JP4461696B2 - Patterning method - Google Patents

Description

【００５３】
ただし、ｎは２以上の整数であり、Ｒ^１，Ｒ^２はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アリールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ^１，Ｒ^２がメチル基であるものが、表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。
【００５４】
また、前記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコーン化合物を混合してもよい。
【００５５】
本発明における濡れ性変化層（特性変化層１６）には、さらに界面活性剤を含有させることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることかでき、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００５６】
また、濡れ性変化層には前記の界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を含有させることができる。
【００５７】
このような濡れ性変化層（特性変化層１６）は、前述した成分を必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を前記透光性基板１５上に塗布することで形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート、液滴吐出法等の公知の塗布方法により行うことができる。また、紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより濡れ性変化層（特性変化層１６）を形成することもできる。
【００５８】
このような濡れ性変化層（特性変化層１６）の厚さについては、光触媒による濡れ性の変化速度等の関係より、０．００１μｍから１μｍであることが好ましく、０．０１〜０．１μｍの範囲内であるのが特に好ましい。
【００５９】
特性変化層１６をこのような濡れ性変化層とすれば、後述するように接触する光触媒含有層１１中の光触媒の作用によって前記成分の一部である有機基や添加剤の酸化、分解等が起こり、露光部の濡れ性が変化して親液性となり、これによって非露光部との濡れ性に大きな差が生じるようになる。したがって、機能性材料からなる液状体、例えば金属微粒子を分散させてなる分散液等との受容性（親液性）および反撥性（撥液性）をそれぞれ高めることにより、品質が良好でかつコスト的にも有利な配線等の機能性要素を得ることができる。
【００６０】
次に、特性変化層１６が光触媒の作用によって分解除去される、分解除去層である場合について説明する。この分解除去層は、露光された際に光触媒含有層１１中の光触媒の作用により、露光された部分が分解除去されるように形成された層である。したがって、この分解除去層（特性変化層１６）によれば、光触媒の作用によって特性が変化した部位が分解除去されることにより、下地となる透光性基板１５が露出して凹凸のパターンを形成した被パターニング体１７を得ることができる。
【００６１】
このように分解除去層は、露光した部分が光触媒の作用によって分解除去されることから、現像工程や洗浄工程を行うことなく分解除去層のある部分と無い部分とからなるパターン、すなわち凹凸を有するパターンを形成することができる。したがって、例えばレジスト特性を有する素材でこの分解除去層を形成すれば、露光用マスク１０と接触させてパターン露光することにより、容易にレジストのパターンを形成することができる。したがって、現像・洗浄工程の無いフォトレジストとして、半導体製造工程等に用いることも可能である。
【００６２】
また、この分解除去層（特性変化層１６）を用いた場合には、凹凸を形成するのみならず、分解除去されて露出する露出部材（透光性基板１５）と分解除去層との特性の相違により、パターンを形成することもできる。このような特性として具体的には、接着性、発色性等種々のものを挙げることができるが、本発明においては、中でも濡れ性を挙げることができる。この濡れ性の相違により、前述した濡れ性変化層の場合と同様にしてパターンを形成することができる。
【００６３】
すなわち、本発明においては、分解除去層（特性変化層１６）とこの分解除去層が分解除去されて露出する露出部材（透光性基板１５）との間で機能性液体材料の接触角が異なるように構成されているのが好ましく、特に透光性基板１５の機能性液体材料の接触角より分解除去層上の機能性液体材料の接触角が大きいことが好ましい。また、その場合に、分解除去層の機能性液体材料との接触角が６０度以上であるのが特に好ましい。
【００６４】
これは、分解除去層（特性変化層１６）において光触媒の作用を受けない部分は、分解除去層が残存する部分、すなわち凸部となることから、この凸部に機能性材料を付着させるより分解除去層が除去され露出部材（透光性基板１５）が露出した凹部に機能性材料を付着させるほうが、安定性等に優れており好ましいからである。このため、分解除去層（特性変化層１６）は機能性材料からなる液状体が付着しにくいように撥液性を示す方が好ましく、露出部材（透光性基板１５）の機能性液体材料の接触角より分解除去層上の機能性液体材料の接触角の方が大きいのが好ましいのである。なお、分解除去層上の機能性液体材料の接触角が６０度より小さい場合には、撥液性が十分でなく、ここに機能性材料からなる液状体が残存する可能性が生じるため好ましくない。
【００６５】
このような分解除去層に用いられる材料としては、前述した分解除去層の特性、すなわち接触する光触媒含有層１１中の光触媒の露光による作用によって分解除去される材料で、かつ好ましくは機能性液体材料との接触角が６０度以上となる材料である。このような材料としては、例えば炭化水素系、フッ素系またはシリコーン系の非イオン界面活性剤を挙げることができ、具体的には、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、パーフルオロアルキルエチレンオキシド付加物、もしくはパーフルオロアルキルアミンオキシド等を挙げることができる。
【００６６】
このような材料としては、炭化水素系の非イオン系界面活性剤であれば、ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ（商品名、日本サーファクタント工業社製）、フッ素系あるいはシリコン系の非イオン系界面活性剤であれば、ＺＯＮＹＬ ＦＳＮ、ＦＳＯ（商品名、デュポン社製）、サーフロンＳ−１４１、１４５（商品名、旭硝子社製）、メガファックＦ−１４１、１４４（商品名、大日本インキ社製）、フタージェント Ｆ２００、Ｆ２５１（商品名、ネオス社製）、ユニダインＤＳ−４０１、４０２（商品名、ダイキン工業社製）、フロラードＦＣ−１７０、１７６（商品名、スリーエム社製）として入手することができる。
【００６７】
また、この分解除去層の材料としては、他にもカチオン系、アニオン系、両性界面活性剤を用いることが可能であり、具体的には、アルキルベンゼンスルホン酸ナトリウム、アルキルトリメチルアンモニウム塩、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルベタイン等を挙げることができる。
【００６８】
さらに、分解除去層の材料としては、界面活性剤以外にも種々のポリマーもしくはオリゴマーを用いることができる。このようなポリマーもしくはオリゴマーとしては、例えばポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ナイロン、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等を挙げることができる。本発明においては、中でもポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル等の機能性液体材料との接触角の高い撥液性のポリマーを用いることが好ましい。
【００６９】
このような分解除去層は、前述した成分を必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基板もしくは露出部材（基板と露出部材が共通しても良い。）上に塗布することにより形成することができる。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。
また、このような分解除去層（特性変化層１６）の厚さについては、光触媒による分解速度等の関係より、０．００１μｍから１μｍであるのが好ましく、０．０１〜０．１μｍの範囲内であるのが特に好ましい。
【００７０】
次に、このような構成の被パターニング体１７に対して、前記の露光用マスク１０を用いて露光しパターニングする方法について説明する。
まず、図１に示した露光用マスク１０と被パターニング体１７とを用意し、これらを、図２（Ａ）に示すようにその光触媒含有層１１と特性変化層１６とが接触するように当接させる。
【００７１】
ここで、光触媒含有層１１と特性変化層１６との接触とは、本発明においては実質的に光触媒の作用が特性変化層１６に及ぶような状態で配置された状態をいう。すなわち、光触媒含有層１１が特性変化層１６に物理的に接触している状態はもちろん、例えば物理的な接触が無い場合でも、これらの間に水もしくは空気等が介在して光触媒含有層中の光触媒の作用が特性変化層に及ぶように配置されている場合をも含むものとする。本発明においては、このような接触状態は、少なくとも露光の間だけ維持されればよい。
【００７２】
次に、このように光触媒含有層１１と特性変化層１６とを接触させた状態のもとで、図２（Ｂ）に示すように被パターニング体１７の透光性基板１５側から前記光触媒含有層１１に向けて露光用の光、例えば紫外線（ＵＶ光）をフォトマスク１４によって選択的に照射し、露光を行う。このような露光に用いる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプなどの従来公知のものが使用される。また、露光に際しての光の照射量については、特性変化層１６が光触媒含有層１１中の光触媒の作用によって特性を変化させるのに必要な照射量とする。なお、この露光の際、光触媒含有層１１を加熱しながら露光を行うことにより、感度を上げることができる。これは、特に後述する光描画照射を用いる場合に有効となる。
【００７３】
このようにして露光を行うと、図２（Ｃ）中矢印で示すようにフォトマスク１４を設けた箇所以外では、照射した光が一旦光触媒含有層１１を通過して通過した部分の光触媒を活性化させ、さらに、光反射層１２で反射して再度同じ光触媒含有層１１の部分を通過することにより、ここを再度活性化させるようになる。なお、図２（Ｃ）中では、説明上、見易くするため入射光と反射光とを別の矢印で示しているが、実際には同じ光軸で入射・反射（出射）がなされる。このように、一度の露光で照射した光が入射・反射によって光触媒含有層１１を二度通過することから、光触媒含有層１１中の光触媒の活性化を従来に比べ格段に高めることができ、したがって照射する光の利用効率を高め、かつ光触媒の性質を十分に活かすことができる。よって、この光触媒含有層１１における光照射部分（露光部分）に接触している特性変化層１６の特性をより良好に変化させ、これにより特性が良好に変化した特性変化部位１８を低コスト、短時間で形成することができる。
【００７４】
なお、前記の特性変化部位１８は、前述したように特性変化層１６が露光により濡れ性が変化する濡れ性変化層であれば、濡れ性変化部位となり、また分解除去される分解除去層であれば、凹部が形成される部位となり、さらに接着性が変化する接着性変化層であれば、接着性の異なる部位となる。
【００７５】
このような露光マスク１０を用いたパターニング方法によれば、廃液を生じることなく特性の変化したパターン（特性変化部位１８）をより良好にかつ低コスト、短時間で形成することができる。また、露光後、被パターニング体１７から露光用マスク１０を取り外すことにより、被パターニング体１７自体には光触媒含有層１１が含まれることがないので、特性変化層１６に光触媒の作用による経時的劣化が起こることもない。
【００７６】
なお、前記の露光マスク１０においては、フォトマスク１４を設けた構造としたが、前述したようにフォトマスク１４を有さない構造としてもよい。その場合、従来と同様にして図３（Ａ）に示すように遮光パターン１９をガラスなどの透光性基板に形成してフォトマスク２０としておき、これを被パターニング体１７の透光性基板１５側にセットする。また、前述したように光触媒含有層１１と特性変化層１６とが接触するよう、露光用マスク１０と被パターニング体１７とを当接させる。そして、この状態のもとで、図３（Ｂ）に示すようにフォトマスク２０を介して被パターニング体１７の透光性基板１５側から前記光触媒含有層１１に向けて、露光用の光（例えば紫外線）を選択的に照射し、露光を行う。ここで、このようなフォトマスク２０を用いた場合、縮小光学系によってマスクパターンの画像を縮小する縮小投影露光方法を用いることにより、微細なパターンを形成することも可能になる。
【００７７】
このようにして露光を行うと、先の例と同様に、一度の露光で照射した光が入射・反射によって光触媒含有層１１を二度通過することから、光触媒含有層１１中の光触媒の活性化を従来に比べ格段に高めることができ、したがって照射する光の利用効率を高め、かつ光触媒の性質を十分に活かすことができる。よって、図３に示した例でも、光触媒含有層１１における光照射部分（露光部分）に接触している特性変化層１６の特性をより良好に変化させ、これにより特性が良好に変化した特性変化部位１８を低コスト、短時間で形成することができる。また、光触媒含有層１１上にフォトマスク１４を形成しないことから、光触媒含有層１１と特性変化層１６とがその間にフォトマスク１４を介在することなく直接当接するので、これらの間の密着性、すなわち接触の度合いを高めることができる。
【００７８】
また、本発明においては、光触媒含有層１１に向けて光を選択的に照射し露光することができれば、フォトマスク１４、２０を用いる必要もない。その場合に、例えばレーザー光等を用いた光描画照射によって直接所定のパターンを描くことにより、選択的に露光を行うことができる。このような光描画照射を行うための光源としては、例えばエキシマレーザーやＹＡＧレーザー等を挙げることができる。
【００７９】
このようにして被パターニング体１７に形成した特性変化部位１８に対し、機能性材料を設けることにより、種々の機能性要素を形成することができる。ここで、機能性とは、光学的（光選択吸収、反射性、偏光性、光選択透過性、非線形光学性、蛍光あるいはリン光等のルミネッセンス、フォトクロミック性等）、磁気的（硬磁性、軟磁性、非磁性、透磁性等）、電気・電子的（導電性、絶縁性、圧電性、焦電性、誘電性等）、化学的（吸着性、脱着性、触媒性、吸水性、イオン伝導性、酸化還元性、電気化学特性、エレクトロクロミック性等）、機械的（耐摩耗性等）、熱的（伝熱性、断熱性、赤外線放射性等）、生体機能的（生体適合性、抗血栓性等）な各種の機能を意味するものである。
また、このような機能性材料から得られる機能性要素についても、種々のものを挙げることができる。例えば、液晶装置や有機エレクトロルミネセンス装置などの電気光学装置における、配線等の各種要素などが好適とされる。
【００８０】
特性変化部位１８への機能性材料の配置については、特性変化層１６の特性に対応した方法が採用される。
例えば、特性変化層１６が濡れ性変化層である場合には、特性変化部位１８は濡れ性が例えば親液性に変化したパターンとなっていることから、機能性材料からなる液状体を特性変化層１６上に塗布することにより、濡れ性の良好な親液性領域にのみ機能性材料を付着させることができる。したがって、特性変化部位１８に対応して機能性材料を容易に付着させることができ、これにより、特性変化部位１８に対応したパターンを容易に形成することができる。
【００８１】
ここで、特性変化部位１８上に機能性材料の液状体を配する場合には、ディップコート、ロールコート、ブレードコート、スピンコート等の塗布方法や、インクジェット法等の液滴吐出法などが採用可能であるが、特に液滴吐出法を用いて行うのが好ましい。このようにすれば、液滴吐出法で吐出し塗布することにより、機能性材料の必要量を精度良く所望位置に塗布することができる。また、機能性材料を例えば配線材料とすれば、微細な配線パターンを精度良く形成することができる。
【００８２】
また、特性変化層１６が分解除去層である場合は、特性変化層１８上に凹凸が変化したパターンが形成される。したがって、例えば凹部に機能性材料を配置・付着させることにより、機能性材料をパターンに対応して容易に配置することができ、これにより機能性材料からなるパターンを容易に形成することができる。この場合、凹部と凸部との間の濡れ性に相違がある場合、例えば凹部が濡れ性の良好な親液性領域であり、凸部が濡れ性の悪い撥液性領域であれば、さらにこの機能性材料配置・付着が容易になる。
【００８３】
また、特性変化層１６が接着性を変化させる接着性変化層であった場合には、特性変化部位１８は接着性が変化したパターンとなっていることから、特性変化層１６上に全面にわたって金属等の機能性部用組成物を蒸着させ、その後粘着剤等により引き剥がすことにより、接着性が良好な部分にのみ機能性材料としての金属をパターニングすることができる。これにより容易に回路等を形成することができる。
【００８４】
また、本発明に用いられる機能性材料としては、特性変化部位１８に対応して特性変化層１６上に選択的に配置され、すなわちパターニングされることにより、機能性要素となるものであれば特に限定されることなく種々のものが使用可能である。例えば、特性変化層１６上にパターニングされた後、薬剤により処理され、もしくは紫外線、熱等により処理された後に機能性要素となるものであってもよい。この場合に、機能性材料の結着剤として、紫外線、熱、電子線等で硬化する成分を含有している場合には、硬化処理を行うことにより素早く機能性要素を形成することができ、好ましい。
【００８５】
本発明に用いられる機能性材料の使用形態としては、前述したように機能性要素の機能、機能性要素の形成方法等によって異なる。例えば、特性変化層１６が濡れ性変化層である場合には、機能性材料を溶媒で溶解しあるいは分散媒で分散させた液状体が用いられる。溶媒あるいは分散媒としては、特に限定されないものの、水やエチレングリコール等の高表面張力を示すものであることが好ましい。なお、機能性材料からなる液状体としては、粘度が低いほど短時間にパターン形成を行うことができ好ましい。また、溶剤で希釈して形成する液状体の場合には、パターン形成時に溶剤の揮発によって粘度が上昇し、表面張力が変化するため、溶剤が低揮発性であるのが望ましい。
【００８６】
（実験例１）
図２に示した露光用マスク１０および被パターニング体１７を、それぞれ以下のようにして作製した。
まず、支持基板１３として４インチのガラス基板を用意し、これの一方の面にアルミニウムを厚さ２００ｎｍに蒸着し、紫外線（ＵＶ）に対する光反射層１２を形成した。
次に、光触媒の分散した水溶液（商品名；ミラクルチタン、金森藤平商事株式会社）を前記支持基板１３の光反射層１２上にスピンコート法で塗布した。続いて、塗布後の支持基板１３をオーブンに入れ、５０℃で２時間加熱して厚さ３００ｎｍの二酸化チタンからなる光触媒含有層１１を形成した。
その後、前記光触媒含有層１１上の全面にクロムを蒸着し、このクロム層をフォトリソグラフィーを用いてパターン状にエッチングした。このようにして、支持基板１３上に光反射層１２、光触媒含有層１１、クロムパターンからなるフォトマスク１４を作製し、露光用マスク１０を得た。
【００８７】
また、これとは別に、透光性基板１５として４インチの石英基板を用意し、この透光性基板１５とオクタデシルトリクロロシラン１００μｌとを密閉容器内に入れ、１００℃で１時間加熱して透光性基板１５上に特性変化層１６としてのオクタデシルトリクロロシランの単分子膜を形成し、被パターニング体１７を得た。このオクタデシルトリクロロシランの単分子膜からなる特性変化層１６は濡れ性変化層であり、その水の接触角は１３０度であった。
【００８８】
このようにして形成した被パターニング体１７を前記の露光用マスク１０の上にセットし、光触媒含有層１１に特性変化層１６を当接させ接触させた状態のもとで、被パターニング体１７の透光性基板１５上から３０８ｎｍの波長のＵＶ光を、エネルギー密度８０ｍＷ／ｃｍ^２で照射した。照射時間と、単分子膜（特性変化層１６）の分解部分（露光部分）、未分解部分（未露光部分）の水に対する接触角との関係を調べた。結果を以下に示す。

以上に示したように、露光した部分は短時間の露光で水に対する接触角が小さくなり、したがって、露光用マスク１０の光触媒含有層１１中の光触媒による効果が確認された。
【００８９】
（実験例２）
前記実験例１と同様にして露光用マスク１０を作製した。ただし、フォトマスク１４については、２０μｍの回路パターン（配線パターン）に形成した。
また、これとは別に、透光性基板１５として４インチの石英基板を用意し、この透光性基板１５とヘプタデカフルオロ１，１，２，２−テトラヒドロデシルトリエトキシシラン１００μｌとを密閉容器内に入れ、
１５０℃で１時間加熱して透光性基板１５上に特性変化層１６としてのヘプタデカフルオロ１，１，２，２−テトラヒドロデシルトリエトキシシランの単分子膜を形成し、被パターニング体１７を得た。
【００９０】
このようにして形成した被パターニング体１７を前記の露光用マスク１０の上にセットし、光触媒含有層１１に特性変化層１６を当接させ接触させた状態のもとで、被パターニング体１７の透光性基板１５上から１７２ｎｍの波長のＵＶ光を、エネルギー密度１００ｍＷ／ｃｍ^２で１５秒間照射した。
照射後、単分子膜（特性変化層１６）のトルエンに対する接触角を調べたところ、露光部分（特性変化部位１８）では５度以下であり、未露光部分では９０度であった。
【００９１】
このようにして露光により特性変化部位１８を形成した被パターニング体１７の、特性変化層１６上に、銀微粒子をトルエンに分散させてなる分散液（商品名；パーフェクトシルバー、真空冶金社製）１ｍｌを、回転数１０００ｒｐｍでスピンコートした。
スピンコート後、配線パターンである露光部分（特性変化部位１８）にだけ材料の分散液（液状体）が付着していた。この被パターニング体１７を大気中にて４００℃で３０分焼成したところ、幅２５μｍ、厚さ１μｍの金属配線パターンを得ることができた。
【００９２】
（実験例３）
実験例２と同様にして作製したＵＶ露光済みの被パターニング体１７に対し、液滴吐出法（インクジェット法）によって前記パーフェクトシルバーを、露光したパターン、すなわち特性変化部位１８の形状に合わせて吐出した。特性変化部位１８全体に吐出を完了した後、４００℃で１０分焼成した。さらに、同様の吐出／焼成処理を３回繰り返したところ、幅２１μｍ、厚さ２μｍの金属配線パターンを得ることができた。
【図面の簡単な説明】
【図１】 本発明の露光用マスクと被パターニング体の側断面図である。
【図２】 （Ａ）〜（Ｃ）は本発明のパターニング方法の説明図である。
【図３】 （Ａ）、（Ｂ）は本発明のパターニング方法の説明図である。
【図４】 （Ａ）〜（Ｃ）は従来のパターニング方法の説明図である。
【符号の説明】
１０…露光用マスク、１１…光触媒含有層、１２…光反射層、
１３…支持基板、１４…フォトマスク、１５…透光性基板、
１６…特性変化層、１７…被パターニング体、１８…特性変化部位、
１９…遮光パターン、２０…フォトマスク[0001]
BACKGROUND OF THE INVENTION
  The present invention is used for manufacturing various devices.RuIt relates to a turning method.
[0002]
[Prior art]
In a device constituted by a semiconductor device or the like, miniaturization and high integration are achieved by making various patterns formed on a substrate finer and higher definition.
As a patterning method for forming a fine and high-definition pattern, a method in which pattern exposure is performed on a photoresist layer coated on a substrate, the photoresist is developed after the exposure, and etching is generally performed. Also known is a patterning method by photolithography, in which a functional material is used as a photoresist and a desired pattern is directly formed by exposing the photoresist.
[0003]
Such a photolithography patterning method is used for the formation of colored patterns for color filters used in liquid crystal display devices, the formation of microlenses, the production of fine electrical circuit boards, the production of chromium masks used for pattern exposure, etc. It is used. However, in these methods, after the photoresist is exposed, the photoresist is developed with a developing solution, and thus a waste solution is generated, and the waste solution needs to be processed. In addition, when a functional substance is used as a photoresist, there is a problem that the functional substance is deteriorated by an alkali solution or the like used for development.
[0004]
As a method for solving such a problem, research on a patterning method using a substance whose wettability is changed by the action of a photocatalyst has been advanced. For example, a method is known in which a functional substance is directly patterned without using a photoresist by utilizing the organic substance decomposition effect of a photocatalyst, thereby generating no waste liquid and producing a pattern-forming body in a short time ( For example, see Patent Document 1).
[0005]
In this method, first, as shown in FIG. 4A, a photocatalyst containing layer side substrate 3 comprising a transparent substrate 1 and a photocatalyst containing layer 2 formed on the transparent substrate 1, a substrate 4 and the substrate 4 are formed. A pattern forming body substrate 6 including the provided characteristic change layer 5 is prepared.
Next, as shown in FIG. 4B, the photocatalyst containing layer 2 of the photocatalyst containing layer side substrate 3 and the characteristic change layer 5 of the pattern forming substrate 6 are brought into close contact with each other, For example, exposure is performed with UV light or the like through the photomask 7. As a result, the characteristic of the exposed portion on the characteristic change layer 5 changes to become a characteristic change portion 8.
Next, as shown in FIG. 4C, the pattern forming body in which the pattern of the characteristic changing portion 8 is drawn on the characteristic changing layer 5 by removing (separating) the photocatalyst containing layer side substrate 3 from the substrate for the pattern forming body. 9 is formed.
[0006]
[Patent Document 1]
JP 2000-249821 A
[0007]
[Problems to be solved by the invention]
However, since the above method does not require development with a developing solution, there is no waste liquid, and patterning can be performed in a shorter time than when a normal exposure mask that does not use a photocatalyst is used. However, there is a problem to be improved such that the utilization efficiency of the light to be irradiated is insufficient and the properties of the photocatalyst are not fully utilized.
[0008]
  The present invention has been made in view of the above circumstances, and its object is to use light more efficiently by using a photocatalyst, thereby significantly reducing the time required for patterning. CanRuIt is to provide a turning method.
[0009]
[Means for Solving the Problems]
  In order to achieve the above object, the patterning method of the present invention comprises subjecting an object to be patterned having a property-changing layer whose properties are changed by the action of a photocatalyst on a light-transmitting substrate, using an exposure mask. A patterning method for forming a pattern with a changed characteristic in the characteristic change layer, the photocatalyst containing layer containing the photocatalystAnd a light reflecting layer comprising a mirror provided on one side of the photocatalyst-containing layer,The photocatalyst containing layer of the exposure mask is brought into contact with the property changing layer of the patterning object through a photomask, and in this state, the light-transmitting substrate side of the patterning object is used. The photocatalyst containing layer is selectively irradiated with light and exposed to light..
[0010]
  thisAccording to the patterning method, the exposure mask comprisesSince it comprises a photocatalyst-containing layer containing a photocatalyst and a light reflecting layer provided on one side of the photocatalyst-containing layer, the photocatalyst-containing layer is brought into contact with the property change layer of the object to be patterned, and in this state If the light is selectively irradiated from the light-transmitting substrate side of the object to be patterned toward the photocatalyst containing layer and exposed, the photocatalyst of the portion where the irradiated light has once passed through the photocatalyst containing layer In addition, the light is reflected by the light reflecting layer and again passes through the same photocatalyst-containing layer portion, so that it is activated again. The properties are fully utilized, and the characteristics of the characteristic changing layer of the light irradiated portion (exposed portion) change more favorably. Therefore, it is possible to form a pattern whose characteristics are changed more favorably and at a lower cost and in a short time without generating waste liquid.
  Further, by removing the exposure mask from the object to be patterned after exposure, the object to be patterned itself does not contain the photocatalyst containing layer, and therefore the object to be patterned does not deteriorate with time due to the action of the photocatalyst.
[0011]
In the exposure mask, the light reflecting layer is preferably a mirror.
In this way, the light reflected by the light reflection layer passes again through the incident optical path without being irregularly reflected, and sufficient exposure accuracy is maintained.
[0012]
In the exposure mask, the photocatalyst contained in the photocatalyst-containing layer is one or two selected from titanium dioxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide. It is preferably a seed or more, and particularly preferably titanium dioxide. In addition, oxygen defects or impurities may be introduced into such a photocatalyst.
In particular, titanium dioxide is effective as a photocatalyst because of its high band gap energy, is chemically stable, has no toxicity, and is easily available. Moreover, it is preferable to introduce oxygen defects or impurities into the photocatalyst because the photocatalyst becomes highly sensitive to ultraviolet light and visible light.
[0013]
According to the patterning method of the present invention, the object to be patterned having a characteristic change layer whose characteristic is changed by the action of a photocatalyst on a light-transmitting substrate is exposed to light using an exposure mask so that the characteristic change layer has a characteristic. A patterning method for forming a changed pattern, wherein the exposure mask is used, the photocatalyst-containing layer of the exposure mask is brought into contact with the property change layer of the patterning object, and in this state, The exposure is performed by selectively irradiating light from the translucent substrate side toward the photocatalyst-containing layer.
[0014]
According to this patterning method, as described above, the portion of the photocatalyst containing layer that has been irradiated once is activated by activating the portion of the photocatalyst that has once passed through the photocatalyst containing layer and reflected by the light reflecting layer. Since this is reactivated by passing, the use efficiency of the irradiated light can be increased and the characteristics of the photoirradiation part (exposure part) can be improved by making full use of the properties of the photocatalyst. It can be changed well. Therefore, it is possible to form a pattern whose characteristics are changed more favorably and at a lower cost and in a short time without generating waste liquid.
Further, by removing the exposure mask from the object to be patterned after exposure, the object to be patterned itself does not contain the photocatalyst containing layer, and therefore the object to be patterned does not deteriorate with time due to the action of the photocatalyst.
[0015]
In the patterning method, the characteristic change layer is preferably a wettability change layer in which the wettability of the surface changes due to the action of the photocatalyst in the photocatalyst-containing layer.
By making the characteristic change layer a wettability change layer, it becomes possible to form a pattern with a change in wettability by the action of the photocatalyst on the pattern-formed body, and thus various liquid functional materials are formed in the part where the wettability has changed. As described later, various functional elements such as wirings can be formed.
[0016]
In the patterning method, the property change layer may be a decomposition removal layer that is decomposed and removed by the action of the photocatalyst in the photocatalyst containing layer.
By using the property change layer as a decomposition removal layer, the exposed portion is decomposed and removed by the action of the photocatalyst. In this way, the portion exposed to light can be completely decomposed and removed without the need for post-treatment, for example, the decomposition removal layer is a photoresist, and the photocatalyst-containing layer side substrate is brought into contact therewith. The exposure has various advantages such as the ability to form a pattern on a photoresist without the necessity of performing a conventional development process.
In this case, the contact angle of water is preferably different between the decomposition removal layer and the exposed member exposed when the decomposition removal layer is decomposed and removed.
[0017]
In the patterning method, the exposure may be performed by arranging a photomask on the surface side of the photocatalyst containing layer of the exposure mask, or may be performed by light drawing irradiation.
A better pattern can be formed by appropriately selecting according to the properties and applications of the pattern from which these exposure methods can be obtained.
[0018]
In the patterning method, it is preferable to discharge and apply a liquid material made of a functional material by a droplet discharge method onto the characteristic change layer having the changed characteristics. A wiring material is preferable.
In this way, the required amount of functional material can be accurately applied to a desired position by discharging and applying by the droplet discharge method. If the functional material is a wiring material, a fine wiring pattern can be formed with high accuracy.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
FIG. 1 is a view showing an example of an exposure mask according to the present invention. Reference numeral 10 in FIG. 1 denotes an exposure mask. This exposure mask 10 includes a photocatalyst containing layer 11 and a light reflecting layer 12 provided on one side of the photocatalyst containing layer 11, and has a support substrate 13 on the back side of the light reflecting layer 12. is there. Further, in this exposure mask 10, an exposure photomask 14 is formed on the surface of the photocatalyst containing layer 11.
[0020]
As shown in FIG. 1, the exposure mask 10 having such a configuration particularly exposes a patterning object 17 having a characteristic change layer 16 whose characteristics are changed by the action of a photocatalyst on a translucent substrate 15. That is, it is used for pattern formation on the characteristic change layer 16.
[0021]
In the exposure mask 10, the photocatalyst-containing layer 11 is not particularly limited as long as the photocatalyst-containing layer 11 is configured to change the characteristics of the characteristic change layer 16 in contact with the photocatalyst in the photocatalyst-containing layer 11. It may be composed of a photocatalyst and a binder, or may be a film formed of a single photocatalyst. Further, the wettability of the surface may be particularly lyophilic or lyophobic.
[0022]
The action mechanism of the photocatalyst represented by titanium dioxide as will be described later in this photocatalyst-containing layer 11 is not sufficiently clarified, but the carrier generated by light irradiation reacts directly with a nearby compound, Alternatively, it is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of the organic substance. And in this invention, it is thought that this carrier acts on the compound in the characteristic change layer 16 which contacts the photocatalyst containing layer 11.
[0023]
As a photocatalyst contained in the photocatalyst-containing layer 11, for example, titanium dioxide (TiO 2) known as a photo semiconductor₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃1) or a mixture of two or more selected from these. In addition, it is preferable to introduce oxygen defects or impurities into such a photocatalyst because the sensitivity of the photocatalyst to ultraviolet light or visible light increases.
[0024]
Among such photocatalysts, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes an anatase type, a rutile type, and a brookite type, and any of them can be used in the present invention, but the anatase type is particularly preferable.
[0025]
Examples of the anatase type titanium dioxide include hydrochloric acid peptization type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitrate peptization type Anatase type titania sol (TA-15 manufactured by Nissan Chemical Industries, Ltd. (average particle size 12 nm)) and the like can be mentioned.
Regarding the particle size of the photocatalyst, the smaller the particle size, the more effective the photocatalytic reaction occurs. Specifically, the average particle size is preferably 50 nm or less, and particularly preferably 20 nm or less.
[0026]
As described above, the photocatalyst-containing layer 11 may be formed of a photocatalyst alone, or may be formed by mixing with a binder. In order to form the photocatalyst-containing layer 11 with a photocatalyst alone, for example, when titanium dioxide is used, amorphous titania is formed on the light reflecting layer 12 and then baked to change the phase to crystalline titania. Can be adopted. As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. This amorphous titania is denatured into anatase titania by baking at 400 ° C. to 500 ° C., and denatured into rutile type titania by baking at 600 ° C. to 700 ° C.
[0027]
When the photocatalyst-containing layer 11 is formed using a binder, it is preferable that the binder has a high binding energy such that the main skeleton is not decomposed by photoexcitation of the photocatalyst. Is preferred.
When an organopolysiloxane is used as a binder, a binder comprising this organopolysiloxane and a photocatalyst are dispersed in a solvent together with other additives as necessary to prepare a coating solution. The photocatalyst containing layer 11 can be formed by applying to. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. As a coating method, known coating methods such as spin coating, spray coating, dip coating, roll coating, bead coating, and a droplet discharge method can be employed. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer 11 can be formed by irradiating ultraviolet rays and performing a curing treatment.
[0028]
An amorphous silica precursor can be used as the binder. This amorphous silica precursor has the general formula SiX₄X is preferably a silicon compound such as a halogen, a methoxy group, an ethoxy group, or an acetyl group, a silanol that is a hydrolyzate thereof, or a polysiloxane having an average molecular weight of 3000 or less.
[0029]
Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles were uniformly dispersed in a non-aqueous solvent, and hydrolyzed with moisture in the air on the light reflecting layer 12 to form silanol. Thereafter, the photocatalyst-containing layer 11 can be formed by dehydration condensation polymerization at room temperature. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.
The content of the photocatalyst in the photocatalyst-containing layer 11 is 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.
[0030]
The photocatalyst-containing layer 11 can contain a surfactant in addition to the photocatalyst and the binder. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYLFSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Ink Chemical industry Co., Ltd. Megafax F-141, 144, Neos Co., Ltd., Fategent F-200, F251, Daikin Industries Co., Ltd. Unidyne DS-401, 402, 3M Co., Ltd. Fluorado FC-170, Fluorine-based or silicone-based nonionic surfactants such as 176 can be mentioned, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0031]
Furthermore, in addition to the surfactant, the photocatalyst-containing layer 11 includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, Polycarbonate, polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene and other oligomers and polymers Etc. can be contained.
[0032]
The light reflecting layer 12 is formed of a reflective metal such as aluminum. Such a light reflection layer 12 is formed, for example, by providing aluminum or the like on the surface of the support substrate 13 by vapor deposition or the like. As the support substrate 13, various substrates are used without particular limitation, but a glass substrate, a metal substrate, or the like is preferably used in consideration of heat treatment particularly when the photocatalyst containing layer 11 is formed. However, if the heat treatment for forming the photocatalyst-containing layer 11 can be performed at a low temperature, a resin substrate, a resin sheet, a film, or the like can be used.
[0033]
In this example, the light reflecting layer 12 is formed on the support substrate 13, but the light reflecting layer 12 is formed on the back surface of a transparent substrate such as glass, for example, and a mirror body is constituted by the transparent substrate and the light reflecting layer 12. And you may make it form the said photocatalyst content layer 11 on the transparent substrate of this mirror.
The light reflecting layer 12 preferably does not diffusely reflect, but totally reflects light incident perpendicularly to the reflecting surface on the same optical axis. Therefore, the reflecting surface of the light reflecting layer 12 is smooth. It is necessary to have a specular shape. In order to make the reflection surface of the light reflection layer 12 have such a mirror surface shape, the surface of the support substrate 13 on which the light reflection layer 12 is formed is smoothed in advance, or the reflection surface of the formed light reflection layer 12 is polished. Can be smoothed by using the above-mentioned mirror body.
[0034]
Further, in the exposure mask 10 of this example, the photomask 14 for exposure is formed on the surface of the photocatalyst containing layer 11 as described above. The photomask 14 can be formed, for example, by vapor-depositing metal chromium on the photocatalyst containing layer 11 and patterning the metal chromium layer by photolithography. Since the photomask 14 serves as a light shielding layer, the photomask 14 has a pattern opposite to the pattern formed on the characteristic change layer 16 via the photocatalyst containing layer 11, that is, a negative pattern. Further, the photomask 14 is formed sufficiently thin by vapor deposition or the like. Therefore, when the photocatalyst containing layer 11 and the property changing layer 16 of the patterning target 17 are brought into contact with each other as will be described later, the photomask 14 is formed between them. As a result, the contact (contact) between the photocatalyst containing layer 11 and the characteristic change layer 16 is not hindered. The exposure mask of the present invention may have a structure without the photomask 14 as will be described later.
[0035]
On the other hand, the to-be-patterned body 17 patterned by the exposure mask 10 having such a configuration has the characteristic change layer 16 on the translucent substrate 15 as described above. The translucent substrate 15 has flexibility such as a non-flexible transparent rigid material such as quartz glass, Pyrex (registered trademark) glass, and synthetic quartz plate, a transparent resin film, an optical resin plate, and the like. A transparent flexible material or the like is used.
[0036]
The characteristic change layer 16 may be any layer as long as the characteristic is changed by the action of the photocatalyst. For example, a photochromic material such as spiropyran or an organic dye decomposed by the action of the photocatalyst is characteristic in the characteristic change layer. It is good also as a layer mixed with a change layer and coloring a characteristic change layer by the effect | action of a photocatalyst.
[0037]
In addition, for example, by using a polymer material such as polyethylene such as polyethylene or polypropylene, a polar group is introduced into the exposed part due to the action of a photocatalyst, or the surface state becomes rough. A layer in which the adhesive property is improved may be used as the characteristic change layer 16. Thus, by making the characteristic change layer 16 an adhesive change layer in which the adhesiveness changes, it is possible to form a pattern with good adhesiveness by pattern exposure.
[0038]
The object to be patterned 17 on which a pattern of such a part having good adhesion is formed, for example, by depositing a metal component on the object to be patterned 17 to form a metal thin film, and then utilizing the difference in adhesion Then, by peeling off the metal thin film with, for example, an adhesive or a drug, a metal thin film pattern can be formed. According to this method, it is possible to form a metal thin film pattern without forming a resist pattern, and it is possible to form a printed circuit board or an electronic circuit element having a finer pattern than that obtained by the printing method. it can.
[0039]
As described above, the characteristic changing layer 16 is not particularly limited as long as it has various characteristics that are changed by the action of the photocatalyst. However, in the present invention, the wettability of the characteristic changing layer 16 is changed by the action of the photocatalyst. There are two cases: a wettability changing layer where a pattern due to wettability is formed, and a case where the characteristic changing layer 16 is a decomposition removing layer where a pattern due to unevenness is formed by being decomposed and removed by the action of the photocatalyst. In particular, it is preferable because the effectiveness of the present invention can be further extracted from the relationship of the functional elements and the like obtained.
[0040]
The wettability changing layer in the present invention refers to a layer in which the wettability of the surface is changed by the action of the photocatalyst at the time of exposure, and a pattern can be formed by the site having changed wettability. Although this wettability changing layer is not particularly limited, this wettability changing layer is a wettability changing layer whose wettability changes so that the contact angle of a functional liquid material such as water is reduced by exposure. Preferably there is.
[0041]
In this way, the wettability changing layer in which the wettability is changed so that the contact angle of the functional liquid material is reduced by exposure, so that the wettability can be easily changed by performing pattern exposure, etc. A pattern of a lyophilic region having a small contact angle of the material can be formed. Therefore, for example, by exposing only the portion where the functional element is formed on the wettability changing layer (characteristic changing layer 16), this portion can be easily made a lyophilic region, and thus this portion. A functional element can be easily and efficiently formed by adhering a liquid material made of a functional material to the substrate. As described above, since the functional element can be easily and efficiently manufactured, the manufacturing of the functional element can be made cost-effective by using the characteristic change layer 16 as the wettability change layer. .
[0042]
Here, the lyophilic region is a region where the contact angle of the functional liquid material is small, and a liquid made of the functional material, for example, a dispersion liquid in which fine metal particles used as the wiring material are dispersed, or a coloring liquid An area having good wettability with respect to ink, a liquid material for forming a microlens, and the like. The liquid repellent region is a region where the contact angle of the functional liquid material is large, and the liquid repellent region is for a dispersion liquid in which the metal fine particles are dispersed, a coloring ink, a liquid material for forming a microlens, or the like. An area with poor wettability is used.
[0043]
In the wettability changing layer (characteristic changing layer 16), the contact angle of the functional liquid material is 90 ° or more, preferably 140 ° or more in a portion where the action of the photocatalyst is not applied. This is because the portion not subjected to the action of the photocatalyst is a portion that requires liquid repellency in this example. That is, when the contact angle of the functional liquid material is smaller than 90 degrees, the liquid repellency is not sufficient, and a liquid material made of the functional material, for example, a dispersion liquid in which metal fine particles are dispersed is used for the action of the photocatalyst. This is not preferable because it may remain in a portion that does not receive.
[0044]
The wettability changing layer (characteristic changing layer 16) is a layer that, when exposed to light and subjected to the action of a photocatalyst, reduces the contact angle of the functional liquid material to 30 ° or less, more preferably 20 ° or less. It is preferable that The angle of 30 degrees or less is preferable. When the angle exceeds 30 degrees, the spread of the liquid material composed of the functional material in this portion may be inferior, and the functional element may be missing. Because there is.
[0045]
The material used for such a wettability changing layer is a material whose wettability changes due to the characteristics of the wettability changing layer, that is, the photocatalyst in the photocatalyst-containing layer 11 that comes into contact when exposed. In addition, any material can be used without particular limitation as long as it has a main chain that is hardly deteriorated or decomposed by the action of the photocatalyst. For example, (1) organopolysiloxane that exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction or the like, and (2) organo crosslinked with reactive silicone having excellent water repellency and oil repellency. Mention may be made of organopolysiloxanes such as polysiloxanes.
[0046]
In the case of (1) above, the general formula: Y_nSiX_(4-n)(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. It is preferable that it is an organopolysiloxane which is one or two or more hydrolysis condensates or cohydrolysis condensates of the silicon compound represented by Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0047]
Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxy Silane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Lutriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n -Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane Tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, Diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxy Hydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane, vinyltri Methoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyl Triisopropoxysilane, trifluoropropyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimethyl Xysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyl Tri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ- Aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrieth Xysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane And partial hydrolysates thereof; and mixtures thereof can be used.
[0048]
In particular, a polysiloxane containing a fluoroalkyl group can be preferably used. Specific examples include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes: In general, those known as fluorine-based silane coupling agents can be used.
[0049]
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃; (CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃; (CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃; (CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃CF₃(C₆H₄) C₂H₄Si (OCH₃)₃CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂; (CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂; (CF₃)₂CF (CF₂)₆CH₂CH₂SiCH₃(OCH₃)₂; (CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃; And CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃.
[0050]
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-exposed portion of the wettability changing layer (the portion not subjected to the action of the photocatalyst) is greatly improved. The function which prevents adhesion of the composition for functional parts is exhibited.
[0051]
In addition, examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0052]
[Chemical 1]

[0053]
However, n is an integer greater than or equal to 2, R¹, R²Each represents a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the total is vinyl, phenyl or phenyl halide in a molar ratio. R¹, R²Is a methyl group because the surface energy is minimized, and it is preferable that the methyl group is 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
[0054]
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with the said organopolysiloxane.
[0055]
The wettability changing layer (characteristic changing layer 16) in the present invention may further contain a surfactant. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0056]
In addition to the surfactants described above, the wettability changing layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate. , Polyvinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, etc. Can be contained.
[0057]
Such a wettability changing layer (characteristic changing layer 16) is prepared by dispersing the above-described components in a solvent together with other additives as necessary to prepare a coating solution, and this coating solution is used for the translucent substrate 15. It can be formed by coating on top. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating, bead coating, or a droplet discharge method. In the case where an ultraviolet curable component is contained, the wettability changing layer (characteristic changing layer 16) can be formed by irradiating the ultraviolet ray to perform the curing treatment.
[0058]
The thickness of such a wettability changing layer (characteristic changing layer 16) is preferably 0.001 μm to 1 μm, and preferably 0.01 to 0.1 μm from the relationship of the wettability change rate by the photocatalyst. It is particularly preferred that it is within the range.
[0059]
If the characteristic change layer 16 is such a wettability change layer, as described later, the action of the photocatalyst in the photocatalyst-containing layer 11 that comes into contact causes oxidation, decomposition, etc. of organic groups and additives that are part of the components. As a result, the wettability of the exposed portion changes to become lyophilic, which causes a large difference in wettability with the non-exposed portion. Therefore, by improving the acceptability (lyophilicity) and repellent property (liquid repellency) of a liquid material composed of functional materials, for example, a dispersion liquid in which metal fine particles are dispersed, the quality is good and the cost is reduced. Therefore, it is possible to obtain functional elements such as wiring that are advantageous.
[0060]
Next, the case where the characteristic change layer 16 is a decomposition removal layer that is decomposed and removed by the action of the photocatalyst will be described. The decomposition removal layer is a layer formed so that the exposed portion is decomposed and removed by the action of the photocatalyst in the photocatalyst containing layer 11 when exposed. Therefore, according to this decomposition / removal layer (characteristic changing layer 16), the portion having changed characteristics due to the action of the photocatalyst is decomposed and removed, so that the transparent substrate 15 serving as a base is exposed to form an uneven pattern. The patterned object 17 thus obtained can be obtained.
[0061]
As described above, since the exposed portion is decomposed and removed by the action of the photocatalyst, the decomposition / removal layer has a pattern composed of a portion with and without the decomposition / removal layer without performing a development process or a washing step, that is, has an unevenness. A pattern can be formed. Therefore, for example, if this decomposition / removal layer is formed of a material having resist characteristics, a resist pattern can be easily formed by pattern exposure in contact with the exposure mask 10. Therefore, it can be used in a semiconductor manufacturing process or the like as a photoresist without a development / cleaning process.
[0062]
When this decomposition / removal layer (characteristic changing layer 16) is used, not only the unevenness is formed, but the characteristics of the exposed member (translucent substrate 15) and the decomposition / removal layer exposed by decomposition and removal are not limited. Depending on the difference, a pattern can also be formed. Specific examples of such characteristics include various properties such as adhesiveness and color developability, but in the present invention, wettability can be mentioned among others. Due to the difference in wettability, a pattern can be formed in the same manner as the wettability changing layer described above.
[0063]
That is, in the present invention, the contact angle of the functional liquid material differs between the decomposition removal layer (characteristic change layer 16) and the exposed member (translucent substrate 15) exposed by the decomposition removal layer being decomposed and removed. The contact angle of the functional liquid material on the decomposition removal layer is preferably larger than the contact angle of the functional liquid material of the translucent substrate 15. In that case, it is particularly preferable that the contact angle of the decomposition removal layer with the functional liquid material is 60 degrees or more.
[0064]
This is because the portion of the decomposition removal layer (characteristic change layer 16) that is not subjected to the action of the photocatalyst becomes a portion where the decomposition removal layer remains, that is, a convex portion, so that the functional material is attached to the convex portion. This is because it is excellent in stability and the like, and it is preferable to attach the functional material to the concave portion where the removal layer is removed and the exposed member (translucent substrate 15) is exposed. For this reason, it is preferable that the decomposition removal layer (characteristic change layer 16) exhibits liquid repellency so that a liquid material made of a functional material is less likely to adhere, and the functional liquid material of the exposed member (translucent substrate 15). It is preferable that the contact angle of the functional liquid material on the decomposition removal layer is larger than the contact angle. In addition, when the contact angle of the functional liquid material on the decomposition removal layer is smaller than 60 degrees, the liquid repellency is not sufficient, and there is a possibility that the liquid material made of the functional material may remain there. .
[0065]
The material used for such a decomposition / removal layer is a material that is decomposed and removed by the above-described characteristics of the decomposition / removal layer, that is, the action of exposure of the photocatalyst in the photocatalyst-containing layer 11 in contact, and preferably a functional liquid material Is a material having a contact angle of 60 ° or more. Examples of such materials include hydrocarbon-based, fluorine-based, and silicone-based nonionic surfactants, and specifically include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, perfluoroalkyl. Examples thereof include an ethylene oxide adduct or a perfluoroalkylamine oxide.
[0066]
Examples of such materials include hydrocarbon-based nonionic surfactants, NIKKOL BL, BC, BO, and BB series (trade name, manufactured by Nippon Surfactant Kogyo Co., Ltd.), fluorine-based or silicon-based non-ionic surfactants. If it is an ionic surfactant, ZONYL FSN, FSO (trade name, manufactured by DuPont), Surflon S-141, 145 (trade name, manufactured by Asahi Glass Co., Ltd.), MegaFuck F-141, 144 (trade name, Dainippon) Ink Co., Ltd., Aftergent F200, F251 (trade name, manufactured by Neos), Unidyne DS-401, 402 (trade name, manufactured by Daikin Industries), Florard FC-170, 176 (trade name, manufactured by 3M) It can be obtained.
[0067]
In addition, as the material for the decomposition removal layer, other cationic, anionic and amphoteric surfactants can be used. Specifically, sodium alkylbenzenesulfonate, alkyltrimethylammonium salt, perfluoroalkyl Examples thereof include carboxylates and perfluoroalkylbetaines.
[0068]
Furthermore, as a material for the decomposition removal layer, various polymers or oligomers can be used in addition to the surfactant. Examples of such polymers or oligomers include polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide. Styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, and the like. In the present invention, it is particularly preferable to use a liquid repellent polymer having a high contact angle with a functional liquid material such as polyethylene, polypropylene, polystyrene and polyvinyl chloride.
[0069]
Such a decomposition / removal layer is prepared by dispersing the above-described components in a solvent together with other additives as necessary to prepare a coating solution, and applying the coating solution to a substrate or an exposed member (a substrate and an exposed member are in common). It can also be formed by coating on top. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating.
In addition, the thickness of the decomposition removal layer (characteristic change layer 16) is preferably 0.001 μm to 1 μm in the range of 0.01 to 0.1 μm from the relationship of the decomposition rate by the photocatalyst. Is particularly preferred.
[0070]
Next, a description will be given of a method for exposing and patterning the object to be patterned 17 having such a configuration using the exposure mask 10 described above.
First, the exposure mask 10 and the patterning object 17 shown in FIG. 1 are prepared, and these are applied so that the photocatalyst containing layer 11 and the characteristic change layer 16 are in contact with each other as shown in FIG. Make contact.
[0071]
Here, the contact between the photocatalyst-containing layer 11 and the characteristic change layer 16 means a state in which the action of the photocatalyst substantially reaches the characteristic change layer 16 in the present invention. That is, not only the state in which the photocatalyst-containing layer 11 is in physical contact with the characteristic change layer 16 but also, for example, even when there is no physical contact, water or air or the like intervenes therebetween, The case where it arrange | positions so that the effect | action of a photocatalyst may reach a characteristic change layer shall be included. In the present invention, such a contact state need only be maintained at least during exposure.
[0072]
Next, under the state where the photocatalyst containing layer 11 and the characteristic change layer 16 are in contact with each other as described above, the photocatalyst containing is seen from the light transmitting substrate 15 side of the object to be patterned 17 as shown in FIG. Exposure is performed by selectively irradiating the layer 11 with light for exposure, for example, ultraviolet light (UV light) through the photomask 14. As a light source used for such exposure, conventionally known light sources such as a mercury lamp, a metal halide lamp, and a xenon lamp are used. In addition, the light irradiation amount at the time of exposure is set to an irradiation amount necessary for the characteristic change layer 16 to change the characteristic by the action of the photocatalyst in the photocatalyst containing layer 11. In this exposure, the sensitivity can be increased by performing exposure while heating the photocatalyst-containing layer 11. This is particularly effective when light drawing irradiation described later is used.
[0073]
When the exposure is performed in this manner, the photocatalyst in the portion where the irradiated light has once passed through the photocatalyst containing layer 11 is activated except for the portion where the photomask 14 is provided as shown by the arrow in FIG. In addition, the light is reflected by the light reflecting layer 12 and passes again through the same photocatalyst containing layer 11 to activate again. In FIG. 2C, for the sake of explanation, incident light and reflected light are indicated by separate arrows for ease of explanation, but in actuality, incident light is incident / reflected (emitted) on the same optical axis. Thus, since the light irradiated by one exposure passes through the photocatalyst containing layer 11 twice by incidence and reflection, the activation of the photocatalyst in the photocatalyst containing layer 11 can be remarkably increased as compared with the prior art, and therefore The utilization efficiency of the light to irradiate can be improved and the properties of the photocatalyst can be fully utilized. Therefore, the characteristics of the characteristic change layer 16 that is in contact with the light irradiated portion (exposed portion) in the photocatalyst containing layer 11 are changed more favorably, whereby the characteristic change portion 18 in which the characteristics are changed favorably is reduced at low cost and short. Can be formed in time.
[0074]
The characteristic change portion 18 may be a wettability change portion if the characteristic change layer 16 changes wettability by exposure as described above, and may be a decomposition removal layer that is decomposed and removed. For example, it becomes a site | part in which a recessed part is formed, and if it is an adhesive change layer from which adhesiveness changes, it will become a site | part from which adhesiveness differs.
[0075]
According to such a patterning method using the exposure mask 10, it is possible to form a pattern with changed characteristics (characteristic change portion 18) in a shorter time and at a lower cost without generating waste liquid. Further, by removing the exposure mask 10 from the patterned body 17 after exposure, the patterned body 17 itself does not include the photocatalyst-containing layer 11, and therefore the characteristic change layer 16 is deteriorated over time due to the action of the photocatalyst. Will never happen.
[0076]
Although the exposure mask 10 has a structure in which the photomask 14 is provided, it may have a structure without the photomask 14 as described above. In that case, as shown in FIG. 3A, a light shielding pattern 19 is formed on a light-transmitting substrate such as glass to form a photomask 20 as in the conventional case, and this is used as the light-transmitting substrate 15 of the object to be patterned 17. Set to the side. Further, as described above, the exposure mask 10 and the object to be patterned 17 are brought into contact with each other so that the photocatalyst containing layer 11 and the characteristic change layer 16 are in contact with each other. Then, under this state, as shown in FIG. 3B, exposure light (from the light-transmitting substrate 15 side of the object to be patterned 17 toward the photocatalyst-containing layer 11 via the photomask 20 is applied. For example, ultraviolet rays are selectively irradiated to perform exposure. Here, when such a photomask 20 is used, it is possible to form a fine pattern by using a reduction projection exposure method in which an image of a mask pattern is reduced by a reduction optical system.
[0077]
When exposure is performed in this manner, the light irradiated in one exposure passes through the photocatalyst containing layer 11 twice by incidence / reflection, as in the previous example, so that the photocatalyst in the photocatalyst containing layer 11 is activated. As compared with the prior art, therefore, the utilization efficiency of the irradiated light can be increased and the properties of the photocatalyst can be fully utilized. Therefore, in the example shown in FIG. 3 as well, the characteristics of the characteristic change layer 16 that is in contact with the light irradiated part (exposed part) in the photocatalyst containing layer 11 are changed more favorably, and thereby the characteristic change is changed favorably. The part 18 can be formed at a low cost and in a short time. Further, since the photomask 14 is not formed on the photocatalyst-containing layer 11, the photocatalyst-containing layer 11 and the property change layer 16 are in direct contact with each other without interposing the photomask 14 therebetween. That is, the degree of contact can be increased.
[0078]
Further, in the present invention, it is not necessary to use the photomasks 14 and 20 as long as the photocatalyst containing layer 11 can be selectively irradiated with light and exposed. In that case, it is possible to selectively perform exposure by drawing a predetermined pattern directly by, for example, light drawing irradiation using a laser beam or the like. Examples of the light source for performing such light drawing irradiation include an excimer laser and a YAG laser.
[0079]
Thus, various functional elements can be formed by providing a functional material for the characteristic change portion 18 formed on the patterning target 17. Here, the functionality is optical (light selective absorption, reflectivity, polarization, light selective transmission, nonlinear optical property, luminescence such as fluorescence or phosphorescence, photochromic property, etc.), magnetic (hard magnetism, softness, etc.). Magnetic, non-magnetic, magnetically permeable), electrical / electronic (conductive, insulating, piezoelectric, pyroelectric, dielectric, etc.), chemical (adsorbent, desorbable, catalytic, water-absorbing, ionic conductivity) , Redox properties, electrochemical properties, electrochromic properties, etc.), mechanical properties (wear resistance, etc.), thermal properties (heat transfer properties, heat insulation properties, infrared radiation properties, etc.), biofunctional properties (biocompatibility, antithrombotic properties) Etc.) means various functions.
Moreover, various things can be mentioned also about the functional element obtained from such a functional material. For example, various elements such as wiring in an electro-optical device such as a liquid crystal device or an organic electroluminescence device are suitable.
[0080]
As for the arrangement of the functional material in the characteristic change portion 18, a method corresponding to the characteristic of the characteristic change layer 16 is employed.
For example, when the characteristic change layer 16 is a wettability change layer, the characteristic change portion 18 has a pattern in which the wettability is changed to, for example, lyophilicity. By applying on the layer 16, the functional material can be attached only to the lyophilic region having good wettability. Therefore, the functional material can be easily attached corresponding to the characteristic change site 18, and thus a pattern corresponding to the characteristic change site 18 can be easily formed.
[0081]
Here, in the case where a liquid material of a functional material is disposed on the characteristic change portion 18, a coating method such as dip coating, roll coating, blade coating, or spin coating, or a droplet discharge method such as an ink jet method is employed. Although possible, it is particularly preferable to use a droplet discharge method. In this way, the required amount of functional material can be accurately applied to a desired position by discharging and applying by the droplet discharge method. If the functional material is, for example, a wiring material, a fine wiring pattern can be formed with high accuracy.
[0082]
When the characteristic change layer 16 is a decomposition removal layer, a pattern with unevenness is changed on the characteristic change layer 18. Therefore, for example, by disposing / attaching the functional material in the concave portion, the functional material can be easily disposed corresponding to the pattern, and thereby the pattern made of the functional material can be easily formed. In this case, if there is a difference in wettability between the concave portion and the convex portion, for example, if the concave portion is a lyophilic region having good wettability and the convex portion is a liquid repellent region having poor wettability, This functional material arrangement and adhesion becomes easy.
[0083]
When the characteristic change layer 16 is an adhesive change layer that changes the adhesiveness, the characteristic change portion 18 has a pattern in which the adhesiveness has changed. The metal as the functional material can be patterned only in a portion having good adhesiveness by depositing a functional part composition such as the above and then peeling off with a pressure-sensitive adhesive or the like. Thereby, a circuit etc. can be formed easily.
[0084]
In addition, as the functional material used in the present invention, any functional material can be used as long as it becomes a functional element by being selectively disposed on the characteristic change layer 16 corresponding to the characteristic change portion 18, that is, by patterning. Various things can be used without limitation. For example, it may be a functional element after being patterned on the characteristic change layer 16 and then treated with a drug, or treated with ultraviolet rays, heat, or the like. In this case, as a binder of the functional material, when it contains a component that is cured by ultraviolet rays, heat, electron beam, etc., a functional element can be quickly formed by performing a curing treatment, preferable.
[0085]
As described above, the usage form of the functional material used in the present invention varies depending on the function of the functional element, the method of forming the functional element, and the like. For example, when the characteristic change layer 16 is a wettability change layer, a liquid material in which a functional material is dissolved with a solvent or dispersed with a dispersion medium is used. Although it does not specifically limit as a solvent or a dispersion medium, It is preferable that it is what shows high surface tension, such as water and ethylene glycol. In addition, as a liquid material made of a functional material, the lower the viscosity, the better the pattern can be formed in a short time. Further, in the case of a liquid material formed by diluting with a solvent, it is desirable that the solvent has low volatility because the viscosity increases due to volatilization of the solvent during pattern formation and the surface tension changes.
[0086]
(Experimental example 1)
The exposure mask 10 and the patterning object 17 shown in FIG. 2 were respectively produced as follows.
First, a 4-inch glass substrate was prepared as the support substrate 13, and aluminum was vapor-deposited to a thickness of 200 nm on one surface thereof to form a light reflecting layer 12 for ultraviolet rays (UV).
Next, an aqueous solution (trade name: Miracle Titanium, Kanamori Tohei Shoji Co., Ltd.) in which a photocatalyst was dispersed was applied onto the light reflecting layer 12 of the support substrate 13 by a spin coating method. Then, the support substrate 13 after application | coating was put into oven, and it heated at 50 degreeC for 2 hours, and formed the photocatalyst containing layer 11 which consists of titanium dioxide with a thickness of 300 nm.
Thereafter, chromium was vapor-deposited on the entire surface of the photocatalyst-containing layer 11, and this chromium layer was etched into a pattern using photolithography. Thus, the photomask 14 which consists of the light reflection layer 12, the photocatalyst containing layer 11, and a chromium pattern on the support substrate 13 was produced, and the exposure mask 10 was obtained.
[0087]
Separately, a 4-inch quartz substrate is prepared as the light-transmitting substrate 15, and the light-transmitting substrate 15 and 100 μl of octadecyltrichlorosilane are placed in a hermetically sealed container and heated at 100 ° C. for 1 hour to transmit the light. A monomolecular film of octadecyltrichlorosilane as the characteristic change layer 16 was formed on the optical substrate 15 to obtain a patterning object 17. The characteristic change layer 16 composed of a monomolecular film of octadecyltrichlorosilane was a wettability change layer, and the water contact angle was 130 degrees.
[0088]
The patterning object 17 thus formed is set on the above-described exposure mask 10, and the property change layer 16 is brought into contact with and contacted with the photocatalyst containing layer 11. UV light having a wavelength of 308 nm from above the translucent substrate 15 is irradiated with an energy density of 80 mW / cm.²Irradiated with. The relationship between the irradiation time and the contact angle with respect to water of the decomposed portion (exposed portion) and the undecomposed portion (unexposed portion) of the monomolecular film (characteristic changing layer 16) was examined. The results are shown below.

As described above, the exposed portion has a small contact angle with water after a short exposure, and thus the effect of the photocatalyst in the photocatalyst containing layer 11 of the exposure mask 10 was confirmed.
[0089]
(Experimental example 2)
An exposure mask 10 was produced in the same manner as in Experimental Example 1. However, the photomask 14 was formed in a 20 μm circuit pattern (wiring pattern).
Separately, a 4-inch quartz substrate is prepared as the translucent substrate 15, and the translucent substrate 15 and 100 μl of heptadecafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane are sealed in a sealed container. Put in
A monomolecular film of heptadecafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane as the characteristic change layer 16 is formed on the translucent substrate 15 by heating at 150 ° C. for 1 hour, and the object to be patterned 17 is formed. Obtained.
[0090]
The patterning object 17 thus formed is set on the above-described exposure mask 10, and the property change layer 16 is brought into contact with and contacted with the photocatalyst containing layer 11. UV light having a wavelength of 172 nm from above the light-transmitting substrate 15 is applied with an energy density of 100 mW / cm.²For 15 seconds.
After irradiation, the contact angle of the monomolecular film (characteristic change layer 16) with toluene was examined. As a result, the exposed part (characteristic change part 18) was 5 degrees or less, and the unexposed part was 90 degrees.
[0091]
1 ml of a dispersion liquid (trade name: Perfect Silver, manufactured by Vacuum Metallurgy Co., Ltd.) in which silver fine particles are dispersed in toluene on the characteristic change layer 16 of the object to be patterned 17 having the characteristic change portion 18 formed by exposure in this way. Was spin-coated at a rotation speed of 1000 rpm.
After the spin coating, the dispersion liquid (liquid material) was attached only to the exposed portion (characteristic changing portion 18) as the wiring pattern. When this object to be patterned 17 was baked at 400 ° C. for 30 minutes in the atmosphere, a metal wiring pattern having a width of 25 μm and a thickness of 1 μm could be obtained.
[0092]
(Experimental example 3)
The perfect silver was discharged in accordance with the exposed pattern, that is, the shape of the characteristic change portion 18 by the droplet discharge method (inkjet method) onto the UV-exposed patterning object 17 produced in the same manner as in Experimental Example 2. . After the discharge was completed over the entire characteristic changing portion 18, baking was performed at 400 ° C. for 10 minutes. Further, when the same discharge / firing process was repeated three times, a metal wiring pattern having a width of 21 μm and a thickness of 2 μm could be obtained.
[Brief description of the drawings]
FIG. 1 is a side sectional view of an exposure mask and an object to be patterned according to the present invention.
FIGS. 2A to 2C are explanatory views of a patterning method of the present invention.
FIGS. 3A and 3B are explanatory diagrams of a patterning method of the present invention. FIGS.
4A to 4C are explanatory views of a conventional patterning method.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 ... Mask for exposure, 11 ... Photocatalyst containing layer, 12 ... Light reflection layer,
13 ... Support substrate, 14 ... Photomask, 15 ... Translucent substrate,
16 ... Characteristic change layer, 17 ... Object to be patterned, 18 ... Characteristic change part,
19 ... light-shielding pattern, 20 ... photomask

Claims (9)

Patterning that forms a pattern with a changed characteristic in the characteristic change layer by exposing the object to be patterned having a characteristic change layer on the translucent substrate whose characteristic is changed by the action of a photocatalyst using an exposure mask A method,
Using an exposure mask comprising a photocatalyst-containing layer containing the photocatalyst and a light reflecting layer comprising a mirror provided on one side of the photocatalyst-containing layer, the photocatalyst-containing layer of the exposure mask Contact with the property change layer of the object to be patterned through a mask, and in that state, light is selectively irradiated from the light-transmitting substrate side of the object to be patterned toward the photocatalyst-containing layer and exposed. A patterning method. The photocatalyst contained in the photocatalyst-containing layer is one or more selected from titanium dioxide, zinc oxide, tin oxide, strontium titanate, tungsten oxide, bismuth oxide, and iron oxide. The patterning method according to claim 1. The patterning method according to claim 2, wherein oxygen defects or impurities are introduced into the photocatalyst contained in the photocatalyst-containing layer. The patterning method according to claim 1, wherein the property change layer is a wettability change layer in which a surface wettability is changed by the action of a photocatalyst in the photocatalyst-containing layer. The patterning method according to claim 1, wherein the characteristic change layer is a decomposition removal layer that is decomposed and removed by the action of a photocatalyst in the photocatalyst-containing layer. The patterning method according to claim 1, wherein the exposure mask is formed by forming the photomask on a surface on one side of the photocatalyst-containing layer. The patterning method according to claim 1, wherein the exposure is performed by light drawing irradiation. The patterning method according to claim 1, wherein a liquid material made of a functional material is discharged and applied onto the characteristic change layer having the changed characteristics by a droplet discharge method. 9. The patterning method according to claim 8, wherein the functional material is a wiring material.

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