JP3981720B2 - Method for manufacturing molecular device - Google Patents

Description

一般式（Ａ）中、Ａ〜Ｄは、それぞれ、桂皮酸基、α−シアノ桂皮酸基、クマリン基、カルコン基、シンナミリデンアセテート基、ｐ―フェニレンジアクリレート基、アセチレン基、ジアセチレン基、ジフェニルアセチレン基のいずれかである。
（２）前記一般式（Ａ）で表されるデンドリマーの替わりに，下記一般式（Ｉ）で表されるデンドリマーを用いる上記（１）に記載の分子デバイスの製造方法。
【化１０】

（上記式において、ｎは３以上１０以下の数を示す。）
（３）前記一般式（Ａ）で表されるデンドリマーの替わりに，下記一般式（ＩＩ）で表されるデンドリマーを用いる上記（１）に記載の分子デバイスの製造方法。
【化１１】

（上記式(II)において、ｎは３以上１０以下の数を示し，ＲはＣ_１−Ｃ_１０アルキニレン基又はＣ_２−Ｃ_１０アルケニレン基を示す。）
（４） 結合性残基をその末端部位に有する下記の一般式（Ａ）で表されるデンドリマーと、前記結合性残基をスペクトル増感できる分子（増感剤）とを含む固体に光を照射し、前記増感剤に光エネルギーを吸収させ、前記増感剤が吸収したエネルギーを前記デンドリ マーへ伝え、前記デンドリマーの結合性残基に架橋反応を起こさせる工程を含む、架橋反応部分によって形成された殻構造を有する分子デバイスの製造方法。
【化１２】

一般式（Ａ）中、Ａ〜Ｄは、それぞれ、桂皮酸基、α−シアノ桂皮酸基、クマリン基、カルコン基、シンナミリデンアセテート基、ｐ―フェニレンジアクリレート基、アセチレン基、ジアセチレン基、ジフェニルアセチレン基のいずれかである。
（５）前記一般式（Ａ）で表されるデンドリマーの替わりに，下記一般式（Ｉ）で表されるデンドリマーを用いる上記（４）に記載の分子デバイスの製造方法。
【化１３】

（上記式において、ｎは３以上１０以下の数を示す。）
（６）前記一般式（Ａ）で表されるデンドリマーの替わりに，下記一般式（ＩＩ）で表されるデンドリマーを用いる上記（４）に記載の分子デバイスの製造方法。
【化１４】

（上記式(II)において、ｎは３以上１０以下の数を示し，ＲはＣ_１−Ｃ_１０アルキニレン基又はＣ_２−Ｃ_１０アルケニレン基を示す。）
（７）４，４’−ビス（ジメチルアミノ）ベンゾフェノンを包接した下記一般式（Ｉ）で示される化合物に光を照射し、前記４，４’−ビス（ジメチルアミノ）ベンゾフェノンに光エネルギーを吸収させ、前記４，４’−ビス（ジメチルアミノ）ベンゾフェノンが吸収したエネルギーを前記デンドリマーへ伝え、前記デンドリマーの結合性残基に架橋反応を起こさせる工程を含む、
架橋反応部分によって形成された殻構造を有する分子デバイスの製造方法。
【化１５】

（上記式において、ｎは３以上１０以下の数を示す。）
（８）前記光を照射する工程における光は、３６５ｎｍの波長を有する光である上記（７）に記載の分子デバイスの製造方法。
（９）下記一般式（Ｉ）で示されるデンドリマーに４，４’−ビス（ジメチルアミノ）ベンゾフェノンを混合して得られる溶液を沈殿させて得られる沈殿物を含有する溶液に、３６５ｎｍの波長を有する光を照射し、前記４，４’−ビス（ジメチルアミノ）ベンゾフェノンに光エネルギーを吸収させ、前記４，４’−ビス（ジメチルアミノ）ベンゾフェノンが吸収したエネルギーを前記デンドリマーへ伝え、前記デンドリマーの結合性残基に架橋反応を起こさせる工程を含む、
架橋反応部分によって形成された殻構造を有する分子デバイスの製造方法。
【化１６】

（上記式において、ｎは３又は５を示す。）
【０００６】
【発明の実施の形態】
以下、本発明の分子構造体、分子集合体、および高密度分子分子デバイスの製造方法などについて詳述する。
本発明の高密度分子分子デバイスの製造方法は、例えば、内部よりも周囲部分の原子密度が高く、周囲部分に結合性残基を有する分子構造体を用いる。本発明の一態様によれば、分子構造体の周囲に存在する結合性残基を分子構造体内であるいは分子構造体間で架橋させることによって分子構造体または分子集合体を製造する。
本発明においては、分子構造体および増感剤を含む溶液または固体に前記増感剤が吸収する波長の光などのエネルギーを与える。溶液または固体中には、結着樹脂（バインダー）やその他の副資材が含まれていてもよい。本発明においては、増感剤に光エネルギーを吸収させ、増感剤が吸収したエネルギーをデンドリマーなどの分子構造体へ伝え、または、電子、イオンやラジカルが移動し、分子構造体に存在する結合性残基が結合反応や架橋反応を起こすことなどを利用して、殻構造を有する分子構造体や分子構造体が3次元的に連結した分子集合体などを製造する。
それぞれの分子構造体は、光メモリ効果など様々な機能を有する分子素子として機能することが好ましい。そして、それら分子構造体が、直線状、格子状、放射状など1次元的、2次元的または３次元的に次々と連結することで様々な機能を有する分子集合体（または分子デバイス）を製造することができる。分子構造体のなかの結合性残基位置を制御することで分子構造体が連結する位置を制御することができ、分子構造体が連結しあい次々と拡大し分子集合体を形成する成長の方向を制御することにつながる。そして、分子集合体を構成する分子構造体同士の間隔も架橋剤の長さなどを制御することにより制御できる。
【０００７】
分子構造体としては、増感剤を包接することができる分子や、増感剤と共有結合、イオン結合、配位結合、金属結合や水素結合した分子が好ましく、特に光・電子機能性を有するデンドリマー（ハイパーブランチポリマー）が好ましいが、結合性残基を有する化合物であれば特に限定されるものではない。デンドリマー分子は、それ自身ナノメートル空間を有し、その空間に異分子や異原子を包接可能という特徴がある。デンドリマーの包接現象に関する詳細は学術誌である、Ｊ．Ｊａｎｓｅｎ，Ｅ．Ｂｅｒｇ，Ｅ．Ｍｅｉｊｅｒ，Ｓｃｉｅｎｃｅ，２６６，１２２６（１９９４）；Ａ．Ｃｏｏｐｅｒ，Ｊ．Ｌｏｎｄｏｎｏ，Ｇ．Ｗｉｇｎａｌｌ，Ｊ．ＭｃＣｌａｉｎ，Ｅ．Ｓａｍｕｌｓｋｉ，Ｊ．Ｌｉｎ，Ａ．Ｄｏｂｒｙｎｉｎ，Ｍ．Ｒｕｂｉｎｓｔｅｉｎ，Ａ．Ｂｕｒｋｅ，Ｊ．Ｆｒｅｃｈｅｔ，Ｊ．ＤｅＳｉｍｏｎｅ，Ｎａｔｕｒｅ，３８９，３６８（１９９７）に記載されている。
【０００８】
分子構造体中の結合性残基（光架橋性残基）としては、（ａ）ビニル基、アクリレート基やメタクリレート基のような不飽和二重結合を有する脂肪族系残基、（ｂ）桂皮酸基、α-シアノ桂皮酸基、クマリン基、カルコン基、シンナミリデンアセテート基、ｐ―フェニレンジアクリレート基やジスチリルピラジン基といった不飽和二重結合を有する芳香族系残基、（ｃ）アセチレン基やジアセチレン基のような不飽和三重結合を有する脂肪族系残基、（ｄ）ジフェニルアセチレン基、フェニルアジド基やジピリジルジアセチレン基のような不飽和三重結合を有する芳香族系残基が挙げられる。また、これら誘導体でも構わない。（ａ）はラジカル重合反応を示すために、光ラジカル重合開始剤を必要とする。一方、（ｂ−ｄ）の光架橋性残基は、〔２π−２π〕光二量化反応のようなウッドワード・ホフマン則に従った光付加反応を示すので、（ａ）の場合のような光重合開始剤は不要である。これら感光性基に関する詳細は、永松 元太郎、乾 英夫 共著、「感光性高分子」、講談社サイエンティフィック、（１９７７）に記載されている。
【０００９】
光により架橋体を作成する場合の照射する光としてはＸ線、電子線、紫外線、可視光線または赤外線（熱線）が用いられる。こららの中でも、紫外線もしくは可視光線が特に好ましい。光源としては、超高圧水銀ランプ、低圧水銀ランプ、キセノンランプ、水銀キセノンランプ、ハロゲンランプ、蛍光灯、気体レーザー、液体レーザー、固体レーザーなどが用いられる。また、これらの光源から放出される光の表面プラズモン輻射などを用いても良い。
結合性残基同士を結合（架橋）させたり、各分子構造体を連結するために、結合性残基を直接励起し、分子内結合や分子間結合を誘起してもよいし、架橋剤などを用いて架橋させることにより分子内架橋および分子間架橋を形成してもよい。各分子構造体を連結するために、結合性残基（光架橋性残基）を直接励起し、光架橋反応を誘起しても構わないが、本発明の特徴は、より効率的かつ選択的にナノメートル領域の分子構造体内や分子構造体間を結合させるために、「スペクトル増感」を利用する。このようにスペクトル増感を利用することで、図１および図２に示したように、分子構造体のナノパーティクルやナノワイヤの作製が容易になる。その際、前述したようにデンドリマー分子の分子内に異分子や異原子を包接できる特徴を利用して、結合性残基（光架橋性残基）をスペクトル増感できるような分子、いわば増感剤を添加することが好ましい。増感剤の詳細については、徳丸 克己、大河原 信 共著、「増感剤」、講談社サイエンティフィック、（１９８７）に記述されている。スペクトル増感の機構には、光電子移動と光エネルギー移動とがあるが、この光エネルギー移動は、さらに光励起状態の違いによって二種類にあり、双極子―双極子相互作用に基づく一重項エネルギー移動（フェルスター型）と電子交換相互作用に基づく三重項エネルギー移動（デックスター型）に大別できる。光エネルギー移動に関する詳細は、Ｎ．Ｔｕｒｒｏ，Ｍｏｄｅｒｎ Ｍｏｌｅｃｕｌａｒ Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ，Ｕｎｉｖｅｒｓｉｔｙ Ｓｃｉｅｎｃｅ Ｂｏｏｋｓ（１９９１）に記載されている。光電子移動の移動距離は０．４ｎｍ〜２．０ｎｍ程度であり、一重項、三重項エネルギー移動の移動距離はそれぞれ１．０〜１０ｎｍ、０．３〜１．０ｎｍ程度である。これらのスペクトル増感機構のうち、本発明は、ナノメートル領域でスペクトル増感する三重項エネルギー移動を利用して、光・電子機能性分子構造体を光連結することが好ましい。
【００１０】
本明細書において架橋とは、２以上の分子構造体を連結する橋渡しとなる連結方法のほかに、結合性残基同士が結合する場合をも意味する。本発明において、架橋剤分子は、分子構造体の結合性残基同士を連結する分子を意味する。例えば、ブタジエン、ペンタジエン、分子構造体の結合性残基の置換物などが挙げられる。架橋剤を用いることで、間隔を制御しつつ分子構造体同士を連結し規則性のある分子集合体を得ることが可能となる。
【００１１】
本発明の、分子デバイスの製造方法では、例えば以下の殻構造を有する分子構造体、または分子集合体が中間生成物として得られてもよい。
殻構造を有する分子構造体（以下、「ナノパーティクル」ともいう。）は、例えば、内部よりも周囲部分の原子密度が高く、周囲部分に結合性残基を有する分子構造体の、結合性残基を架橋させ殻とさせることにより製造される。すなわち、分子構造体の周囲に存在する結合性残基部分同士が結合しあい、殻のような状態になったものが、殻構造を有する分子構造体である。特に、分子構造体の密度が高くなく、分子構造体同士の分子間距離が大きい場合は、ナノパーティクルが主に製造される。図１を用いて、ナノパーティクルの一例を説明する。デンドリマーなどの分子構造体１（ａ）は、その周囲や、内部に増感剤３を有している。そして、増感剤が光照射によるエネルギーを吸収する。増感剤が吸収したエネルギーは、分子構造体へと移行する１０。すると、分子構造体１では、移行されたエネルギーにより、結合性残基同士が結合（架橋）し、架橋反応部分９を形成する（図１ｂ）。このようにして、架橋反応部分が殻を形成し、ナノパーティクルを形成する。
【００１２】
本発明の分子集合体（以下、「ナノワイヤ」ともいう。）は、例えば内部よりも周囲部分の原子密度が高く、周囲部分に結合性残基を有する分子構造体の結合性残基を架橋させ、隣接する分子構造体の結合性残基を結合させることにより製造される。本発明の分子構造体は、例えば分子内に複数の結合性残基を有しているので、架橋が進行すると、例えば、放射状に複数の分子構造体が集合することとなる。特に、分子構造体の密度が高く、分子構造体同士の分子間距離が小さい場合は、ナノワイヤが主に製造される。図２を用いて、ナノワイヤについて説明する。図２ａにあるように結合性残基を周囲部分に有する分子構造体１や増感剤３に光を照射する。増感剤が光照射によるエネルギーを吸収する。増感剤が吸収したエネルギーは、分子構造体へと移行する１０。すると図２ｂにあるように、分子構造体１内の架橋性残基と架橋剤５が架橋し、架橋反応部分９を形成し、分子集合体７が得られる(図２ｂ)。
また、架橋剤を加え架橋を進行させた場合は、分子構造体の結合性残基と架橋剤とが架橋反応を起こし、分子構造体同士の距離を制御した形で分子構造体が集合することにより分子集合体を得ることもできる。
【００１３】
分子デバイスは、例えば、上記のナノパーティクルやナノワイヤを用いたものが挙げられる。分子構造体は、様々な機能を有するが、この分子構造体の集合様式を分子・ナノレベルで制御し分子デバイスを得ることができる。例えば、分子構造体のうち、結合性残基の位置を制御し、架橋させることで、分子集合体の３次元的な構造を制御することができる。
【００１４】
例えば、分子構造体は様々な機能を持つが、このような分子構造体同士を連結し、好ましい方向へ架橋剤を介して次々と連結させることにより分子デバイスを得ることができる。この架橋部分は、機能性のある分子構造体が電気信号などの情報を伝達する際の情報伝達路となり得る。このようにすることで、あたかもニューロンが他のニューロンに向けて軸索を伸ばしていくかのように情報伝達システムとして機能する分子デバイスをえることができる。また、電極間において、この分子デバイスの製造方法を適用させると、分子構造体が連結し、情報を伝達することができる分子デバイスを得ることができる。この分子デバイスを用いれば、機能性を有する分子素子（分子構造体）の連結からなる分子デバイスを用いた機能性製品を得ることができる。図３は、そのような製造方法によって製造され得る分子デバイスである単一電子トランジスタ（ＳＥＴ）の一例を表す概図である。図３において、１は分子素子として機能しうる分子構造体を表し、５は、架橋剤を表し、９は架橋反応部分を表し、１１は電極を表す。図３に示されるＳＥＴは、以下のようにして製造した。まず、５０ｎｍ程度の間隔をもった電極１１を用意した。この電極１１の間隔は、１０ｎｍ〜１μｍ程度とすることができる。その後、その電極間を連結するように、両極（正対照の位置）に結合性残基を有するデンドリマー、増感剤及び架橋剤を有する溶液を用意した。その後、デンドリマーを有する溶液に光を照射した。すると、図３に示されるような分子デバイス（ＳＥＴ）を得ることができた。この分子デバイスに電圧を印加したところ、電流−電圧特性が階段状の現象（クーロンブロッケード現象）が観測された。これから、光照射によって連結した架橋剤が、トンネル層として機能していることがわかった。
【００１５】
図４は、本発明の別の分子デバイスであるＴ字型オプトエレクトロニクス素子（ＴＯＥＤ）の一例を表す概念図である。
以下にＴＯＥＤの製造方法の一例を説明する。まず、雲母からなる基板を用意した。基板は、金、銅、白金、又は雲母などの絶縁体であってもよい。次に、４種類の分子構造体Ａ、Ｂ、ＣおよびＤ、増感剤を含む溶液に基板を浸した。この際、溶液には、架橋剤が含まれていても良い。分子構造体Ａは、１位が、分子構造体Ｂのある結合性残基と結合するような結合性残基を有している。なお、１０位が分子構造体Ｃのある結合性残基と結合する結合性残基を有していてもよい。（この場合、得られる分子デバイスは、ＴＯＥＤではなく、Ｔ字型オプトエレクトロニクスの連続体となる。）また、分子構造体Ｂは、１位、５位、１０位がそれぞれ、分子構造体Ｃ，Ｄ，Ａのある結合性残基と結合するような結合性残基を有する。なお、１５位に、分子構造体Ｄのある結合性残基と結合するような結合性残基を有していても良い。（この場合、得られる分子デバイスは、ＴＯＥＤではなく、Ｔ字型オプトエレクトロニクスの連続体となる。）
この溶液に光を照射したところ、基板上に分子デバイスが形成された。
分子デバイスのうち分子構造体Ａに光信号を入力したところ、約３０ｐｓで、分子構造体Ｂから出力が観測された。
一方、分子構造体Ｄ部分を酸化したところ、分子構造体Ａに光信号を入力しても分子構造体Ｂ部分からの出力は得られなかった。
【００１６】
また、本発明の分子デバイスを用いて、例えば、特開２００１−４４４１３号公報に記載された分子集積回路を製造することができる。本発明の分子デバイスを用いた分子集積回路は、特開２００１−４４４１３号公報に記載された分子集積回路と同様にして、NAND回路、NOR回路、インバーター回路、ランダムアクセスメモリーセル、リードオンリーメモリーセルなどとして利用することができる。本発明においては、光増感反応を利用して、分子デバイスを構築することができるので、より正確かつ迅速に、分子デバイスを製造することができる。
【００１７】
【実施例】
（参考例１−１）桂皮酸アミド残基を分子周囲に有する第一世代ポリプロピレンイミンデンドリマー（一般式（Ｉ）においてｎ＝１）のジクロロメタン溶液に、増感剤として４，４'−ビス（ジメチルアミノ）ベンゾフェノンを各々混合し、過剰量のヘキサンに再沈殿した。この沈殿物をジクロロメタンで透析し、再度、再沈殿を行った。４，４'−ビス（ジメチルアミノ）ベンゾフェノンを包接した第一世代ポリプロピレンイミンデンドリマーのジクロロメタン溶液に、出力が２００Ｗの水銀キセノンランプから波長が３６５ｎｍの光を取り出し、光照射した。この際、溶液の温度は、室温であった。桂皮酸アミド残基は３６５ｎｍの光を吸収しないが、４，４'−ビス（ジメチルアミノ）ベンゾフェノンは３６５ｎｍ付近に吸収帯を持つ。紫外・可視吸収スペクトル測定から、デンドリマー中に包接した４，４'−ビス（ジメチルアミノ）ベンゾフェノンの分子数は、第一世代では０個であることがわかった。前記のように調整したデンドリマーを含むジクロロメタン溶液に３６５ｎｍの光を充分に照射しても、紫外・可視吸収スペクトルに変化が見られなかった。
【００１８】
（実施例１−１）第三世代ポリプロピレンイミンデンドリマー（一般式（Ｉ）においてｎ＝３）を用いた以外は、参考例１−１と同様にした。紫外・可視吸収スペクトル測定から、デンドリマー中に包接した４，４'−ビス（ジメチルアミノ）ベンゾフェノンの分子数は、第三世代では３個であることがわかった。
【００１９】
（実施例１−２）第五世代ポリプロピレンイミンデンドリマー（一般式（Ｉ）においてｎ＝５）を用いた以外は、参考例１−１と同様にした。紫外・可視吸収スペクトル測定から、デンドリマー中に包接した４，４'−ビス（ジメチルアミノ）ベンゾフェノンの分子数は、第五世代では８個であることがわかった。
【００２０】
（実施例２−１）
デンドリマーの桂皮酸アミド単位とメタクリル酸メチルモノマー単位が１：１０になるように、４，４’−ビス（ジメチルアミノ）ベンゾフェノンを包接した光架橋性デンドリマー分子（第三世代ポリプロピレンイミンデンドリマー）をポリ（メタクリル酸メチル）に希釈分散した溶液を調整した。
このように調整したポリ（メタクリル酸メチル）溶液をスピンコート法によってガラス基板上に塗布した。溶液をガラス基板に塗布した後、室温にて乾燥させデンドリマーを含んだ固体を製造した。
出力が２００Ｗの水銀キセノンランプから波長が３６５ｎｍの光を取り出し、このガラス基板に照射した。光照射にともなって、桂皮酸アミド残基由来の２８０ｎｍ付近の吸収帯が減少した。光照射後の吸収スペクトルを測定し、桂皮酸アミド残基のトランス体、シス体、光架橋体の存在比率を算出した。その結果を表１に示す。
【００２１】
（実施例２−２）第五世代ポリプロピレンイミンデンドリマーを用いた以外は、実施例２−１と同様にした。実施例２-１と同様にして、光照射後の吸収スペクトルを測定し、桂皮酸アミド残基のトランス体、シス体、光架橋体の存在比率を算出した。その結果を表１に示す。
【００２２】
【表１】

表１に示す結果により、光照射に伴って桂皮酸アミド残基のトランス体生成比率は減少し、シス体と光架橋体生成比率は増加したことがわかる。
また、第三世代と第五世代デンドリマーにおいて、桂皮酸アミドの光架橋体の生成比率を比較すると、第三世代のデンドリマーの方が第五世代よりも多いことがわかった。４，４’−ビス（ジメチルアミノ）ベンゾフェノンを包接したデンドリマーは、３６５ｎｍ光で３．０Ｊ／ｃｍ²という低露光エネルギーで光架橋体を形成することができた。３．０Ｊ／ｃｍ²という露光エネルギーは、桂皮酸アミド残基を３１３ｎｍの光で直接励起して光架橋体を製造する場合に比べて低いエネルギーである。これは、増感剤が光を吸収し、増感剤が吸収した光エネルギーによって結合性残基が効果的に結合（架橋）したからであると考えられる。従って、本発明によれば、低エネルギーの照射光を用いて高感度に単一分子構造体を光架橋することに成功したといえる。
【００２３】
（実施例３）
光照射後のデンドリマー／ポリ（メタクリル酸メチル）薄膜をスピン塗布溶媒であるジクロロメタンに浸漬した。その結果、ガラス基板上から膜が除去されていることが紫外・可視吸収スペクトル測定から判断できた。このことから、デンドリマー希薄溶液に光を照射した場合は、高分子が発生していないと考えられる。これは、光照射によりデンドリマーの結合性残基が結合し、主にナノパーティクルが生成したことによると考えられる。
【００２４】
（実施例４）
光架橋性デンドリマーのみの薄膜に３６５ｎｍの光を充分照射して先と同様にジクロロメタンに浸漬した。その結果、膜はガラス基板上に残存した。このことからデンドリマーのみの薄膜に光を照射した場合は、高分子化が進行したと考えられる。これは、光照射によりデンドリマー分子間に光架橋反応が進行し、ナノワイヤが主に生成したことによると考えられる。
【発明の効果】
本発明によれば、ナノパーティクルやナノワイヤを効率的に製造できる。
本発明によれば、ボトムアップ型の設計により分子デバイスを適切に製造できる。
本発明のナノパーティクルやナノワイヤは、液晶材料、機能性材料、電子機能性材料、触媒、ナノレベル電子素子、ナノレベルＦＥＴ、トナー原料、帯電制御剤、電荷付与剤などプラスチックの副剤光、ドラッグデリバリーシステムなどとして利用可能である。
本発明の、ナノワイヤは、数ｎｍ〜数１００ｎｍレベルの周期性を利用した、超高密度記憶材料、発光素子等で利用可能である。
【図面の簡単な説明】
【図１】 本発明の、ナノパーティクルの概念図である。
【図２】 本発明の、ナノワイヤの概念図である。
【図３】 単一電子トランジスタ（ＳＥＴ）の一例を表す概図である。
【図４】 Ｔ字型オプトエレクトロニクス素子（ＴＯＥＤ）の一例を表す概念図である。
【符号の説明】
１ 分子構造体
２ エネルギー
３ 増感剤
５ 架橋剤
７ 分子集合体
９ 架橋反応部分
１０ エネルギー移動
１１ 電極[0001]
BACKGROUND OF THE INVENTION
The present invention irradiates light to a molecular structure having a binding residue around it, and uses a photochemical process or photophysical process to selectively and efficiently connect the molecular structure or molecular structures to each other, The present invention relates to a method for producing a molecular assembly in which a binding mode is controlled at a molecular level. By applying this method, it becomes easy to produce various three-dimensional high-density molecular devices.
[0002]
[Prior art]
Today's silicon semiconductor devices have greatly improved the computer's ability by ultra-miniaturization and high-density integration. In a silicon semiconductor element, a small amount of impurities are mixed with silicon to form an n-type or p-type semiconductor, but the principle is that the number of impurity atoms contained in one element is extremely reduced by the progress of ultrafine processing. In fact, it can no longer operate as a semiconductor. The element size, which is regarded as the limit, is several tens of nanometers. If the ultra-fine processing technology advances at the current pace, it is predicted that the limit will be reached in several decades.
In a microfabrication technique by photolithography using a chemically amplified photoresist, a shift from visible light to ultraviolet light and deep ultraviolet light irradiation has been made, but the resolution of about 70 nm is the limit. Recently, the application of X-rays with shorter irradiation wavelengths, focused ion beams, electron beam lithography, etc. has been studied, but in order to use these irradiation wavelengths, new photoresists, electron beam resists, optical systems, Although development of masks and reduction of production costs are desired, this technical / practical problem has not been improved at this stage. Therefore, the technology based on the top-down concept has reached its limit.
As a technique based on the bottom-up concept, a technique using a scanning probe microscope is currently attracting attention. For one, a nanometer structure can be fabricated by placing and reacting atoms and molecules at arbitrary locations using a scanning tunneling microscope (STM). This study is a scientific journal, Y. Okawa and M.M. Aono, Nature, 409, 683 (2001). It is described in. In addition, by drawing a solution of thiol molecules on a substrate with a fine needle tip of an atomic force microscope (AFM), a self-assembled film patterned with nanometers has been successfully produced. This study is a scientific journal, R.D. D. Piner, J .; Zhu, F.A. Xu, S .; Hong and C.H. A. Mirkin, Science, 283, 661 (1999). It is described in. Both technologies are excellent methods for producing a two-dimensional structure in the nanometer range, but it is difficult to construct a three-dimensional structure and is practical from the viewpoint of production cost. is not.
The above device fabrication method is based on the concept of so-called top-down technology, and it is difficult to fabricate a three-dimensional molecular device with a smaller size.
[0003]
[Problems to be solved by the invention]
At present, the development of new high-density molecular devices that can operate even at nanometer dimensions is underway worldwide. For example, single-electron elements that control on / off of a switch with one electron, molecular devices that use functional organic molecules as molecular structures, and the like have been proposed. In order to put molecular devices based on these new concepts into practical use, many problems must still be solved. One major problem is how to selectively link individual molecules. This is a major problem of bottom-up technology, and is mentioned in the scientific journal Nikkei Science, December 2001, page 37. Therefore, an effective method for controlling the binding of individual molecular elements has not been found so far.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that each molecular structure required for producing a high-density molecular device can be connected by light irradiation or the like. At least one of the above problems is solved by the following invention.
[0005]
(1) Light is applied to a solution containing a dendrimer represented by the following general formula (A) having a binding residue at its terminal site and a molecule (sensitizer) capable of spectrally sensitizing the binding residue. IrradiationThe sensitizer absorbs light energy, transmits the energy absorbed by the sensitizer to the dendrimer, and causes a cross-linking reaction to the binding residue of the dendrimer.The manufacturing method of the molecular device which has a shell structure formed of the crosslinking reaction part including a process.
[Chemical 9]

In general formula (A), A to D are each a cinnamic acid group, an α-cyanocinnamic acid group, a coumarin group, a chalcone group, a cinnamylidene acetate group, a p-phenylene diacrylate group, an acetylene group, and a diacetylene group. , Any one of diphenylacetylene groups.
(2) Instead of the dendrimer represented by the general formula (A), it is represented by the following general formula (I)DendrimerThe method for producing a molecular device according to (1) above, wherein
[Chemical Formula 10]

(In the above formula, n represents a number of 3 or more and 10 or less.)
(3) Instead of the dendrimer represented by the general formula (A), it is represented by the following general formula (II)DendrimerThe method for producing a molecular device according to (1) above, wherein
Embedded image

(In the above formula (II), n represents a number of 3 to 10, and R represents C₁-C₁₀Alkynylene group or C₂-C₁₀An alkenylene group is shown. )
(4) Light is applied to a solid containing a dendrimer represented by the following general formula (A) having a binding residue at its terminal site and a molecule (sensitizer) capable of spectrally sensitizing the binding residue. IrradiationThe sensitizer absorbs light energy, and the energy absorbed by the sensitizer is To cause the cross-linking reaction of the binding residue of the dendrimerThe manufacturing method of the molecular device which has a shell structure formed of the crosslinking reaction part including a process.
Embedded image

In general formula (A), A to D are each a cinnamic acid group, an α-cyanocinnamic acid group, a coumarin group, a chalcone group, a cinnamylidene acetate group, a p-phenylene diacrylate group, an acetylene group, and a diacetylene group. , Any one of diphenylacetylene groups.
(5) Instead of the dendrimer represented by the general formula (A), it is represented by the following general formula (I)DendrimerThe method for producing a molecular device according to (4) above, wherein
Embedded image

(In the above formula, n represents a number of 3 or more and 10 or less.)
(6) Instead of the dendrimer represented by the general formula (A), it is represented by the following general formula (II)DendrimerThe method for producing a molecular device according to (4) above, wherein
Embedded image

(In the above formula (II), n represents a number of 3 to 10, and R represents C₁-C₁₀Alkynylene group or C₂-C₁₀An alkenylene group is shown. )
(7) Irradiating light to a compound represented by the following general formula (I) including 4,4'-bis (dimethylamino) benzophenoneAnd the 4,4′-bis (dimethylamino) benzophenone absorbs light energy, transmits the energy absorbed by the 4,4′-bis (dimethylamino) benzophenone to the dendrimer, and the binding residue of the dendrimer Causes a crosslinking reactionIncluding steps,
A method for producing a molecular device having a shell structure formed by a crosslinking reaction portion.
Embedded image

(In the above formula, n represents a number of 3 or more and 10 or less.)
(8) The method for producing a molecular device according to (7), wherein the light in the step of irradiating with light is light having a wavelength of 365 nm.
(9) represented by the following general formula (I)Dendrimer4,4'-bis (dimethylamino) benzophenone and a solution containing a precipitate obtained by precipitating a solution obtained by mixing with 4,4'-bis (dimethylamino) benzophenone are irradiated with light having a wavelength of 365 nmAnd the 4,4′-bis (dimethylamino) benzophenone absorbs light energy, transmits the energy absorbed by the 4,4′-bis (dimethylamino) benzophenone to the dendrimer, and the binding residue of the dendrimer Causes a crosslinking reactionIncluding steps,
A method for producing a molecular device having a shell structure formed by a crosslinking reaction portion.
Embedded image

(In the above formula, n represents 3 or 5.)
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the manufacturing method of the molecular structure, molecular assembly, and high-density molecular device according to the present invention will be described in detail.
The manufacturing method of the high-density molecular device according to the present invention uses, for example, a molecular structure having a higher atomic density in the surrounding portion than in the interior and having a binding residue in the surrounding portion. According to one embodiment of the present invention, a molecular structure or a molecular assembly is produced by crosslinking a binding residue present around a molecular structure within the molecular structure or between the molecular structures.
In the present invention, energy such as light having a wavelength absorbed by the sensitizer is applied to a solution or solid containing the molecular structure and the sensitizer. The solution or solid may contain a binder resin (binder) and other auxiliary materials. In the present invention, the sensitizer absorbs light energy, and the energy absorbed by the sensitizer is transmitted to a molecular structure such as a dendrimer, or electrons, ions, and radicals move to form a bond existing in the molecular structure. Utilizing the fact that sex residues cause a binding reaction or a cross-linking reaction, a molecular structure having a shell structure or a molecular assembly in which molecular structures are three-dimensionally connected are manufactured.
Each molecular structure preferably functions as a molecular element having various functions such as an optical memory effect. These molecular structures are connected one after another in a one-dimensional, two-dimensional or three-dimensional manner such as linear, lattice, and radial to produce molecular assemblies (or molecular devices) having various functions. be able to. By controlling the position of the binding residue in the molecular structure, the position where the molecular structure is linked can be controlled, and the growth direction in which the molecular structure is linked and expanded one after another to form a molecular assembly It leads to control. The spacing between the molecular structures constituting the molecular assembly can also be controlled by controlling the length of the crosslinking agent.
[0007]
The molecular structure is preferably a molecule that can include a sensitizer, or a molecule that is covalently bonded, ionic bond, coordinate bond, metal bond or hydrogen bond with the sensitizer, and particularly has photo / electronic functionality. Although a dendrimer (hyperbranched polymer) is preferable, it is not particularly limited as long as it is a compound having a binding residue. Dendrimer molecules themselves have a nanometer space, and are characterized by the inclusion of different molecules and different atoms in that space. Details on the inclusion phenomenon of dendrimers are academic journals, J. Jansen, E .; Berg, E .; Meijer, Science, 266, 1226 (1994); Cooper, J.A. Londono, G.M. Wignall, J. et al. McClain, E .; Samulski, J .; Lin, A .; Dobrinin, M .; Rubinstein, A.M. Burke, J. et al. Frechet, J. et al. DeSimone, Nature, 389, 368 (1997).
[0008]
As the binding residue (photocrosslinkable residue) in the molecular structure, (a) an aliphatic residue having an unsaturated double bond such as a vinyl group, an acrylate group or a methacrylate group, (b) cinnamon An aromatic residue having an unsaturated double bond such as acid group, α-cyanocinnamic acid group, coumarin group, chalcone group, cinnamylidene acetate group, p-phenylenediacrylate group or distyrylpyrazine group, (c) An aliphatic residue having an unsaturated triple bond such as an acetylene group or a diacetylene group; (d) an aromatic residue having an unsaturated triple bond such as a diphenylacetylene group, a phenylazide group or a dipyridyl diacetylene group; Is mentioned. These derivatives may also be used. (A) requires a radical photopolymerization initiator to show a radical polymerization reaction. On the other hand, the photocrosslinkable residue of (b-d) exhibits a photoaddition reaction according to the Woodward-Hoffman rule such as a [2π-2π] photodimerization reaction. A polymerization initiator is not required. Details regarding these photosensitive groups are described in Mototaro Nagamatsu and Hideo Inui, “Photosensitive Polymers”, Kodansha Scientific, (1977).
[0009]
X-rays, electron beams, ultraviolet rays, visible rays, or infrared rays (heat rays) are used as the light to be irradiated when the crosslinked body is formed by light. Among these, ultraviolet rays or visible rays are particularly preferable. As the light source, an ultra-high pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, a mercury xenon lamp, a halogen lamp, a fluorescent lamp, a gas laser, a liquid laser, a solid laser, or the like is used. Further, surface plasmon radiation of light emitted from these light sources may be used.
In order to bond (crosslink) the binding residues or link each molecular structure, the binding residues may be directly excited to induce intramolecular bonds or intermolecular bonds, or crosslinking agents, etc. Intramolecular crosslinks and intermolecular crosslinks may be formed by cross-linking. In order to link each molecular structure, a binding residue (photocrosslinkable residue) may be directly excited to induce a photocrosslinking reaction, but the feature of the present invention is more efficient and selective. In order to bond the molecular structure in the nanometer region and between the molecular structures, "spectral sensitization" is used. By utilizing spectral sensitization in this way, as shown in FIGS. 1 and 2, it becomes easy to produce nanoparticles or nanowires of molecular structures. At that time, as mentioned above, a molecule that can spectrally sensitize a binding residue (photocrosslinkable residue) by utilizing the characteristic that a different molecule or different atom can be included in the dendrimer molecule, so-called sensitization. It is preferable to add an agent. Details of the sensitizer are described in Katsumi Tokumaru and Nobuo Okawara, “Sensitizer”, Kodansha Scientific, (1987). There are two types of spectral sensitization mechanisms: photoelectron transfer and light energy transfer. There are two types of light energy transfer depending on the photoexcited state. Singlet energy transfer based on dipole-dipole interaction ( Forster type) and triplet energy transfer based on electron exchange interaction (Deckster type). Details on light energy transfer can be found in N.W. Turro, Modern Molecular Photochemistry, University Science Books (1991). The moving distance of photoelectron movement is about 0.4 nm to 2.0 nm, and the moving distance of singlet and triplet energy transfer is about 1.0 to 10 nm and 0.3 to 1.0 nm, respectively. Of these spectral sensitization mechanisms, it is preferable that the present invention photocouples photo / electronic functional molecular structures using triplet energy transfer that is spectrally sensitized in the nanometer range.
[0010]
In this specification, the term “crosslinking” refers to a case where binding residues are bonded to each other in addition to a connecting method for connecting two or more molecular structures. In the present invention, the cross-linking agent molecule means a molecule that links the binding residues of the molecular structure. For example, butadiene, pentadiene, a substituent of a binding residue of a molecular structure, and the like can be given. By using the cross-linking agent, it is possible to link the molecular structures while controlling the interval to obtain a molecular assembly having regularity.
[0011]
In the method for producing a molecular device of the present invention, for example, a molecular structure or molecular assembly having the following shell structure may be obtained as an intermediate product.
A molecular structure having a shell structure (hereinafter also referred to as “nanoparticle”) has, for example, a molecular structure having a higher atomic density in the surrounding part than in the interior and having a binding residue in the surrounding part. Manufactured by crosslinking groups into shells. That is, a binding structure in which the binding residue portions present around the molecular structure are bonded to each other to form a shell is a molecular structure having a shell structure. In particular, when the density of the molecular structures is not high and the intermolecular distance between the molecular structures is large, nanoparticles are mainly produced. An example of nanoparticles will be described with reference to FIG. A molecular structure 1 (a) such as a dendrimer has a sensitizer 3 around or inside thereof. And a sensitizer absorbs the energy by light irradiation. The energy absorbed by the sensitizer is transferred to the molecular structure 10. Then, in the molecular structure 1, due to the transferred energy, the binding residues are bonded (crosslinked) to form a crosslinking reaction portion 9 (FIG. 1b). In this way, the cross-linking reaction part forms a shell and forms nanoparticles.
[0012]
The molecular assembly of the present invention (hereinafter also referred to as “nanowire”) has, for example, a higher density of atoms in the surrounding part than in the interior, and crosslinks the binding residues of the molecular structure having binding residues in the surrounding part. , By binding the binding residues of adjacent molecular structures. Since the molecular structure of the present invention has, for example, a plurality of binding residues in the molecule, when the crosslinking proceeds, for example, a plurality of molecular structures are gathered radially. In particular, when the density of the molecular structures is high and the intermolecular distance between the molecular structures is small, nanowires are mainly produced. The nanowire will be described with reference to FIG. As shown in FIG. 2a, the molecular structure 1 and the sensitizer 3 having a binding residue in the surrounding portion are irradiated with light. A sensitizer absorbs energy from light irradiation. The energy absorbed by the sensitizer is transferred to the molecular structure 10. Then, as shown in FIG. 2b, the crosslinkable residue in the molecular structure 1 and the cross-linking agent 5 are cross-linked to form a cross-linking reaction portion 9 to obtain a molecular assembly 7 (FIG. 2b).
In addition, when a crosslinking agent is added and crosslinking proceeds, the binding residue of the molecular structure and the crosslinking agent cause a crosslinking reaction, and the molecular structure is assembled in a manner that controls the distance between the molecular structures. A molecular assembly can also be obtained.
[0013]
Examples of the molecular device include those using the above-described nanoparticles and nanowires. A molecular structure has various functions, and a molecular device can be obtained by controlling the assembly mode of the molecular structure at a molecular / nano level. For example, the three-dimensional structure of the molecular assembly can be controlled by controlling the position of the binding residue in the molecular structure and cross-linking it.
[0014]
For example, although molecular structures have various functions, a molecular device can be obtained by linking such molecular structures together and successively connecting them in a preferred direction via a crosslinking agent. This cross-linked portion can serve as an information transmission path when a functional molecular structure transmits information such as an electrical signal. By doing so, it is possible to obtain a molecular device that functions as an information transmission system as if a neuron extends an axon toward another neuron. Further, when this molecular device manufacturing method is applied between electrodes, a molecular device can be obtained in which molecular structures are connected and can transmit information. By using this molecular device, it is possible to obtain a functional product using a molecular device composed of linked molecular elements (molecular structures) having functionality. FIG. 3 is a schematic diagram illustrating an example of a single electron transistor (SET), which is a molecular device that can be manufactured by such a manufacturing method. In FIG. 3, 1 represents a molecular structure that can function as a molecular element, 5 represents a crosslinking agent, 9 represents a crosslinking reaction portion, and 11 represents an electrode. The SET shown in FIG. 3 was manufactured as follows. First, an electrode 11 having an interval of about 50 nm was prepared. The distance between the electrodes 11 can be about 10 nm to 1 μm. Thereafter, a solution having a dendrimer having a binding residue at both electrodes (positive control position), a sensitizer, and a cross-linking agent was prepared so as to connect the electrodes. Thereafter, the solution having the dendrimer was irradiated with light. Then, a molecular device (SET) as shown in FIG. 3 could be obtained. When a voltage was applied to this molecular device, a stepped current-voltage characteristic (Coulomb blockade phenomenon) was observed. From this, it was found that the crosslinking agent linked by light irradiation functions as a tunnel layer.
[0015]
FIG. 4 is a conceptual diagram showing an example of a T-shaped optoelectronic element (TOED) which is another molecular device of the present invention.
Below, an example of the manufacturing method of TOED is demonstrated. First, a substrate made of mica was prepared. The substrate may be an insulator such as gold, copper, platinum, or mica. Next, the substrate was immersed in a solution containing four types of molecular structures A, B, C and D and a sensitizer. At this time, the solution may contain a crosslinking agent. The molecular structure A has a binding residue such that the 1-position binds to a certain binding residue of the molecular structure B. Note that the 10-position may have a binding residue that binds to a binding residue in the molecular structure C. (In this case, the obtained molecular device is not a TOED, but a continuum of T-shaped optoelectronics.) In addition, the molecular structure B has the first, fifth, and tenth positions, respectively. It has a binding residue that binds to a binding residue of D or A. In addition, you may have a binding residue which couple | bonds with a certain binding residue of the molecular structure D in 15th position. (In this case, the obtained molecular device is not a TOED, but a continuum of T-shaped optoelectronics.)
When this solution was irradiated with light, a molecular device was formed on the substrate.
When an optical signal was input to the molecular structure A of the molecular device, an output was observed from the molecular structure B at about 30 ps.
On the other hand, when the molecular structure D portion was oxidized, even when an optical signal was input to the molecular structure A, no output from the molecular structure B portion was obtained.
[0016]
Further, using the molecular device of the present invention, for example, a molecular integrated circuit described in JP-A-2001-44413 can be produced. A molecular integrated circuit using the molecular device of the present invention is similar to the molecular integrated circuit described in Japanese Patent Application Laid-Open No. 2001-44413, and includes a NAND circuit, a NOR circuit, an inverter circuit, a random access memory cell, and a read-only memory cell. It can be used as such. In the present invention, a molecular device can be constructed by utilizing a photosensitization reaction, and thus a molecular device can be produced more accurately and rapidly.
[0017]
【Example】
(Reference example1-1) First generation polypropyleneimine dendrimer having a cinnamic amide residue around the molecule (general formula (I4), 4,4′-bis (dimethylamino) benzophenone was mixed with the dichloromethane solution of n = 1) as a sensitizer and reprecipitated in an excess amount of hexane. The precipitate was dialyzed against dichloromethane and reprecipitated again. Light having a wavelength of 365 nm was taken out from a mercury xenon lamp having an output of 200 W and irradiated with light in a dichloromethane solution of first-generation polypropyleneimine dendrimer in which 4,4′-bis (dimethylamino) benzophenone was included. At this time, the temperature of the solution was room temperature. Cinnamic acid amide residues do not absorb light at 365 nm, while 4,4′-bis (dimethylamino) benzophenone has an absorption band near 365 nm. From the ultraviolet / visible absorption spectrum measurement, it was found that the number of molecules of 4,4′-bis (dimethylamino) benzophenone included in the dendrimer was zero in the first generation. Even when the dichloromethane solution containing the dendrimer prepared as described above was sufficiently irradiated with 365 nm light, no change was observed in the ultraviolet / visible absorption spectrum.
[0018]
Example 11) Third generation polypropylene imine dendrimer (general formula (I) Except that n = 3) is used.Same as Reference Example 1-1. From the UV / visible absorption spectrum measurement, it was found that the number of molecules of 4,4′-bis (dimethylamino) benzophenone included in the dendrimer was 3 in the third generation.
[0019]
Example 12) Fifth generation polypropylene imine dendrimer (general formula (I) Except that n = 5) is used.Same as Reference Example 1-1. From the UV / visible absorption spectrum measurement, it was found that the number of molecules of 4,4′-bis (dimethylamino) benzophenone included in the dendrimer was 8 in the fifth generation.
[0020]
(Example 2-1)
A photocrosslinkable dendrimer molecule (third generation polypropyleneimine dendrimer) including 4,4′-bis (dimethylamino) benzophenone so that the cinnamamide unit and methyl methacrylate monomer unit of the dendrimer are 1:10. A solution diluted and dispersed in poly (methyl methacrylate) was prepared.
The poly (methyl methacrylate) solution thus prepared was applied on a glass substrate by a spin coating method. After apply | coating a solution to a glass substrate, it dried at room temperature and manufactured the solid containing a dendrimer.
Light with a wavelength of 365 nm was taken out from a mercury xenon lamp with an output of 200 W, and this glass substrate was irradiated. Along with the light irradiation, the absorption band near 280 nm derived from the cinnamic acid amide residue decreased. The absorption spectrum after light irradiation was measured, and the abundance ratio of trans cis, cis isomer, and photocrosslinked cinnamate amide residue was calculated. The results are shown in Table 1.
[0021]
(Example 2-2) Except for using the fifth generation polypropylene imine dendrimer,Same as Example 2-1. In the same manner as in Example 2-1, the absorption spectrum after light irradiation was measured, and the abundance ratio of the trans isomer, cis isomer and photocrosslinked cinnamate amide residue was calculated. The results are shown in Table 1.
[0022]
[Table 1]

From the results shown in Table 1, it can be seen that the trans-form formation ratio of cinnamic amide residues decreased and the cis-form and photo-crosslink formation ratio increased with light irradiation.
In addition, when comparing the generation ratio of the photocrosslinked cinnamate amide between the third generation and the fifth generation dendrimers, it was found that the third generation dendrimers were more than the fifth generation. The dendrimer that includes 4,4'-bis (dimethylamino) benzophenone is 3.0 J / cm at 365 nm light.²A photocrosslinked body could be formed with such low exposure energy. 3.0 J / cm²The exposure energy is lower than that in the case of producing a photocrosslinked product by directly exciting a cinnamic amide residue with 313 nm light. This is presumably because the sensitizer absorbs light and the binding residues are effectively bound (crosslinked) by the light energy absorbed by the sensitizer. Therefore, according to the present invention, it can be said that the single molecular structure was photocrosslinked with high sensitivity using low energy irradiation light.
[0023]
(Example 3)
The dendrimer / poly (methyl methacrylate) thin film after light irradiation was immersed in dichloromethane as a spin coating solvent. As a result, it was determined from ultraviolet / visible absorption spectrum measurement that the film was removed from the glass substrate. From this, it is considered that no polymer is generated when light is applied to the dendrimer dilute solution. This is considered to be mainly because the binding residues of the dendrimer were bound by light irradiation and nanoparticles were generated mainly.
[0024]
Example 4
A thin film of only photocrosslinkable dendrimer was sufficiently irradiated with 365 nm light and immersed in dichloromethane as before. As a result, the film remained on the glass substrate. From this, it is considered that polymerization progressed when light was applied to a thin film only of dendrimer. This is thought to be due to the fact that the photocrosslinking reaction proceeded between the dendrimer molecules by light irradiation and nanowires were mainly produced.
【The invention's effect】
According to the present invention, nanoparticles and nanowires can be efficiently produced.
According to the present invention, a molecular device can be appropriately manufactured by a bottom-up design.
Nanoparticles and nanowires of the present invention include liquid crystal materials, functional materials, electronic functional materials, catalysts, nano-level electronic devices, nano-level FETs, toner raw materials, charge control agents, charge imparting agents, etc. It can be used as a delivery system.
The nanowire of the present invention can be used in an ultra-high-density memory material, a light emitting element, etc., utilizing periodicity on the order of several nanometers to several hundred nanometers.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram of nanoparticles according to the present invention.
FIG. 2 is a conceptual diagram of a nanowire according to the present invention.
FIG. 3 is a schematic diagram illustrating an example of a single electron transistor (SET).
FIG. 4 is a conceptual diagram illustrating an example of a T-shaped optoelectronic element (TOED).
[Explanation of symbols]
1 Molecular structure
2 Energy
3 Sensitizer
5 Cross-linking agent
7 Molecular assembly
9 Cross-linking reaction part
10 Energy transfer
11 electrodes

Claims (9)

Irradiating a solution containing a dendrimer represented by the following general formula (A) having a binding residue at its terminal site and a molecule (sensitizer) capable of spectrally sensitizing the binding residue , A shell formed by a crosslinking reaction part, comprising the steps of causing the sensitizer to absorb light energy, transmitting the energy absorbed by the sensitizer to the dendrimer, and causing a crosslinking reaction to occur on the binding residue of the dendrimer. A method for producing a molecular device having a structure.

In the general formula (A), A to D are cinnamic acid group, α-cyanocinnamic acid group, coumarin group, chalcone group, cinnamylidene acetate group, p-phenylene diacrylate group, acetylene group, diacetylene group, respectively. , Any one of diphenylacetylene groups. The method for producing a molecular device according to claim 1, wherein a dendrimer represented by the following general formula (I) is used instead of the dendrimer represented by the general formula (A).

(In the above formula, n represents a number of 3 or more and 10 or less.) The method for producing a molecular device according to claim 1, wherein a dendrimer represented by the following general formula (II) is used instead of the dendrimer represented by the general formula (A).

(In the above formula (II), n represents a number of 3 to 10, R represents shows the _C 1 _{-C 10} alkynylene group or a _C 2 _{-C 10} alkenylene group.) Irradiating light to a solid containing a dendrimer represented by the following general formula (A) having a binding residue at its terminal site and a molecule (sensitizer) capable of spectrally sensitizing the binding residue , A shell formed by a crosslinking reaction part, comprising the steps of causing the sensitizer to absorb light energy, transmitting the energy absorbed by the sensitizer to the dendrimer, and causing a crosslinking reaction to occur on the binding residue of the dendrimer. A method for producing a molecular device having a structure.

In the general formula (A), A to D are cinnamic acid group, α-cyanocinnamic acid group, coumarin group, chalcone group, cinnamylidene acetate group, p-phenylene diacrylate group, acetylene group, diacetylene group, respectively. , Any one of diphenylacetylene groups. The method for producing a molecular device according to claim 4, wherein a dendrimer represented by the following general formula (I) is used in place of the dendrimer represented by the general formula (A).

(In the above formula, n represents a number of 3 or more and 10 or less.) The method for producing a molecular device according to claim 4, wherein a dendrimer represented by the following general formula (II) is used in place of the dendrimer represented by the general formula (A).

(In the above formula (II), n represents a number of 3 to 10, R represents shows the _C 1 _{-C 10} alkynylene group or a _C 2 _{-C 10} alkenylene group.) The compound represented by the following general formula (I) encapsulating 4,4′-bis (dimethylamino) benzophenone is irradiated with light, and the 4,4′-bis (dimethylamino) benzophenone absorbs light energy, Transferring the energy absorbed by the 4,4′-bis (dimethylamino) benzophenone to the dendrimer, and causing a cross-linking reaction to a binding residue of the dendrimer ,
A method for producing a molecular device having a shell structure formed by a crosslinking reaction portion.

(In the above formula, n represents a number of 3 or more and 10 or less.) The method for producing a molecular device according to claim 7, wherein the light in the step of irradiating light is light having a wavelength of 365 nm. Light having a wavelength of 365 nm is added to a solution containing a precipitate obtained by precipitating a solution obtained by mixing 4,4′-bis (dimethylamino) benzophenone with a dendrimer represented by the following general formula (I). Irradiating , the 4,4′-bis (dimethylamino) benzophenone absorbs light energy, the energy absorbed by the 4,4′-bis (dimethylamino) benzophenone is transmitted to the dendrimer, and the binding residue of the dendrimer is Including a step of causing a crosslinking reaction on the group ,
A method for producing a molecular device having a shell structure formed by a crosslinking reaction portion.

(In the above formula, n represents 3 or 5.)

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