有機部のどちらかに含まれている場合には、各電荷は有機・無機界面で再結合を行うまでは効率よく移動することができる。また、厚みが１ミクロン程度も有るために、無機ポリマーあるいは有機ポリマーのどちらか一方にのみ、正電荷輸送剤と負電荷輸送剤とが同時に含まれたとしても、正負の各電荷は対向する別々の電極から注入されるために、両電荷は対向方向に輸送されていき、両電極とは離れた所で再結合し、電極近傍でのエキシトンの失活が抑えられ、エキシトンによる発光性分子を効率よく励起し、高効率な電界発光が達成される。なお、有機部と無機部のどの部分も、蛇行しながら、それぞれ両電極と接している。
【０１１９】
請求項２１の発明によれば、一方の面が透明電極に接し、他方の面に金属電極が施されている請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、透明電極側から発光した光を外部に取り出すことができる。また、透明電極と金属電極の両電極は、図１、図２及び図３に示されるように、無機部と有機部の双方が接触しており、それぞれ選択的にホールとエレクトロンとを無機部と有機部とに注入することができる。また、有機・無機複合材料であるため加工性が良く表面研磨を行える。その結果、表面は無機部と有機部とが明確に区別できる。即ち、密着した状態で分離している（図３）。厚みのコントロールもでき、表面の平滑性も得られる。その結果、電極材料が均一に密着され、電荷注入の効率が良くなる。無機部に正電荷輸送剤が含まれている場合には、無機部には仕事関数の大きな透明電極のみから正電荷が注入される。有機部には負電荷輸送剤含まれることになるので、有機部には仕事関数の小さな金属電極のみから負電荷が注入される。各電荷輸送剤が含まれる材料部が逆の場合には（無機部に負電荷輸送剤、有機部に正電荷輸送剤が含まれる場合）、無機部には金属電極からのみ、負電荷が注入される。有機部には透明電極のみから正電荷が注入される。この様に、各電極は、選択的に正か負の電荷を無機部あるいは有機部に注入する。即ち、各材料部（有機部と無機部）は、そこに含まれる電荷輸送剤の性質により、正電荷か負電荷のどちらかのみが選択的に注入される。有機ポリマーか無機ポリマーのどちらか一方に、正負の両電荷輸送剤が含まれる場合には、透明電極から正電荷が、対向電極である金属電極から負電荷が、それぞれ両電荷輸送剤を含む同一の材料部に注入される。しかし、これら両電荷は１ミクロン程度の厚みの材料内を対向して移動するため、電極面から離れた材料内部で両電荷が再結合し、エキシトンを生成し、発光性分子を効率よく励起し発光させる。電極から離れたところでホールとエレクトロンが再結合できるので、電極近傍でのエキシトンの失活が抑えられ、発光効率が増す。無機部と有機部との比率、あるいは、正電荷輸送剤と負電荷輸送剤との比率を最適にすれば、注入される正電荷と負電荷とのバランスを最適化でき、エキシトンの生成効率と発光性分子の励起確率と発光効率を上げることができる。ただし、電荷輸送剤の種類によりこの比率は一般には変化する。
【０１２０】
請求項２２の発明によれば、透明電極が、仕事関数が大きな酸化インジュウム錫（ＩＴＯ）、酸化錫（ＳｎＯ₂）、酸化インジュウム（ＩｎＯ_ｘ）の内から形成されていることを特長とする請求項２１記載の発光型有機・無機複合材料であるため、請求項２１記載の発光型有機・無機複合材料におけるホールとエレクトロンとの選択的な注入がさらに改善される。
【０１２１】
請求項２３の発明によれば、金属電極が、仕事関数が小さなアルミニウム、アルミニウムリチウム合金、アルミニウムマグネシウム合金、マグネシウム、マグネシウム銀合金、マグネシウムインジュウム合金の内の少なくとも一つから形成されていることを特長とする請求項２１記載の発光型有機・無機複合材料であるため、請求項２１記載の発光型有機・無機複合材料におけるホールとエレクトロンとの選択的な注入がさらに改善される。
【０１２２】
請求項２４の発明によれば、透明電極と金属電極の双方が直接蒸着により形成されている請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料にける有機・無機複合材料と透明電極および金属電極の両電極との接触をより密にすることができ、電荷注入効率を上げることができる。
【０１２３】
請求項２５の発明によれば、透明電極を施したガラス基板上で有機・無機複合材料を作製した後、金属電極が直接蒸着により施されている請求項１、２、３、４、５または６記載の発光型有機・無機複合材料であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料における有機・無機複合材料と透明電極および金属電極の両電極との接触をより密にすることができ、電荷注入効率を上げることができる。
【０１２４】
請求項２６の発明によれば、透明電極をアノード電極（陰極）とし、金属電極をカソード電極（陽極）とし、電界を印加することにより発光することを特長とする請求項２１、２４または２５記載の発光型有機・無機複合材料であるため、仕事関数の大きな透明電極よりホールが効率よく材料中に注入され、仕事関数の小さい金属電極よりエレクトロンが効率よく材料中に注入され、請求項２１、２４または２５記載の発光型有機・無機複合材料における電荷注入効率をさらに改善することができる。
【０１２５】
請求項２７の発明によれば、透明電極をアノード電極（陰極）とし、金属電極をカソード電極（陽極）とし、それぞれにリード線を取り付けた後に、透明電極側を透明のガラスあるいはプラスチックで覆い、金属電極側を絶縁物で覆った後に、材料端面を封止樹脂で封止し、電界を印加することにより発光することを特長とする請求項２１、２４、２５または２６記載の発光型有機・無機複合材料であるため、請求項２１、２４、２５または２６記載の発光型有機・無機複合材料における使用環境中の酸素及び水分等の、電界発光材料を劣化させる要因との接触を避けることができ、駆動寿命の長寿命化を達成することができる。
【０１２６】
請求項２８の発明によれば、金属電極を覆う絶縁物がプラスチック絶縁物であり、封止樹脂がエポキシ樹脂であることを特長とする請求項２７記載の発光型有機・無機複合材料であるため、請求項２７記載の発光型有機・無機複合材料における使用環境中の酸素及び水分等の電界発光材料を劣化させる要因との接触を避けることができ、駆動寿命の長寿命化をより一層達成することができる。
【０１２７】
請求項２９の発明によれば、有機ポリマーと無機ポリマーの前駆体を混合し同時にポリマー化させることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料の製造法であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料における無機部と有機部との界面が密着した状態のものを常圧下で超高真空条件を必要としないで製造することができる。このため大面積の発光型有機・無機複合材料を作ることができる。
【０１２８】
請求項３０の発明によれば、無機ポリマーを作製した後にその空孔内に有機ポリマーを含浸させる方法で有機ポリマーと無機ポリマーとを混在させることを特長とする請求項１、２、３、４、５または６記載の発光型有機・無機複合材料の製造法であるため、請求項１、２、３、４、５または６記載の発光型有機・無機複合材料における無機部と有機部との界面が密着した状態のものを常圧下で超高真空条件を必要としないで製造することができる。この様な、有機・無機複合材料に電荷輸送剤、発光剤を入れて高輝度・高効率・長寿命のエレクトロルミネッセンス材料を提供することができる。また、本発明の有機・無機複合材料は大面積の発光型有機・無機複合材料を作ることができる。
【０１２９】
以上のように、本発明の発光型有機・無機複合材料は、１ミクロン程度の厚みであるために、従来の有機ＥＬ材料よりも１０倍程度厚く、ピンホールが生成しなくなり、電極間での導通が無くなり、発光輝度の面内の均一性が良くなると共に、電界発光素子としての寿命が長くなる。また、電界印加により、効率よく正負の両電荷が注入され、それらは、また、効率よく再結合しエキシトンを形成し、そのエネルギーで発光性分子を励起し、電界発光が効率よく起こる。また、有機ポリマー部を含んでいるため、複合材料の加工性に優れ、無機ポリマー部を含んでいるために、材料の剛直性のみならず材料の光学特性にも優れる。また、無機ポリマー部は発光時の発熱を放逸してくれるために、材料の駆動動作寿命が延びる。また、レーザ発振の可能性も示している。
【図面の簡単な説明】
【図１】 本発明の発光型有機・無機複合材料の模式図である。
【図２】 本発明の発光型有機・無機複合材料の内部構造と電荷の移動を表わす模式図である。
【図３】 本発明の発光型有機・無機複合材料の研磨後の表面状態の模式図である。
【図４】 実施例１の印加電圧と発光輝度との関係を表わす特性図である。
【図５】 有機電界発光材料の発光機構の基本原理を表わす模式図である。
【図６】 従来の有機電界発光材料の模式図である。
【符号の説明】
１ 有機ポリマー、２ 無機ポリマー、３ 透明電極、４ 金属電極、５ 発光型有機・無機複合材料、６ 透明電極の透明カバー、７ 金属電極のカバー、８ 封止樹脂、９ リード線、１０ 有機電界発光材料、１１ 正電荷輸送層、１２ 負電荷輸送層、ａ 発光性分子からの発光、ｂ エキシトン。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a light-emitting organic / inorganic composite material, which is an electric field-driven light-emitting material, which is used for information display, a flat light source, a laser oscillation element, and the like and emits electroluminescence by applying a voltage, and a method for producing the same. Specific applications include surface emitters, lasers, backlights, mobile phones, character displays, image displays, monitor screens, wall-mounted televisions, large screen information display boards, sign boards, guide lights, watches, calculators, touch panels, light Communication light source, car navigation system, vehicle instrument panel, vehicle destination display, in-car guidance, in-car advertisement, night billboard, information display panel for various home appliances, room light, image light, information display panel for various measuring instruments, artistic light, Night safety clothes / caps, in-flight guide lights / guide displays / passage displays, various medical equipment information display panels, floor guide display boards, faint lighting equipment in dark places, interior lighting equipment, showcase lighting equipment, showcase display boards, Nighttime store name display board, night light-emitting signboard, night signboard for automobile bodies, night signboard for motorcycle bodies, night for bicycles A sign board or the like and a laser oscillator material.
[0002]
[Prior art]
Conventional materials using the EL (electroluminescence) effect have been distinguished into those made of inorganic materials and those made of organic materials.
[0003]
Among inorganic materials, zinc sulfide (ZnS) or the like is a typical material (reference document: Tanaka, Journal of the Illuminating Society of Japan, Vol. 78, No. 12 (1994) p. 651). In such an inorganic material system, the EL effect is efficiently produced, and the three primary colors of red, blue and green are efficiently emitted, and the practical application is progressing. However, in the case of the inorganic material, a voltage of 100 volts or more (electric field strength of 1 million volts / cm or more) is required with a thickness of 1 micron, which is a bottleneck when promoting practical use.
[0004]
In order to eliminate such drawbacks, EL materials using organic materials have been developed (Reference: Molecular Functional Materials and Device Development (1994) p. 568, NTS, etc.). In particular, Tang et al. Of Kodak Company in 1987 has received much attention since the development of a highly efficient EL material system having a multilayer structure (Reference: Tang et al., Appl. Phys. Lett., 51 ( 12), 913 (1987)). Then, 4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA) and 4,4′-bis (3-methyl) function as excellent hole transport materials for organic EL devices. It has been announced that an EL device comprising a double hole transport layer from (phenylphenylamino) biphenyl and a light emitting layer from tri (8-quinolinolato) aluminum exhibits high luminous efficiency and meaningful durability (references). : Yasuhiko Shirota et al., Appl. Phys. Lett., 65 (7), 15 (1994)) In addition, an N-substituted polymethacrylamide having a hole-transporting triphenylamine in the side chain was synthesized to form a stacked organic Used as a hole transport layer of EL element, indium-tin oxide (ITO) as anode and magnesium-silver (1 : 1), tris electron transporting the light-emitting layer (8-quinolinolato) aluminum (III) complex (Alq _Three ) 6000 cd / m at 10 V from a two-layered device using ² It has been shown that this polymer has a high hole transport property and is effective as a hole transport layer of an organic EL device (Polymer Papers, Vol. 52, No. 4, pp. 216-220 (1995)).
[0005]
As shown in FIG. 5, the basic principle of electroluminescence in an organic material is that positively charged holes are injected from an ITO transparent electrode having a large work function, and move in a positive charge transport agent toward the counter electrode. On the other hand, negative charge electrons are injected from a metal electrode having a small work function, such as an aluminum electrode, and move in the negative charge transport agent toward the counter electrode. In FIG. 5, 3 is a transparent electrode, 4 is a metal electrode, 10 is an organic electroluminescent material, a is light emitted from an excited molecule, and b is exciton. These positive and negative charges recombine to generate electron-hole pair excitons. The exciton energy excites the light-emitting organic molecule to a singlet state, and light is emitted from the excited molecule. Note that the light-emitting organic molecule may have a role for the charge transporting agent itself or a fluorescent light-emitting compound or molecule that is a dopant. When the emission wavelength of the charge transfer agent matches the desired wavelength, no fluorescent compound or molecule is added as a dopant. However, when light emission at other wavelengths is desired, a fluorescent compound or molecule having an emission wavelength at the desired wavelength is added as a dopant. The dopant concentration is preferably up to several percent. As shown in FIG. 6, in the conventional organic EL material, the thickness of the organic EL material layer itself is approximately 100 nm. In FIG. 6, 3 is a transparent electrode, 4 is a metal electrode, 11 is a positive charge transport layer, and 12 is a negative charge transport layer. In such an organic material system having a thickness of about 100 nm, it is only necessary to apply a low voltage of 10 volts or less between the transparent electrode and the metal electrode shown in FIG. However, the electric field strength is 1 million volts / cm, which is as large as that of the inorganic material system. This is because, as shown in FIG. 6, since a thin film can be formed, it is possible to drive a DC voltage of 10 volts or less, and research into practical use has been advanced. Since the conventional organic EL material is an ultrathin film, it has a high probability of reaching the counter electrode before the injected positive and negative charges are recombined. Even if recombination occurs, the excitons are deactivated at the electrode because the electrode is in the vicinity of the electrode, and the excitation efficiency of the luminescent molecule is poor.
[0006]
Thus, in the conventional organic EL material, deterioration of the material is a major drawback as well as light emission luminance and light emission efficiency. In addition, the conventional organic EL material is manufactured because a thin film must be formed in an ultra-high vacuum, and a transparent electrode substrate, for example, an ITO glass electrode portion must be kept extremely clean. In addition to complicating the process, it is difficult to increase the area. In addition, since it is a thin film, pinholes are easily formed, short-circuiting / conduction between electrodes occurs, black points occur, the uniformity of in-plane light emission characteristics deteriorates, and the life as an electroluminescent element is shortened. Yes. Since it is a thin film, its mechanical strength is weak. In addition, since it is a thin film, the number of luminescent molecules is small, and in order to emit light with high luminance, it is necessary to increase the applied voltage and almost all of the luminescent molecules are excited. The luminescent molecule may be a charge transport agent itself or a fluorescent compound or a molecular dopant. This depends on the desired emission wavelength. For example, even if all the materials are made of luminescent molecules, the number of molecules is 0.2 to 0.3 / nm. ^Three Degree. As described above, in the light emission in a state where the number of light emitting molecules is not enough, a high voltage application is required to achieve high luminance light emission. Since a light emitting molecule is applied with a high voltage, the light emission characteristics deteriorate, and it is difficult to emit light with high brightness for a long time. Furthermore, laser oscillation is also difficult because the emission luminance cannot be stably increased. Moreover, since an ITO glass substrate is used, the weight increases. Since only organic materials are used, it is difficult to dissipate the heat generated during electric field-applied light emission.
[0007]
[Problems to be solved by the invention]
As described above, with the conventional EL material, the EL characteristics can be stably obtained with the inorganic material, but the drive applied voltage is as high as 100V to 200V. In this case, the electric field strength is 1 million to 2 million V / cm. The illuminant is excited at a rate corresponding to the applied electric field strength, emits light therefrom, and returns to the ground state. Some inorganic EL materials have been put into practical use as display panels. However, high drive voltage and low luminous efficiency are disadvantages. The luminous efficiency is at most 4-5 lm / W (lumens / watt) even under the highest driving conditions. Generally, it is about 1 lm / w. In particular, the luminous efficiency of the blue light emitting material is less than 1 lm / w. In addition, in LED, 10 lm / w or more is obtained.
[0008]
In order to solve such a high driving voltage, an organic EL material has been developed, and as a result, it is driven at an applied voltage of 10 V or less. However, since it is an ultrathin film (about 100 nanometers), the applied electric field strength is still as high as 1 million V / cm, which is as high as that of inorganic materials. In addition, there are problems with light emission brightness and lifetime. In particular, the conversion efficiency is almost less than several lm / w under the conditions required for practical use with a drive operation life of several thousand hours or more. Since it is an ultrathin film, the number of molecules involved in light emission is small, and application of a high voltage is necessary to improve the light emission luminance. It is considered that high voltage application greatly affects the light emission life of the material because it degrades the material itself. In addition, the emission mechanism of organic materials is different from that of inorganic materials. In organic material systems, injected positive and negative charges recombine in the material to form excitons. The luminescent molecule is excited by the energy, and the excited molecule returns to the ground state with light emission. Therefore, in the organic material system, positive and negative charges are efficiently injected into the material, and the generated energy must be given to the light-emitting molecule by efficiently recombining with the counter charge without trapping and extinguishing each charge. There is. However, since the conventional organic EL material is an ultra-thin film, it has a high probability of reaching the counter electrode before the injected positive and negative charges are recombined. Even if recombination occurs, the excitons are deactivated at the electrode because the electrode is in the vicinity of the electrode, and the excitation efficiency of the luminescent molecule is poor.
[0009]
Further, since the conventional organic EL material is an ultra-thin film, pinholes are easily formed, the material is short-circuited and conducted, and the light emission luminance is not uniform in the plane. Pinholes also shorten the drive life of the material. In addition, since such a conventional ultra-thin organic EL material is manufactured by a vacuum deposition method, the manufacturing process becomes complicated and it is difficult to increase the area of the material.
[0010]
As described above, organic electroluminescent materials (organic EL materials) have major problems in light emission efficiency, in-plane uniformity of light emission luminance, drive life, and area increase.
[0011]
In the present invention, a composite material composed of an organic polymer and an inorganic polymer is used as a host material, and the above-described conventional organic electroluminescent material (organic EL material) has the luminous efficiency, in-plane uniformity of luminance, and driving life. It is intended to solve the disadvantages such as increasing the area.
[0012]
[Means for Solving the Problems]
The present invention has been made to solve these drawbacks,
The invention according to claim 1 comprises both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, the organic polymer has a positive charge transporting ability, and the inorganic polymer Is a light-emitting organic / inorganic composite material having a negative charge transport ability and a thickness of 0.5 to 1.5 microns.
[0013]
The invention according to claim 2 comprises both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, the organic polymer has a positive charge transport agent, and the inorganic polymer Is a light-emitting organic / inorganic composite material having a negative charge transport agent and a thickness of 0.5 to 1.5 microns.
[0014]
The invention according to claim 3 comprises both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, the organic polymer has a negative charge transporting capability, and the inorganic polymer Is a light-emitting organic / inorganic composite material having a positive charge transport ability and a thickness of 0.5 to 1.5 microns.
[0015]
The invention according to claim 4 comprises both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, the organic polymer has a negative charge transport agent, and the inorganic polymer Is a light-emitting organic / inorganic composite material having a positive charge transport agent and a thickness of 0.5 to 1.5 microns.
[0016]
The invention according to claim 5 comprises both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, and at least one of the organic polymer and the inorganic polymer is positively charged. It is a light-emitting organic / inorganic composite material characterized by having both a high-performance and negative charge transporting capability and a thickness of 0.5 to 1.5 microns.
[0017]
The invention according to claim 6 includes both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, and at least one of the organic polymer and the inorganic polymer is positively charged. It is a light-emitting organic / inorganic composite material characterized by having both an agent and a negative charge transport agent and having a thickness of 0.5 to 1.5 microns.
[0018]
The invention according to claim 7 provides TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′- as a positive charge transport agent. Diamine (N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine)), α-NPD (N, N'-diphenyl- N, N′-bis (α-naphthyl)-[1,1′-biphenyl] -4,4′-diamine (N, N′-diphenyl-N, N′-bis (α-naphtyl)-[1, 1'-biphenyl] -4,4'-diamine): 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl (4,4'-bis [N- (1-naphtyl) ) -N-phenyl-amino] biphenyl)), Cz-TPD (4,4′-bis (9-carbazolyl) -1,1′-biphenyl (4,4′-Bis (9-carbazolyl) -1,1) '-Biphenyl)), PTCDA (3,4,9,10-perylenetetracarboxylic) Dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride)), CuPc (copper phthalocyanine), ZnTPP (zinc (II) 5,10,15,20-tetraphenylporphyrin (Zinc (II) 5,10 , 15,20-tetraphenylporphyrin)), PO-TPD (4,4′-bis (10-phenoxazinyl) biphenyl)), PT-TPD (4,4′- Bis (10-phenothiazinyl) biphenyl (4,4'-Bis (10-phenothiazinyl) biphenyl)), DPBI (4,4 '-(2,2-diphenylvinylene) -1,1'-biphenyl (4,4 '-(2,2-diphenylvinylene) -1,1'-biphenyl)), DTVBI (4,4'-(2,2-di-paramethylphenylvinylene) -1,1'-biphenyl (4,4 ' -(2,2-di-paramethylphenylvinylene) -1,1'-biphenyl)), m-MTDA A (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine)), HDRZ (4-biphenylaminophenyl-biphenyl) 7. The light-emitting organic / inorganic composite according to claim 2, 4 or 6, wherein at least one of hydrazone (4-biphenylaminophenyl-biphenylhydrazone)) and Ru (II) complex (ruthenium (II) complex) is used. Material.
[0019]
In the invention according to claim 8, as the negative charge transfer agent, AlQ _Three (Tris (8-hydroxy-quinolino) aluminum), BeQ ₂ (Bis (8-hydroxy-quinolino) beryllium), Zn (BOZ) ₂ (Zinc-bis-benzoxazole), Zn (BTZ) ₂ (Zinc-bis-benzothiazole), Eu (DBM) _Three (Phen) (tris (1,3-diphenyl-1,3-propanediono) (monophenanthroline) europium (III) (tris (1,3-diphenyl-1,3-propanediono) (monophenanthroline) Eu (III)) ), Butyl-PBD (2-biphenyl-5- (para-tert-butylphenyl) -1,3,4-oxadiazole (2-biphenyl-5- (para-ter-butylphenyl) -1,3,4) -oxadiazole)), TAZ (1-phenyl-2-biphenyl-5-para-ter-butylphenyl-1, 1-phenyl-2-biphenyl-5-para-ter-butylphenyl-1, The light-emitting organic / inorganic composite material according to claim 2, 4 or 6, wherein at least one of 3,4-triazole)) is used.
[0020]
The invention according to claim 9 includes a fluorescent compound or molecule as a dopant in at least one of the organic polymer part and the inorganic polymer part, according to claim 1, 2, 3, 4, 5 or 6. This is a light-emitting organic / inorganic composite material.
[0021]
The invention according to claim 10 is the light-emitting organic / inorganic composite material according to claim 9, wherein the fluorescent compound or molecule is a luminescent dye.
[0022]
The invention according to claim 11 is the light-emitting organic / inorganic composite material according to claim 10, wherein the luminescent dye is at least one of coumarin 540, DCM1, DCM2, rubrene, and quinacridone derivatives. .
[0023]
The invention according to claim 12 is the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6, wherein the organic polymer is a conductive polymer.
[0024]
The invention according to claim 13 is characterized in that at least one conductive polymer of polyvinyl carbazole, polyvinyl ferrocene, polyvinyl pyrazoline, polyparaphenylene vinylene, polyparaphenylene, and polythiophene is used as the conductive polymer. Item 13. A light-emitting organic / inorganic composite material according to Item 12.
[0025]
The invention according to claim 14 is the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6, wherein the organic polymer is an acrylate polymer.
[0026]
The invention according to claim 15 is characterized in that the acrylate polymer is at least one acrylate polymer of polymethacrylate, polyalkyl methacrylate, polyhydroxy methacrylate, and polyhydroxyalkyl methacrylate. 14. The light-emitting organic / inorganic composite material according to 14.
[0027]
The invention according to claim 16 is characterized in that the inorganic polymer is a polymer obtained by hydrolysis and polycondensation reaction with a metal alkoxide as a precursor, according to claim 1, 2, 3, 4, 5 or 6. A light-emitting organic / inorganic composite material.
[0028]
The invention according to claim 17 is the light-emitting organic / inorganic composite material according to claim 16, wherein the metal alkoxide is at least one metal alkoxide of alkoxysilane, alkoxytitanium, and alkoxyzirconia.
[0029]
The invention according to claim 18 uses, as the organic polymer and the inorganic polymer, an organic polymer and an inorganic polymer obtained by mixing and simultaneously polymerizing respective precursors. 5. A light-emitting organic / inorganic composite material according to 5 or 6.
[0030]
The invention according to claim 19 is characterized in that the organic polymer and the inorganic polymer are mixed by a method of impregnating the organic polymer into the pores after the inorganic polymer is produced. 5. A light-emitting organic / inorganic composite material according to 5 or 6.
[0031]
The invention according to claim 20 is characterized in that the structure of the organic polymer and the inorganic polymer is controlled in the order of nanometers. The light-emitting organic / inorganic composite according to claim 1, 2, 3, 4, 5 or 6 Material.
[0032]
21. The light-emitting organic / inorganic composite material according to claim 1, wherein one surface is in contact with the transparent electrode, and the other surface is provided with a metal electrode. It is.
[0033]
In the invention according to claim 22, the transparent electrode is composed of indium tin oxide (ITO), tin oxide (SnO) having a large work function. ₂ ), Indium oxide (InO) _x The light-emitting organic / inorganic composite material according to claim 21, wherein
[0034]
The invention according to claim 23 is characterized in that the metal electrode is formed of at least one of aluminum, aluminum lithium alloy, aluminum magnesium alloy, magnesium, magnesium silver alloy and magnesium indium alloy having a small work function. The light-emitting organic / inorganic composite material according to claim 21.
[0035]
The invention according to claim 24 is the light-emitting organic / inorganic composite material according to claim 1, wherein both the transparent electrode and the metal electrode are formed by direct vapor deposition.
[0036]
According to a twenty-fifth aspect of the present invention, the metal electrode is applied directly by vapor deposition after producing an organic / inorganic composite material on a glass substrate provided with a transparent electrode. The light-emitting organic / inorganic composite material described.
[0037]
26. The invention according to claim 26, wherein the transparent electrode is an anode electrode (cathode), the metal electrode is a cathode electrode (anode), and light is emitted by applying an electric field. A light-emitting organic / inorganic composite material.
[0038]
According to a twenty-seventh aspect of the present invention, a transparent electrode is an anode electrode (cathode), a metal electrode is a cathode electrode (anode), a lead wire is attached to each, and then the transparent electrode side is covered with transparent glass or plastic. 27. The light-emitting organic / inorganic according to claim 21, 24, 25 or 26, wherein the electrode side is covered with an insulating material, the material end face is sealed with a sealing resin, and an electric field is applied to emit light. It is a composite material.
[0039]
The invention according to claim 28 is the light-emitting organic / inorganic composite material according to claim 27, wherein the insulator covering the metal electrode is a plastic insulator and the sealing resin is an epoxy resin.
[0040]
The invention according to claim 29 is characterized in that an organic polymer and an inorganic polymer precursor are mixed and polymerized at the same time, and the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6 It is a manufacturing method.
[0041]
The invention according to claim 30 is characterized in that the organic polymer and the inorganic polymer are mixed by a method of impregnating the organic polymer into the pores after the inorganic polymer is produced. 5. A process for producing a light-emitting organic / inorganic composite material according to 5 or 6.
[0042]
DETAILED DESCRIPTION OF THE INVENTION
The light-emitting organic / inorganic composite material of the present invention comprises both components of an organic polymer and an inorganic polymer, and the organic polymer is contained in the pores of the porous inorganic polymer, and the organic polymer has a positive charge transport ability. Or it has a positive charge transport agent, and the inorganic polymer may have a negative charge transport ability or a negative charge transport agent.
[0043]
Further, the light-emitting organic / inorganic composite material of the present invention comprises both organic polymer and inorganic polymer components, and the organic polymer is contained in the pores of the porous inorganic polymer. Or having a negative charge transport agent, and the inorganic polymer may have a positive charge transport ability or a positive charge transport agent.
[0044]
Furthermore, the light-emitting organic / inorganic composite material of the present invention comprises both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, and at least of the organic polymer and the inorganic polymer. One may have both a positive charge transport ability and a negative charge transport ability or may have both a positive charge transport agent and a negative charge transport agent.
[0045]
The organic polymer or the inorganic polymer has a positive charge transporting ability means that the organic polymer or the inorganic polymer itself has a positive charge transporting ability (in addition, a positive charge transporting agent is added to improve the positive charge transporting ability) And a case in which a positive charge transport agent is added to an organic polymer or an inorganic polymer that does not have a positive charge transport ability.
[0046]
The same applies when the organic polymer or inorganic polymer has a negative charge transporting ability.
[0047]
Regarding the charge transport capability, the hole drift mobility is 10 ^-2 -10 ^-Five cm ² / Vs is preferred, more preferably 10 ^-3 cm ² / Vs or higher. The room temperature dark conductivity is 10 ^-11 -10 ^-9 Scm ^-1 Is preferred, more preferably 10 ^-Ten Scm ^-1 That's it.
[0048]
The organic polymer may be one or more of conductive polymers such as polyvinyl carbazole, polyvinyl ferrocene, polyvinyl pyrazoline, polyparaphenylene vinylene, polyparaphenylene, polythiophene, and the like. One or more acrylate polymers such as acrylate, polyhydroxymethacrylate, polyhydroxyalkylmethacrylate and the like may be used. In the case of a conductive polymer, itself has a charge transporting ability, and in the case of an acrylate-based polymer, it has a charge transporting ability by adding a charge transporting agent.
[0049]
The inorganic polymer may be a polymer obtained by hydrolysis and polycondensation reaction using, for example, one or more metal alkoxides of alkoxysilane, alkoxytitanium, and alkoxyzirconia as a precursor.
[0050]
The ratio of the organic polymer to the inorganic polymer in the light-emitting organic / inorganic composite material is preferably 45:55 to 55:45, and most preferably 50:50 in terms of wt%.
[0051]
The porous portion of the porous inorganic polymer is a porous portion having a porosity (pore volume ratio) formed by the inorganic polymer of preferably 50 to 65%. Is generally 10-20 nanometers. Such an inorganic polymer can be obtained, for example, by causing hydrolysis and polycondensation reaction of a metal alkoxide at a temperature of room temperature to about 100 ° C. under gelation conditions (acidic state around pH 5).
[0052]
Examples of the positive charge transfer agent include TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine), α- NPD (N, N′-diphenyl-N, N′-bis (α-naphthyl)-[1,1′-biphenyl] -4,4′-diamine: 4,4′-bis [N- (1-naphthyl) ) -N-phenyl-amino] biphenyl), Cz-TPD (4,4'-bis (9-carbazolyl) -1,1'-biphenyl), PTCDA (3,4,9,10-perylenetetracarboxylic dian Hydride), CuPc (copper phthalocyanine), ZnTPP (zinc (II) 5,10,15,20-tetraphenylporphyrin), PO-TPD (4,4'-bis (10-phenoxazinyl) biphenyl), PT -TPD (4,4'-bis (10-phenothiazinyl) biphenyl), DPBI (4,4 '-(2,2-diphenylvinylene) -1,1'-biphenyl), DTVBI (4,4'-( 2,2-di-paramethylphenylvinylene) -1,1'-biphenyl), m-MTDATA (4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine), HDRZ (4- Biphenylaminophenyl-biphenylhydrazone), Ru (II) complexes (ruthenium (II) complexes, such as 2,2'-bipyridylruthenium complexes [Ru (bpy) _Three ] ²⁺ Etc.) is used.
[0053]
The ratio of the positive charge transfer agent is preferably 15 to 40 wt%, more preferably about 25 wt% in the light emitting organic / inorganic composite material.
[0054]
Examples of the negative charge transfer agent include AlQ. _Three (Tris (8-hydroxy-quinolino) aluminum), BeQ ₂ (Bis (8-hydroxy-quinolino) beryllium), Zn (BOZ) ₂ (Zinc-bis-benzoxazole), Zn (BTZ) ₂ (Zinc-bis-benzothiazole), Eu (DBM) _Three (Phen) (tris (1,3-diphenyl-1,3-propanediono) (monophenanthroline) europium (III)), Butyl-PBD (2-biphenyl-5- (para-tert-butylphenyl) -1, 3,4-oxadiazole), TAZ (1-phenyl-2-biphenyl-5-para-tert-butylphenyl-1,3,4-triazole) and the like are used.
[0055]
The ratio of the negative charge transfer agent is preferably 15 to 40 wt%, more preferably about 25 wt% in the light emitting organic / inorganic composite material.
[0056]
In the present invention, an organic polymer part (phase that may contain an organic polymer such as an organic polymer and a charge transport agent, hereinafter also referred to as an organic part) and an inorganic polymer part (including an inorganic polymer such as an inorganic polymer and a charge transport agent) At least one of the good phases (hereinafter also referred to as “inorganic part”) may contain a fluorescent compound or molecule (dopant luminescent agent) as a dopant.
[0057]
The concentration of the fluorescent compound or molecule (dopant luminescent agent) is preferably 0.1 to 5 wt%, more preferably several wt% with respect to the entire material. The dopant concentration may be low if the fluorescence quantum efficiency of the dopant is large, and a high concentration is necessary if the fluorescence quantum efficiency is small. On the other hand, if the concentration exceeds 5%, the charge transporting ability of the material part containing the dopant tends to decrease. That is, it is desirable that the dopant has high fluorescence quantum efficiency and can be added at a low concentration. A fluorescent compound or molecule is added to emit light having a desired wavelength when light emission other than the emission wavelength of the charge transport agent is desired. Therefore, the dopant luminescent agent is not always added.
[0058]
Examples of the fluorescent compound or molecule include a luminescent dye such as coumarin 540 (3- (2′-Benzothiazole) -7-N, N-diethylaminocoumarin, formula:
[0059]
[Chemical 1]

[0060]
), DCM1 (4-Dicyanmethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran, formula:
[0061]
[Chemical 2]

[0062]
), DCM2 (4-Dicyanmethylene-2-methyl-6- (octahydroquinolizine [c, d] styryl) -4H-pyran, formula:
[0063]
[Chemical 3]

[0064]
), Rubrene, formula:
[0065]
[Formula 4]

[0066]
), Quinacridone derivatives (formula:
[0067]
[Chemical formula 5]

[0068]
) And the like.
[0069]
The organic polymer and the inorganic polymer may be prepared by mixing respective precursors and polymerizing the precursors at the same time. Alternatively, after the inorganic polymer is produced, the organic polymer is impregnated in the pores. It may be a mixture of a polymer and an inorganic polymer. A charge transport agent, a fluorescent compound, or a molecule may be added to each.
[0070]
In the manufactured light-emitting organic / inorganic composite material, it is preferable that the structure of the organic polymer and the inorganic polymer is controlled on the order of nanometers.
[0071]
The organic / inorganic composite material of the present invention has one surface in contact with the transparent electrode and the other surface provided with a metal electrode.
[0072]
The transparent electrode is composed of indium tin oxide (ITO), tin oxide (SnO) having a large work function. ₂ ), Indium oxide (InO) _x The metal electrode is preferably formed from at least one of aluminum, aluminum lithium alloy, aluminum magnesium alloy, magnesium, magnesium silver alloy, magnesium indium alloy, etc. having a small work function. It is preferable that
[0073]
Both of the transparent electrode and the metal electrode may be formed by direct vapor deposition, or after producing an organic / inorganic composite material on a glass substrate provided with the transparent electrode, the metal electrode may be formed by direct vapor deposition. .
[0074]
The organic / inorganic composite material of the present invention is brought into contact with a transparent electrode and a metal electrode, the transparent electrode is used as an anode electrode (cathode), the metal electrode is used as a cathode electrode (anode), and an electric field is applied. The material emits light. Also, the transparent electrode is the anode electrode (cathode), the metal electrode is the cathode electrode (anode), the lead wire is attached to each, the transparent electrode side is covered with transparent glass or plastic, and the metal electrode side is made of plastic, etc. After covering with an insulator, the end face of the material is sealed with a sealing resin such as an epoxy resin to prevent intrusion of impurities as a deterioration factor from the outside, and light can be emitted by applying an electric field stably for a long time. .
[0075]
The present invention will be described with reference to FIG. 1, which is a schematic view of a light-emitting organic / inorganic composite material of the present invention.
[0076]
As shown in FIG. 1, the present invention has a thickness of 0.5 to 1.5 microns, further 0.9 to 1.4 microns, for example, about 1 micron, and emits light as compared with the current organic EL material. This is a light-emitting organic / inorganic composite material in which a sufficient amount of the active molecule is present and high-luminance light emission can be performed with a margin. In FIG. 1, 3 is a transparent electrode, 4 is a metal electrode, 5 is a light-emitting organic / inorganic composite material, 6 is a transparent cover for the transparent electrode, 7 is a cover for the metal electrode, 8 is a sealing resin, and 9 is a lead. Is a line.
[0077]
As the inorganic polymer in the present invention, for example, a porous material having many pores by a sol-gel method is used. For example, the light emitting organic / inorganic composite material of the present invention is produced by impregnating the pores with an organic polymer. The interface between the inorganic part and the organic part is in close contact. By adding a charge transport agent and a dopant light-emitting agent to the organic / inorganic composite material as necessary, an electroluminescent material having high luminance, high efficiency, and long life can be provided. The concentration of the charge transfer agent is preferably about 15 to 40 wt%, more preferably about 25 wt% with respect to the whole material for both positive and negative charges. The organic polymer part contains 25 wt% of a positive charge transfer agent (negative charge transfer agent), and the inorganic polymer part contains 25 wt% of a negative charge transfer agent (positive charge transfer agent). The charge transfer agent accounts for 50 wt% of the whole. Most preferably.
[0078]
The above organic / inorganic composite material can be produced under normal pressure and does not require ultra-high vacuum conditions. Therefore, a light emitting material having a large area can be made. In addition, since the heat generated during light emission can be dissipated in the inorganic material portion, light can be emitted stably and efficiently for a long time.
[0079]
In addition, a material excellent in workability that synergistically combines the flexibility of the organic material and the rigidity of the inorganic material can be obtained.
[0080]
The composite material itself of the present invention itself has a thickness of, for example, about 1 micron, but the inside is shown in FIG. 2 (schematic diagram showing the internal structure and charge transfer of the light-emitting organic / inorganic composite material of the present invention. 1 is an organic polymer part, and 2 is an inorganic polymer part), it is controlled on the order of nanometers. Therefore, the light-emitting molecules can be efficiently excited by charge recombination and its exciton energy. Therefore, the applied electric field can also be lower than 1 million volts / cm, which has been used for conventional organic EL materials and inorganic EL materials. Further, since the luminescent molecule is excited by exciton at a distance from the electrode, the luminous efficiency from the luminescent molecule is also increased. Further, since the material of the present invention has a thickness of about 1 micron, the number of molecules of the light emitting component is increased, and high luminance light emission can be performed with a margin. That is, high luminance light emission can be performed without applying a high voltage as in the conventional method. As a result, the driving life is extended.
[0081]
In addition, since the composite material of the present invention itself has a thickness of about 1 micron, pinholes are not generated, conduction between the electrodes is eliminated, the in-plane uniformity of light emission luminance is improved, and the electroluminescent element is obtained. As a long life.
[0082]
The organic / inorganic composite material of the present invention is an organic / inorganic composite in which a positive charge transport agent and a negative charge transport agent are separately contained in either an inorganic part (inorganic polymer part) or an organic part (organic polymer part). It may be a material, or may be an organic / inorganic composite material in which at least one of the inorganic part and the organic part contains both a positive charge transport agent and a negative charge transport agent.
[0083]
When the positive charge transport agent and the negative charge transport agent are separately contained in either the inorganic part or the organic part, each charge can efficiently move until recombination is performed at the organic / inorganic interface. This is because both the inorganic part and the organic part have a size of several nanometers to several tens of nanometers, so that each charge efficiently reaches the organic / inorganic interface without being trapped in the middle. Since the distance to the organic / inorganic interface is a knit structure in which each material portion meanders, the distance to the interface is at most about 100 nanometers. Therefore, it is not necessary for each electric charge to move even if the thickness of the material is about 1 micron, and can reach the material interface between the organic part and the inorganic part, and efficiently recombine only at the interface between the inorganic part and the organic part. Furthermore, the deactivation of excitons in the vicinity of the electrode, which is disadvantageous for excitation of the luminescent molecules by excitons, can be suppressed. Furthermore, since the contact interface between the inorganic part and the organic part is not a conventional planar structure but a curved surface structure, the contact area is widened, and the probability of recombination of positive and negative charges is further increased and efficiency is improved.
[0084]
Even when a positive charge transporting agent and a negative charge transporting agent are included in either an inorganic polymer or an organic polymer at the same time, since the material has a thickness of about 1 micron, the positive charge transporting agent and the negative charge transporting agent are included. Are included at the same time, both positive and negative charges are injected from separate electrodes facing each other, so both charges move in the opposite direction and recombine at a distance from both electrodes. The deactivation of excitons in the vicinity is suppressed, and the light-emitting molecules due to excitons are efficiently excited to achieve highly efficient electroluminescence. As a luminescent molecule, when the charge transport agent itself plays a role, and when it is desired to emit light other than the emission wavelength of the charge transport agent, a fluorescent compound or molecule having the wavelength as the fluorescence wavelength is added as a dopant. There is a case to do. Therefore, a fluorescent compound or molecule is not necessarily added. When added, it is possible to emit light of various wavelengths. In addition, every part of the organic part and the inorganic part has a structure in contact with both electrodes while meandering.
[0085]
Each electrode is directly deposited after polishing the surface of the organic / inorganic composite material. For this reason, the contact between the organic / inorganic composite material of the present invention, both the transparent electrode and the metal electrode becomes close, and the charge injection efficiency increases.
[0086]
In the present invention, each electrode has both an inorganic part and an organic part as shown in FIGS. 1, 2 and 3 (schematic diagram of the surface state after polishing of the light-emitting organic / inorganic composite material of the present invention). Contact. However, for example, when the inorganic part contains a positive charge transport agent and the organic part contains a negative charge transport agent, positive charge is injected into the inorganic part only from the ITO electrode having a large work function. Is done. Also, negative charges are injected into the organic part only from a metal electrode having a small work function. When the material part containing each charge transport agent is reversed (when the inorganic part contains a negative charge transport agent and the organic part contains a positive charge transport agent), negative charge is injected into the inorganic part only from the metal electrode. Is done. Positive charges are injected into the organic part only from the ITO electrode. In this way, each electrode selectively injects positive or negative charges into the inorganic part or the organic part. That is, each material part (organic part and inorganic part) is selectively injected with either positive charge or negative charge depending on the nature of the charge transport agent contained therein. In addition, the ratio between the inorganic part and the organic part, or the ratio between the positive charge transport agent and the negative charge transport agent is optimally selected (although this ratio may vary depending on the type of the charge transport agent), the positive part injected is injected. Optimize the balance between charge and negative charge. The optimal choice is to ensure that the positive and negative charge injection amounts are as equal as possible. As a result, recombination of positive charges and negative charges and exciton formation can be made highly efficient. Further, since holes and electrons can be recombined at a distance from the electrode, deactivation of excitons in the vicinity of the electrode can be suppressed, and luminous efficiency is increased. As described above, an electroluminescent material having high efficiency, high luminance, long life drive, and a large area can be provided.
[0087]
Even if the organic part contains a polymer having a hole transport property such as polyvinylcarbazole (PVK), aluminoquinolinium (AlQ _Three If an electron transporting agent such as) is contained up to 50 wt% or more with respect to PVK, electron transport can be performed. If a hole transport agent is contained in PVK, the hole transport ability will finally increase.
[0088]
When both positive and negative charge transport agents are included in either the organic polymer or the inorganic polymer, the positive charge from the ITO electrode and the negative charge from the metal electrode as the counter electrode are the same including both charge transport agents. It is injected into the material part. However, these charges move oppositely in a material with a thickness of about 1 micron, so both charges recombine inside the material away from the electrode surface, generating excitons, and efficiently excite the luminescent molecules. Make it emit light.
[0089]
With the organic / inorganic composite material of the present invention, surface polishing can be performed due to good workability. As a result, the surface has a distinction between the inorganic part and the organic part. That is, they are separated in close contact (FIG. 3). Therefore, both the transparent electrode and the metal electrode can selectively inject holes and electrons into the inorganic part and the organic part, respectively. Thickness can be controlled and surface smoothness can be obtained. As a result, the electrode material is uniformly adhered, and the efficiency of charge injection is improved.
[0090]
As described above, in the organic / inorganic composite material of the present invention, both positive and negative charges are efficiently injected by applying an electric field, and they also recombine efficiently to form excitons, and the luminescent molecules are formed by the energy. When excited, electroluminescence occurs efficiently. Also, the thickness is about 1 micron, but it is 10 times thicker than conventional organic EL materials, no pinholes are generated, the light emission brightness is uniform in the material plane, and the driving operation life is extended. Give me. In addition, since the organic material is included, the processability of the material is excellent, and since the inorganic material is included, the optical characteristics of the material are also excellent. Further, since the inorganic material dissipates heat generated during light emission, the driving operation life of the material is extended.
[0091]
【Example】
Next, the present invention will be described based on examples, but the present invention is not limited thereto.
[0092]
Example 1
Tetraethoxysilane is used as the inorganic polymer precursor, and vinylcarbazole is used as the organic polymer precursor. Tetraethoxysilane (TEOS) 10g and negative charge transfer agent AlQ _Three Dissolve 1.5 g in 2.5 g of ethanol to make a solution, add nitric acid aqueous solution to the solution to adjust to pH 5.0, put this solution in Teflon petri dish, and make it gel by hydrolysis / polycondensation method Heat treatment (90 ° C., 20 hours) _Three SiO containing ₂ Inorganic glass (diameter: 15 cm) was obtained. This glass had pores of 15 nanometers (measured by nitrogen adsorption experiment and BET method). Moreover, the porosity (volume ratio of holes) was 58%. This glass was placed in a tetrahydrofuran (THF) solution containing 3 g of vinylcarbazole, 1 mg of 2,2′-azobisisobutyronitrile and 1.5 g of the positive charge transfer agent TPD, and the above-mentioned SiO. ₂ Polymerization of vinylcarbazole was caused in the inorganic glass. Note that all the THF solution was consumed. As a result, the above AlQ _Three SiO containing ₂ In this inorganic glass, an organic / inorganic composite material containing polyvinyl carbazole containing TPD as an organic polymer portion was obtained. The thickness of the obtained organic / inorganic composite material was 1.3 micrometers, and polishing such as buffing was performed to obtain an organic / inorganic composite material having a thickness of 1.1 micrometers and excellent optical characteristics. Transparent conductive indium tin oxide (ITO) was deposited on one surface of the obtained composite material by a direct current sputtering method to form an anode electrode. The surface resistance of ITO was set to 20Ω / □. Next, an alloy of Al and Li (Al / Li = 10/1) was deposited to a thickness of 30 nm on the other surface of the composite material to form a cathode electrode. Copper leads were attached to both electrodes with a conductive paste. The ITO electrode surface of the composite material obtained as described above was covered with a transparent acrylic plate, the Al / Li electrode surface was covered with a polypropylene resin plate, and all the end surfaces thereof were sealed with an epoxy resin. A DC voltage was applied so that the ITO electrode of the composite material to which this electrode was attached had a positive potential and the Al / Li electrode had a negative potential. As a result, an applied voltage / light emission luminance characteristic as shown in FIG. 4 was shown. That is, an applied voltage of 30 volts (V) to about 0.1 cd / m ² Began to emit light. As the applied voltage is increased, the light emission luminance increases, and the applied voltage is 500 cd / m at 70V. ² Luminescence, 2500 cd / m at 100V applied voltage ² Luminescence was achieved. This light emission is yellow-green light emission having a light emission wavelength center of 545 nm and a light emission wavelength half width of about 100 nm. The emission wavelength characteristic shows the same characteristic regardless of the applied voltage. Next, when the voltage applied to the composite material to which the electrode was attached was fixed at 70 V and the light emission was continued, the initial 500 cd / m was obtained. ² It was after 5000 hours that the luminescence of was halved. Thus, in this example, it was found that high-luminance light emission lasts for a long time and can be used for various surface-emitting display devices. The current 500 cd / m ² Even if it is good, it is about 1000 hours (Reference: Hosokawa et al., Synth. Met., 91, (1997) p. 3).
[0093]
Example 2
Tetraethoxysilane is used as the inorganic polymer precursor, and vinylcarbazole is used as the organic polymer precursor. Tetraethoxysilane (TEOS) 10 g and positive charge transfer agent TPD 1.5 g are dissolved in 2.5 g ethanol to form a solution, and an aqueous nitric acid solution is added to the solution to adjust the pH to 5.0. This solution is added to a Teflon petri dish. And then gelled by hydrolysis / polycondensation method and heat treated (90 ° C., 20 hours) to contain SiOD containing TPD ₂ Inorganic glass (diameter: 15 cm) was obtained. This glass had 14 nanometer pores (measured by nitrogen adsorption experiment and BET method). In addition, the porosity (volume ratio of pores) was 59%. This glass was mixed with 3 g of vinylcarbazole and 1 mg of 2,2′-azobisisobutyronitrile and a negative charge transport agent AlQ. _Three In a tetrahydrofuran solution containing 1.5 g, and the above-mentioned SiO. ₂ Polymerization of vinylcarbazole was caused in the inorganic glass. Note that all the THF solution was consumed. As a result, SiO containing the above TPD ₂ AlQ in AlQ _Three Thus, an organic / inorganic composite material containing polyvinylcarbazole containing as an organic polymer part was obtained. The thickness of the obtained organic / inorganic composite material was 1.2 micrometers, and polishing such as buffing was performed to obtain an organic / inorganic composite material having a thickness of 1.1 micrometers and excellent optical characteristics. Transparent conductive indium tin oxide (ITO) was deposited on one surface of the obtained composite material by a direct current sputtering method to form an anode electrode. The surface resistance of ITO was set to 20Ω / □. Next, an alloy of Al and Li (Al / Li = 10/1) was deposited to a thickness of 30 nm on the other surface of the composite material to form a cathode electrode. Copper leads were attached to both electrodes with a conductive paste. The ITO electrode surface of the composite material obtained as described above was covered with a transparent glass plate, the Al / Li electrode surface was covered with ABS resin, and all the end surfaces thereof were sealed with epoxy resin. A DC voltage was applied so that the ITO electrode of the composite material to which this electrode was attached had a positive potential and the Al / Li electrode had a negative potential. As a result, voltage / light emission characteristics similar to those in FIG. 4 were shown. That is, an applied voltage of 28 volts (V) to about 0.1 cd / m ² Began to emit light. As the applied voltage is increased, the light emission luminance increases, and the applied voltage is 73 cd and 500 cd / m. ² Light emission, applied voltage is 100V, 2300cd / m ² Luminescence was achieved. This light emission is yellow-green light emission with a light emission wavelength center of 547 nm and a light emission wavelength half width of about 100 nm. The emission wavelength characteristic shows the same characteristic regardless of the applied voltage. Next, when the applied voltage was fixed to 73 V on the composite material to which the electrodes were attached and the light emission was continued, the initial 500 cd / m was obtained. ² It was after 5000 hours that the luminescence of was halved. Thus, in this example, it was found that high-luminance light emission lasts for a long time and can be used for various surface-emitting display devices. The current 500 cd / m ² Even if it is good, it is about 1000 hours (Reference: Hosokawa et al., Synth. Met., 91, (1997) p. 3).
[0094]
Example 3
Tetraethoxysilane is used as the inorganic polymer precursor, and vinylcarbazole is used as the organic polymer precursor. Tetraethoxysilane (TEOS) 10g and negative charge transfer agent AlQ _Three 1.5 g and 15 mg of fluorescent luminescent molecule (luminescent pigment) DCM2 in 2.5 g of ethanol are dissolved in a solution, and an aqueous nitric acid solution is added to the solution to adjust the pH to 5.0. Put in, gelled by hydrolysis / polycondensation method, heat treated (90 ° C., 20 hours), AlQ _Three And SiO 2 containing fluorescent luminescent molecule DCM2 ₂ Inorganic glass (diameter: 15 cm) was obtained. This glass had pores of 15 nanometers (measured by nitrogen adsorption experiment and BET method). Moreover, the porosity (volume ratio of holes) was 58%. This glass was placed in a tetrahydrofuran solution containing 3 g of vinylcarbazole, 1 mg of 2,2′-azobisisobutyronitrile and 1.5 g of the positive charge transfer agent TPD, and the above-mentioned SiO. ₂ Polymerization of vinylcarbazole was caused in the inorganic glass. Note that all the THF solution was consumed. As a result, the above AlQ _Three And SiO2 containing DCM2 ₂ In this inorganic glass, an organic / inorganic composite material containing polyvinyl carbazole containing TPD as an organic polymer portion was obtained. The thickness of the obtained organic / inorganic composite material was 1.3 micrometers, and polishing such as buffing was performed to obtain an organic / inorganic composite material having a thickness of 1.1 micrometers and excellent optical characteristics. Transparent conductive indium tin oxide (ITO) was deposited on one surface of the obtained composite material by a direct current sputtering method to form an anode electrode. The surface resistance of ITO was set to 20Ω / □. Next, an alloy of Al and Li (Al / Li = 10/1) was deposited to a thickness of 30 nm on the other surface of the composite material to form a cathode electrode. Copper leads were attached to both electrodes with a conductive paste. The ITO electrode surface of the composite material obtained as described above was covered with a transparent acrylic plate, the Al / Li electrode surface was covered with ABS resin, and all the end surfaces thereof were sealed with epoxy resin. A DC voltage was applied so that the ITO electrode of the composite material to which this electrode was attached had a positive potential and the Al / Li electrode had a negative potential. As a result, voltage / light emission characteristics similar to those in FIG. 4 were shown. That is, an applied voltage of 35 volts (V) to about 0.1 cd / m ² Began to emit light. As the applied voltage is increased, the light emission luminance increases, and the applied voltage is 75 V and 500 cd / m. ² Light emission, applied voltage is 100V, 2000cd / m ² Luminescence was achieved. This light emission is red light emission having an emission wavelength center of 630 nm and an emission wavelength half width of about 70 nm. The emission wavelength characteristic shows the same characteristic regardless of the applied voltage. Next, when the applied voltage was fixed to 75 V on the composite material to which the electrodes were attached and the light emission was continued, the initial 500 cd / m was obtained. ² It was after 3000 hours that the luminescence of was halved. Thus, in this example, it was found that high-luminance light emission lasts for a long time and can be used for various surface-emitting display devices. The current 500 cd / m ² Even if it is good, it is about 1000 hours (Reference: Hosokawa et al., Synth. Met., 91, (1997) p. 3).
[0095]
Example 4
Tetraethoxysilane is used as the inorganic polymer precursor, and vinylcarbazole is used as the organic polymer precursor. Tetraethoxysilane (TEOS) 10g and negative charge transfer agent AlQ _Three 1.5 g of the positive charge transfer agent TPD 1.5 g in ethanol of 2.5 g to obtain a solution, and an aqueous nitric acid solution is added to the solution to adjust the pH to 5.0. This solution is placed in a Teflon dish. Gelation is performed by hydrolysis and polycondensation, and heat treatment (90 ° C., 20 hours) is performed. _Three And SiO containing TPD ₂ Inorganic glass (diameter: 15 cm) was obtained. This glass had pores of 15 nanometers (measured by nitrogen adsorption experiment and BET method). Moreover, the porosity (volume ratio of holes) was 58%. This glass was placed in a tetrahydrofuran solution containing 3 g of vinylcarbazole, 1 mg of 2,2′-azobisisobutyronitrile and 1.5 g of the positive charge transfer agent TPD, and the above-mentioned SiO. ₂ Polymerization of vinylcarbazole was caused in the inorganic glass. Note that all the THF solution was consumed. As a result, the above AlQ _Three And SiO containing TPD ₂ In this inorganic glass, an organic / inorganic composite material containing polyvinyl carbazole containing TPD as an organic polymer portion was obtained. The thickness of the obtained organic / inorganic composite material was 1.3 micrometers, and polishing such as buffing was performed to obtain an organic / inorganic composite material having a thickness of 1.1 micrometers and excellent optical characteristics. Transparent conductive indium tin oxide (ITO) was deposited on one surface of the obtained composite material by a direct current sputtering method to form an anode electrode. The surface resistance of ITO was set to 20Ω / □. Next, an alloy of Mg and Ag (Mg / Ag = 9/1) was deposited to a thickness of 50 nm on the other surface of the composite material to form a cathode electrode. Copper leads were attached to both electrodes with a conductive paste. The ITO electrode surface of the composite material obtained as described above was covered with a transparent acrylic plate, the Mg / Ag electrode surface was covered with a polypropylene resin plate, and all the end surfaces thereof were sealed with an epoxy resin. A DC voltage was applied so that the ITO electrode of the composite material to which this electrode was attached had a positive potential and the Mg / Ag electrode had a negative potential. As a result, voltage / light emission characteristics similar to those in FIG. 4 were shown. That is, an applied voltage of 40 volts (V) to about 0.1 cd / m ² Began to emit light. As the applied voltage is increased, the emission luminance increases, and the applied voltage is 80 cd and 500 cd / m. ² Light emission, applied voltage is 100V, 2300cd / m ² Luminescence was achieved. This light emission is yellow-green light emission having a light emission wavelength center of 540 nm and a light emission wavelength half width of about 80 nm. The emission wavelength characteristic shows the same characteristic regardless of the applied voltage. Next, when the applied voltage was fixed to 80 V on the composite material to which the electrodes were attached and the light emission was continued, the initial 500 cd / m ² It was after 4000 hours that the luminescence of was halved. Thus, in this example, it was found that high-luminance light emission lasts for a long time and can be used for various surface-emitting display devices. The current 500 cd / m ² Even if it is good, it is about 1000 hours (Reference: Hosokawa et al., Synth. Met., 91, (1997) p. 3).
[0096]
Example 5
Tetraethoxysilane is used as the inorganic polymer precursor, and methyl methacrylate (MMA) is used as the organic polymer precursor. Tetraethoxysilane (TEOS) 10g and negative charge transfer agent AlQ _Three Is dissolved in 2.5 g of ethanol to prepare a solution, and an aqueous nitric acid solution is added to adjust the pH to 5.0. This solution is applied on a glass substrate on which an ITO electrode is deposited, and then hydrolyzed. -Gelled by polycondensation and heat-treated (90 ° C, 20 hours) _Three SiO containing ₂ Inorganic glass (diameter: 15 cm) was obtained. This glass had pores of 15 nanometers (measured by nitrogen adsorption experiment and BET method). Moreover, the porosity (volume ratio of holes) was 58%. This glass was placed in a tetrahydrofuran solution containing 2.8 g of methyl methacrylate (MMA), 1 mg of 2,2′-azobisisobutyronitrile and 1.5 g of a positive charge transport agent TPD, and the above-mentioned SiO. ₂ Polymerization of MMA was caused in the inorganic glass. Note that all the THF solution was consumed. As a result, the above AlQ _Three SiO containing ₂ An organic / inorganic composite material containing polymethylmethacrylate (PMMA) containing TPD as an organic polymer portion was obtained. The thickness of the obtained organic / inorganic composite material was 1.3 micrometers. The organic / inorganic composite material on the ITO glass substrate was polished by buffing or the like, and an organic / inorganic composite material having a thickness of 1.1 micrometers and excellent optical characteristics was obtained. On the opposite surface of the obtained composite material ITO glass substrate, an alloy of Al and Li (Al / Li = 10/1) was deposited to a thickness of 30 nm to form a cathode electrode. Copper leads were attached to both electrodes with a conductive paste. The Al / Li electrode surface of the composite material obtained as described above was covered with a polypropylene resin plate, and all the end surfaces thereof were sealed with an epoxy resin. A DC voltage was applied so that the ITO electrode of the composite material to which this electrode was attached had a positive potential and the Al / Li electrode had a negative potential. As a result, voltage / light emission characteristics similar to those in FIG. 4 were shown. That is, an applied voltage of 45 volts (V) to about 0.1 cd / m ² Began to emit light. As the applied voltage is increased, the light emission luminance increases, and the applied voltage is 400 cd / m at 70V. ² Light emission, applied voltage is 100V, 2000cd / m ² Luminescence was achieved. This light emission is yellow-green light emission having a light emission wavelength center of 545 nm and a light emission wavelength half width of about 100 nm. The emission wavelength characteristic shows the same characteristic regardless of the applied voltage. Next, when the applied voltage was fixed to 70 V on the composite material to which the electrodes were attached and the light emission was continued, the initial 400 cd / m ² It was after 4000 hours that the luminescence of was halved. Thus, in this example, it was found that high-luminance light emission lasts for a long time and can be used for various surface-emitting display devices. The current 500 cd / m ² Even if it is good, it is about 1000 hours (Reference: Hosokawa et al., Synth. Met., 91, (1997) p. 3).
[0097]
Example 6
Tetraethoxysilane is used as the inorganic polymer precursor, and vinylcarbazole is used as the organic polymer precursor. 10g tetraethoxysilane (TEOS) and AlQ _Three 1.5 g, 1.5 g of vinylcarbazole, 1.5 g of α-NPD and 1 mg of 2,2′-azobisisobutyronitrile were dissolved in a mixed solution of 5 g of ethanol and 5 g of tetrahydrofuran. A nitric acid aqueous solution was added to the above solution to adjust the pH to 5.0, and this solution was placed in a Teflon petri dish to cause gelation of TEOS and polymerization of vinyl carbazole by hydrolysis and polycondensation. As a result, the compatibility of AlQ _Three SiO containing most of and a part of α-NPD ₂ And inorganic polymer part, most of α-NPD and some AlQ _Three Organic-inorganic composite material with polyvinyl carbazole containing and organic polymer part (those eluted with THF have 18 nanometer pores (measured by nitrogen adsorption experiment and BET method), The porosity was 57%). The thickness of the obtained organic / inorganic composite material was 1.3 micrometers, and polishing such as buffing was performed to obtain an organic / inorganic composite material having a thickness of 1.1 micrometers and excellent optical characteristics. Transparent conductive indium tin oxide (ITO) was deposited on one surface of the obtained composite material by a direct current sputtering method to form an anode electrode. The surface resistance of ITO was set to 20Ω / □. Next, an alloy of Al and Li (Al / Li = 10/1) was deposited to a thickness of 30 nm on the other surface of the composite material to form a cathode electrode. Copper leads were attached to both electrodes with a conductive paste. The ITO electrode surface of the composite material obtained as described above was covered with a transparent glass plate, the Al / Li electrode surface was covered with a polypropylene resin plate, and all the end surfaces thereof were sealed with an epoxy resin. A DC voltage was applied so that the ITO electrode of the composite material to which this electrode was attached had a positive potential and the Al / Li electrode had a negative potential. As a result, voltage / light emission characteristics similar to those in FIG. 4 were shown. That is, an applied voltage of 45 volts (V) to about 0.1 cd / m ² Began to emit light. As the applied voltage is increased, the light emission luminance increases, and the applied voltage is 400 cd / m at 70V. ² Light emission, applied voltage is 100V, 2000cd / m ² Luminescence was achieved. This light emission is yellow-green light emission having a light emission wavelength center of 545 nm and a light emission wavelength half width of about 100 nm. The emission wavelength characteristic shows the same characteristic regardless of the applied voltage. Next, when the applied voltage was fixed to 70 V on the composite material to which the electrodes were attached and the light emission was continued, the initial 400 cd / m ² It was after 4000 hours that the luminescence of was halved. Thus, in this example, it was found that high-luminance light emission lasts for a long time and can be used for various surface-emitting display devices. The current 500 cd / m ² Even if it is good, it is about 1000 hours (Reference: Hosokawa et al., Synth. Met., 91, (1997) p. 3).
[0098]
Example 7
Tetraethoxyzirconia is used as the precursor of the inorganic polymer, and vinylcarbazole is used as the precursor of the organic polymer. Tetraethoxyzirconia (TEOZr) 6g and negative charge transfer agent BeQ ₂ Dissolve 1.5 g in 3.5 g ethanol to make a solution, add nitric acid aqueous solution to the solution to adjust to pH 5.0, put this solution in Teflon petri dish, and gel by hydrolysis / polycondensation method Heat treatment (100 ° C., 20 hours) and BeQ ₂ ZrO containing ₂ Inorganic glass (diameter: 15 cm) was obtained. The glass had 13 nanometer pores (measured by nitrogen adsorption experiment and BET method). Moreover, the porosity (volume ratio of holes) was 55%. This glass was put in a tetrahydrofuran solution containing 3 g of polyvinylcarbazole and 1.9 g of a positive charge transfer agent m-MTDATA, and tetrahydrofuran was removed by evaporation. As a result, the above BeQ ₂ ZrO containing ₂ An organic-inorganic composite material containing polyvinyl carbazole containing m-MTDATA as an organic polymer part in the inorganic glass was obtained. The thickness of the obtained organic / inorganic composite material was 1.3 micrometers, and polishing such as buffing was performed to obtain an organic / inorganic composite material having a thickness of 1.1 micrometers and excellent optical characteristics. Transparent conductive indium tin oxide (ITO) was deposited on one surface of the obtained composite material by a direct current sputtering method to form an anode electrode. The surface resistance of ITO was set to 20Ω / □. Next, an alloy of Al and Li (Al / Li = 10/1) was deposited to a thickness of 30 nm on the other surface of the composite material to form a cathode electrode. Copper leads were attached to both electrodes with a conductive paste. The ITO electrode surface of the composite material obtained as described above was covered with a transparent acrylic plate, the Al / Li electrode surface was covered with ABS resin, and all the end surfaces thereof were sealed with epoxy resin. A DC voltage was applied so that the ITO electrode of the composite material to which this electrode was attached had a positive potential and the Al / Li electrode had a negative potential. As a result, voltage / luminescence characteristics similar to those in FIG. That is, an applied voltage of 30 volts (V) to about 0.1 cd / m ² Began to emit light. As the applied voltage is increased, the light emission luminance increases, and the applied voltage is 450 cd / m at 78V. ² Light emission, applied voltage is 100V, 2100cd / m ² Luminescence was achieved. This light emission is green light emission having a light emission wavelength center of 516 nm and a light emission wavelength half width of about 80 nm. The emission wavelength characteristic shows the same characteristic regardless of the applied voltage. Next, when the applied voltage was fixed to 78 V on the composite material to which the electrode was attached and the light emission was continued, the initial 450 cd / m was obtained. ² It was after 5500 hours that the luminescence of was halved. Thus, in this example, it was found that high-luminance light emission lasts for a long time and can be used for various surface-emitting display devices. The current 500 cd / m ² Even if it is good, it is about 1000 hours (Reference: Hosokawa et al., Synth. Met., 91, (1997) p. 3).
[0099]
【The invention's effect】
According to invention of Claim 1, it consists of both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the void | hole part of a porous inorganic polymer, an organic polymer has a positive charge transport capability, and inorganic Since the polymer is a light-emitting organic / inorganic composite material that has a negative charge transport ability and a thickness of 0.5 to 1.5 microns, it deteriorates when a voltage is applied at a thickness of about 1 micron. Therefore, it is possible to provide an electroluminescent material which has a sufficient amount of light emitting molecules and can emit high-luminance light with a margin as compared with organic electroluminescent materials. That is, in the conventional method, high luminance light emission is realized by increasing the applied voltage. However, in the present invention, high luminance light emission can be performed without applying a high voltage as in the conventional method. In addition, since the heat generated during light emission can be dissipated in the inorganic part, light can be emitted stably and efficiently for a long time. As a result, the life of the material can be extended even under driving conditions of high luminance light emission. In addition, the interface between the inorganic polymer and the organic polymer is in close contact, and an electroluminescent material with high luminance, high efficiency, and long life can be provided. Furthermore, the flexibility of the organic polymer and the rigidity of the inorganic polymer are synergistically combined to provide excellent processability.
[0100]
According to the invention of claim 2, the organic polymer is comprised of both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the pores of the porous inorganic polymer, the organic polymer has a positive charge transport agent, and is inorganic. Since the polymer is a light-emitting organic / inorganic composite material having a negative charge transporting agent and a thickness of 0.5 to 1.5 microns, it deteriorates when a voltage is applied at a thickness of about 1 micron. Therefore, it is possible to provide an electroluminescent material which has a sufficient amount of light emitting molecules and can emit high-luminance light with a margin as compared with organic electroluminescent materials. That is, in the conventional method, high luminance light emission is realized by increasing the applied voltage. However, in the present invention, high luminance light emission can be performed without applying a high voltage as in the conventional method. Moreover, since the heat generated during light emission can be dissipated in the inorganic part, light can be emitted stably and efficiently for a long time. As a result, the life of the material can be extended even under driving conditions of high luminance light emission. In addition, the interface between the inorganic polymer and the organic polymer is in close contact, and an electroluminescent material with high luminance, high efficiency, and long life can be provided. Furthermore, the flexibility of the organic polymer and the rigidity of the inorganic polymer are synergistically combined to provide excellent processability.
[0101]
According to invention of Claim 3, it consists of both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the void | hole part of a porous inorganic polymer, an organic polymer has negative charge transport ability, inorganic Since the polymer is a light-emitting organic / inorganic composite material that has a positive charge transport ability and a thickness of 0.5 to 1.5 microns, it deteriorates when a voltage is applied at a thickness of about 1 micron. Therefore, it is possible to provide an electroluminescent material which has a sufficient amount of light emitting molecules and can emit high-luminance light with a margin as compared with organic electroluminescent materials. That is, in the conventional method, high luminance light emission is realized by increasing the applied voltage. However, in the present invention, high luminance light emission can be performed without applying a high voltage as in the conventional method. In addition, since the heat generated during light emission can be dissipated in the inorganic part, light can be emitted stably and efficiently for a long time. As a result, the life of the material can be extended even under driving conditions of high luminance light emission. In addition, the interface between the inorganic polymer and the organic polymer is in close contact, and an electroluminescent material with high luminance, high efficiency, and long life can be provided. Furthermore, the flexibility of the organic polymer and the rigidity of the inorganic polymer are synergistically combined to provide excellent processability.
[0102]
According to invention of Claim 4, it consists of both components of an organic polymer and an inorganic polymer, the organic polymer is contained in the void | hole part of the porous inorganic polymer, an organic polymer has a negative charge transport agent, inorganic Since the polymer is a light-emitting organic / inorganic composite material having a positive charge transport agent and a thickness of 0.5 to 1.5 microns, it deteriorates when a voltage is applied at a thickness of about 1 micron. Therefore, it is possible to provide an electroluminescent material which has a sufficient amount of light emitting molecules and can emit high-luminance light with a margin as compared with organic electroluminescent materials. That is, in the conventional method, high luminance light emission is realized by increasing the applied voltage. However, in the present invention, high luminance light emission can be performed without applying a high voltage as in the conventional method. In addition, since the heat generated during light emission can be dissipated in the inorganic part, light can be emitted stably and efficiently for a long time. As a result, the life of the material can be extended even under driving conditions of high luminance light emission. In addition, the interface between the inorganic polymer and the organic polymer is in close contact, and an electroluminescent material with high luminance, high efficiency, and long life can be provided. Furthermore, the flexibility of the organic polymer and the rigidity of the inorganic polymer are synergistically combined to provide excellent processability.
[0103]
According to the invention of claim 5, the organic polymer is contained in the pores of the porous inorganic polymer, which is composed of both the organic polymer and the inorganic polymer, and at least one of the organic polymer and the inorganic polymer is positively charged. Since it is a light-emitting organic / inorganic composite material having both a transport ability and a negative charge transport ability and a thickness of 0.5 to 1.5 microns, the thickness is about 1 micron and voltage is applied. It is possible to provide an electroluminescent material which is less likely to deteriorate and has a sufficient amount of light emitting molecules as compared with an organic electron luminescent material, and can perform high-luminance emission with a margin. That is, in the conventional method, high luminance light emission is realized by increasing the applied voltage. However, in the present invention, high luminance light emission can be performed without applying a high voltage as in the conventional method. In addition, since the heat generated during light emission can be dissipated in the inorganic part, light can be emitted stably and efficiently for a long time. As a result, the life of the material can be extended even under driving conditions of high luminance light emission. In addition, the interface between the inorganic polymer and the organic polymer is in close contact, and an electroluminescent material with high luminance, high efficiency, and long life can be provided. Furthermore, the flexibility of the organic polymer and the rigidity of the inorganic polymer are synergistically combined to provide excellent processability.
[0104]
According to the sixth aspect of the present invention, the organic polymer is contained in the pores of the porous inorganic polymer, which is composed of both components of the organic polymer and the inorganic polymer, and at least one of the organic polymer and the inorganic polymer is positively charged. Since it is a light-emitting organic / inorganic composite material having both a transport agent and a negative charge transport agent and having a thickness of 0.5 to 1.5 microns, the thickness is about 1 micron and voltage is applied. It is possible to provide an electroluminescent material which is less likely to deteriorate and has a sufficient amount of light emitting molecules as compared with an organic electron luminescent material, and can perform high-luminance emission with a margin. That is, in the conventional method, high luminance light emission is realized by increasing the applied voltage. However, in the present invention, high luminance light emission can be performed without applying a high voltage as in the conventional method. In addition, since the heat generated during light emission can be dissipated in the inorganic part, light can be emitted stably and efficiently for a long time. As a result, the life of the material can be extended even under driving conditions of high luminance light emission. In addition, the interface between the inorganic polymer and the organic polymer is in close contact, and an electroluminescent material with high luminance, high efficiency, and long life can be provided. Furthermore, the flexibility of the organic polymer and the rigidity of the inorganic polymer are synergistically combined to provide excellent processability.
[0105]
According to the invention of claim 7, TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4 ′ is used as the positive charge transport agent. -Diamine), α-NPD (N, N′-diphenyl-N, N′-bis (α-naphthyl)-[1,1′-biphenyl] -4,4′-diamine: 4,4′-bis [ N- (1-naphthyl) -N-phenyl-amino] biphenyl), Cz-TPD (4,4′-bis (9-carbazolyl) -1,1′-biphenyl), PTCDA (3,4,9,10 -Perylenetetracarboxylic dianhydride), CuPc (copper phthalocyanine), ZnTPP (zinc (II) 5,10,15,20-tetraphenylporphyrin), PO-TPD (4,4'-bis (10-phenoxazinyl) biphenyl) ), T-TPD (4,4'-bis (10-phenothiazinyl) biphenyl), DPBI (4,4 '-(2,2-diphenylvinylene) -1,1'-biphenyl), DTVBI (4,4'- (2,2-di-paramethylphenylvinylene) -1,1′-biphenyl), m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine), HDRZ (4 A light-emitting organic / inorganic composite material according to claim 2, 4 or 6, wherein at least one of -biphenylaminophenyl-biphenylhydrazone) and Ru (II) complex (ruthenium (II) complex) is used. Therefore, the characteristics of the electroluminescent material having high luminance, high efficiency and long life in the light-emitting organic / inorganic composite material according to claim 2, 4 or 6 are further improved. Can.
[0106]
According to the invention of claim 8, as the negative charge transfer agent, AlQ _Three (Tris (8-hydroxy-quinolino) aluminum), BeQ ₂ (Bis (8-hydroxy-quinolino) beryllium), Zn (BOZ) ₂ (Zinc-bis-benzoxazole), Zn (BTZ) ₂ (Zinc-bis-benzothiazole), Eu (DBM) _Three (Phen) (tris (1,3-diphenyl-1,3-propanediono) (monophenanthroline) europium (III)), Butyl-PBD (2-biphenyl-5- (para-ter-butylphenyl) -1, 3,4-oxadiazole) and TAZ (1-phenyl-2-biphenyl-5-para-ter-butylphenyl-1,3,4-triazole) are used. Since the light-emitting organic / inorganic composite material according to Item 2, 4 or 6, the characteristics of the electroluminescent material having high luminance, high efficiency and long life in the light-emitting organic / inorganic composite material according to Claim 2, 4 or 6 Can be further improved.
[0107]
According to the ninth aspect of the present invention, the fluorescent light-emitting compound or molecule is contained as a dopant in at least one of the organic polymer portion and the inorganic polymer portion. The light-emitting organic / inorganic composite material according to claim 1, wherein the light-emitting organic / inorganic composite material has high luminance, high efficiency, and long life. Can be further improved. That is, when emitting light other than the emission wavelength of the charge transfer agent, a fluorescent compound or molecule having a fluorescence wavelength as the emission wavelength can be added as a luminescent molecule as a dopant. Can be provided.
[0108]
According to the invention of claim 10, the light-emitting organic / inorganic composite material according to claim 9, wherein the fluorescent light-emitting compound or molecule is a light-emitting dye. The characteristics of the electroluminescent material having high luminance, high efficiency, and long life in the inorganic composite material can be further improved.
[0109]
According to the invention of claim 11, the light-emitting organic / inorganic composite material according to claim 10, wherein the luminescent dye is at least one of coumarin 540, DCM1, DCM2, rubrene, and quinacridone derivatives. Therefore, the characteristics of the electroluminescent material having high luminance, high efficiency, and long life in the light-emitting organic / inorganic composite material according to claim 10 can be further improved.
[0110]
According to the invention of claim 12, since the organic polymer is a conductive polymer, the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6, Even if the organic part in the light-emitting organic / inorganic composite material according to 1, 2, 3, 4, 5 or 6 is a polymer having a positive charge transport ability such as PVK, aluminoquinolinium (AlQ _Three ), The negative charge transporting agent can be made to be contained at 50 wt% or more with respect to PVK, and if the positive charge transporting agent is contained in PVK, the positive charge is finally reached. Increases transport capacity.
[0111]
According to the invention of claim 13, at least one conductive polymer of polyvinyl carbazole, polyvinyl ferrocene, polyvinyl pyrazoline, polyparaphenylene vinylene, polyparaphenylene, and polythiophene is used as the conductive polymer. Since the light-emitting organic / inorganic composite material according to claim 12 is used, the negative charge transport ability and the positive charge transport ability in the light-emitting organic / inorganic composite material according to claim 12 can be further improved.
[0112]
According to the invention of claim 14, since the organic polymer is an acrylate polymer, the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6, The transparency in the light-emitting organic / inorganic composite material according to Item 1, 2, 3, 4, 5 or 6 is increased, and light transmittance can be improved.
[0113]
According to the invention of claim 15, the acrylate polymer is at least one acrylate polymer of polymethacrylate, polyalkyl methacrylate, polyhydroxy methacrylate, polyhydroxyalkyl methacrylate. Since the light-emitting organic / inorganic composite material according to item 14, the characteristics of the light-emitting organic / inorganic composite material according to claim 14 can be further improved.
[0114]
According to the invention of claim 16, the inorganic polymer is a polymer obtained by subjecting a metal alkoxide as a precursor to hydrolysis / polycondensation reaction. The light-emitting organic / inorganic composite material of claim 1, 2, 3, 4, 5 or 6, wherein the porous organic part having many porous pores is subjected to ultrahigh vacuum under normal pressure. It can be easily manufactured without requiring conditions. As a result, a large-area light-emitting organic / inorganic composite material can be produced.
[0115]
According to the invention of claim 17, the light-emitting organic / inorganic composite material according to claim 16, wherein the metal alkoxide is at least one metal alkoxide of alkoxysilane, alkoxytitanium, and alkoxyzirconia. Therefore, an inorganic part with many porous pores in the light-emitting organic / inorganic composite material according to claim 16 can be more easily produced.
[0116]
According to the invention of claim 18, an organic polymer and an inorganic polymer obtained by mixing and simultaneously polymerizing respective precursors are used as the organic polymer and the inorganic polymer. Since the light-emitting organic / inorganic composite material according to claim 5 or 6 is used, the inorganic part having many porous pores in the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5, or 6 is usually used. It can be manufactured easily without requiring ultrahigh vacuum conditions under pressure, and the interface between the inorganic part and the organic part can be in close contact. As a result, a large-area light-emitting organic / inorganic composite material can be produced. By adding a charge transport agent and a luminescent agent to such an organic / inorganic composite material, an electroluminescent material having high luminance, high efficiency, and long life can be provided.
[0117]
According to the invention of claim 19, the organic polymer and the inorganic polymer are mixed by a method of impregnating the organic polymer into the pores after the inorganic polymer is produced. Since the light-emitting organic / inorganic composite material according to claim 5 or 6, the interface between the inorganic part and the organic part in the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5, or 6 is adhered. It can be in the state. By adding a charge transport agent and a luminescent agent to such an organic / inorganic composite material, an electroluminescent material having high luminance, high efficiency, and long life can be provided.
[0118]
According to the invention of claim 20, the organic polymer and the inorganic polymer are structurally controlled on the order of nanometers. The light-emitting organic / inorganic according to claim 1, 2, 3, 4, 5 or 6 Since it is a composite material, the holes and electrons generated in the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6 are not trapped in the middle, and efficiently enter the organic / inorganic interface. Can reach up to. Since the distance to the interface is a knit structure in which each material portion meanders, the distance to the organic / inorganic interface is at most about 100 nanometers. Therefore, it is not necessary to move the thickness of the material about 1 micron, it can reach the interface between the organic part and the inorganic part, and recombination efficiently only at the interface between the inorganic part and the organic part. Furthermore, the deactivation of excitons in the vicinity of the electrode, which is disadvantageous for excitation of the luminescent molecules by excitons, can be suppressed. Furthermore, since the contact interface between the inorganic part and the organic part is not a conventional planar structure but a curved surface structure, the contact area is widened, and the probability of recombination of positive and negative charges is further improved. The applied electric field should be less than 1 million volts / cm applied to conventional inorganic electroluminescent materials and organic electroluminescent materials, because the recombination and excitation of the luminescent molecules by the exciton energy can be performed efficiently. Can do. Furthermore, since the luminescent molecule is excited away from the electrode, the luminous efficiency from the luminescent molecule is also increased. When the positive charge transport agent and the negative charge transport agent are separately contained in either the inorganic part or the organic part, each charge can move efficiently until recombination at the organic / inorganic interface. it can. In addition, since the thickness is about 1 micron, even if the positive charge transport agent and the negative charge transport agent are simultaneously contained in only one of the inorganic polymer and the organic polymer, the positive and negative charges are separated from each other. The two charges are transported in the opposite direction and are recombined at a distance from the two electrodes to suppress the deactivation of excitons in the vicinity of the electrodes. Excited efficiently and highly efficient electroluminescence is achieved. In addition, any part of the organic part and the inorganic part is in contact with both electrodes while meandering.
[0119]
The light-emitting organic / inorganic composite according to claim 1, wherein one surface is in contact with the transparent electrode and the other surface is provided with a metal electrode. Since it is a material, light emitted from the transparent electrode side can be extracted to the outside. In addition, as shown in FIGS. 1, 2 and 3, both the transparent electrode and the metal electrode are in contact with both the inorganic part and the organic part, and selectively select holes and electrons respectively. And the organic part. In addition, since it is an organic / inorganic composite material, it has good processability and surface polishing. As a result, the surface can clearly distinguish between the inorganic part and the organic part. That is, they are separated in close contact (FIG. 3). Thickness can be controlled and surface smoothness can be obtained. As a result, the electrode material is uniformly adhered, and the efficiency of charge injection is improved. When a positive charge transfer agent is contained in the inorganic part, positive charge is injected into the inorganic part only from the transparent electrode having a large work function. Since the organic portion contains a negative charge transport agent, negative charges are injected into the organic portion only from a metal electrode having a small work function. When the material part containing each charge transport agent is reversed (when the inorganic part contains a negative charge transport agent and the organic part contains a positive charge transport agent), negative charge is injected into the inorganic part only from the metal electrode. Is done. Positive charges are injected into the organic part only from the transparent electrode. In this way, each electrode selectively injects positive or negative charges into the inorganic part or the organic part. That is, only positive charge or negative charge is selectively injected into each material part (organic part and inorganic part) depending on the nature of the charge transport agent contained therein. When either the organic polymer or the inorganic polymer contains both positive and negative charge transfer agents, the positive charge from the transparent electrode and the negative charge from the metal electrode as the counter electrode are the same including both charge transfer agents. It is injected into the material part. However, these charges move oppositely in a material with a thickness of about 1 micron, so both charges recombine inside the material away from the electrode surface, generating excitons, and efficiently excite the luminescent molecules. Make it emit light. Since holes and electrons can be recombined away from the electrode, deactivation of excitons in the vicinity of the electrode is suppressed, and luminous efficiency is increased. By optimizing the ratio of inorganic part to organic part, or the ratio of positive charge transport agent to negative charge transport agent, the balance between injected positive charge and negative charge can be optimized, and exciton production efficiency The excitation probability and luminous efficiency of the luminescent molecule can be increased. However, this ratio generally varies depending on the type of charge transfer agent.
[0120]
According to the invention of claim 22, the transparent electrode is composed of indium tin oxide (ITO), tin oxide (SnO) having a large work function. ₂ ), Indium oxide (InO) _x The light-emitting organic / inorganic composite material according to claim 21, wherein the light-emitting organic / inorganic composite material is selectively formed between holes and electrons. Injection is further improved.
[0121]
According to the invention of claim 23, the metal electrode is formed of at least one of aluminum, aluminum lithium alloy, aluminum magnesium alloy, magnesium, magnesium silver alloy and magnesium indium alloy having a small work function. Since the light-emitting organic / inorganic composite material according to claim 21 is characterized, selective injection of holes and electrons in the light-emitting organic / inorganic composite material according to claim 21 is further improved.
[0122]
According to the invention of claim 24, since both the transparent electrode and the metal electrode are formed by direct vapor deposition, the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6, The contact between the organic / inorganic composite material and the transparent electrode and the metal electrode in the light emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6, Charge injection efficiency can be increased.
[0123]
According to invention of Claim 25, after producing an organic-inorganic composite material on the glass substrate which gave the transparent electrode, the metal electrode is directly given by vapor deposition, 1, 2, 3, 4, 5 or 6. The light-emitting organic / inorganic composite material according to claim 6, so that both the organic / inorganic composite material, the transparent electrode and the metal electrode in the light-emitting organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6 are used. Contact with the electrode can be made denser and charge injection efficiency can be increased.
[0124]
According to the invention of claim 26, the transparent electrode is an anode electrode (cathode), the metal electrode is a cathode electrode (anode), and light is emitted by applying an electric field. The hole is more efficiently injected into the material than the transparent electrode having a large work function, and the electrons are more efficiently injected into the material than the metal electrode having a low work function. Charge injection efficiency in the light-emitting organic / inorganic composite material according to 24 or 25 can be further improved.
[0125]
According to the invention of claim 27, the transparent electrode is an anode electrode (cathode), the metal electrode is a cathode electrode (anode), the lead wire is attached to each, and then the transparent electrode side is covered with transparent glass or plastic, 27. The light-emitting organic organic material according to claim 21, 24, 25, or 26, wherein after the metal electrode side is covered with an insulator, the material end face is sealed with a sealing resin, and an electric field is applied to emit light. Since it is an inorganic composite material, avoid contact with factors that deteriorate the electroluminescent material such as oxygen and moisture in the use environment in the light-emitting organic / inorganic composite material according to claim 21, 24, 25 or 26. And a longer driving life can be achieved.
[0126]
According to the invention of claim 28, the light-emitting organic / inorganic composite material according to claim 27, wherein the insulator covering the metal electrode is a plastic insulator and the sealing resin is an epoxy resin. In the light-emitting organic / inorganic composite material according to claim 27, contact with factors causing deterioration of electroluminescent materials such as oxygen and moisture in the use environment can be avoided, and the driving life can be further extended. be able to.
[0127]
The light-emitting organic / inorganic composite according to claim 1, 2, 3, 4, 5 or 6, wherein an organic polymer and an inorganic polymer precursor are mixed and polymerized at the same time. Since this is a method for producing a material, the light-emitting organic / inorganic composite material according to claim 1, wherein the interface between the inorganic part and the organic part is in close contact with each other under normal pressure. It can be manufactured without the need for high vacuum conditions. Therefore, a large-area light-emitting organic / inorganic composite material can be produced.
[0128]
According to the invention of claim 30, the organic polymer and the inorganic polymer are mixed by a method of impregnating the organic polymer into the pores after the inorganic polymer is produced. Since it is a manufacturing method of the luminescent organic / inorganic composite material according to 5 or 6, the inorganic part and the organic part in the luminescent organic / inorganic composite material according to claim 1, 2, 3, 4, 5 or 6 are used. A product in which the interface is in close contact can be produced under normal pressure without requiring ultrahigh vacuum conditions. Such an organic / inorganic composite material can be provided with an electroluminescent material having high luminance, high efficiency, and long life by adding a charge transport agent and a luminescent agent. Further, the organic / inorganic composite material of the present invention can produce a light-emitting organic / inorganic composite material having a large area.
[0129]
As described above, since the light-emitting organic / inorganic composite material of the present invention has a thickness of about 1 micron, it is about 10 times thicker than the conventional organic EL material, and no pinholes are generated. There is no continuity, the in-plane uniformity of light emission luminance is improved, and the life as an electroluminescent element is extended. Also, by applying an electric field, both positive and negative charges are efficiently injected, and they also recombine efficiently to form excitons, which excite luminescent molecules with their energy, and electroluminescence occurs efficiently. In addition, since the organic polymer portion is included, the composite material is excellent in processability, and since the inorganic polymer portion is included, not only the rigidity of the material but also the optical characteristics of the material are excellent. In addition, since the inorganic polymer portion dissipates heat generated during light emission, the driving operation life of the material is extended. It also shows the possibility of laser oscillation.
[Brief description of the drawings]
FIG. 1 is a schematic view of a light-emitting organic / inorganic composite material of the present invention.
FIG. 2 is a schematic view showing the internal structure and charge transfer of the light-emitting organic / inorganic composite material of the present invention.
FIG. 3 is a schematic view of a surface state after polishing of the light-emitting organic / inorganic composite material of the present invention.
4 is a characteristic diagram showing the relationship between applied voltage and light emission luminance in Example 1. FIG.
FIG. 5 is a schematic diagram showing the basic principle of the light emission mechanism of an organic electroluminescent material.
FIG. 6 is a schematic view of a conventional organic electroluminescent material.
[Explanation of symbols]
1 Organic polymer, 2 Inorganic polymer, 3 Transparent electrode, 4 Metal electrode, 5 Light emitting organic / inorganic composite material, 6 Transparent electrode transparent cover, 7 Metal electrode cover, 8 Sealing resin, 9 Lead wire, 10 Organic electric field Luminescent material, 11 positive charge transport layer, 12 negative charge transport layer, a luminescence from luminescent molecule, b exciton.

Claims (30)

It consists of both organic polymer and inorganic polymer, and the porous polymer has an organic polymer in its pores. The organic polymer has positive charge transport ability, and the inorganic polymer has negative charge transport ability. A light-emitting organic / inorganic composite material characterized by having a thickness of 0.5 to 1.5 microns. It consists of both organic polymer and inorganic polymer, and the organic polymer is contained in the pores of the porous inorganic polymer. The organic polymer has a positive charge transport agent and the inorganic polymer has a negative charge transport agent. A light-emitting organic / inorganic composite material characterized by having a thickness of 0.5 to 1.5 microns. Consists of both organic polymer and inorganic polymer. Porous inorganic polymer contains organic polymer in the pores. Organic polymer has negative charge transport ability and inorganic polymer has positive charge transport ability. A light-emitting organic / inorganic composite material characterized by having a thickness of 0.5 to 1.5 microns. It consists of both organic polymer and inorganic polymer, and the organic polymer is contained in the pores of the porous inorganic polymer. The organic polymer has a negative charge transport agent and the inorganic polymer has a positive charge transport agent. A light-emitting organic / inorganic composite material characterized by having a thickness of 0.5 to 1.5 microns. It consists of both organic polymer and inorganic polymer, and the porous polymer has pores with an organic polymer. At least one of the organic polymer and inorganic polymer has both positive charge transport ability and negative charge transport ability. A light-emitting organic / inorganic composite material characterized by having a thickness of 0.5 to 1.5 microns. It consists of both organic polymer and inorganic polymer, and the pores of the porous inorganic polymer contain the organic polymer, and at least one of the organic polymer and the inorganic polymer is both a positive charge transport agent and a negative charge transport agent. A light-emitting organic / inorganic composite material characterized by having a thickness of 0.5 to 1.5 microns. TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine), α-NPD (N , N′-Diphenyl-N, N′-bis (α-naphthyl)-[1,1′-biphenyl] -4,4′-diamine: 4,4′-bis [N- (1-naphthyl) -N -Phenyl-amino] biphenyl), Cz-TPD (4,4'-bis (9-carbazolyl) -1,1'-biphenyl), PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride), CuPc (copper phthalocyanine), ZnTPP (zinc (II) 5,10,15,20-tetraphenylporphyrin), PO-TPD (4,4'-bis (10-phenoxazinyl) biphenyl), PT-TPD (4 4′-bis (10-phenothiazinyl) biphenyl), DPBI (4,4 ′-(2,2-diphenylvinylene) -1,1′-biphenyl), DTVBI (4,4 ′-(2,2-di) -Paramethylphenylvinylene) -1,1'-biphenyl), m-MTDATA (4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine), HDRZ (4-biphenylaminophenyl-biphenyl) 7. The light-emitting organic / inorganic composite material according to claim 2, 4 or 6, wherein at least one of a hydrazone and a Ru (II) complex (ruthenium (II) complex) is used. As negative charge transport agents, AlQ ₃ (tris (8-hydroxy-quinolino) aluminum), BeQ ₂ (bis (8-hydroxy-quinolino) beryllium), Zn (BOZ) ₂ (zinc-bis-benzoxazole), Zn (BTZ) ₂ (zinc-bis-benzothiazole), Eu (DBM) ₃ (Phen) (tris (1,3-diphenyl-1,3-propanediono) (monophenanthroline) europium (III)), Butyl-PBD (2-biphenyl-5- (para-tert-butylphenyl) -1,3,4-oxadiazole), TAZ (1-phenyl-2-biphenyl-5-para-tert-butylphenyl-1,3, The light-emitting organic / inorganic composite material according to claim 2, 4 or 6, wherein at least one of 4-triazole) is used. 7. The light-emitting organic / inorganic composite material according to claim 1, wherein the light-emitting organic / inorganic composite material contains a fluorescent compound or molecule as a dopant in at least one of the organic polymer part and the inorganic polymer part. . The luminescent organic / inorganic composite material according to claim 9, wherein the fluorescent luminescent compound or molecule is a luminescent dye. The luminescent organic / inorganic composite material according to claim 10, wherein the luminescent dye is at least one of coumarin 540, DCM1, DCM2, rubrene, and quinacridone derivatives. 7. The light-emitting organic / inorganic composite material according to claim 1, wherein the organic polymer is a conductive polymer. 13. The light-emitting organic organic compound according to claim 12, wherein at least one conductive polymer selected from the group consisting of polyvinyl carbazole, polyvinyl ferrocene, polyvinyl pyrazoline, polyparaphenylene vinylene, polyparaphenylene, and polythiophene is used as the conductive polymer. Inorganic composite material. 7. The light-emitting organic / inorganic composite material according to claim 1, wherein the organic polymer is an acrylate polymer. The light-emitting organic / inorganic according to claim 14, wherein the acrylate polymer is at least one acrylate polymer selected from the group consisting of polymethacrylate, polyalkyl methacrylate, polyhydroxy methacrylate, and polyhydroxyalkyl methacrylate. Composite material. 7. The light-emitting organic / inorganic composite material according to claim 1, wherein the inorganic polymer is a polymer obtained by hydrolysis and polycondensation reaction using a metal alkoxide as a precursor. The light-emitting organic / inorganic composite material according to claim 16, wherein the metal alkoxide is at least one metal alkoxide of alkoxysilane, alkoxytitanium, and alkoxyzirconia. 7. The light emitting organic material according to claim 1, wherein an organic polymer and an inorganic polymer obtained by mixing and simultaneously polymerizing respective precursors are used as the organic polymer and the inorganic polymer.・ Inorganic composite materials. 7. The light emitting organic material according to claim 1, wherein the organic polymer and the inorganic polymer are mixed by a method of impregnating the organic polymer into the pores after the inorganic polymer is produced.・ Inorganic composite materials. 7. The light-emitting organic / inorganic composite material according to claim 1, wherein the structure of the organic polymer and the inorganic polymer is controlled on the order of nanometers. 7. The light-emitting organic / inorganic composite material according to claim 1, wherein one surface is in contact with the transparent electrode and the other surface is provided with a metal electrode. The light-emitting organic / inorganic material according to claim 21, wherein the transparent electrode is made of indium tin oxide (ITO), tin oxide (SnO ₂ ), or indium oxide (InO _x ) having a high work function. Composite material. The light emission according to claim 21, wherein the metal electrode is formed of at least one of aluminum, aluminum lithium alloy, aluminum magnesium alloy, magnesium, magnesium silver alloy, and magnesium indium alloy having a small work function. Type organic / inorganic composite material. 7. The light-emitting organic / inorganic composite material according to claim 1, wherein both the transparent electrode and the metal electrode are formed by direct vapor deposition. 7. The light-emitting organic / inorganic composite according to claim 1, wherein the organic / inorganic composite material is produced on a glass substrate provided with a transparent electrode, and then the metal electrode is applied directly by vapor deposition. material. 26. The light-emitting organic / inorganic composite material according to claim 21, 24 or 25, wherein the transparent electrode is an anode electrode (cathode), the metal electrode is a cathode electrode (anode), and light is emitted by applying an electric field. The transparent electrode was the anode electrode (cathode), the metal electrode was the cathode electrode (anode), the lead wire was attached to each, the transparent electrode side was covered with transparent glass or plastic, and the metal electrode side was covered with an insulator 27. The light-emitting organic / inorganic composite material according to claim 21, 24, 25, or 26, wherein the material end face is sealed with a sealing resin and light is emitted by applying an electric field. 28. The light-emitting organic / inorganic composite material according to claim 27, wherein the insulator covering the metal electrode is a plastic insulator and the sealing resin is an epoxy resin. 7. The method for producing a light-emitting organic / inorganic composite material according to claim 1, wherein an organic polymer and an inorganic polymer precursor are mixed and polymerized simultaneously. 7. The light emitting organic material according to claim 1, wherein the organic polymer and the inorganic polymer are mixed by a method of impregnating the organic polymer into the pores after the inorganic polymer is produced.・ Method of manufacturing inorganic composite materials.

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