JP3703380B2 - ORGANIC ELECTRONIC DEVICE, ITS MANUFACTURING METHOD, ITS OPERATION METHOD, DISPLAY DEVICE USING THE SAME, AND ITS MANUFACTURING METHOD - Google Patents

Description

脱水したジメチルシリコーン系の有機溶媒で１％に薄めて化学吸着液を調製した。
【０１６２】
次に、単分子膜を形成する部分を残してフォトレジストでマスクパターン形成した絶縁性の基板２１（ガラス基板）を前記化学吸着液に浸漬して化学吸着を行い、前記マスクパターン開口部に選択的に化学吸着を行い、さらに表面に残った未反応の前記物質をクロロフォルムで洗浄除去し、続いて前記フォトレジストのマスクパターンを除去して、前記物質よりなる単分子膜２４を選択的に形成した。化学吸着を行う際、マスクパターン開口部のガラス基板１１表面には活性水素を含む水酸基が多数存在するので、前記物質のクロロシリル基（−ＳｉＣｌ）は水酸基と脱塩酸反応し、基板２１表面に共有結合した化学式（２）で構成される単分子膜２４が形成されている。（図５（ａ））
【化２】

【０１６３】
その後、トルエン溶媒中でチグラーナッタ触媒を用いて前記単分子膜内の前記アセチレン基を重合してポリアセチレン型の導電ネットワーク２５を形成した。（図５（ｂ））
【０１６４】
次に、全面にニッケル薄膜を蒸着形成し、ホトリソグラフィ法を用いてギャップ間距離が１０μｍで長さが３０μｍの第１の電極２２及び第２の電極２３をエッチングして形成した。
【０１６５】
これらにより、基板２１上に形成された、第１の電極２２と、第２の電極２３と、第１の電極２２と第２の電極２３を電気的に接続する単分子膜とを備えた２端子有機電子デバイスであって、単分子膜２４はアゾ基を有する有機分子群からなり、前記有機分子群を構成する分子相互がポリアセチレン型に共役結合した導電ネットワーク２５を有する２端子有機電子デバイスを製造した。（図５（ｃ））
【０１６６】
このデバイスでは、第１の電極２２と第２の電極２３との電極間はポリアセチレン型の導電ネットワーク２５で接続されているので、前記第１の電極２２と第２の電極２３との間に数ボルトの電圧を印加すると数ナノアンペアの電流（１Ｖで２ｎＡ程度）が流れた。ただし、測定前に単分子膜２４には可視光線を照射している。
【０１６７】
次に、引き続き単分子膜２４に紫外線を照射すると、アゾ基がトランス型からシス型に転移して、電流値がほぼ０Ａとなった。また、その後、可視光線を照射すると、アゾ基がシス型からトランス型に転移して元の導電性が再現された。
【０１６８】
なお、このような紫外線の照射による導電性の低下は、アゾ基の光異性化（トランス型からシス型への転移）により、単分子膜２４内のポリアセチレン型の共役結合が歪み導電ネットワーク２５の導電率が低下することにより生じるものと考えられる。
【０１６９】
すなわち、光照射により、導電ネットワーク２５の導電率を制御して第１の電極２２と第２の電極２３との電極間に流れる電流をスイッチングできた。
【０１７０】
なお、ポリアセチレン型の共役系を導電ネットワーク２５として用いる場合、重合度が低いと抵抗が高くなる。すなわち、オン電流が低くなるが、その場合には、電荷移動性の官能基を有するドーパント物質（例えば、アクセプタ分子としてハロゲンガスやルイス酸、ドナー分子としてアルカリ金属やアンモニウム塩）を導電ネットワーク２５に拡散する、すなわちドーピングすることで、オン電流を大きくできた。例えば、この単分子膜２４に沃素をドープした場合、第１の電極２２と第２の電極２３との間に１Ｖの電圧を印加すると０．２ｍＡの電流が流れた。
【０１７１】
ここで、基板として金属等の導電性の基板を用いる場合には、導電性の基板表面に絶縁性の薄膜を介して単分子膜を形成しておけばよい。なお、このような構造では、基板自体が帯電することがないので、有機電子デバイスの動作安定性が向上した。
【０１７２】
なお、より大きなオン電流を必要とする場合には、第１の電極２２と第２の電極２３との電極間距離を小さくするか、電極幅を広げればよい。さらに大きなオン電流を必要とする場合には、単分子膜を累積する、または第１の電極２２と第２の電極２３との間に導電ネットワークを有する被膜を形成しておけばよい。
【０１７３】
上記実施例１では、導電ネットワークの形成に触媒重合法を用いたが、電解重合法、または光や電子線やＸ線等のエネルギービーム照射による重合法を用いて、同様に導電ネットワークを形成できた。
【０１７４】
また、導電ネットワークとしてポリアセチレン型の共役系以外に、ポリジアセチレン型、ポリアセン型、ポリピロール型、ポリチェニレン型等の共役系が利用できた。なお、触媒重合を行う際には、重合性基として前記アセチレン基以外にピロール基、チェニレン基、ジアセチレン基等が適していた。
【０１７５】
さらに、単分子膜または単分子累積膜の作製には、化学吸着法以外に、ラングミュアーブロジェット法が適用できた。
【０１７６】
また、前記有機薄膜を構成する分子相互を重合する前記導電ネットワーク形成工程の前に、前記第１と第２の電極を形成する前記対電極形成工程を行うと、導電ネットワークの作製に際して、前記第１と第２電極を電解重合に利用できた。すなわち、電解重合性の官能基としてピロール基またはチェニレン基を有する有機分子群から成る前記有機薄膜の前記第１と第２の電極間に電圧を印加して、第１と第２の電極間の有機薄膜を選択的に電解重合できた。
【０１７７】
基板上にピロール基またはチェニレン基を有する有機分子群から成る単分子膜と第１の電極と、第２の電極とを形成した後に、ピロール基またはチェニレン基を含む物質を溶かした有機溶媒中に浸漬し、且つ前記第１の電極と第２の電極との間に第１の電圧を印加し、さらに前記第１または第２の電極と前記有機溶媒に接触し前記単分子膜の上方に配置された外部電極との電極間に第２の電圧を印加して、前記単分子膜の表面にさらに被膜を形成すると同時に前記単分子膜と前記被膜にそれぞれ導電ネットワークを形成できた。この場合、有機電子デバイスは、それぞれに導電ネットワークを有する単分子膜部とポリマー膜状の被膜部とからなる有機薄膜を備えている。
【０１７８】
また、基板上に、ピロール基またはチェニレン基を有する有機分子群から成る単分子膜と第１の電極と第２の電極とを形成し、単分子膜に第１の構造の導電ネットワークを形成した後に、ピロール基またはチェニレン基を含む物質を溶かした有機溶媒中に浸漬し、第１と第２の電極間に第１の電圧を印加し、且つ前記第１または第２の電極と前記有機溶媒に接触し前記有機薄膜の上方に配置された外部電極との電極間に第２の電圧を印加して、ポリピロール型またはポリチェニレン型の導電ネットワークが形成された単分子膜の表面にさらに被膜を形成すると同時に前記被膜にもポリピロール型またはポリチェニレン型の第２の構造の導電ネットワークを形成できた。この場合、有機電子デバイスは、それぞれに導電ネットワークを有する単分子膜部とポリマー膜状の被膜部とからなる有機薄膜を備えている。
【０１７９】
また、重合性基としてエネルギービームにより重合する官能基であるアセチレン基やジアセチレン基等を有する有機分子群から成る単分子膜または単分子累積膜に、紫外線、遠紫外線、電子線またはＸ線等のエネルギービームを照射して、単分子膜または単分子累積膜の分子相互を重合させ、導電ネットワークを形成できた。
【０１８０】
なお、単分子膜の材料として使用できる物質は、一般に化学式（３）で示される物質であり、本実施例１と同様にして使用できる。
【化３】

ここで、Ａは共役結合で結合して導電ネットワークを形成する官能基、Ｂは光応答性の官能基、Ｄはハロゲン原子、イソシアネート基、またはアルコキシル基等の基板表面の活性水素と反応する原子または官能基、Ｅは水素、メチル基、エチル基、メトキシ基、エトキシ基、または他のアルキル基、等の官能基である。また、ｍ、ｎは整数であり、ｍ＋ｎは２以上２５以下、特に好ましくは１０以上２０以下である。さらに、ｐは整数であり、１、２、または３である。
【０１８１】
さらに詳しくは、化学式（４）から（７）で表される物質等が使用できた。
【化４】

【化５】

【化６】

【化７】

ここで、ｍ，ｎは整数であり、ｍ＋ｎは２以上２５以下である。
【０１８２】
（実施例２）
まず、電解重合により導電ネットワークを形成するピロール基（Ｃ₄Ｈ₄Ｎ−）と、分極性の官能基であるオキシカルボニル基（−ＯＣＯ−）と、基板表面の活性水素（例えば水酸基（−ＯＨ））と反応するクロロシリル基（−ＳｉＣｌ）とを有する化学式（８）の物質を用い、
【化８】

脱水したジメチルシリコーン系の有機溶媒で１％に薄めて化学吸着液を調製した。
【０１８３】
次に、絶縁性のポリイミド基板３１（あるいは導電性のメタル基板表面に第１の絶縁膜、例えばシリカ膜３８を介してでも良い）表面にアルミニウム（Ａｌ）を蒸着し、フォトリソグラフィ法を適用し長さが１５μｍで幅が４０μｍの第３の電極２３をエッチング形成した。さらに前記Ａｌ製の第３の電極３７を電解酸化して表面に絶縁性のアルミナ（Ａｌ₂Ｏ₃）膜３９を形成した。（図６（ａ））
【０１８４】
次に、単分子膜を形成する部分を残してレジストでマスクパターンを形成した後、前記吸着液に浸漬して化学吸着を行い、前記マスクパターン開口部に選択手的に化学吸着を行い、さらに表面に残った未反応の前記物質をクロロホルムで洗浄除去し、続いて前記レジストのマスクパターンを除去して、前記物質よりなる単分子膜３４を選択的に形成した。（図６（ｂ））
【０１８５】
このとき、開口部の基板３１表面（シリカ膜３８およびＡｌ₂Ｏ₃膜３９表面）には活性水素を含む水酸基が多数存在するので、前記物質のクロロシリル基（−ＳｉＣｌ）が水酸基と脱塩酸反応を生じて基板３１表面に共有結合した化学式（９）で示される分子で構成された単分子膜３４が形成された。
【化９】

【０１８６】
次に、全面にニッケル薄膜を蒸着形成した後、ホトリソグラフィ法を適用しギャップ間距離が１０μｍ長さが３０μｍの第１の電極２２及び第２電極２３を第３の電極３７を挟むようにエッチングして形成した。（図２（ｃ））
次に、アセトニトリル溶液中に浸漬し、第１及び第２電極間に５Ｖ／ｃｍ程度の電界を印加し、電解重合により導電ネットワーク３５を第１の電極２２及び第２の電極２３の電極間を接続するように形成した。このとき、電界の方向に沿って共役結合が自己組織的に形成されて行くので、完全に重合が終われば、第１の電極２２と第２の電極２３とは導電ネットワーク３５で電気的に接続されていることになる。（図６（ｃ））
最後に、第３の電極３７を基板３１側から取り出して、３端子有機電子デバイスを製造できた。
【０１８７】
この３端子有機電子デバイスでは、第１の電極２２と第２の電極２３との間は、ポリピロール型の導電ネットワーク３５で接続されているので、ＢＦ−イオンをドープした後、第１の電極２２と第２の電極２３との間に１Ｖの電圧を印加し、且つ第１の電極２２と第３の電極２７との間の電圧を０Ｖにすると、０．５ｍＡ程度の電流が流れた。
【０１８８】
次に、第１の電極２２と第２の電極２３との間に１Ｖの電圧を印加した状態で、第１の電極２２と第３の電極３７との間に５Ｖの電圧を印加すると、第１の電極２２と第２の電極２３との電極間の電流値がほぼ０Ａとなった。その後、第１の電極２２と第３の電極２７との間の電圧を５Ｖから０Ｖにもどすと元の導電性が再現された。
【０１８９】
このような導電性の低下は、第３の電極３７と第１の電極２２との電極間に５Ｖの電圧を印加した際、有極性の官能基であるオキシカルボニル基（−ＯＣＯ−）の分極が大きくなることにより、ポリピロール型の共役系が歪み導電ネットワーク３５の導電率が低下することにより生じた考えられる。
【０１９０】
すなわち、第１の電極２２と第３の電極３７との間に印加された電圧で、前記導電ネットワークの導電率を制御して第１の電極２２と第２の電極２３との間に流れる電流をスイッチングできた。
ここで、有極性の官能基が分極性のオキシカルボニル基であると、スイッチングを極めて高速で行えた。オキシカルボニル基以外に、カルボニル基等の官能基を有する分子を使用できた。
【０１９１】
また、導電ネットワークとしてポリアセチレン型、ポリジアセチレン型、ポリアセン型、ポリピロール型、ポリチェニレン型の共役系が使用でき、導電率が高かった。
また、導電ネットワークを形成する共役結合で結合する重合性基として、電解重合性の官能基であるピロール基以外に、チェニレン基が利用できた。なお、重合方法を変えれば、アセチレン基、ジアセチレン基を有する物質も利用できた。
【０１９２】
単分子膜または単分子累積膜の作製には、化学吸着法以外に、ラングミュアーブロジェット法を使用できた。
【０１９３】
また、有機薄膜を重合する工程の前に、第１の電極２２と第２の電極２３を形成する工程を行うと、導電ネットワークの作製に際して、第１の電極２２と第２の電極２３を電解重合に利用できた。すなわち、電解重合性の官能基としてピロール基またはチェニレン基を有する有機分子群から成る有機薄膜の第１の電極２２と第２の電極２３との電極間に電圧を印加し第１の電極２２と第２の電極２３との電極間の有機薄膜を選択的に電解重合できた。
【０１９４】
基板上に第３の電極３７とピロール基またはチェニレン基を有する有機分子群から成る単分子膜３４と、第１の電極と、第２の電極とを形成した後に、ピロール基またはチェニレン基を含む物質を溶かした有機溶媒中に浸漬して、第１の電極２２と第２の電極２３との間に第１の電圧を印加し、且つ第１の電極２２または第２の電極２３と前記有機溶媒に接触し単分子膜３４の上方に配置された外部電極との電極間に第２の電圧を印加して、単分子膜３４の表面に被膜を形成すると同時に単分子膜と被膜のそれぞれにポリピロール型またはポリチェニレン型の導電ネットワークを形成できた。この場合、有機電子デバイスは、それぞれに導電ネットワークを有する単分子膜部とポリマー膜状の被膜部とからなる有機薄膜を備えている。
【０１９５】
また、基板上に第３の電極とピロール基またはチェニレン基を有する有機分子群から成る単分子膜と第１の電極と第２の電極とを形成し、単分子膜にポリピロールまたはポリチェニレン型の第１の構造の導電ネットワークを形成した後に、ピロール基またはチェニレン基を含む物質を溶かした有機溶媒中に浸漬して、第１の電極と第２の電極との間に第１の電圧を印加し、且つ前記第１または第２の電極と前記有機溶媒に接触し前記有機薄膜の上方に配置された外部電極との間に第２の電圧を印加して、導電ネットワークが形成された単分子膜の表面にさらに被膜を形成すると同時に被膜にポリピロール型またはポリチェニレン型の第２の構造の導電ネットワークを形成できた。この場合、有機電子デバイスは、それぞれに導電ネットワークを有する単分子膜部とポリマー膜状の被膜部とから成る有機薄膜を備えている。
【０１９６】
導電ネットワークの形成において電解重合以外では、重合性基として触媒重合性の官能基であるピロール基、チェニレン基、アセチレン基、またはジアセチレン基等を有する単分子膜または単分子累積膜の分子相互を触媒重合して、導電ネットワークを形成できた。
さらにまた、重合性基としてアセチレン基、ジアセチレン基等のビーム照射重合性基を有する有機分子群から成る単分子膜または単分子累積膜に、紫外線、遠紫外線、電子線またはＸ線等のエネルギービームを照射して、有機分子相互を重合し導電ネットワークを形成できた。
【０１９７】
（実施例３）
上記実施例２と同様の方法で、複数の有機電子デバイスを液晶の動作スイッチとしてアクリル基板表面に配列配置してＴＦＴアレイ基板を作製し、さらにその表面に配向膜を作製した。
次に、スクリーン印刷法を用いてシール接着剤を封口部を除いてパターン形成した後、プレキュアーしてカラーフィルター基板の配向膜面を向かい合わせにし、貼り合わせて圧着し前記パターン形成された接着剤を硬化させ、液晶セルを作製した。
最後に、所定の液晶を真空注入して封止すると、液晶表示装置を製造できた。
【０１９８】
この方法では、ＴＦＴアレイの製造において、基板加熱の必要がないので、アクリル基板のようなガラス転移（Ｔｇ）点が低い基板を用いても十分高画質なＴＦＴ型液晶表示装置を製造できた。
【０１９９】
（実施例４）
上記実施例２と同様の方法で、複数の３端子有機電子デバイスを液晶の動作スイッチとしてアクリル基板表面に配列配置してＴＦＴアレイ基板を作製した。その後、公知の方法を用いて前記３端子有機電子デバイスのに接続される画素電極を形成し、ＴＦＴアレイ基板上に電界が印加されると発光する蛍光物質から成る発光層を形成し、ＴＦＴアレイ基板に対向する透明共通電極を発光層上に形成して、エレクトロルミネッセンス型カラー表示装置を製造できた。
【０２００】
発光層を形成する際、赤、青、緑色の光を発光する３種類の素子をそれぞれ所定の位置に形成することにより、エレクトロルミネッセンス型カラー表示装置が製造できた。
【０２０１】
【発明の効果】
以上で説明したように、本発明では第１に、基板上に形成された、第１の電極と、前記第１の電極と離隔した第２の電極と、前記第１と第２の電極を電気的に接続する有機薄膜と、を備えた２端子有機電子デバイスであって、前記有機薄膜は、光応答性の官能基を有する有機分子群からなり、前記有機分子群を構成する分子相互が共役結合した導電ネットワークを有する２端子有機電子デバイスを提供できる効果がある。
【０２０２】
第２に、基板上に形成された、第１の電極と、前記第１の電極と離隔した第２の電極と、前記第１と第２の電極を電気的に接続する有機薄膜と、前記基板と前記有機薄膜の間に挟まれ、それぞれと絶縁された第３の電極とを備えた３端子有機電子デバイスであって、前記第３の電極は前記第１の電極または前記第２の電極と前記第３の電極間の電圧印加により前記有機薄膜に作用させる電界を制御できる電極であり、前記有機薄膜は有極性の官能基を有する有機分子群からなり、前記有機分子群を構成する分子相互が共役結合した導電ネットワークを有する３端子有機電子デバイスを提供できる効果がある。
【０２０３】
第３に、有極性の官能基を有する材料物質を使用する３端子有機電子デバイスにより、従来例に比べ極めて高速なスイッチングを行う有機系ＴＦＴを提供できる効果がある。したがって、３端子有機電子デバイスを表示素子の動作スイッチとして用いた液晶表示装置やエレクトロルミネッセンス型表示装置等を提供できる効果がある。
【０２０４】
第４に、本発明の３端子有機電子デバイス動作スイッチを基板表面に配列配置してアレイ基板を形成する際、高温で処理する工程が含まれない為、フレキシビリティーに優れたプラスチック基板等を使用した表示装置を提供できる効果がある。
【０２０５】
【図面の簡単な説明】
【図１】２端子有機電子デバイスの構造を分子レベルまで拡大した断面概念図であり、
（ａ）は第１と第２の電極が基板に直接形成された構造の断面概念図、
（ｂ）は第１と第２の電極が有機薄膜上に形成された構造の断面概念図である。
【図２】光照射に対する２端子有機電子デバイスの導電性の変化を説明する概念図であり、
（ａ）は光照射に対する有機薄膜の導電性の変化を説明する概念図、
（ｂ）は光異性化に伴うスイッチング動作を説明する概念図である。
【図３】３端子有機電子デバイスの構造を分子レベルまで拡大した断面概念図であり、
（ａ）は第１と第２の電極が基板に直接形成された構造の断面概念図、
（ｂ）は第１と第２の電極が有機薄膜上に形成された構造の断面概念図である。
【図４】印加電界に対する３端子有機電子デバイスの導電性の変化を説明する概念図であり、
（ａ）は導電ネットワークの導電率と第３の電極に印加された電圧との依存性を説明する概念図、
（ｂ）は第３の電極への電圧印加の有無によるスイッチング動作を説明する概念図である。
【図５】実施例１における２端子有機電子デバイスの製造プロセスを説明するための工程断面概念図であり、
（ａ）は単分子膜を形成した状態を分子レベルまで拡大した断面概念図、
（ｂ）は重合により導電ネットワークを形成した状態を分子レベルまで拡大した断面概念図である。
【図６】実施例３における３端子有機電子デバイスの製造プロセスを説明するための工程断面概念図であり、
（ａ）は第３の電極を形成した状態を拡大した断面概念図、
（ｂ）は単分子膜を形成した状態を分子レベルまで拡大した断面概念図、
（ｃ）は重合により導電ネットワークを形成した状態を分子レベルまで拡大した断面概念図である。
【符号の説明】
１ 基板
２ 第１の電極
３ 第２の電極
４ 光応答性の官能基を有する単分子膜
５ 導電ネットワーク
６ 集光された照射光
１１ 基板
１２ 第１の電極
１３ 第２の電極
１４ 有極性の官能基を有する単分子膜
１５ 導電ネットワーク
１７ 第３の電極
１８ 第１の絶縁膜
１９ 第２の絶縁膜
２１ ガラス基板
２２ ニッケル製の第１の電極
２３ ニッケル製の第２の電極
２４ アセチレン基とアゾ基を含む分子から成る化学吸着単分子膜
２５ ポリアセチレン型の導電ネットワーク
３１ ポリイミド基板
３４ ピロール基とオキシカルボニル基を含む分子から成る単分子膜
３５ ポリピロール型の導電ネットワーク
３７ アルミ製の第３の電極
３８ シリカ膜
３９ アルミナ膜[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a two-terminal and three-terminal electronic device (hereinafter referred to as an organic electronic device) using an organic material for a channel portion, a manufacturing method thereof, and an operating method thereof. More specifically, the present invention relates to an organic electronic device using a conductivity change of a monomolecular film, a monomolecular cumulative film, or a thin film having conductivity, a manufacturing method thereof, and an operation method thereof. Moreover, it is related with the display apparatus using the same, and its manufacturing method.
[0002]
[Prior art]
Conventionally, inorganic semiconductor materials have been used for electronic devices, as represented by silicon crystals.
Organic electronic devices (hereinafter referred to as organic electronic devices) are disclosed in, for example, Japanese Patent Nos. 2034197 and 2507153. The organic electronic devices described in these publications are organic electronic devices that switch a current flowing between terminals in response to an applied electric field.
[0003]
[Problems to be solved by the invention]
Inorganic crystals that have been used in the past have a problem of crystal defects as the miniaturization progresses, and there is a drawback that device performance is greatly influenced by crystals. In addition, there is a drawback of poor flexibility.
In addition, even though the organic electronic device of the conventional example achieves the intended purpose of providing a current switching element, application to an electronic device that requires a high-speed response has not been realized.
[0004]
The present invention has been made in view of the above, and an object thereof is to produce a device using an organic material that does not depend on crystallinity even if the device becomes more dense and fine processing of 0.1 μm or less is performed. It is to provide a highly integrated device. Another object of the present invention is to provide an organic electronic device having excellent flexibility by being formed on a plastic substrate or the like.
[0005]
Another object of the present invention is to provide a device having a high-speed response that can be applied to an electronic device that requires a high-speed response, such as a display device.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problem, the invention according to claim 1 includes a first electrode formed on a substrate, a second electrode spaced apart from the first electrode, the first and first electrodes. An organic thin film for electrically connecting two electrodes, wherein the organic thin film includes an organic molecule including a plurality of organic molecules having one molecular terminal bonded and fixed to the substrate. A group of the organic molecules in the molecule Conjugation bond by polymerization A polymerizable group that forms a conductive network and a photoresponsive functional group that changes its spatial arrangement upon irradiation with light, and between the organic molecules constituting the organic molecule group, The conductive network is formed by conjugated bonding to each other by polymerization of the polymerizable group, and the photoresponsive functional group is irradiated with light to change its spatial arrangement, whereby the conductive network of the conductive network is changed. The conjugate bond is distorted, whereby the conductivity of the conductive network is controlled.
[0007]
According to the said structure, the channel part which electrically connects between said 1st and 2nd electrodes is formed with an organic thin film, and the organic electronic device from which the electroconductivity of the said organic thin film changes with irradiation of light can be provided. Further, since the organic molecule contains a photoresponsive functional group, the sensitivity to light is increased and the response speed is increased. Therefore, the conductivity of the organic thin film can be changed at high speed.
The change in the conductivity of the organic thin film when irradiated with light is considered to have occurred because the influence of the response of the photoresponsive functional group has spread to the structure of the conductive network.
[0008]
The organic thin film is a conductive thin film that electrically connects the first and second electrodes, and a part or all of the organic thin film is a monomolecular film or a monomolecular cumulative film in which monomolecular films are laminated. There may be.
[0009]
Photoresponsiveness is a characteristic that reversibly changes the state of a molecule upon irradiation with light. In photoresponse, the order (arrangement) of the bonds that make up a molecule is the same, and the spatial arrangement changes. It includes isomerization and other photoisomerization. Therefore, the change in conductivity of the organic thin film is reversible and can be returned to a predetermined state by a combination of irradiation with light having different wavelengths.
[0010]
The conductive network is an aggregate of molecules that form a conduction path involved in electrical conduction between the first and second electrodes. Furthermore, the conductivity can be improved if a dopant substance is incorporated into the conductive network by doping.
[0011]
The invention according to claim 2 is the two-terminal organic electronic device according to claim 1, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film in which organic molecules are fixed on a substrate. And
[0012]
According to the above configuration, the group of molecules constituting each monomolecular layer is in a state of being oriented to some extent, and the polymerizable group of each molecule is almost in a plane and can be easily conjugated and bonded. It is possible to form a highly conductive conductive network in which the molecules are connected by a conjugated bond. Furthermore, since the conductive network is developed on a flat surface, it is considered that two-dimensional electrical conduction is possible even if a molecule forming a one-dimensional chain conjugated polymer is used as a material substance of an organic thin film. . Therefore, even if the film thickness is thin, it has good conductivity.
[0013]
Further, since the film thickness can be made extremely thin, the response speed can be improved. In addition, since it is bonded and fixed to the substrate, it has excellent durability such as peeling resistance and can operate stably for a long period of use. Therefore, it is possible to provide a two-terminal organic electronic device having good and uniform conductivity and high speed and stable response even when the film thickness is small.
[0014]
In addition, when doping is performed, the dopant substance can be effectively incorporated into the conductive network. The conductivity of the organic thin film can be easily adjusted by forming an organic thin film having an arbitrary thickness or performing doping.
[0015]
The invention according to claim 3 is the two-terminal organic electronic device according to claim 1 or 2, wherein the conductivity of the conductive network varies depending on the amount of light irradiated on the organic thin film. To do.
[0016]
According to the above configuration, the conductivity of the conductive network can be changed by adjusting the light energy absorbed by the organic thin film according to the light irradiation intensity, the irradiation time, or the like. In addition, an organic electronic device such as a variable resistor can be provided due to the property of changing the conductivity.
[0017]
In general, in the absorption spectrum, each photoresponsive functional group has its own absorption characteristics, so it is possible to change the conductivity efficiently and at high speed by using light with an excellent absorption rate. It becomes.
[0018]
According to a fourth aspect of the present invention, in the two-terminal organic electronic device according to the third aspect, the conductivity of the conductive network is the first light or the second light having different wavelengths with which the organic thin film is irradiated. Thus, the first conductivity or the second conductivity is transferred to the first conductivity, and the first conductivity or the second conductivity is maintained even after the light is blocked.
[0019]
According to said structure, by irradiating 1st or 2nd light in the state which applied the voltage between 1st and 2nd electrodes, and changing between the stable states which have 1st or 2nd conductivity, The conductivity of the conductive network can be switched. Further, since a stable state is maintained even after light shielding, it has a memory function.
Therefore, an organic electronic device such as a variable resistor, a switch element, a memory element, or an optical sensor can be provided.
[0020]
In addition, since the first or second conductivity depends on the state before irradiating light and the amount of the first or second light to be irradiated, each light intensity, irradiation time, and the like can be adjusted by adjusting the light intensity and the irradiation time. The conductivity of the stable state can be variably controlled.
[0021]
The invention according to claim 5 is the two-terminal organic electronic device according to any one of claims 1 to 4, wherein the photoresponsive functional group is a functional group capable of photoisomerization.
[0022]
According to said structure, it becomes possible to take the stable state which has said 1st and 2nd conductivity with isomerization. Also, extremely high speed control of the conductivity of the conductive network is possible.
[0023]
Here, the stable state may be a state where the conductive network is stable and has a predetermined conductivity. For example, when the first isomer and the second isomer are present in a certain ratio, the conductivity of the conductive network is the first conductivity, and the state is a stable state having the first conductivity. .
[0024]
The invention described in claim 6 is the two-terminal organic electronic device according to claim 5, wherein the photoisomerizable functional group is an azo group.
[0025]
According to the above configuration, the transduction-type first isomer is isomerized by irradiation with visible light, and the cis-type second isomer is irradiated by ultraviolet irradiation, so that the conductivity of the conductive network changes.
[0026]
A seventh aspect of the present invention is the two-terminal organic electronic device according to any one of the first to sixth aspects, wherein the conductive network is a conjugate of a polyacetylene type, a polydiacetylene type, a polypyrrole type, a polychenylene type, or a polyacene type. It includes one or more conjugated systems selected from the group consisting of systems.
[0027]
According to said structure, the 2 terminal organic electronic device which has a conductive network of high conductivity can be provided. Here, the bonding structure of the polymer main chain of polyacetylene is a polyacetylene type. (Hereafter, polyacetylene type. The same applies to other polymers)
[0028]
The invention according to claim 8 electrically connects the first electrode, the second electrode spaced apart from the first electrode, and the first and second electrodes formed on the substrate. A three-terminal organic electronic device comprising: an organic thin film; and a third electrode sandwiched between and insulated from the substrate and the organic thin film, wherein the third electrode is the first electrode An electrode for controlling an electric field applied to the organic thin film by applying a voltage between the electrode or the second electrode and the organic thin film, One of the molecular terminals is composed of an organic molecule group including a plurality of organic molecules bonded and fixed to the substrate, and the organic molecule includes a polymerizable group that forms a conductive network by conjugated bonding within the molecule by polymerization and a polarization thereof. Having a polar functional group that distorts the conjugated bond of the conductive network, and conjugated bond to each other by polymerization of the polymerizable group between the organic molecules constituting the organic molecule group. And the polarization of the polar functional group distorts the conjugated bond of the conductive network, thereby controlling the conductivity of the conductive network. It is characterized by that.
[0029]
According to said structure, the electroconductivity of the said organic thin film changes with the voltage applied to the said 3rd electrode. Further, by including a polar functional group, the sensitivity to an applied electric field is increased, and the response speed is increased. Therefore, the change in conductivity of the organic thin film becomes faster.
The change in conductivity of the organic thin film when an electric field is applied to the organic thin film is considered to have occurred because the influence of the electric field response of the polar functional group has spread to the structure of the conductive network.
[0030]
The organic thin film is a conductive thin film that electrically connects the first and second electrodes, and a part or all of the organic thin film is a monomolecular film or a monomolecular cumulative film in which monomolecular films are laminated. There may be.
[0031]
The invention according to claim 9 is the three-terminal organic electronic device according to claim 8, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film fixed on a substrate.
[0032]
According to the above configuration, the group of molecules constituting each monomolecular layer is in a state of being oriented to some extent, and the polymerizable group of each molecule is almost in a plane and can be easily conjugated and bonded. It is possible to form a highly conductive conductive network in which the molecules are connected by a conjugated bond. Furthermore, since the conductive network is developed on a plane, two-dimensional electrical conduction is possible even if the molecules forming the one-dimensional chain conjugated polymer are used as the material substance of a monomolecular film or a monomolecular cumulative film. Is considered possible. Therefore, the conductivity of the organic thin film is good even when the film thickness is thin.
[0033]
Further, since the film thickness can be made extremely thin, the response speed can be improved. In addition, since it is bonded and fixed to the substrate, it has excellent durability such as peeling resistance and can operate stably for a long period of use. Therefore, it is possible to manufacture a three-terminal organic electronic device having good and uniform conductivity even when the film thickness is small, and having a stable response at high speed.
[0034]
In addition, when doping is performed, the dopant substance can be effectively incorporated into the conductive network. The conductivity of the organic thin film can be easily adjusted by forming an organic thin film having an arbitrary thickness or performing doping.
[0035]
The invention according to claim 10 is the three-terminal organic electronic device according to claim 8 or 9, wherein the conductivity of the conductive network is changed by an electric field applied to the organic thin film.
[0036]
According to the above configuration, since the electric field applied to the organic thin film can be controlled by the voltage applied to the third electrode, the conductivity of the conductive network can be controlled by the applied voltage.
[0037]
The invention according to claim 11 is the three-terminal organic electronic device according to any one of claims 8 to 10, wherein the polar functional group is a polarizable functional group that is polarized by applying an electric field. Features.
[0038]
According to the above configuration, if the polar functional group is a functional group whose polarization is increased by application of an electric field (hereinafter, polarizable functional group), the sensitivity to the applied electric field is extremely high, so the response speed is also extremely high. become.
[0039]
According to a twelfth aspect of the present invention, in the three-terminal organic electronic device according to the eleventh aspect, the polarizable functional group is a carbonyl group or an oxycarbonyl group.
[0040]
A carbonyl group or an oxycarbonyl group is suitable as a functional group for improving the response speed.
[0041]
The invention according to claim 13 is the three-terminal organic electronic device according to any one of claims 9 to 12, wherein the conductive network is a conjugate of polyacetylene type, polydiacetylene type, polychenylene type, polypyrrole type, polyacene type. It includes one or more conjugated systems selected from the group consisting of systems.
[0042]
According to said structure, the 3 terminal organic electronic device provided with the organic thin film which has a conductive network of high conductivity can be provided.
[0043]
The invention according to claim 14 is an insulating substrate or a substrate with an insulating film in which an insulating film is formed on the surface of an arbitrary substrate. Conjugation bond by polymerization An organic thin film composed of an organic molecule group including a plurality of organic molecules having a polymerizable group that forms a conductive network and a photoresponsive functional group that changes its spatial arrangement when irradiated with light. The polymerizable group is polymerized between the film forming step formed on the substrate and the organic molecules constituting the organic molecule group by bonding and fixing one of the molecular terminals on the substrate. A conductive network forming step of forming the conductive network connected by a conjugated bond to each other, and a counter electrode forming step of forming a first electrode and a second electrode spaced apart from each other so as to be in contact with the conductive network It is characterized by including these.
[0044]
According to said structure, the channel part which connects the said 1st and 2nd electrode is formed with an electroconductive organic material, and the 2 terminal organic electron which changes the electroconductivity between 1st and 2nd electrodes by light irradiation Devices can be manufactured.
When an insulating substrate such as a glass substrate or a plastic substrate is used, the first insulating film is not necessary, and an organic thin film can be formed directly on the substrate.
[0045]
The invention according to claim 15 is the method for producing a two-terminal organic electronic device according to claim 14, characterized in that the photoresponsive functional group is a functional group capable of photoisomerization.
[0046]
According to said structure, the electrical conductivity of an electroconductive network transfers to the 1st or 2nd electrical conductivity by irradiation of the 1st or 2nd light from which a wavelength differs, respectively, and after light-shielding, it is 1st or 2nd, respectively. A two-terminal organic electronic device that maintains the electrical conductivity can be manufactured. This organic electronic device can be used as a variable resistor, a switch element, an optical sensor element, a memory element, or the like.
[0047]
According to a sixteenth aspect of the present invention, there is provided a method of forming a third electrode on an insulating substrate or on a substrate with an insulating film in which the first insulating film is formed on an arbitrary substrate surface; On the substrate so as to cover the third electrode through two insulating films, Conjugation bond by polymerization An organic thin film composed of an organic molecule group including a plurality of organic molecules having a polymerizable group that forms a conductive network and a polar functional group that distorts a conjugated bond of the conductive network due to polarization of the polymerizable group. By bonding and fixing molecular terminals on the substrate, the polymerizable groups are bonded to each other by a conjugated bond between the film forming step to be formed and the organic molecules constituting the organic molecule group. A conductive network forming step of forming the conductive network, and a counter electrode forming step of forming a first electrode and a second electrode spaced apart from each other and spaced apart from the third electrode so as to be in contact with the conductive network. It is characterized by including these.
[0048]
According to said structure, the channel part which electrically connects the 1st and 2nd electrode is formed with an electroconductive organic material, and the application between the electrodes of the 1st or 2nd electrode and the 3rd electrode is carried out A three-terminal organic electronic device that changes the conductivity between the first and second electrodes according to the voltage can be manufactured. Further, by including a polar functional group, the response to the electric field is accelerated.
[0049]
When an insulating substrate such as a glass substrate or a plastic substrate is used, the first insulating film is not necessary, and the third electrode can be formed directly on the substrate. When the third electrode is an insulating electrode such as a silicon electrode, the second insulating film is not necessary, and the organic thin film can be directly formed so as to cover the third electrode.
[0050]
The invention according to claim 17 is the method for producing a three-terminal organic electronic device according to claim 16, wherein the polar functional group is a polarizable functional group that is polarized by applying an electric field. To do.
[0051]
According to said structure, since a polarizable functional group has a higher sensitivity with respect to an electric field than a polar functional group, a 3 terminal organic electronic device with a very high response speed can be manufactured.
[0052]
The invention according to claim 18 is the method for producing an organic electronic device according to any one of claims 14 to 17, wherein the organic thin film is a monomolecular film or a monomolecular film in which organic molecules are arranged in a monomolecular layer form. Is a monomolecular cumulative film in which a plurality of layers are stacked.
[0053]
According to the above configuration, the group of molecules constituting each monomolecular layer is in a state of being oriented to some extent, and since the polymerizable group of each molecule exists in a plane, it can be easily conjugated and bonded. It becomes possible to form a highly conductive conductive network in which molecules are connected by a conjugated bond. Furthermore, since the conductive network is developed on a plane, it is considered that two-dimensional electrical conduction is possible even if a molecule forming a one-dimensional chain conjugated polymer is used as a membrane material. Therefore, even if the film thickness is thin, it is possible to manufacture a three-terminal organic electronic device having good conductivity.
[0054]
Further, since the film thickness can be made extremely thin, the response speed can be improved. In addition, since it is bonded and fixed to the substrate, it has excellent durability such as peeling resistance and can operate stably for long-term use. Therefore, it is possible to manufacture an organic electronic device having good and uniform conductivity even when the film thickness is small, and having a stable response at high speed.
[0055]
In addition, when doping is performed, the dopant substance can be efficiently incorporated into the conductive network. The conductivity can be easily adjusted by forming an organic thin film having an arbitrary thickness or performing doping.
[0056]
According to a nineteenth aspect of the present invention, in the organic electronic device manufacturing method according to the eighteenth aspect, a chemical adsorption method or a Langmuir-Blodgett method is applied in the film forming step.
[0057]
According to the above configuration, a monomolecular film or a monomolecular cumulative film bonded and fixed on the substrate can be produced. In addition, a monomolecular cumulative film having an arbitrary thickness can be easily produced.
[0058]
According to a twentieth aspect of the present invention, in the organic electronic device manufacturing method according to the nineteenth aspect, a silane-based surfactant is used in a film forming process to which the chemical adsorption method is applied.
[0059]
As described above, when a silane surfactant is used, the film can be formed efficiently.
[0060]
The invention according to claim 21 is the method of manufacturing an organic electronic device according to any one of claims 14 to 18, wherein in the conductive network forming step, molecules constituting the organic thin film are polymerized with each other, or A conductive network is formed by conjugated bonding by polymerization and crosslinking after the polymerization.
[0061]
According to the above configuration, it is possible to form a conductive network that allows electrical conduction by linking the polymerizable groups of the molecules with a conjugated bond. As the type of polymerization, electrolytic polymerization, catalytic polymerization, polymerization by irradiation with an energy beam, or the like can be used.
[0062]
In addition, when the molecule forming the organic thin film has a plurality of polymerizable groups bonded by a conjugated bond, the polymer formed by polymerization of one polymerizable group is further subjected to a crosslinking reaction to the other polymerizable group. By conjugated bonding, a conductive network having a structure different from the structure after polymerization can be formed. In this case, the other polymerizable group in the side chain of the polymer formed by polymerization is a linking group that is crosslinked.
[0063]
For example, when a monomolecular film composed of a group of molecules having a diacetylene group is formed, subjected to catalytic polymerization, and then crosslinked by energy beam irradiation, a conductive network including a conjugated system of extremely high conductivity polyacene type is formed. be able to.
[0064]
According to a twenty-second aspect of the present invention, in the method of manufacturing an organic electronic device according to the twenty-first aspect, the crosslinking step is a crosslinking step by a catalytic action, a crosslinking step by an electrolytic action, or a crosslinking step by an energy beam irradiation action. It is one or more bridge | crosslinking processes selected from the group which consists of, It is characterized by the above-mentioned.
[0065]
According to said structure, even if it is a case where the polymer | macromolecule after superposition | polymerization has two or more different crosslinkable coupling groups, a crosslinking process can be performed in multiple times and a conductive network can be formed.
Further, a crosslinking reaction by a catalytic action, an electrolytic action or an energy beam action can be used for the crosslinking.
[0066]
The cross-linking step of multiple times includes not only a combination of cross-linking steps by different actions but also a combination of steps having the same action but different reaction conditions. For example, the conductive network is formed by performing a crosslinking step by irradiation with a first type of energy beam after performing a crosslinking step by catalytic action, and further by performing a crosslinking step by irradiation of a second type of energy beam.
[0067]
A twenty-third aspect of the present invention is the method of manufacturing an organic electronic device according to the twenty-first aspect, wherein the counter electrode forming step is performed before the conductive network forming step.
[0068]
According to said structure, it becomes possible to perform electrolytic polymerization using the said 1st and 2nd electrode formed at the counter electrode formation process.
[0069]
The invention according to claim 24 is the method for producing an organic electronic device according to claim 23, wherein the polymerizable group of the molecules constituting the organic thin film is an electrolytic polymerizable group having electrolytic polymerizability. In addition, a voltage is applied between the first and second electrodes to perform electrolytic polymerization.
[0070]
According to said structure, it is possible to electropolymerize the molecules which comprise the organic thin film which has an electropolymerizable polymeric group (henceforth electric field polymeric group), and to form a conductive network.
[0071]
In addition, the first and second electrodes can be used in the conductive network forming step, and by conducting the polymerization by applying a voltage between the first and second electrodes, the conductive network is self-grown to the first and second electrodes. Formed between the electrodes. Therefore, the conductivity between the electrodes can be easily ensured, and a conductive network having a uniform conductivity can be formed.
[0072]
A twenty-fifth aspect of the present invention is the method of manufacturing an organic electronic device according to the twenty-fourth aspect, wherein the electrolytic polymerizable group is a pyrrole group or a chenylene group.
[0073]
As in the above configuration, a pyrrole group or a chainylene group can be used as the electropolymerizable group. An organic electronic device having a highly conductive conductive network can be produced by electropolymerizing molecules of an organic thin film having a pyrrole group or a chainylene group as an electropolymerizable group.
[0074]
The invention according to claim 26 is the method for producing an organic electronic device according to claim 24, wherein the electropolymerizable group is a pyrrole group or a chainylene group, and the organic thin film is a monomolecular film. After the step of forming the counter electrode, the substrate is immersed in an organic solvent in which a substance containing a pyrrole group or a chainylene group is dissolved, and is in contact with the first or second electrode and between the first or second electrode and the organic solvent. A voltage is applied between the electrode and the external electrode disposed above the organic thin film to form a film made of molecules having a pyrrole group or a chelenylene group on the surface of the monomolecular film, and the monomolecule A conductive network is formed on each of the film and the film.
[0075]
According to said structure, a film can be formed and a conductive network can be formed in a monomolecular film and a film, respectively. In this case, the organic thin film which is a component of the organic electronic device is composed of a monomolecular film having a conductive network and a polymer film. Since the thickness of the film depends on the time during which the voltage is applied, the film having a predetermined thickness can be formed by adjusting the time. Further, the conductivity of the conductive network as a whole organic thin film depends on the thickness of the coating film to be formed. Therefore, an organic electronic device having predetermined conductive characteristics can be easily manufactured by adjusting the voltage application time.
[0076]
Further, when a film made of organic molecules of the same type as the monomolecular film is formed, if there is a gap in which more molecules can enter in the monomolecular film, the gap is filled with molecules and the density increases. Therefore, more reliable and good conductivity can be ensured.
[0077]
A twenty-seventh aspect of the present invention is the method for manufacturing an organic electronic device according to the twenty-first aspect, wherein the organic thin film having a catalytic polymerizable catalytic polymerizable group as the polymerizable group in the conductive network forming step. It is characterized in that the constituting molecules are subjected to catalytic polymerization.
[0078]
According to said structure, it becomes possible to superpose | polymerize the molecular group which has a catalyst polymerizable group (henceforth, a catalyst polymerizable group), and to form a conductive network.
[0079]
A twenty-eighth aspect of the present invention is the organic electronic device manufacturing method according to the twenty-seventh aspect, wherein the catalytic polymerizable group is a pyrrole group, a chelenylene group, an acetylene group, or a diacetylene group. .
[0080]
According to the above configuration, an organic electronic device having a conductive network with high conductivity can be produced by catalytic polymerization of an organic molecule group having a pyrrole group, a chainylene group, an acetylene group, or a diacetylene group as a catalytic polymerizable group. .
[0081]
The invention according to claim 29 is the method for producing an organic electronic device according to claim 21, wherein in the conductive network forming step, the polymerizable group has a beam irradiation polymerizable group that is polymerized by energy beam irradiation. The molecules constituting the organic thin film are polymerized by energy beam irradiation.
[0082]
According to said structure, the molecular group which has a polymeric group (henceforth beam irradiation polymeric group) which has the characteristic (henceforth beam irradiation polymeric property) which superposition | polymerization advances by energy beam irradiation superposes | polymerizes, and forms a conductive network. It is possible.
The energy beam includes rays such as infrared rays, visible rays, and ultraviolet rays, radiations such as X-rays, and particle beams such as electron beams.
[0083]
A thirty-third aspect of the present invention is the method of manufacturing an organic electronic device according to the twenty-ninth aspect, wherein the energy beam polymerizable group is an acetylene group or a diacetylene group.
[0084]
According to said structure, the molecule | numerator of the organic thin film which has an acetylene group or a diacetylene group as a beam irradiation polymeric group can superpose | polymerize, and the organic electronic device which has a highly conductive conductive network can be manufactured.
[0085]
A thirty-first aspect of the invention is the method of manufacturing an organic electronic device according to the thirty-ninth or thirty-third aspect, wherein ultraviolet, far-ultraviolet, X-ray, or electron beam is used as the energy beam in the conductive network forming step. It is characterized by
[0086]
According to said structure, since many beam irradiation polymeric groups have an absorption characteristic with respect to at least 1 of these beams, it can apply to the molecular group which has various types of beam irradiation polymeric groups. Since the absorption characteristics differ depending on the beam irradiation polymerizable group, the reaction efficiency can be improved by selecting the type and energy of the energy beam having good absorption efficiency.
[0087]
According to a thirty-second aspect of the present invention, the first electrode formed on the substrate, the second electrode spaced apart from the first electrode, and the first and second electrodes are electrically connected. An organic thin film, the organic thin film comprising an organic molecule group including a plurality of organic molecules having one molecular terminal bonded and fixed to the substrate, and the organic molecule is contained in the molecule. Conjugation bond by polymerization A polymerizable group that forms a conductive network and a photoresponsive functional group that changes its spatial arrangement upon irradiation with light, and between the organic molecules constituting the organic molecule group, A method for operating a two-terminal organic electronic device in which the conductive network is formed by conjugated bonding to each other by polymerization of a polymerizable group, wherein the organic compound is applied with a voltage applied between the first and second electrodes. By irradiating the thin film with light, the spatial arrangement of the photoresponsive functional groups is changed, thereby distorting the conjugate bond of the conductive network, thereby changing the conductivity of the conductive network. And switching a current flowing between the second electrode and the second electrode.
[0088]
According to said structure, the irradiated light is absorbed by the photoresponsive functional group, and the electrical conductivity of a conductive network changes by the influence by the response. Therefore, the current flowing between the first and second electrodes can be switched by irradiating the organic thin film with light while a voltage is applied between the first and second electrodes.
[0089]
In general, in the absorption spectrum, each photoresponsive functional group has its own absorption characteristics, so it is possible to change the conductivity efficiently and at high speed when using light with a wavelength with excellent absorption. It becomes.
[0090]
According to a thirty-third aspect of the present invention, the photoresponsive functional group is a functional group that undergoes photoisomerization, and the conductive film is irradiated with the first light or the second light with different wavelengths irradiated on the organic thin film. A method of operating a two-terminal organic electronic device, characterized in that the conductivity of the network is changed.
[0091]
According to the above configuration, the conductivity of the conductive network is changed to the first conductivity or the second conductivity by the isomerization of the molecules constituting the organic thin film by the first light or the second light with different wavelengths. Since the first conductivity or the second conductivity is maintained after the transition to the second conductivity and the light is blocked, the first voltage is applied to the organic thin film with the voltage applied between the first and second electrodes. Alternatively, the current flowing between the first and second electrodes can be switched by irradiating the second light.
[0092]
In addition, since the photoresponsive functional group is a photoisomerizable functional group, the conductivity of the conductive network can be changed at a very high speed.
Further, since the progress of isomerization depends on the amount of irradiated light, the first or second conductivity can be variably controlled by adjusting the intensity of irradiation light or the irradiation time. Therefore, it is possible to adjust the change range of the conductivity for the switching operation by the intensity of irradiation light or the irradiation time.
[0093]
However, since it has a memory function that maintains a stable state even after the light is blocked when one of the first or second light is irradiated, the other of the first or second light is subsequently used to perform the switching operation. I have to irradiate.
[0094]
The invention according to claim 34 is the operation method of the two-terminal organic electronic device according to claim 33, wherein the photoisomerizable functional group is an azo group.
[0095]
According to the above configuration, the transduction-type first isomer is isomerized by irradiation with visible light, and the cis-type second isomer is irradiated by ultraviolet irradiation, and the conductivity of the conductive network is set to the first isomer. Since the first conductivity or the second conductivity is maintained after the transition to the conductivity or the second conductivity and the light is shielded, the organic thin film is applied with a voltage applied between the first and second electrodes. It is possible to switch the current flowing between the first and second electrodes by irradiating UV light after irradiation with visible light or irradiating visible light after UV light irradiation.
[0096]
A thirty-fifth aspect of the present invention is the operation method of the two-terminal organic electronic device according to the thirty-third or thirty-fourth aspect, wherein the first or second light irradiated to the organic thin film is ultraviolet light or visible light, respectively. It is characterized by using.
[0097]
According to the above configuration, most of the photoisomerizable functional groups are isomerized to the first isomer or the second isomer by irradiation with ultraviolet rays or visible light, respectively. Suitable for groups.
[0098]
Furthermore, generally, in the absorption spectrum, each functional group of photoisomerization has an inherent absorption characteristic. Therefore, it is efficient to use light having a wavelength with excellent absorption efficiency. It can be changed.
[0099]
According to a thirty-sixth aspect of the present invention, the first electrode formed on the substrate, the second electrode spaced apart from the first electrode, and the first and second electrodes are electrically connected. An organic thin film; and a third electrode sandwiched between and insulated from the substrate and the organic thin film, the third electrode being applied between the first or second electrode It is an electrode for controlling an electric field applied to the organic thin film by voltage, and the organic thin film is One of the molecular terminals is composed of an organic molecule group including a plurality of organic molecules bonded and fixed to the substrate, and the organic molecule includes a polymerizable group that forms a conductive network by conjugated bonding within the molecule by polymerization and a polarization thereof. Has a polar functional group that distorts the conjugated bond of the conductive network A method of operating a three-terminal organic electronic device, wherein a voltage is applied between the first and second electrodes and applied between the first or second electrode and the third electrode. Voltage Polarizing the polarizable functional group distorts the conjugated bond of the network, thereby making the conductivity of the conductive network And the current flowing between the first and second electrodes is switched.
[0100]
According to said structure, since it has a polar functional group which responds with sufficient sensitivity to the applied electric field, high-speed electric current switching operation | movement is attained.
[0101]
A thirty-seventh aspect of the invention is the operation method of the three-terminal organic electronic device according to the thirty-sixth aspect, wherein the polar functional group is a polarizable functional group.
[0102]
According to the above configuration, the polarizable functional group has extremely high sensitivity to the applied electric field, and thus enables extremely high-speed switching operation.
[0103]
The invention according to claim 38 is the operation method of the organic electronic device according to any one of claims 32 to 37, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film in which the organic thin film is bonded and fixed on the substrate. It is characterized by being.
[0104]
According to the above configuration, since the molecular groups constituting each layer are oriented as a whole, a conductive network formed by polymerization can be formed on a plane, and even if the film thickness is small, it is good and homogeneous. Have good electrical conductivity. Furthermore, since the film thickness is very thin, a very high speed switching operation is possible.
The lowermost layer is bonded and fixed to the substrate and has excellent durability such as peel resistance. Therefore, a switching operation with excellent stability, high speed, and durability is possible.
[0105]
The invention according to claim 39 provides Multiple The switch elements are arranged in a matrix on the first substrate and the first alignment film is formed on the surface of the switch element, and the color elements are arranged in a matrix on the second substrate. Sealed between the color filter substrate having the second alignment film formed on the surface, and the array substrate and the color filter substrate facing each other with the first alignment film and the second alignment film inside. Liquid crystal display device provided with liquid crystal The switch element electrically connects the first electrode formed on the first substrate, the second electrode spaced apart from the first electrode, and the first and second electrodes. An organic thin film to be connected; and a third electrode sandwiched between and insulated from the substrate and the organic thin film, wherein the third electrode is connected to the first electrode or the second electrode. Is an electrode that controls the electric field applied to the organic thin film by applying a voltage between the electrodes, The organic thin film is One of the molecular terminals is composed of an organic molecule group including a plurality of organic molecules bonded and fixed to the substrate, and the organic molecule includes a polymerizable group that forms a conductive network by conjugated bonding within the molecule by polymerization and a polarization thereof. Having a polar functional group that distorts the conjugated bond of the conductive network, and conjugated bond to each other by polymerization of the polymerizable group between the organic molecules constituting the organic molecule group. The polar functional group is polarized by application of the electric field, whereby the conjugated bond of the network is distorted, thereby controlling the conductivity of the conductive network. It is characterized by that.
[0106]
According to the above configuration, a liquid crystal display device using an organic TFT can be provided in place of an existing inorganic thin film transistor (hereinafter referred to as TFT). In addition, since an organic TFT is used, there is no process at a high temperature, and a substrate such as a plastic substrate that could not be used conventionally can be used. As a result, the range of substrate selection is widened, and the size and weight can be reduced by selecting an appropriate substrate.
[0107]
The invention of claim 40 is , Double A plurality of switch elements arranged in a matrix on the substrate, a common electrode facing the array substrate, and light emission by applying an electric field formed between the array substrate and the common electrode In an electroluminescence type display device having a light emitting layer made of a fluorescent material, The switch element includes: a first electrode formed on the substrate; a second electrode spaced apart from the first electrode; and an organic thin film electrically connecting the first and second electrodes. A third electrode sandwiched between and insulated from the substrate and the organic thin film, wherein the third electrode is a voltage between the first electrode and the second electrode. Is an electrode that controls the electric field applied to the organic thin film by applying The organic thin film is One of the molecular terminals is composed of an organic molecule group including a plurality of organic molecules bonded and fixed to the substrate. Having a polar functional group that distorts the conjugated bond of the conductive network, and conjugated bond to each other by polymerization of the polymerizable group between the organic molecules constituting the organic molecule group. The polar functional group is polarized by application of the electric field, whereby the conjugated bond of the network is distorted, thereby controlling the conductivity of the conductive network. It is characterized by that.
[0108]
According to the above configuration, an electroluminescent display device using an organic TFT in place of an existing inorganic thin film transistor (hereinafter referred to as TFT) can be provided. In addition, since an organic TFT is used, there is no process at a high temperature, and a substrate such as a plastic substrate that could not be used conventionally can be used. As a result, the range of substrate selection is widened, and it is possible to reduce the size and weight by selecting an appropriate substrate.
[0109]
The invention according to claim 41 is the electroluminescence display device according to claim 40, wherein the three kinds of fluorescent materials emitting red, blue or green light are arranged and arranged to perform color display. Features.
[0110]
According to the above configuration, an electroluminescent color display device using organic TFTs can be provided.
[0111]
The invention according to claim 42 is the display device according to any one of claims 39 to 41, characterized in that the organic thin film is a monomolecular film or a monomolecular cumulative film fixed on a substrate. To do.
[0112]
According to the above configuration, an electroluminescent display device, an electroluminescent color display device, or a liquid crystal display device with extremely high display speed and high operational stability can be provided.
[0113]
The invention according to claim 43 is the array substrate forming step of forming a plurality of switch elements on the first substrate so as to be arranged in a matrix and forming a first alignment film on the surface thereof, A color filter substrate forming step in which color elements are arranged in a matrix on the surface of the substrate 2 to produce a color filter, and a second alignment film is formed on the surface; a first alignment film and a second alignment film; The array substrate and the color filter substrate facing each other at a predetermined interval, filling the liquid crystal between the array substrate and the color filter substrate, and sealing the liquid crystal. In the device manufacturing method, the step of forming the switch element includes a step of forming a third electrode on the first substrate and a step of covering the third electrode directly or via the second insulating film. In addition, On top of the serial first substrate, Conjugation bond by polymerization An organic thin film composed of an organic molecule group including a plurality of organic molecules having a polymerizable group that forms a conductive network and a polar functional group that distorts a conjugated bond of the conductive network due to polarization of the polymerizable group. The polymerizable group is polymerized between a film forming step to be formed by bonding and fixing a molecular terminal on the first substrate or the third electrode and between the organic molecules constituting the organic molecule group. A conductive network forming step for forming the conductive network connected by a conjugated bond to each other, and a first electrode and a second electrode separated from each other and from the third electrode so as to be in contact with the conductive network. And a counter electrode forming step for forming the electrode.
[0114]
According to the above configuration, a liquid crystal display device using an organic TFT can be manufactured in place of an existing inorganic thin film transistor (hereinafter, TFT). In addition, since an organic TFT is used, a process at a high temperature is not necessary. It becomes possible to use a plastic substrate that could not be used conventionally.
[0115]
Invention of Claim 44 Is the group Multiple so that they are arranged in a matrix on the plate Switch An array substrate forming step for forming elements, a light emitting layer forming step for forming a light emitting layer made of a fluorescent material that emits light upon application of a voltage, and a common electrode for forming a common electrode film on the light emitting layer In a manufacturing method of an electroluminescence type display device including a forming step, The step of forming the switch element includes a step of forming a third electrode on the substrate, and a polymerization process on the substrate so as to cover the third electrode directly or via the second insulating film. An organic thin film composed of an organic molecule group including a plurality of organic molecules having a polymerizable functional group covalently bonded to form a conductive network and a polar functional group that distorts a conjugated bond of the conductive network by polarization thereof. The polymerizable group is polymerized between the organic molecule constituting the organic molecule group and the film forming step to be formed by bonding and fixing one of the molecular terminals on the substrate or the third electrode. A conductive network forming step of forming the conductive network connected to each other by a conjugated bond, and a third step to be in contact with the conductive network and separated from each other A first electrode and a counter electrode forming step of forming a second electrode spaced apart both poles, It is characterized by including.
[0116]
According to the above configuration, an electroluminescence type display device using an organic TFT can be manufactured in place of an existing inorganic thin film transistor (hereinafter referred to as TFT). In addition, since an organic TFT is used, there is no process at a high temperature, and it is possible to use a substrate such as a plastic substrate that could not be used conventionally.
[0117]
The invention according to claim 45 is the method of manufacturing an electroluminescence type display device according to claim 44, wherein the three kinds of light-emitting substances that emit red, blue, or green light in the light emitting layer forming step. Is formed at a predetermined position and is displayed in color.
[0118]
According to said structure, the electroluminescent color display apparatus using organic type TFT can be manufactured.
[0119]
The invention according to claim 46 is the method of manufacturing a display device according to any of claims 43 to 45, wherein the organic thin film is a monomolecular film or a monomolecular film in which organic molecules are arranged in a monomolecular layer. Is a monomolecular cumulative film formed by laminating.
[0120]
According to the above configuration, it is possible to manufacture an electroluminescent display device, an electroluminescent color display device, and a liquid crystal display device that have a very high display speed and high operational stability.
[0121]
DETAILED DESCRIPTION OF THE INVENTION
The embodiment of the present invention will be described in detail with reference to the drawings based on an example in which the organic thin film is a monomolecular film.
[0122]
(Embodiment 1)
FIGS. 1A and 1B are explanatory diagrams schematically illustrating an example of the structure of a two-terminal organic electronic device. The manufacturing method and structure of a two-terminal organic electronic device will be described with reference to FIG.
[0123]
First, a single molecule composed of an organic molecule group having a photo-responsive functional group and a polymerizable group bonded by a conjugated bond on an insulating substrate or a substrate with an insulating film having an insulating film formed on the surface of an arbitrary substrate A film 4 is formed, and molecules constituting the monomolecular film 4 are conjugated to each other to form a conductive network 5. The first electrode 2 and the second electrode 3 that are separated from each other so as to contact the conductive network 5 To form a two-terminal organic electronic device.
[0124]
Thereby, the first electrode 2 formed on the substrate, the second electrode 3 spaced apart from the first electrode 2, and the first electrode 2 and the second electrode 3 are electrically connected. A two-terminal organic electronic device comprising an organic thin film, wherein the monomolecular film 4 is composed of an organic molecule group having a photoresponsive functional group, and a conductive network in which the molecules constituting the organic molecule group are conjugatedly bonded to each other A two-terminal organic electronic device having 5 can be provided.
[0125]
FIG. 1A shows a two-terminal organic electronic device having a structure in which the first electrode 2 and the second electrode 3 are in contact with the surface of the substrate 1 and the side surface of the monomolecular film 4, and FIG. This is a two-terminal organic electronic device having a structure in which the electrode 2 and the second electrode 3 are formed on the surface of the monomolecular film.
In the formation of the first electrode 2 and the second electrode 3, after vapor-depositing substances for forming the respective electrodes, a mask pattern is formed with a photoresist, and the predetermined first electrode 2 and second electrode are formed by etching. When the electrode 3 is formed, a two-terminal organic electronic device having the structure shown in FIG. 1A or 1B can be manufactured by using different mask patterns.
[0126]
With the structure shown in FIG. 1 (a), an organic molecule containing a polymerizable group can be used at an arbitrary position in the molecule, and the first electrode and the second electrode can be used even when a plurality of polymerizable groups exist in the molecule. A plurality of conductive networks that electrically connect the two electrodes can be formed. If the organic thin film is a monomolecular cumulative film, a conductive network can be formed in each monomolecular layer.
Moreover, when manufacturing the two-terminal organic electronic device of this structure, you may perform the said counter electrode process before the said film-forming process.
[0127]
In the structure shown in FIG. 1B, if the conductive network does not exist on the surface of the monomolecular film on the side opposite to the substrate, the electrical conduction between the conductive network and the electrode is deteriorated. Therefore, it is better to use a material having a polymerizable group at the end of the molecule.
When such molecules are used, the contact area between the conductive network of the monomolecular film and the electrode can be increased, so that the contact resistance can be reduced, and good conductivity can be ensured even with a monomolecular film. There are advantages.
[0128]
If higher conductivity is required, a film having a conductive network can be formed between the first electrode 2 and the second electrode 3. For example, after the counter electrode step, the electrode is immersed in an organic solvent in which a substance containing an electrolytic polymerizable functional group is dissolved, and a first voltage is applied between the first electrode 2 and the second electrode 3. In addition, if a second voltage is applied between the first electrode 2 or the second electrode 3 and the external electrode disposed in contact with the organic solvent and disposed above the organic thin film, the conductivity of the first structure A film is further formed on the surface of the monomolecular film having a network, and the molecules constituting the film are electropolymerized to form a conductive network having a second structure.
[0129]
When forming a film, if a substance containing an electropolymerizable functional group is applied and a voltage is applied between the first electrode 12 and the second electrode 13, a polymer film having a conductive network is similarly formed. Can be formed.
[0130]
As long as the organic thin film does not include a monomolecular film in which the organic molecules constituting the organic thin film are arranged in a monomolecular layer, there is no difference as described above regardless of the structure of FIGS. 1 (a) and 1 (b). .
[0131]
The time change and switching operation of the conductivity due to light irradiation of the two-terminal organic electronic device will be described with reference to FIG.
[0132]
FIG. 2A is a schematic diagram qualitatively showing the change in conductivity with the irradiation time when the organic thin film is irradiated with light of a certain intensity.
Assuming that the amount of irradiated light is proportional to the product of the intensity of irradiation light and the irradiation time, the horizontal axis represents the amount of light irradiated to the organic thin film, the time taken for the light intensity to be constant, or irradiation. Taking light intensity under constant time conditions is equivalent. Hereinafter, the case where the light intensity is constant will be described. The change in conductivity is described as a change in current when a constant voltage is applied between the first and second electrodes.
[0133]
The conductivity of the conductive network changes with irradiation and becomes a certain value. Unlike the case of FIG. 2A, the current value may reach 0 A when light is irradiated for a sufficient time to change. Furthermore, FIG. 2A shows a case where the current value decreases due to light irradiation, but it may increase. These depend on the constituent material and structure of the organic thin film or the structure of the conductive network.
[0134]
Next, FIG. 2B is a functional group in which a photofunctional functional group undergoes photoisomerization, and has first and second electrical conductivity associated with isomerization by first or second light irradiation, respectively. It is a conceptual diagram of the switching operation | movement by the transition between stable states. The lines L1 and L2 in FIG. 2B are being irradiated with the first and second lights, respectively (P _1ON , P _2ON ) Or during light shielding (P _1OFF , P _2OFF ) Irradiation state. The line L3 in FIG. 2B represents the response, and the current value when the first light is irradiated is I. ₁ The current value when the second light is irradiated is I ₂ It is.
[0135]
The figure shows switching of a current flowing between the first and second electrodes in a state where a voltage is applied between the first and second electrodes. From the line L3 in FIG. 2B, the current switching is triggered by the first light and the second light, and the operation is the same as that of the reset-set type (RS type) flip-flop. Understand.
[0136]
However, in FIG. 2B, the case where only one of the different isomers is included is defined as a stable state having the first conductivity, and the case including only the other isomer is defined as a stable state having the second conductivity. That is, two completely isomerized states are stable states having the first or second conductivity. In this case, the electrical conductivity does not change even when the first light is further irradiated to the first stable state. The same applies to the second stable state.
[0137]
(Embodiment 2)
In the first embodiment, the operation as a switching element for the current between the first and second electrodes has been exemplified. However, since the conductivity of the organic thin film is changed by light irradiation, it can be used as a variable resistor for light control.
[0138]
In the case of an organic thin film composed of a molecular group having a functional group that photoisomerizes as a photoresponsive functional group, the first thin film is applied in a state where a constant current is applied between the first and second electrodes or a constant voltage is applied. Alternatively, the light receiving element of the illuminometer can be used as an optical sensor by reading the voltage change or current change between the first and second electrodes by irradiating the second light, or by reading the voltage change or current change with the irradiation time. It can also be used as However, at this time, it is necessary to use one of the first or second light as light for initializing the state and initialize the conductivity of the organic thin film after irradiation with the other light.
[0139]
In addition, since the state of two isomers accompanying isomerization is transferred and the state of the isomers is maintained even after light shielding, it can be used as a memory element.
[0140]
(Embodiment 3)
FIGS. 3A and 3B are explanatory diagrams schematically illustrating an example of the structure of a three-terminal organic electronic device. The manufacturing method and structure of a three-terminal organic electronic device will be described with reference to FIG.
[0141]
First, the third electrode 17 is formed on an insulating substrate or a substrate with an insulating film in which an insulating film 18 is formed on the surface of an arbitrary substrate 11. Next, an organic thin film 14 made of an organic molecule group having a polar functional group and a polymerizable group bonded by a conjugated bond is formed so as to cover the third electrode 13 directly or via the insulating film 19. Next, the molecules constituting the organic thin film 14 are conjugated to each other to form a conductive network 15. Next, a three-terminal organic electronic device can be manufactured by forming the first electrode 12 and the second electrode 13 that are spaced apart from each other and spaced apart from the third electrode 17 so as to contact the conductive network 15.
[0142]
Thereby, the first electrode 12 formed on the substrate, the second electrode 13 spaced apart from the first electrode 12, and the first electrode 12 and the second electrode 13 are electrically connected. A three-terminal organic electronic device comprising: an organic thin film 14 to be electrically connected; and a third electrode 17 sandwiched between and insulated from the substrate 11 and the organic thin film 14. Is an electrode capable of controlling an electric field applied to the organic thin film by applying a voltage between the first electrode or the second electrode and the third electrode, and the organic thin film 14 has a polar functional group. It is possible to provide a three-terminal organic electronic device having a conductive network composed of an organic molecule group having a molecule in which the molecules constituting the organic molecule group are conjugated.
[0143]
3A shows a three-terminal organic electronic device having a structure in which the first electrode 12 and the second electrode 13 are in contact with the surface of the insulating film 18 on the substrate 11 and the side surface of the monomolecular film 14. (B) is a three-terminal organic electronic device having a structure in which a first electrode 12 and a second electrode 13 are formed on the surface of a monomolecular film. In the formation of the first electrode 12 and the second electrode 13, after depositing a material for forming the electrode, a mask pattern is formed with a photoresist, and predetermined first electrode 2 and second electrode are formed by etching. 3 is formed, a three-terminal organic electronic device having the structure of FIG. 3A or 3B can be manufactured by using different mask patterns.
[0144]
With the structure shown in FIG. 3 (a), an organic molecule containing a polymerizable group can be used at an arbitrary position, and even when a plurality of polymerizable groups are present in the molecule, a gap between the first and second electrodes can be used. Multiple layers of electrically conductive networks can be formed that are electrically connected. Furthermore, if it is a monomolecular accumulation | storage film | membrane, a conductive network can be formed in each monomolecular layer.
[0145]
In the structure shown in FIG. 3B, if the conductive network does not exist on the surface of the monomolecular film opposite to the substrate, the electrical conduction between the conductive network and the electrode is deteriorated. Therefore, it is better to use a material having a polymerizable group at the end of the molecule.
[0146]
When such molecules are used, the contact area between the conductive network of the monomolecular film and the electrode can be increased, so that the contact resistance can be reduced, and good conductivity can be ensured even with a monomolecular film. There are advantages.
[0147]
If higher conductivity is required, a film having a conductive network can be formed between the first electrode 12 and the second electrode 13. For example, after the counter electrode step, the first voltage is applied between the first electrode 12 and the second electrode 13 by immersing in an organic solvent in which a substance containing an electropolymerizable functional group is dissolved. In addition, if a second voltage is applied between the first electrode 12 or the second electrode 13 and the external electrode disposed in contact with the organic solvent and disposed above the organic thin film, the first structure is obtained. A film is further formed on the surface of the monomolecular film or monomolecular cumulative film having the conductive network, and the molecules constituting the film are electropolymerized to form a second structure conductive network.
[0148]
In addition, when a film is formed, a polymer film-like film having a conductive network can be formed by applying a substance containing an electropolymerizable functional group and applying a voltage between the first and second electrodes. .
[0149]
As long as the organic thin film does not include a monomolecular film in which the organic molecules constituting the organic thin film are arranged in a monomolecular layer, there is no difference as described above regardless of the structure shown in FIGS. 3 (a) and 3 (b). .
[0150]
Next, the temporal change in conductivity and the switching operation of the three-terminal organic electronic device due to the application of an electric field will be described with reference to FIG. FIG. 4A is a schematic diagram qualitatively showing the change in conductivity when a voltage is applied to the third electrode 17. Assuming that the voltage applied to the third electrode 13 is proportional to the electric field applied to the organic thin film, it is equivalent to take the applied electric field or the applied voltage of the third electrode 17 as the horizontal axis. Use to describe. The change in conductivity of the conductive network is described as a change in current when a constant voltage is applied between the first electrode 12 and the second electrode 13.
[0151]
It can be seen that the conductivity of the conductive network varies with the voltage applied to the third electrode 17 and converges to a certain value as the applied voltage increases. That is, the conductivity can be controlled by the applied voltage of the third electrode within the range between the conductivity when no voltage is applied to the third electrode and the converged conductivity.
[0152]
FIG. 4 shows the case where the current during voltage application is 0 A, but it is not limited to the case where either the on-current during voltage application or the off-current without voltage application is 0 V. . Further, although the case where the current value is decreased by voltage application is illustrated, the current may be increased. These depend on the structure of the organic thin film and the structure of the conductive network.
[0153]
The transition between the stable state having the first conductivity with no voltage applied and the stable state having the second conductivity with the predetermined voltage applied allows the conductivity of the conductive network to be switched. .
[0154]
FIG. 4B is a conceptual diagram of the switching operation of the three-terminal organic electronic device, and a predetermined voltage application state in a state where a voltage is applied between the first electrode 12 and the second electrode 13 ( V _ON ) On-current (I _{V = ON} ) And no voltage applied (V _OFF ) Off-current (I _{V = OFF} ) Indicates a switching operation.
Therefore, it can be seen from FIG. 4B that the current can be switched by turning on and off the predetermined voltage applied to the third electrode 17.
[0155]
Although the case of switching by voltage on / off is shown, switching between the current value when the first voltage is applied to the third electrode 17 and the current value when the second voltage is applied is also possible. It is.
[0156]
In the above description, the switch element that switches the current between the first and second electrodes is exemplified, but it can also be used as a variable resistor for electric field control.
[0157]
(Embodiment 4)
A first electrode, a second electrode spaced apart from the first electrode, an organic thin film electrically connecting the first and second electrodes, and sandwiched between the substrate and the organic thin film; A third electrode insulated from each other, and an electrode capable of controlling an electric field applied to the organic thin film by an applied voltage between the first or second electrode and the third electrode, and the organic thin film Comprises a conductive network in which organic molecules having a polar functional group and molecules constituting the organic molecules are conjugated to each other are used as a switch element, and the first substrate An array substrate forming step of forming a plurality of switch elements so as to be arranged in a matrix on the surface and forming a first alignment film on the surface, and arranging color elements in a matrix on the surface of the second substrate Place and color A color filter substrate forming step of forming a second alignment film on the surface of the filter, and forming the array substrate and the color filter substrate with the first alignment film and the second alignment film inside. A liquid crystal display device can be manufactured by a process of filling the liquid crystal between the array substrate and the color filter substrate facing each other at intervals and sealing the liquid crystal.
[0158]
Accordingly, the first electrode, the second electrode spaced apart from the first electrode, the organic thin film electrically connecting the first and second electrodes, and the substrate and the organic thin film between A third electrode sandwiched and insulated from each other, and an electrode capable of controlling an electric field applied to the organic thin film by an applied voltage between the first or second electrode and the third electrode, The organic thin film is composed of an organic molecule group having a polar functional group, and has a conductive network in which molecules constituting the organic molecule group are conjugated to each other, and a three-terminal organic electronic device is used as a switch element A liquid crystal display device, wherein a plurality of the switch elements are arranged in a matrix on a first substrate and a first alignment film is formed on the surface thereof, and a matrix on the second substrate Color A color filter substrate having a second alignment film formed on the surface thereof, the array substrate facing the first alignment film and the second alignment film inside, and the color filter substrate A liquid crystal display device having a liquid crystal sealed between the two.
(Embodiment 5)
A first electrode, a second electrode spaced apart from the first electrode, an organic thin film electrically connecting the first and second electrodes, and sandwiched between the substrate and the organic thin film; A third electrode insulated from each other, and an electrode for controlling an electric field applied to the organic thin film by a voltage applied between the third electrode and the first or second electrode, The organic thin film is composed of an organic molecule group having a polar functional group, and the molecule of the organic molecule group is conjugated to form a conductive network to form a switch element. An array substrate forming step of forming a plurality of the switch elements so as to be arranged in a matrix on the substrate; and a light emitting layer formation for forming a light emitting layer made of a fluorescent material that emits light upon application of a voltage on the array substrate Process, And a common electrode forming step of forming a common electrode film on the serial light-emitting layer, can be manufactured electroluminescent display device by.
[0159]
Accordingly, the first electrode, the second electrode spaced apart from the first electrode, the organic thin film electrically connecting the first and second electrodes, and the substrate and the organic thin film between An electrode for controlling an electric field applied to the organic thin film by a voltage applied between the third electrode and the first or second electrode. A three-terminal organic electronic device, wherein the organic thin film is composed of an organic molecule group having a polar functional group, and the molecules of the organic molecule group are conjugated to each other to form a conductive network. An electroluminescence display device used as a switch element, wherein an array substrate in which a plurality of the switch elements are arranged in a matrix on the substrate, a common electrode facing the array substrate, and the array Formed between the plate and the common electrode to provide an electroluminescent display device having a light emitting layer made of a fluorescent substance which emits light by application of an electric field.
[0160]
【Example】
Hereinafter, based on an Example, the content of this invention is demonstrated concretely.
[0161]
(Example 1)
First, an acetylene group (—C≡C—) that forms a conductive network through a conjugated bond by polymerization, an azo group (—N═N—) that is a photoisomerizable functional group, and active hydrogen (for example, Using a substance of the chemical formula (1) containing a chlorosilyl group (—SiCl) that reacts with a hydroxyl group (—OH)),
[Chemical 1]

A chemisorbed liquid was prepared by diluting to 1% with a dehydrated dimethyl silicone organic solvent.
[0162]
Next, the insulating substrate 21 (glass substrate) on which a mask pattern is formed with a photoresist while leaving a portion for forming a monomolecular film is immersed in the chemical adsorption solution to perform chemical adsorption, and is selected in the mask pattern opening. Then, chemical adsorption is performed, and the unreacted substance remaining on the surface is washed away with chloroform, and then the mask pattern of the photoresist is removed to selectively form a monomolecular film 24 made of the substance. did. When chemical adsorption is performed, a large number of hydroxyl groups containing active hydrogen are present on the surface of the glass substrate 11 at the opening of the mask pattern. Therefore, the chlorosilyl group (—SiCl) of the substance reacts with the hydroxyl group and is shared by the substrate 21 surface. A monomolecular film 24 composed of the combined chemical formula (2) is formed. (Fig. 5 (a))
[Chemical formula 2]

[0163]
Thereafter, the acetylene group in the monomolecular film was polymerized using a Ziegler-Natta catalyst in a toluene solvent to form a polyacetylene type conductive network 25. (Fig. 5 (b))
[0164]
Next, a nickel thin film was formed on the entire surface by vapor deposition, and the first electrode 22 and the second electrode 23 having a gap distance of 10 μm and a length of 30 μm were etched and formed by photolithography.
[0165]
Thus, the first electrode 22, the second electrode 23, and the monomolecular film that electrically connects the first electrode 22 and the second electrode 23 are formed on the substrate 21. A terminal organic electronic device, wherein the monomolecular film 24 is composed of an organic molecule group having an azo group, and a two-terminal organic electronic device having a conductive network 25 in which the molecules constituting the organic molecule group are conjugatedly bonded to each other in a polyacetylene type. Manufactured. (Fig. 5 (c))
[0166]
In this device, the electrodes between the first electrode 22 and the second electrode 23 are connected by a polyacetylene-type conductive network 25, and therefore, a number between the first electrode 22 and the second electrode 23. When a voltage of volt was applied, a current of several nanoamperes (about 2 nA at 1 V) flowed. However, visible light is irradiated to the monomolecular film 24 before the measurement.
[0167]
Next, when the monomolecular film 24 was continuously irradiated with ultraviolet rays, the azo group was changed from the trans type to the cis type, and the current value became approximately 0A. After that, when the visible light was irradiated, the azo group was transferred from the cis type to the trans type, and the original conductivity was reproduced.
[0168]
Note that the decrease in conductivity due to such ultraviolet irradiation is caused by the isomerization of the azo group (trans-type to cis-type), which causes the polyacetylene-type conjugated bond in the monomolecular film 24 to be distorted. This is considered to be caused by a decrease in conductivity.
[0169]
That is, the current flowing between the first electrode 22 and the second electrode 23 can be switched by controlling the conductivity of the conductive network 25 by light irradiation.
[0170]
In the case where a polyacetylene type conjugated system is used as the conductive network 25, the resistance increases when the degree of polymerization is low. In other words, in this case, a dopant substance having a charge transfer functional group (for example, a halogen gas or Lewis acid as an acceptor molecule and an alkali metal or ammonium salt as a donor molecule) is added to the conductive network 25. The on-current can be increased by diffusing, that is, doping. For example, when the monomolecular film 24 is doped with iodine, a current of 0.2 mA flows when a voltage of 1 V is applied between the first electrode 22 and the second electrode 23.
[0171]
Here, when a conductive substrate such as a metal is used as the substrate, a monomolecular film may be formed on the surface of the conductive substrate via an insulating thin film. In such a structure, since the substrate itself is not charged, the operational stability of the organic electronic device is improved.
[0172]
Note that when a larger on-current is required, the distance between the first electrode 22 and the second electrode 23 may be reduced or the electrode width may be increased. When a larger on-state current is required, a monomolecular film may be accumulated, or a film having a conductive network may be formed between the first electrode 22 and the second electrode 23.
[0173]
In Example 1 above, the catalytic polymerization method was used to form the conductive network. However, the conductive network can be similarly formed using an electrolytic polymerization method or a polymerization method using irradiation with an energy beam such as light, electron beam, or X-ray. It was.
[0174]
In addition to polyacetylene-type conjugated systems, conjugated systems such as polydiacetylene-type, polyacene-type, polypyrrole-type, and polychenylene-type can be used as the conductive network. When performing the catalytic polymerization, a pyrrole group, a chelenylene group, a diacetylene group, or the like was suitable as the polymerizable group in addition to the acetylene group.
[0175]
In addition to the chemical adsorption method, the Langmuir Blodget method was applicable to the production of a monomolecular film or a monomolecular cumulative film.
[0176]
When the counter electrode forming step for forming the first and second electrodes is performed before the conductive network forming step for polymerizing the molecules constituting the organic thin film, the first step is performed when the conductive network is formed. 1 and the second electrode could be used for electrolytic polymerization. That is, a voltage is applied between the first and second electrodes of the organic thin film composed of an organic molecule group having a pyrrole group or a chelenylene group as an electropolymerizable functional group, and the first and second electrodes are The organic thin film could be selectively electropolymerized.
[0177]
After forming a monomolecular film composed of an organic molecule group having a pyrrole group or a chelenylene group, a first electrode, and a second electrode on a substrate, the organic solvent containing a substance containing the pyrrole group or the chelenylene group is dissolved in the organic solvent. Immersion and application of a first voltage between the first electrode and the second electrode, contact with the first or second electrode and the organic solvent, and placement above the monomolecular film A second voltage was applied between the electrode and the external electrode to form a film on the surface of the monomolecular film, and at the same time, a conductive network could be formed on each of the monomolecular film and the film. In this case, the organic electronic device includes an organic thin film composed of a monomolecular film part and a polymer film-like film part each having a conductive network.
[0178]
In addition, a monomolecular film made of an organic molecule group having a pyrrole group or a chelenylene group, a first electrode, and a second electrode were formed on the substrate, and a conductive network having the first structure was formed on the monomolecular film. Thereafter, the substrate is immersed in an organic solvent in which a substance containing a pyrrole group or a chenylene group is dissolved, a first voltage is applied between the first and second electrodes, and the first or second electrode and the organic solvent are applied. A second voltage is applied between the electrode and the external electrode disposed above the organic thin film to form a coating on the surface of the monomolecular film on which the polypyrrole type or polychenylene type conductive network is formed. At the same time, a conductive network having a second structure of polypyrrole type or polychenylene type could be formed on the coating film. In this case, the organic electronic device includes an organic thin film composed of a monomolecular film part and a polymer film-like film part each having a conductive network.
[0179]
In addition, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. are added to monomolecular films or monomolecular cumulative films composed of organic molecules having acetylene groups or diacetylene groups which are functional groups that are polymerized by an energy beam as polymerizable groups. Irradiation of the energy beam allowed the molecules of the monomolecular film or monomolecular cumulative film to polymerize and form a conductive network.
[0180]
The substance that can be used as the material of the monomolecular film is generally a substance represented by the chemical formula (3), and can be used in the same manner as in Example 1.
[Chemical 3]

Here, A is a functional group that forms a conductive network by bonding with a conjugated bond, B is a photoresponsive functional group, D is an atom that reacts with active hydrogen on the substrate surface, such as a halogen atom, an isocyanate group, or an alkoxyl group. Or a functional group, E is a functional group such as hydrogen, methyl group, ethyl group, methoxy group, ethoxy group, or other alkyl group. M and n are integers, and m + n is 2 or more and 25 or less, particularly preferably 10 or more and 20 or less. Furthermore, p is an integer and is 1, 2, or 3.
[0181]
More specifically, substances represented by chemical formulas (4) to (7) can be used.
[Formula 4]

[Chemical formula 5]

[Chemical 6]

[Chemical 7]

Here, m and n are integers, and m + n is 2 or more and 25 or less.
[0182]
(Example 2)
First, a pyrrole group (C _Four H _Four N—), an oxycarbonyl group (—OCO—) that is a polarizable functional group, and a chemical formula (8) that reacts with active hydrogen (eg, hydroxyl group (—OH)) on the substrate surface. )
[Chemical 8]

A chemisorbed liquid was prepared by diluting to 1% with a dehydrated dimethyl silicone organic solvent.
[0183]
Next, aluminum (Al) is vapor-deposited on the surface of the insulating polyimide substrate 31 (or the first insulating film such as the silica film 38 may be provided on the surface of the conductive metal substrate), and a photolithography method is applied. A third electrode 23 having a length of 15 μm and a width of 40 μm was formed by etching. Further, the third electrode 37 made of Al is electrolytically oxidized to form an insulating alumina (Al ₂ O _Three ) A film 39 was formed. (Fig. 6 (a))
[0184]
Next, after forming a mask pattern with a resist, leaving a portion for forming a monomolecular film, chemical adsorption is performed by immersing in the adsorption liquid, and chemical adsorption is selectively performed on the opening of the mask pattern. The unreacted substance remaining on the surface was removed by washing with chloroform, and then the resist mask pattern was removed to selectively form a monomolecular film 34 made of the substance. (Fig. 6 (b))
[0185]
At this time, the surface of the substrate 31 in the opening (silica film 38 and Al ₂ O _Three Since a large number of hydroxyl groups containing active hydrogen exist on the surface of the film 39), a molecule represented by the chemical formula (9) in which the chlorosilyl group (-SiCl) of the substance undergoes a dehydrochlorination reaction with the hydroxyl group and is covalently bonded to the surface of the substrate 31. A monomolecular film 34 composed of
[Chemical 9]

[0186]
Next, after a nickel thin film is deposited on the entire surface, the first electrode 22 and the second electrode 23 having a gap distance of 10 μm and a length of 30 μm are sandwiched between the third electrodes 37 by applying a photolithography method. Formed. (Fig. 2 (c))
Next, it is immersed in an acetonitrile solution, an electric field of about 5 V / cm is applied between the first and second electrodes, and the conductive network 35 is interposed between the first electrode 22 and the second electrode 23 by electrolytic polymerization. Formed to connect. At this time, since conjugated bonds are formed in a self-organizing manner along the direction of the electric field, the first electrode 22 and the second electrode 23 are electrically connected by the conductive network 35 when the polymerization is completed. Will be. (Fig. 6 (c))
Finally, the third electrode 37 was taken out from the substrate 31 side, and a three-terminal organic electronic device could be manufactured.
[0187]
In this three-terminal organic electronic device, since the first electrode 22 and the second electrode 23 are connected by a polypyrrole-type conductive network 35, the first electrode 22 is doped after BF- ions are doped. When a voltage of 1 V was applied between the first electrode 22 and the second electrode 23 and the voltage between the first electrode 22 and the third electrode 27 was 0 V, a current of about 0.5 mA flowed.
[0188]
Next, when a voltage of 1 V is applied between the first electrode 22 and the second electrode 23 and a voltage of 5 V is applied between the first electrode 22 and the third electrode 37, The current value between the first electrode 22 and the second electrode 23 was approximately 0A. Thereafter, when the voltage between the first electrode 22 and the third electrode 27 is returned from 5 V to 0 V, the original conductivity is reproduced.
[0189]
Such a decrease in conductivity is caused by polarization of an oxycarbonyl group (—OCO—) that is a polar functional group when a voltage of 5 V is applied between the third electrode 37 and the first electrode 22. It is conceivable that the polypyrrole-type conjugated system is caused by the decrease in the conductivity of the strained conductive network 35 due to the increase in.
[0190]
That is, the current that flows between the first electrode 22 and the second electrode 23 by controlling the conductivity of the conductive network with the voltage applied between the first electrode 22 and the third electrode 37. Could be switched.
Here, when the polar functional group was a polarizable oxycarbonyl group, switching could be performed at a very high speed. In addition to the oxycarbonyl group, a molecule having a functional group such as a carbonyl group could be used.
[0191]
Also, polyacetylene type, polydiacetylene type, polyacene type, polypyrrole type, and polychenylene type conjugated systems can be used as the conductive network, and the conductivity was high.
In addition to the pyrrole group that is an electropolymerizable functional group, a chelenylene group could be used as the polymerizable group that is bonded by a conjugated bond that forms a conductive network. If the polymerization method was changed, a substance having an acetylene group or a diacetylene group could be used.
[0192]
In addition to the chemical adsorption method, the Langmuir Blodget method could be used for the production of a monomolecular film or a monomolecular cumulative film.
[0193]
In addition, when the step of forming the first electrode 22 and the second electrode 23 is performed before the step of polymerizing the organic thin film, the first electrode 22 and the second electrode 23 are electrolyzed in the production of the conductive network. It was available for polymerization. That is, a voltage is applied between the first electrode 22 and the second electrode 23 of an organic thin film made of an organic molecule group having a pyrrole group or a chelenylene group as an electropolymerizable functional group, and the first electrode 22 The organic thin film between the electrodes with the second electrode 23 could be selectively electropolymerized.
[0194]
After forming the third electrode 37, the monomolecular film 34 made of an organic molecule group having a pyrrole group or a chelenylene group, the first electrode, and the second electrode on the substrate, the pyrrole group or the chelenylene group is contained. A first voltage is applied between the first electrode 22 and the second electrode 23 by immersing in an organic solvent in which a substance is dissolved, and the first electrode 22 or the second electrode 23 and the organic A second voltage is applied between the electrode and the external electrode disposed above the monomolecular film 34 in contact with the solvent to form a film on the surface of the monomolecular film 34 and simultaneously to each of the monomolecular film and the film. Polypyrrole type or polychenylene type conductive networks could be formed. In this case, the organic electronic device includes an organic thin film composed of a monomolecular film part and a polymer film-like film part each having a conductive network.
[0195]
A third electrode, a monomolecular film made of an organic molecule group having a pyrrole group or a chelenylene group, a first electrode, and a second electrode are formed on the substrate, and a polypyrrole or polychenylene type first molecule is formed on the monomolecular film. After forming a conductive network having a structure of 1, a first voltage is applied between the first electrode and the second electrode by immersing in an organic solvent in which a substance containing a pyrrole group or a chenylene group is dissolved. And a monomolecular film in which a conductive network is formed by applying a second voltage between the first or second electrode and the external electrode disposed in contact with the organic solvent and disposed above the organic thin film A conductive film having a second structure of the polypyrrole type or polychenylene type could be formed simultaneously with the formation of a film on the surface of the film. In this case, the organic electronic device includes an organic thin film composed of a monomolecular film part and a polymer film-like film part each having a conductive network.
[0196]
In the formation of the conductive network, other than the electropolymerization, molecules of a monomolecular film or a monomolecular cumulative film having a pyrrole group, a chelenylene group, an acetylene group, a diacetylene group, etc., which are catalytic polymerizable functional groups as a polymerizable group can be combined. It was possible to form a conductive network by catalytic polymerization.
Furthermore, energy such as ultraviolet rays, far ultraviolet rays, electron beams or X-rays is added to a monomolecular film or a monomolecular cumulative film composed of an organic molecule group having a beam irradiation polymerizable group such as an acetylene group or a diacetylene group as a polymerizable group. Beams were irradiated to polymerize organic molecules and form a conductive network.
[0197]
(Example 3)
In the same manner as in Example 2, a plurality of organic electronic devices were arranged on the acrylic substrate surface as liquid crystal operation switches to produce a TFT array substrate, and an alignment film was produced on the surface.
Next, after forming a pattern of the sealing adhesive except for the sealing portion by using a screen printing method, precuring is performed so that the alignment film surfaces of the color filter substrate face each other, and bonding and pressure bonding are performed. Was cured to produce a liquid crystal cell.
Finally, when a predetermined liquid crystal was vacuum-injected and sealed, a liquid crystal display device could be manufactured.
[0198]
In this method, since it is not necessary to heat the substrate in the production of the TFT array, a TFT type liquid crystal display device having a sufficiently high image quality can be produced even when a substrate having a low glass transition (Tg) point such as an acrylic substrate is used.
[0199]
(Example 4)
In the same manner as in Example 2, a plurality of three-terminal organic electronic devices were arranged on the acrylic substrate surface as liquid crystal operation switches to produce a TFT array substrate. Thereafter, a pixel electrode connected to the three-terminal organic electronic device is formed using a known method, and a light emitting layer made of a fluorescent material that emits light when an electric field is applied is formed on the TFT array substrate. An electroluminescent color display device could be manufactured by forming a transparent common electrode facing the substrate on the light emitting layer.
[0200]
When the light emitting layer was formed, an electroluminescent color display device could be manufactured by forming three types of elements that emit red, blue, and green light at predetermined positions.
[0201]
【The invention's effect】
As described above, in the present invention, first, the first electrode formed on the substrate, the second electrode spaced apart from the first electrode, and the first and second electrodes are provided. An organic thin film that is electrically connected to the two-terminal organic electronic device, wherein the organic thin film is composed of an organic molecule group having a photoresponsive functional group, and the molecules constituting the organic molecule group are There is an effect that it is possible to provide a two-terminal organic electronic device having a conductive network conjugated.
[0202]
Second, a first electrode formed on a substrate, a second electrode spaced apart from the first electrode, an organic thin film electrically connecting the first and second electrodes, A three-terminal organic electronic device comprising a third electrode sandwiched between and insulated from a substrate and the organic thin film, wherein the third electrode is the first electrode or the second electrode And an electrode capable of controlling an electric field applied to the organic thin film by applying a voltage between the third electrode, and the organic thin film is composed of an organic molecule group having a polar functional group, and molecules constituting the organic molecule group There is an effect that it is possible to provide a three-terminal organic electronic device having a conductive network having a conjugate bond to each other.
[0203]
Thirdly, the three-terminal organic electronic device using a material substance having a polar functional group has an effect of providing an organic TFT that performs switching at an extremely high speed as compared with the conventional example. Therefore, there is an effect that it is possible to provide a liquid crystal display device, an electroluminescence type display device, and the like using a three-terminal organic electronic device as an operation switch of a display element.
[0204]
Fourth, when forming the array substrate by arranging and arranging the three-terminal organic electronic device operation switch of the present invention on the substrate surface, a plastic substrate having excellent flexibility is not included because a process at high temperature is not included. There is an effect that the used display device can be provided.
[0205]
[Brief description of the drawings]
FIG. 1 is a cross-sectional conceptual diagram in which the structure of a two-terminal organic electronic device is expanded to the molecular level;
(A) is a conceptual cross-sectional view of a structure in which the first and second electrodes are directly formed on the substrate,
(B) is a conceptual cross-sectional view of a structure in which first and second electrodes are formed on an organic thin film.
FIG. 2 is a conceptual diagram illustrating a change in conductivity of a two-terminal organic electronic device with respect to light irradiation;
(A) is a conceptual diagram illustrating the change in conductivity of an organic thin film with respect to light irradiation,
(B) is a conceptual diagram explaining the switching operation | movement accompanying photoisomerization.
FIG. 3 is a cross-sectional conceptual diagram in which the structure of a three-terminal organic electronic device is expanded to the molecular level;
(A) is a conceptual cross-sectional view of a structure in which the first and second electrodes are directly formed on the substrate,
(B) is a conceptual cross-sectional view of a structure in which first and second electrodes are formed on an organic thin film.
FIG. 4 is a conceptual diagram illustrating a change in conductivity of a three-terminal organic electronic device with respect to an applied electric field;
(A) is a conceptual diagram illustrating the dependency between the conductivity of the conductive network and the voltage applied to the third electrode;
(B) is a conceptual diagram explaining the switching operation | movement by the presence or absence of the voltage application to a 3rd electrode.
5 is a process cross-sectional conceptual diagram for explaining the manufacturing process of the two-terminal organic electronic device in Example 1. FIG.
(A) is a conceptual cross-sectional view in which a state where a monomolecular film is formed is enlarged to a molecular level;
(B) is the conceptual cross-sectional view which expanded the state which formed the conductive network by superposition | polymerization to the molecular level.
6 is a process cross-sectional conceptual diagram for explaining the manufacturing process of the three-terminal organic electronic device in Example 3. FIG.
(A) is the conceptual cross-sectional view which expanded the state which formed the 3rd electrode,
(B) is a cross-sectional conceptual diagram in which a state where a monomolecular film is formed is enlarged to a molecular level;
(C) is a cross-sectional conceptual diagram in which a state in which a conductive network is formed by polymerization is expanded to a molecular level.
[Explanation of symbols]
1 Substrate
2 First electrode
3 Second electrode
4 Monomolecular film with photoresponsive functional group
5 Conductive network
6 Focused irradiation light
11 Substrate
12 First electrode
13 Second electrode
14 Monomolecular film with polar functional group
15 Conductive network
17 Third electrode
18 First insulating film
19 Second insulating film
21 Glass substrate
22 First electrode made of nickel
23 Second electrode made of nickel
24 Chemisorbed monolayer consisting of molecules containing acetylene and azo groups
25 Polyacetylene-type conductive network
31 Polyimide substrate
34 Monomolecular film composed of molecules containing a pyrrole group and an oxycarbonyl group
35 Polypyrrole-type conductive network
37 Third electrode made of aluminum
38 Silica membrane
39 Alumina membrane

Claims (46)

Formed on the substrate,
A first electrode;
A second electrode spaced from the first electrode;
An organic thin film electrically connecting the first and second electrodes;
A two-terminal organic electronic device comprising:
The organic thin film is composed of an organic molecule group including a plurality of organic molecules whose one molecular terminal is bonded and fixed to the substrate.
The organic molecule has a polymerizable group that forms a conductive network by being conjugated and bonded within the molecule, and a photoresponsive functional group that changes its spatial arrangement upon irradiation with light.
Between the organic molecules constituting the organic molecule group, by polymerization of the polymerizable group, conjugated bond to each other to form the conductive network,
The photoresponsive functional group is irradiated with light and changes its spatial arrangement, whereby a conjugate bond of the conductive network is distorted, thereby controlling conductivity of the conductive network. 2-terminal organic electronic device. The two-terminal organic electronic device according to claim 1,
The two-terminal organic electronic device, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film in which organic molecules are fixed on a substrate. The two-terminal organic electronic device according to claim 1 or 2,
The two-terminal organic electronic device according to claim 1, wherein the conductivity of the conductive network varies depending on the amount of light applied to the organic thin film. The two-terminal organic electronic device according to claim 3, wherein
The conductivity of the conductive network is changed to the first conductivity or the second conductivity by the first light or the second light with different wavelengths irradiated to the organic thin film, respectively, and after the light shielding, Alternatively, a two-terminal organic electronic device characterized in that the second conductivity is maintained. The two-terminal organic electronic device according to any one of claims 1 to 4,
The two-terminal organic electronic device, wherein the photoresponsive functional group is a functional group capable of photoisomerization. The two-terminal organic electronic device according to claim 5, wherein
The two-terminal organic electronic device, wherein the photoisomerizable functional group is an azo group. The two-terminal organic electronic device according to any one of claims 1 to 6,
The two-terminal organic electronic device, wherein the conductive network includes one or more conjugated systems selected from the group consisting of a conjugated system of polyacetylene type, polydiacetylene type, polypyrrole type, polychenylene type, and polyacene type. Formed on the substrate,
A first electrode;
A second electrode spaced from the first electrode;
An organic thin film electrically connecting the first and second electrodes;
A third electrode sandwiched between and insulated from the substrate and the organic thin film;
A three-terminal organic electronic device comprising:
The third electrode is an electrode that controls an electric field applied to the organic thin film by applying a voltage between the first electrode and the second electrode.
The organic thin film is composed of an organic molecule group including a plurality of organic molecules whose one molecular terminal is bonded and fixed to the substrate.
The organic molecule has a polymerizable group that forms a conductive network by conjugation by polymerization in the molecule and a polar functional group that distorts the conjugated bond of the conductive network by polarization.
Between the organic molecules constituting the organic molecule group, by polymerization of the polymerizable group,
Conjugated bond to each other to form the conductive network,
A three-terminal organic electronic device , wherein the conjugated bond of the conductive network is distorted by polarization of the polar functional group, whereby the conductivity of the conductive network is controlled . The three-terminal organic electronic device according to claim 8, wherein
A three-terminal organic electronic device, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film fixed on a substrate. The three-terminal organic electronic device according to claim 8 or 9, wherein
The three-terminal organic electronic device according to claim 1, wherein the conductivity of the conductive network is changed by an electric field applied to the organic thin film. The three-terminal organic electronic device according to any one of claims 8 to 10,
A three-terminal organic electronic device, wherein the polar functional group is a polarizable functional group that polarizes when an electric field is applied. The three-terminal organic electronic device according to claim 11, wherein
The three-terminal organic electronic device, wherein the polarizable functional group is a carbonyl group or an oxycarbonyl group. The three-terminal organic electronic device according to any one of claims 9 to 12,
The three-terminal organic electronic device, wherein the conductive network includes one or more conjugated systems selected from the group consisting of polyacetylene type, polydiacetylene type, polychenylene type, polypyrrole type, and polyacene type conjugated systems. On an insulating substrate or a substrate with an insulating film in which an insulating film is formed on the surface of any substrate,
An organic thin film composed of an organic molecule group including a plurality of organic molecules having a polymerizable group that forms a conductive network by conjugation by polymerization and a photoresponsive functional group that changes its spatial arrangement when irradiated with light. Forming a film on the substrate by bonding and fixing one molecular terminal of each organic molecule on the substrate;
A conductive network forming step of forming the conductive network connected to each other by a conjugated bond by polymerizing the polymerizable group between the organic molecules constituting the organic molecule group;
A counter electrode forming step of forming a first electrode and a second electrode spaced apart from each other so as to contact the conductive network;
The manufacturing method of the 2 terminal organic electronic device characterized by including. In the manufacturing method of the 2 terminal organic electronic device of Claim 14,
The two-terminal organic electronic device, wherein the photoresponsive functional group is a functional group capable of photoisomerization. On an insulating substrate or a substrate with an insulating film in which a first insulating film is formed on the surface of an arbitrary substrate,
Forming a third electrode;
A polymerizable group that forms a conductive network by conjugation by polymerization on the substrate so as to cover the third electrode directly or via a second insulating film, and a conjugated bond of the conductive network by polarization thereof A film forming step of forming an organic thin film composed of an organic molecule group including a plurality of organic molecules having a polar functional group that distorts the substrate by bonding and fixing one molecular terminal of each organic molecule on the substrate;
A conductive network forming step of forming the conductive network connected to each other by a conjugated bond by polymerizing the polymerizable group between the organic molecules constituting the organic molecule group;
A counter electrode forming step of forming a first electrode and a second electrode spaced apart from each other and spaced apart from a third electrode so as to contact the conductive network;
The manufacturing method of the 3 terminal organic electronic device characterized by the above-mentioned. In the manufacturing method of the 3 terminal organic electronic device of Claim 16,
The method for producing a three-terminal organic electronic device, wherein the polar functional group is a polarizable functional group that polarizes when an electric field is applied. In the manufacturing method of the organic electronic device in any one of Claim 14 to 17,
The organic thin film is a monomolecular film in which organic molecules are arranged in a monomolecular layer or a monomolecular cumulative film in which a plurality of monomolecular films are laminated. In the manufacturing method of the organic electronic device of Claim 18,
A method for manufacturing an organic electronic device, wherein a chemical adsorption method or a Langmuir-Blodgett method is applied in the film forming step. In the manufacturing method of the organic electronic device of Claim 19,
A method for producing an organic electronic device, wherein a silane-based surfactant is used in a film forming process to which the chemical adsorption method is applied. In the manufacturing method of the organic electronic device in any one of Claim 14 to 18,
A method for producing an organic electronic device, wherein, in the conductive network forming step, molecules constituting the organic thin film are conjugated to each other by polymerization or by polymerization and crosslinking after polymerization to form a conductive network. In the manufacturing method of the organic electronic device of Claim 21,
Production of an organic electronic device, wherein the cross-linking step is one or more cross-linking steps selected from the group consisting of a cross-linking step by catalysis, a cross-linking step by electrolysis, and a cross-linking step by energy beam irradiation. Method. In the manufacturing method of the organic electronic device of Claim 21,
The method of manufacturing an organic electronic device, wherein the counter electrode forming step is performed before the conductive network forming step. In the manufacturing method of the organic electronic device of Claim 23,
When the polymerizable group of the molecules constituting the organic thin film is an electrolytic polymerizable group having an electrolytic polymerizable property, a voltage is applied between the first and second electrodes to perform electrolytic polymerization. A method for manufacturing an organic electronic device. In the manufacturing method of the organic electronic device of Claim 24,
The method for producing an organic electronic device, wherein the electrolytic polymerizable group is a pyrrole group or a chainylene group In the manufacturing method of the organic electronic device of Claim 24,
When the electropolymerizable group is a pyrrole group or a chainylene group, and the organic thin film is a monomolecular film,
After the step of forming the counter electrode, the substrate is immersed in an organic solvent in which a substance containing a pyrrole group or a chelenylene group is dissolved, and is in contact with the first or second electrode and between the first or second electrode and the organic solvent. A voltage is applied between the electrode and the external electrode disposed above the organic thin film to form a film composed of molecules having a pyrrole group or a chelenylene group on the surface of the monomolecular film, and the monomolecule. A method for producing an organic electronic device, comprising forming a conductive network on each of a film and the film. In the manufacturing method of the organic electronic device of Claim 21,
A method for producing an organic electronic device, characterized in that, in the conductive network forming step, molecules constituting the organic thin film having a catalytic polymerizable catalytic polymerizable group as the polymerizable group are subjected to catalytic polymerization. The method of manufacturing an organic electronic device according to claim 27,
The method for producing an organic electronic device, wherein the catalytic polymerizable group is a pyrrole group, a chelenylene group, an acetylene group, or a diacetylene group. In the manufacturing method of the organic electronic device of Claim 21,
An organic electronic device characterized in that, in the conductive network forming step, molecules constituting the organic thin film having a beam irradiation polymerizable group that is polymerized by irradiation with an energy beam as the polymerizable group are polymerized by irradiation with an energy beam. Production method. The method of manufacturing an organic electronic device according to claim 29,
The method for producing an organic electronic device, wherein the beam irradiation polymerizable group is an acetylene group or a diacetylene group. In the manufacturing method of the organic electronic device of Claim 29 or 30,
In the said conductive network formation process, an ultraviolet-ray, a far-ultraviolet ray, an X-ray, or an electron beam is used as said energy beam, The manufacturing method of the organic electronic device characterized by the above-mentioned. Formed on the substrate,
A first electrode;
A second electrode spaced from the first electrode;
An organic thin film electrically connecting the first and second electrodes,
The organic thin film is composed of an organic molecule group including a plurality of organic molecules whose one molecular terminal is bonded and fixed to the substrate.
The organic molecule has a polymerizable group that forms a conductive network by being conjugated and bonded within the molecule, and a photoresponsive functional group that changes its spatial arrangement upon irradiation with light.
A method of operating a two-terminal organic electronic device in which the conductive network is formed by a conjugated bond between the organic molecules constituting the organic molecule group by polymerization of the polymerizable group.
A conjugate bond of the conductive network is obtained by changing a spatial arrangement of the photoresponsive functional groups by irradiating the organic thin film with light while a voltage is applied between the first and second electrodes. And switching the current flowing between the first and second electrodes by changing the conductivity of the conductive network, thereby operating the two-terminal organic electronic device. A method of operating a two-terminal organic electronic device according to claim 32,
The photoresponsive functional group is a functional group that undergoes photoisomerization, and the conductivity of the conductive network is changed by irradiation with the first light or the second light with different wavelengths irradiated on the organic thin film. A method of operating a two-terminal organic electronic device characterized. The method of operating a two-terminal organic electronic device according to claim 33,
The method for operating a two-terminal organic electronic device, wherein the photoisomerizable functional group is an azo group. A method of operating a two-terminal organic electronic device according to claim 33 or 34,
An operation method of a two-terminal organic electronic device, wherein ultraviolet light or visible light is used as the first or second light applied to the organic thin film, respectively. Formed on the substrate,
A first electrode;
A second electrode spaced from the first electrode;
An organic thin film electrically connecting the first and second electrodes;
A third electrode sandwiched between and insulated from the substrate and the organic thin film, wherein the third electrode is formed by the voltage applied between the first electrode or the second electrode; An electrode that controls the electric field applied to the thin film,
The organic thin film is composed of an organic molecule group including a plurality of organic molecules whose one molecular terminal is bonded and fixed to the substrate.
Operation of a three-terminal organic electronic device in which the organic molecule has a polymerizable group that forms a conductive network by conjugated bonding within the molecule and a polar functional group that distorts the conjugated bond of the conductive network by polarization thereof A method,
Polarizing the polarizable functional group with a voltage applied between the first or second electrode and the third electrode in a state where a voltage is applied between the first and second electrodes. Distorting the conjugated bond of the network, thereby changing the conductivity of the conductive network and switching the current flowing between the first and second electrodes. . A method of operating a three terminal organic electronic device according to claim 36,
The method for operating a three-terminal organic electronic device, wherein the polar functional group is a polarizable functional group. In the operation | movement method of the organic electronic device in any one of Claim 32 to 37,
A method of operating an organic electronic device, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film bonded and fixed on a substrate. An array substrate in which a plurality of switch elements are arranged in a matrix on the first substrate and the first alignment film is formed on the surface thereof;
A color filter substrate in which color elements are arranged in a matrix on a second substrate and a second alignment film is formed on the surface thereof;
In a liquid crystal display device comprising the liquid crystal sealed between the array substrate and the color filter substrate facing each other with the first alignment film and the second alignment film facing inside ,
The switch element is formed on the first substrate.
A first electrode;
A second electrode spaced from the first electrode;
An organic thin film electrically connecting the first and second electrodes;
A third electrode sandwiched between and insulated from the substrate and the organic thin film,
The third electrode is an electrode that controls an electric field applied to the organic thin film by applying a voltage between the first electrode and the second electrode.
The organic thin film is composed of an organic molecule group including a plurality of organic molecules whose one molecular terminal is bonded and fixed to the substrate.
The organic molecule has a polymerizable group that forms a conductive network by conjugation by polymerization in the molecule and a polar functional group that distorts the conjugated bond of the conductive network by polarization.
Between the organic molecules constituting the organic molecule group, by polymerization of the polymerizable group, conjugated bond to each other to form the conductive network,
The liquid crystal display device according to claim 1, wherein the polar functional group is polarized by application of the electric field, whereby the conjugated bond of the network is distorted, and thereby the conductivity of the conductive network is controlled . An array substrate on which multiple switch elements arranged arranged in a matrix on a substrate,
A common electrode facing the array substrate;
In an electroluminescence type display device having a light emitting layer made of a fluorescent material that emits light by applying an electric field, formed between the array substrate and the common electrode,
The switch element is formed on the substrate,
A first electrode;
A second electrode spaced from the first electrode;
An organic thin film electrically connecting the first and second electrodes;
A third electrode sandwiched between and insulated from the substrate and the organic thin film,
The third electrode is an electrode that controls an electric field applied to the organic thin film by applying a voltage between the first electrode and the second electrode.
The organic thin film is composed of an organic molecule group including a plurality of organic molecules whose one molecular terminal is bonded and fixed to the substrate.
The organic molecule has a polymerizable group that forms a conductive network by conjugation by polymerization in the molecule and a polar functional group that distorts the conjugated bond of the conductive network by polarization.
Between the organic molecules constituting the organic molecule group, by polymerization of the polymerizable group, conjugated bond to each other to form the conductive network,
The electroluminescent display device, wherein the polar functional group is polarized by application of the electric field, whereby the conjugated bond of the network is distorted, whereby the conductivity of the conductive network is controlled . In the electroluminescence type display device according to claim 40,
An electroluminescence type display device characterized in that three kinds of the fluorescent materials emitting red, blue or green light are arranged and displayed in color. The display device according to any one of claims 39 to 41,
A display device, wherein the organic thin film is a monomolecular film or a monomolecular cumulative film fixed on a substrate. An array substrate forming step of forming a plurality of switch elements so as to be arranged in a matrix on the first substrate and forming a first alignment film on the surface;
Forming a color filter by arranging color elements in a matrix on the second substrate surface and forming a second alignment film on the surface; forming a color filter substrate;
The array substrate and the color filter substrate face each other at a predetermined interval with the first alignment film and the second alignment film inside, and a liquid crystal is filled between the array substrate and the color filter substrate. In a method for manufacturing a liquid crystal display device comprising:
The step of forming the switch element includes:
On the first substrate,
Forming a third electrode;
A polymerizable group that forms a conductive network by conjugation by polymerization on the first substrate so as to cover the third electrode directly or via a second insulating film, and the conductive network by polarization thereof. An organic thin film composed of an organic molecule group including a plurality of organic molecules having a polar functional group that distorts the conjugated bond of the organic molecule, with one molecular terminal of each organic molecule on the first substrate or the third electrode A film forming process to be formed by bonding and fixing;
A conductive network forming step of forming the conductive network connected to each other by a conjugated bond by polymerizing the polymerizable group between the organic molecules constituting the organic molecule group;
A counter electrode forming step of forming a first electrode and a second electrode spaced apart from each other and spaced apart from a third electrode so as to contact the conductive network;
A method of manufacturing a liquid crystal display device comprising: An array substrate forming step of forming a plurality of switch elements so as to be arranged in a matrix on the substrate;
A light emitting layer forming step of forming a light emitting layer made of a fluorescent material that emits light upon application of a voltage on the array substrate;
A common electrode forming step of forming a common electrode film on the light emitting layer;
In the manufacturing method of the electroluminescence type display device comprising:
The step of forming the switch element includes:
On the substrate,
Forming a third electrode;
A polymerizable group that forms a conductive network by conjugation by polymerization on the substrate so as to cover the third electrode directly or via a second insulating film, and a conjugated bond of the conductive network by polarization thereof An organic thin film composed of an organic molecule group including a plurality of organic molecules having a polar functional group that distorts the organic molecule, by binding and fixing one molecular terminal of each organic molecule on the substrate or the third electrode, A film forming step to be formed;
A conductive network forming step of forming the conductive network connected to each other by a conjugated bond by polymerizing the polymerizable group between the organic molecules constituting the organic molecule group;
And a counter electrode forming step of forming a first electrode and a second electrode spaced apart from each other and spaced apart from a third electrode so as to contact the conductive network. Device manufacturing method. In the manufacturing method of the electroluminescence type display device according to claim 44,
3. A method of manufacturing an electroluminescence type display device, comprising: forming three kinds of light emitting materials that emit red, blue, or green light at predetermined positions in the light emitting layer forming step, and performing color display. In the manufacturing method of the display apparatus in any one of Claim 43 to 45,
The method for manufacturing a display device, wherein the organic thin film is a monomolecular film in which organic molecules are arranged in a monomolecular layer or a monomolecular cumulative film formed by laminating monomolecular films.

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