JP4256124B2 - Method for producing pattern forming body - Google Patents

Description

【００８４】
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がメチル基の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。
【００８５】
また、上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。
【００８６】
本実施態様においては、このようにオルガノポリシロキサン等の種々の材料を濡れ性変化層に用いることができるのであるが、上述したように、濡れ性変化層にフッ素を含有させることが、濡れ性のパターン形成に効果的である。したがって、光触媒の作用により劣化・分解しにくい材料にフッ素を含有させる、具体的にはオルガノポリシロキサン材料にフッ素を含有させて濡れ性変化層とすることが好ましいといえる。
【００８７】
本実施態様における濡れ性変化層には、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。
【００８８】
また、濡れ性変化層には上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。
【００８９】
このような濡れ性変化層は、上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、この塗布液を基板上に塗布することにより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を形成することができる。
【００９０】
本実施態様において、この濡れ性変化層の厚みは、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、特に好ましくは０．０１〜０．１μｍの範囲内である。
【００９１】
また、上述したように、本実施態様の濡れ性変化層は自己支持性を有する材料であってもよく、自己支持性を有する材料としては、上述した材料を成膜したものが自己支持性を有するものであれば、これを用いることも可能であるが、例えば、ポリエチレン、ポリカーボネート、ポリプロピレン、ポリスチレン、ポリエステル、ポリビニルフロライド、アセタール樹脂、ナイロン、ABS、PTFE、メタクリル樹脂、フェノール樹脂、ポリ弗化ビニリデン、ポリオキシメチレン、ポリビニルアルコール、ポリ塩化ビニル、ポリエチレンテレフタレート、シリコーン等を挙げることができる。
【００９２】
ｂ．分解除去層
次に分解除去層について説明する。本実施態様に用いられる分解除去層は、エネルギー照射された際に光触媒含有層中の光触媒の作用により、エネルギー照射された部分の分解除去層が分解除去される層であれば、特に限定されるものではない。
【００９３】
このように分解除去層は、エネルギー照射した部分が光触媒の作用により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。
【００９４】
なお、この分解除去層は、エネルギー照射による光触媒の作用により酸化分解され、気化等されることから、現像・洗浄工程等の特別な後処理なしに除去されるものであるが、分解除去層の材質によっては、洗浄工程等を行ってもよい。
【００９５】
また、本実施態様に用いられる分解除去層は、凹凸を形成するのみならず、この分解除去層が、上記基板表面と比較して、液体との接触角が高いことが好ましい。これにより、分解除去層が分解除去され、基板が露出した領域を親液性領域、上記分解除去層が残存する領域を撥液性領域とすることが可能となり、種々のパターンを形成することが容易となるからである。
【００９６】
ここで、上記エネルギー照射により基板が露出した領域である親液性領域と、エネルギー未照射の残存する分解除去層からなる領域である撥液性領域との特性が、その後塗布する機能性部形成用組成物が有する表面張力と同等の表面張力の液体に対する接触角において、少なくとも１°以上、好ましくは５°以上、特に１０°以上異なる親液性領域および撥液性領域から形成されたパターンであることが好ましい。
【００９７】
また、本実施態様の分解除去層表面の液体との接触角は、表面張力４０ｍＮ／ｍの液体との接触角が１０°以上、好ましくは表面張力３０ｍＮ／ｍの液体との接触角が１０°以上、特に表面張力２０ｍＮ／ｍの液体との接触角が１０°以上の値を示すことが好ましい。
【００９８】
また、本実施態様において、特性変化層が分解除去層である場合には、後述する基板が親液性であることが好ましく、具体的には、表面張力４０ｍＮ／ｍの液体との接触角として９°以下であることが好ましく、さらに好ましくは、表面張力４０ｍＮ／ｍの液体との接触角として５°以下、特に好ましくは１°以下であることである。
【００９９】
分解除去層および基板の濡れ性が、上記範囲内であることにより、基板が露出した領域を親液性領域、分解除去層が残存する領域を撥液性領域とすることが可能となり、高精細なパターンの形成が容易となるからである。ここで、液体との接触角は、上述した方法により測定した値である。
【０１００】
この場合、後述する基板は表面を親液性となるように、表面処理したものであってもよい。材料の表面を親液性となるように表面処理した例としては、アルゴンや水などを利用したプラズマ処理による親液性表面処理が挙げられ、基板上に形成する親液性の層としては、例えばテトラエトキシシランのゾルゲル法によるシリカ膜等を挙げることができる。本実施態様においては、通常基板が露出した部分が親液性領域とされる。
【０１０１】
上記のような分解除去層に用いることができる膜としては、具体的にはフッ素系や炭化水素系の撥液性を有する樹脂等による膜を挙げることができる。これらのフッ素系や炭化水素系の樹脂は、撥液性を有するものであれば、特に限定されるものではなく、これらの樹脂を溶媒に溶解させ、例としてスピンコート法等の一般的な成膜方法により形成することが可能である。
【０１０２】
また、本実施態様においては、機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロジェット膜、および交互吸着膜等を用いることにより、欠陥のない膜を形成することが可能であることから、このような成膜方法を用いることがより好ましいといえる。
【０１０３】
ここで、本実施態様に用いられる自己組織化単分子膜、ラングミュア−ブロジェット膜、および交互吸着膜について具体的に説明する。
【０１０４】
（ｉ）自己組織化単分子膜
自己組織化単分子膜(Self-Assembled Monolayer)の公式な定義の存在を発明者らは知らないが、一般的に自己組織化膜として認識されているものの解説文としては、例えばAbraham Ulmanによる総説“Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996)が優れている。本総説を参考にすれば、自己組織化単分子膜とは、適当な分子が適当な基板表面に吸着・結合（自己組織化）した結果生じた単分子層のことと言える。自己組織化膜形成能のある材料としては、例えば、脂肪酸などの界面活性剤分子、アルキルトリクロロシラン類やアルキルアルコキシド類などの有機ケイ素分子、アルカンチオール類などの有機イオウ分子、アルキルフォスフェート類などの有機リン酸分子などが挙げられる。分子構造の一般的な共通性は、比較的長いアルキル鎖を有し、片方の分子末端に基板表面と相互作用する官能基が存在することである。アルキル鎖の部分は分子同士が２次元的にパッキングする際の分子間力の源である。もっとも、ここに示した例は最も単純な構造であり、分子のもう一方の末端にアミノ基やカルボキシル基などの官能基を有するもの、アルキレン鎖の部分がオキシエチレン鎖のもの、フルオロカーボン鎖のもの、これらが複合したタイプの鎖のものなど様々な分子から成る自己組織化単分子膜が報告されている。また、複数の分子種から成る複合タイプの自己組織化単分子膜もある。また、最近では、デンドリマーに代表されるような粒子状で複数の官能基（官能基が一つの場合もある）を有する高分子や直鎖状（分岐構造のある場合もある）の高分子が一層基板表面に形成されたもの（後者はポリマーブラシと総称される）も自己組織化単分子膜と考えられる場合もあるようである。本実施態様は、これらも自己組織化単分子膜に含める。
【０１０５】
（ii）ラングミュア−ブロジェット膜
本実施態様に用いられるラングミュア−ブロジェット膜(Langmuir-Blodgett Film)は、基板上に形成されてしまえば形態上は上述した自己組織化単分子膜との大きな相違はない。ラングミュア−ブロジェット膜の特徴はその形成方法とそれに起因する高度な２次元分子パッキング性（高配向性、高秩序性）にあると言える。すなわち、一般にラングミュア−ブロジェット膜形成分子は気液界面上に先ず展開され、その展開膜がトラフによって凝縮されて高度にパッキングした凝縮膜に変化する。実際は、これを適当な基板に移しとって用いる。ここに概略を示した手法により単分子膜から任意の分子層の多層膜まで形成することが可能である。また、低分子のみならず、高分子、コロイド粒子なども膜材料とすることができる。様々な材料を適用した最近の事例に関しては宮下徳治らの総説“ソフト系ナノデバイス創製のナノテクノロジーへの展望” 高分子 50巻 9月号 644-647 (2001)に詳しく述べられている。
【０１０６】
（iii）交互吸着膜
交互吸着膜(Layer-by-Layer Self-Assembled Film)は、一般的には、最低２個の正または負の電荷を有する官能基を有する材料を逐次的に基板上に吸着・結合させて積層することにより形成される膜である。多数の官能基を有する材料の方が膜の強度や耐久性が増すなど利点が多いので、最近ではイオン性高分子（高分子電解質）を材料として用いることが多い。また、タンパク質や金属や酸化物などの表面電荷を有する粒子、いわゆる“コロイド粒子”も膜形成物質として多用される。さらに最近では、水素結合、配位結合、疎水性相互作用などのイオン結合よりも弱い相互作用を積極的に利用した膜も報告されている。比較的最近の交互吸着膜の事例については、静電的相互作用を駆動力にした材料系に少々偏っているがPaula T. Hammondによる総説“Recent Explorations in Electrostatic Multilayer Thin Film Assembly”Current Opinion in Colloid & Interface Science, 4, 430-442 (2000)に詳しい。交互吸着膜は、最も単純なプロセスを例として説明すれば、正（負）電荷を有する材料の吸着−洗浄−負（正）電荷を有する材料の吸着−洗浄のサイクルを所定の回数繰り返すことにより形成される膜である。ラングミュア−ブロジェット膜のように展開−凝縮−移し取りの操作は全く必要ない。また、これら製法の違いより明らかなように、交互吸着膜はラングミュア−ブロジェット膜のような２次元的な高配向性・高秩序性は一般に有さない。しかし、交互吸着膜及びその作製法は、欠陥のない緻密な膜を容易に形成できること、微細な凹凸面やチューブ内面や球面などにも均一に成膜できることなど、従来の成膜法にない利点を数多く有している。
【０１０７】
また、分解除去層の膜厚としては、後述するエネルギー照射工程において照射されるエネルギーにより分解除去される程度の膜厚であれば特に限定されるものではない。具体的な膜厚としては、照射されるエネルギーの種類や分解除去層の材料等により大きく異なるものではあるが、一般的には、０．００１μｍ〜１μｍの範囲内、特に０．０１μｍ〜０．１μｍの範囲内とすることが好ましい。
【０１０８】
ｃ．基板
次に、本実施態様における基板について説明する。本実施態様においては、上記特性変化層が自己支持性のない材料である場合、また分解除去層である場合に、例えば図１に示すように、基板１上に特性変化層２が設けられる。
【０１０９】
この基板としては、上述した特性変化層が形成されるものであれば、特に限定されるものでなく、機能性素子の用途に応じて、可撓性を有するものであっても、可撓性を有さないものであってもよい。
【０１１０】
また、特に材料等は限定されるものではなく、必要に応じて種々の材料を用いることができる。具体的には、ガラス、アルミニウム、およびその合金等の金属、プラスチック、織物、不織布等を挙げることができる。
【０１１１】
（光触媒含有層側基板）
次に、本実施態様に用いられる光触媒含有層側基板について説明する。例えば図１に示すように、本実施態様の機能性素子の製造方法に用いられる光触媒含有層側基板３は、少なくとも基材４と光触媒含有層５とを有するものであり、通常は基材４上に所定の方法で形成された薄膜状の光触媒含有層５が形成されてなるものである。また、この光触媒含有層側基板には、パターン状に形成された遮光部が形成されたものも用いることができ、この遮光部と光触媒含有層との間にプライマー層が形成されたものも用いることができる。以下、これらの各構成について説明する。
【０１１２】
ａ．光触媒含有層
本実施態様に用いられる光触媒含有層は、光触媒含有層中の光触媒が、対象とする特性変化層の特性を変化させるような構成であれば、特に限定されるものではなく、光触媒とバインダとから構成されているものであってもよく、光触媒単体で製膜されたものであってもよい。また、その表面の特性は特に親液性であっても撥液性であってもよい。
【０１１３】
本実施態様において用いられる光触媒含有層は、例えば図２（ａ）に示すように、光触媒含有層側基板３の基材４上に、光触媒含有層５が全面に形成されたものであってもよいが、例えば図３に示すように、光触媒含有層側基板３の基材４上に光触媒含有層５がパターン上に形成されたものであってもよい。
【０１１４】
このように光触媒含有層をパターン状に形成することにより、後述するエネルギー照射工程において説明するように、光触媒含有層を特性変化層と所定の間隔をおいて配置させてエネルギーを照射する際に、フォトマスク等を用いるパターン照射をする必要がなく、全面に照射することにより、特性変化層上に特性の変化したパターンを形成することができる。
【０１１５】
この光触媒含有層のパターニング方法は、特に限定されるものではないが、例えばフォトリソ法等により行うことが可能である。
【０１１６】
また、実際に光触媒含有層に面する特性変化層上の部分のみの特性が変化するものであるので、エネルギーの照射方向は上記光触媒含有層と特性変化層とが面する部分にエネルギーが照射されるものであれば、いかなる方向から照射されてもよく、さらには、照射されるエネルギーも特に平行光等の平行なものに限定されないという利点を有するものとなる。
【０１１７】
このように光触媒含有層における、後述するような二酸化チタンに代表される光触媒の作用機構は、必ずしも明確なものではないが、光の照射によって生成したキャリアが、近傍の化合物との直接反応、あるいは、酸素、水の存在下で生じた活性酸素種によって、有機物の化学構造に変化を及ぼすものと考えられている。本実施態様においては、このキャリアが光触媒含有層近傍に配置される特性変化層中の化合物に作用を及ぼすものであると思われる。
【０１１８】
本実施態様で使用する光触媒としては、光半導体として知られる例えば二酸化チタン（ＴｉＯ_２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ_２）、チタン酸ストロンチウム（ＳｒＴｉＯ_３）、酸化タングステン（ＷＯ_３）、酸化ビスマス（Ｂｉ_２Ｏ_３）、および酸化鉄（Ｆｅ_２Ｏ_３）を挙げることができ、これらから選択して１種または２種以上を混合して用いることができる。
【０１１９】
本実施態様においては、特に二酸化チタンが、バンドギャップエネルギーが高く、化学的に安定で毒性もなく、入手も容易であることから好適に使用される。二酸化チタンには、アナターゼ型とルチル型があり本実施態様ではいずれも使用することができるが、アナターゼ型の二酸化チタンが好ましい。アナターゼ型二酸化チタンは励起波長が３８０ｎｍ以下にある。
【０１２０】
このようなアナターゼ型二酸化チタンとしては、例えば、塩酸解膠型のアナターゼ型チタニアゾル（石原産業（株）製ＳＴＳ−０２（平均粒径７ｎｍ）、石原産業（株）製ＳＴ−Ｋ０１）、硝酸解膠型のアナターゼ型チタニアゾル（日産化学（株）製ＴＡ−１５（平均粒径１２ｎｍ））等を挙げることができる。
【０１２１】
光触媒の粒径は小さいほど光触媒反応が効果的に起こるので好ましく、平均粒径が５０ｎｍ以下が好ましく、２０ｎｍ以下の光触媒を使用するのが特に好ましい。
【０１２２】
本実施態様における光触媒含有層は、上述したように光触媒単独で形成されたものであってもよく、またバインダと混合して形成されたものであってもよい。
【０１２３】
光触媒のみからなる光触媒含有層の場合は、特性変化層上の特性の変化に対する効率が向上し、処理時間の短縮化等のコスト面で有利である。一方、光触媒とバインダとからなる光触媒含有層の場合は、光触媒含有層の形成が容易であるという利点を有する。
【０１２４】
光触媒のみからなる光触媒含有層の形成方法としては、例えば、スパッタリング法、ＣＶＤ法、真空蒸着法等の真空製膜法を用いる方法を挙げることができる。真空製膜法により光触媒含有層を形成することにより、均一な膜でかつ光触媒のみを含有する光触媒含有層とすることが可能であり、これにより特性変化層上の特性を均一に変化させることが可能であり、かつ光触媒のみからなることから、バインダを用いる場合と比較して効率的に特性変化層上の特性を変化させることが可能となる。
【０１２５】
また、光触媒のみからなる光触媒含有層の形成方法の他の例としては、例えば光触媒が二酸化チタンの場合は、基材上に無定形チタニアを形成し、次いで焼成により結晶性チタニアに相変化させる方法等が挙げられる。ここで用いられる無定形チタニアとしては、例えば四塩化チタン、硫酸チタン等のチタンの無機塩の加水分解、脱水縮合、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン等の有機チタン化合物を酸存在下において加水分解、脱水縮合によって得ることができる。次いで、４００℃〜５００℃における焼成によってアナターゼ型チタニアに変性し、６００℃〜７００℃の焼成によってルチル型チタニアに変性することができる。
【０１２６】
また、バインダを用いる場合は、バインダの主骨格が上記の光触媒の光励起により分解されないような高い結合エネルギーを有するものが好ましく、例えばオルガノポリシロキサン等を挙げることができる。
【０１２７】
このようにオルガノポリシロキサンをバインダとして用いた場合は、上記光触媒含有層は、光触媒とバインダであるオルガノポリシロキサンと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、この塗布液を基材上に塗布することにより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、ビードコート等の公知の塗布方法により行うことができる。バインダとして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光触媒含有層を形成することかできる。
【０１２８】
また、バインダとして無定形シリカ前駆体を用いることができる。この無定形シリカ前駆体は、一般式ＳｉＸ_４で表され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１２９】
具体的には、テトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−プロポキシシラン、テトラブトキシシラン、テトラメトキシシラン等が挙げられる。また、この場合には、無定形シリカの前駆体と光触媒の粒子とを非水性溶媒中に均一に分散させ、基材上に空気中の水分により加水分解させてシラノールを形成させた後、常温で脱水縮重合することにより光触媒含有層を形成できる。シラノールの脱水縮重合を１００℃以上で行えば、シラノールの重合度が増し、膜表面の強度を向上できる。また、これらの結着剤は、単独あるいは２種以上を混合して用いることができる。
【０１３０】
バインダを用いた場合の光触媒含有層中の光触媒の含有量は、５〜６０重量％、好ましくは２０〜４０重量％の範囲で設定することができる。また、光触媒含有層の厚みは、０．０５〜１０μｍの範囲内が好ましい。
【０１３１】
また、光触媒含有層には上記の光触媒、バインダの他に、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。
【０１３２】
さらに、光触媒含有層には上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。
【０１３３】
ｂ．基材
次に、本実施態様における光触媒含有層側基板の基材について説明する。本実施態様においては、例えば図２（ａ）に示すように、光触媒含有層側基板３は、少なくとも基材４とこの基材４上に形成された光触媒含有層５とを有するものである。この際、用いられる基材を構成する材料は、後述するエネルギー照射工程におけるエネルギーの照射方向や、得られる機能性素子が透明性を必要とするか等により適宜選択される。
【０１３４】
後述するように光触媒含有層側基板に遮光部を予め所定のパターンで形成しておき、この遮光部を用いてパターンを形成する場合や、パターンの形成を図２（ｂ）に示すように、光触媒含有層側基板３側に、フォトマスク７を用いてパターンの形成を行う場合には、光触媒含有層側基板３側からエネルギー照射をする必要がある。このような場合、基材４は透明性を有するものであることが必要となる。
【０１３５】
一方、特性変化層側にフォトマスクを配置してエネルギーを照射することも可能である。このような場合においては、基材の透明性は特に必要とされない。
【０１３６】
また本実施態様に用いられる基材は、可撓性を有するもの、例えば樹脂性フィルム等であってもよいし、可撓性を有さないもの、例えばガラス基板等であってもよい。これは、後述するエネルギー照射工程におけるエネルギー照射方法により適宜選択されるものである。
【０１３７】
このように、本実施態様における光触媒含有層側基板に用いられる基材は特にその材料を限定されるものではないが、本実施態様においては、この光触媒含有層側基板は、繰り返し用いられるものであることから、所定の強度を有し、かつその表面が光触媒含有層との密着性が良好である材料が好適に用いられる。具体的には、ガラス、セラミック、金属、プラスチック等を挙げることができる。
【０１３８】
なお、基材表面と光触媒含有層との密着性を向上させるために、基材上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【０１３９】
ｃ．遮光部
次に、本実施態様における光触媒含有層側基板の遮光部について説明する。本実施態様に用いられる光触媒含有層側基板には、パターン状に形成された遮光部が形成されたものを用いても良い。このように遮光部を有する光触媒含有層側基板を用いることにより、エネルギーをパターン状に照射するのに際して、フォトマスクを用いたり、レーザ光による描画照射を行う必要がない。したがって、光触媒含有層側基板とフォトマスクとの位置合わせが不要であることから、簡便な工程とすることが可能であり、また描画照射に必要な高価な装置も不必要であることから、コスト的に有利となるという利点を有する。
【０１４０】
このような遮光部を有する光触媒含有層側基板は、遮光部の形成位置により、下記の二つの実施態様とすることができる。
【０１４１】
一つが、例えば図４に示すように、光触媒含有層側基板３の基材４上に遮光部８を形成し、この遮光部８上に光触媒含有層５を形成する実施態様である。もう一つは、例えば図５に示すように、光触媒含有層側基板３の基材４上に光触媒含有層５を形成し、その上に遮光部８を形成する実施態様である。
【０１４２】
いずれの実施態様においても、フォトマスクを用いる場合と比較すると、遮光部が、上記光触媒含有層と特性変化層とが間隙をもって位置する部分の近傍に配置されることになるので、基材内等におけるエネルギーの散乱の影響を少なくすることができることから、エネルギーのパターン照射を極めて正確に行うことが可能となる。
【０１４３】
さらに、上記光触媒含有層上に遮光部を形成する実施態様においては、光触媒含有層と特性変化層とを所定の間隙をおいて配置する際に、この遮光部の膜厚をこの間隙の幅と一致させておくことにより、上記遮光部を、一定の上記間隙を保つためのスペーサとしても用いることができるという利点を有する。
【０１４４】
すなわち、所定の間隙をおいて上記光触媒含有層と特性変化層とを接触させた状態で配置する際に、上記遮光部と特性変化層とを密着させた状態で配置することにより、上記所定の間隙を正確とすることが可能となり、そしてこの状態で光触媒含有層側基板からエネルギーを照射することにより、特性変化層上にパターンを精度良く形成することが可能となるのである。
【０１４５】
このような遮光部の形成方法は、特に限定されるものではなく、遮光部の形成面の特性や、必要とするエネルギーに対する遮蔽性等に応じて適宜選択されて用いられる。
【０１４６】
このような本実施態様の遮光部の形成方法はとしては、例えばスパッタリング法、真空蒸着法等により、厚み１０００〜２０００Å程度のクロム等の金属薄膜を形成し、この薄膜をパターニングすることにより形成する方法等を挙げることができる。
【０１４７】
また、上記遮光部としては、樹脂バインダ中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた層であってもよく、本実施態様においては、この樹脂性遮光部であることが好ましい。このような樹脂性遮光部の厚みとしては、０．５〜１０μｍの範囲内で設定することができ、一般的に金属薄膜を用いた場合より、厚さを高くすることが可能である。
【０１４８】
また、用いられる樹脂バインダとしては、ポリイミド樹脂、アクリル樹脂、エポキシ樹脂、ポリアクリルアミド、ポリビニルアルコール、ゼラチン、カゼイン、セルロース等の樹脂を１種または２種以上混合したものや、感光性樹脂、さらにはＯ／Ｗエマルジョン型の樹脂組成物、例えば、反応性シリコーンをエマルジョン化したもの等を用いることができる。このような樹脂性遮光部のパターニングの方法は、フォトリソ法、印刷法等一般的に用いられている方法を用いることができる。
【０１４９】
なお、上記説明においては、遮光部の形成位置として、基材と光触媒含有層との間、および光触媒含有層表面の二つの場合について説明したが、その他、基材の光触媒含有層が形成されていない側の表面に遮光部を形成する態様も採ることが可能である。この態様においては、例えばフォトマスクをこの表面に着脱可能な程度に密着させる場合等が考えられ、機能性素子を小ロットで変更するような場合に好適に用いることができる。
【０１５０】
ｄ．プライマー層
次に、本実施態様の光触媒含有層側基板に用いられるプライマー層について説明する。本実施態様において、上述したように基材上に遮光部をパターン状に形成して、その上に光触媒含有層を形成して光触媒含有層側基板とする場合においては、上記遮光部と光触媒含有層との間にプライマー層を形成してもよい。
【０１５１】
このプライマー層の作用・機能は必ずしも明確なものではないが、遮光部と光触媒含有層との間にプライマー層を形成することにより、プライマー層は光触媒の作用による特性変化層の特性変化を阻害する要因となる遮光部および遮光部間に存在する開口部からの不純物、特に、遮光部をパターニングする際に生じる残渣や、金属、金属イオン等の不純物の拡散を防止する機能を示すものと考えられる。したがって、プライマー層を形成することにより、高感度で特性変化の処理が進行し、その結果、高解像度のパターンを得ることが可能となるのである。
【０１５２】
なお、本実施態様においてプライマー層は、遮光部のみならず遮光部間に形成された開口部に存在する不純物が光触媒の作用に影響することを防止するものであるので、プライマー層は開口部を含めた遮光部全面にわたって形成されていることが好ましい。
【０１５３】
図６はこのようなプライマー層を形成した光触媒含有層側基板の一例を示すものである。光触媒含有層側基板３の遮光部８が形成された基材４の遮光部８が形成されている側の表面にプライマー層９が形成されており、このプライマー層９の表面に光触媒含有層５が形成されている。
【０１５４】
本実施態様におけるプライマー層は、光触媒含有層側基板の遮光部と光触媒含有層とが接触しないようにプライマー層が形成された構造であれば特に限定されるものではない。
【０１５５】
このプライマー層を構成する材料としては、特に限定されるものではないが、光触媒の作用により分解されにくい無機材料が好ましい。具体的には無定形シリカを挙げることができる。このような無定形シリカを用いる場合には、この無定形シリカの前駆体は、一般式ＳｉＸ_４で示され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物であり、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１５６】
また、プライマー層の膜厚は、０．００１μｍから１μｍの範囲内であることが好ましく、特に０．００１μｍから０．１μｍの範囲内であることが好ましい。
【０１５７】
（エネルギー照射）
本実施態様においては、上述した光触媒含有層および特性変化層を２００μｍ以下の間隙をおいて配置した後、所定の方向からエネルギーを照射する。この際、光触媒含有層および特性変化層を密着させてもよい。
【０１５８】
本実施態様において上記間隙は、パターン精度が極めて良好であり、光触媒の感度も高く、したがって特性変化の効率が良好である点を考慮すると特に０．２μｍ〜１０μｍの範囲内、好ましくは１μｍ〜５μｍの範囲内とすることが好ましい。このような間隙の範囲は、特に間隙を高い精度で制御することが可能である小面積の特性変化層に対して特に有効である。
【０１５９】
一方、例えば３００ｍｍ×３００ｍｍといった大面積の特性変化層に対して処理を行う場合は、接触することなく、かつ上述したような微細な間隙を光触媒含有層側基板と特性変化層との間に形成することは極めて困難である。したがって、特性変化層が比較的大面積である場合は、上記間隙は、１０〜１００μｍの範囲内、特に５０〜７５μｍの範囲内とすることが好ましい。間隙をこのような範囲内とすることにより、パターンがぼやける等のパターン精度の低下の問題や、光触媒の感度が悪化して特性変化の効率が悪化する等の問題が生じることなく、さらに特性変化層上の特性変化のムラが発生しないといった効果を有するからである。
【０１６０】
このように比較的大面積の特性変化層をエネルギー照射する際には、エネルギー照射装置内の光触媒含有層側基板と特性変化層との位置決め装置における間隙の設定を、１０μｍ〜２００μｍの範囲内、特に２５μｍ〜７５μｍの範囲内に設定することが好ましい。設定値をこのような範囲内とすることにより、パターン精度の大幅な低下や光触媒の感度の大幅な悪化を招くことなく、かつ光触媒含有層側基板と特性変化層とが接触することなく配置することが可能となるからである。
【０１６１】
上述したように、光触媒含有層と特性変化層表面とを所定の間隔で離して配置することにより、酸素と水および光触媒作用により生じた活性酸素種が脱着しやすくなる。すなわち、上記範囲より光触媒含有層と特性変化層との間隔を狭くした場合は、上記活性酸素種の脱着がしにくくなり、結果的に特性の変化速度を遅くしてしまう可能性があることから好ましくない。また、上記範囲より間隔を離して配置した場合は、生じた活性酸素種が特性変化層に届き難くなり、この場合も特性の変化速度を遅くしてしまう可能性があることから好ましくない。
【０１６２】
本実施態様においては、このような間隙をおいた配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０１６３】
このような極めて狭い間隙を均一に形成して光触媒含有層と特性変化層とを配置する方法としては、例えばスペーサを用いる方法を挙げることができる。そして、このようにスペーサを用いることにより、均一な間隙を形成することができると共に、このスペーサが接触する部分は、光触媒の作用が特性変化層表面に及ばないことから、このスペーサを上述したパターンと同様のパターンを有するものとすることにより、特性変化層上に所定のパターンを形成することが可能となる。
【０１６４】
本実施態様においては、このようなスペーサを一つの部材として形成してもよいが、工程の簡略化等のため、上記光触媒含有層側基板の欄で説明したように、光触媒含有層側基板の光触媒含有層表面に形成することが好ましい。なお、上記光触媒含有層側基板調製工程における説明においては、遮光部として説明したが、本実施態様においては、このようなスペーサは特性変化層表面に光触媒の作用が及ばないように表面を保護する作用を有すればよいものであることから、特に照射されるエネルギーを遮蔽する機能を有さない材料で形成されたものであってもよい。
【０１６５】
なお、本実施態様でいうエネルギー照射（露光）とは、光触媒含有層による特性変化層表面の特性を変化させることが可能ないかなるエネルギー線の照射をも含む概念であり、可視光の照射に限定されるものではない。
【０１６６】
通常このようなエネルギー照射に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒含有層に用いられる好ましい光触媒が二酸化チタンであり、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上述した波長の光が好ましいからである。
【０１６７】
このようなエネルギー照射に用いることができる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマーランプ、その他種々の光源を挙げることができる。
【０１６８】
上述したような光源を用い、フォトマスクを介したパターン照射により行う方法の他、エキシマ、ＹＡＧ等のレーザを用いてパターン状に描画照射する方法を用いることも可能である。
【０１６９】
ここで、エネルギー照射に際してのエネルギーの照射量は、特性変化層表面が光触媒含有層中の光触媒の作用により特性変化層表面の特性の変化が行われるのに必要な照射量とする。
【０１７０】
またこの際、光触媒含有層を加熱しながらエネルギー照射することにより、感度を上昇させることが可能となり、効率的な特性の変化を行うことができる点で好ましい。具体的には３０℃〜８０℃の範囲内で加熱することが好ましい。
【０１７１】
本実施態様におけるエネルギー照射方向は、光触媒含有層側基板側からであってもよく、また特性変化層側からであってもよい。ここで、光触媒含有層側基板に遮光部が形成されている場合は、光触媒含有層側基板側からエネルギー照射が行なわれる必要があり、かつこの場合は光触媒含有層側基板が照射されるエネルギーに対して透明である必要がある。なお、この場合、光触媒含有層上に遮光部が形成され、かつこの光触媒含有層側遮光部を上述したようなスペーサとしての機能を有するように用いた場合においては、エネルギー照射方向は光触媒含有層側基板側からでも特性変化層側からであってもよい。
【０１７２】
さらに、光触媒含有層がパターン状に形成されている場合におけるエネルギー照射方向は、光触媒含有層と特性変化層とが接触する部分にエネルギーが照射されるのであればいかなる方向から照射されてもよい。同様に、上述したスペーサを用いる場合も、接触する部分にエネルギーが照射されるのであればいかなる方向から照射されてもよい。ここで、フォトマスクを用いる場合は、フォトマスクが配置された側からエネルギーが照射されることが必要である。
【０１７３】
上述したようなエネルギー照射が終了すると、光触媒含有層側基板が特性変化層との配置位置から離され、特性変化層の特性が変化したパターン形成体を得ることができる。
【０１７４】
（２）光触媒含有層不純物除去工程
次に、本実施態様における光触媒含有層不純物除去工程について説明する。
【０１７５】
本実施態様の光触媒含有層不純物除去工程とは、例えば図１に示すように、上述した基材４と光触媒含有層５とを含有する光触媒含有層側基板３のうち、特性変化層の特性の変化に寄与する光触媒含有層５の不純物を除去する工程である。この光触媒含有層不純物除去工程を、上述したパターン形成工程前に行うことにより、例えば上述した光触媒含有層側基板を形成する際に光触媒含有層表面に存在する不純物や、使用時または保管時に表面に付着する不純物等を除去することが可能となり、光触媒含有層中の光触媒が表面に露出する。これにより、光触媒含有層の高感度化を図ることができ、上述したパターン形成工程において、光触媒含有層の感度を向上させることが可能となり、特性変化層の特性が変化した高精細なパターン形成体を製造することが可能となるのである。
【０１７６】
本実施態様においては、この光触媒含有層の不純物除去方法として、上記光触媒含有層の表面の不純物にエネルギーを照射して分解除去する方法、または上記光触媒含有層表面を液体により洗浄する方法を用いることが可能である。上記の不純物は、通常、炭化水素系の被膜等であり、光触媒含有層にエネルギーを照射し、光触媒の作用により分解する方法や、液体により洗浄する方法により除去することが可能だからである。以下、これらの各方法について説明する。
【０１７７】
（分解除去による方法）
まず、光触媒含有層にエネルギーを照射することにより、光触媒含有層の表面の不純物を分解除去する方法について説明する。
【０１７８】
本方法によれば、光触媒含有層にエネルギーを照射することによって、光触媒が活性化され、上述した光触媒含有層製造後に光触媒含有層表面に存在する不純物や、使用時または保管時に表面に付着する不純物等等が分解され、光触媒含有層中の光触媒が表面に露出される。これにより、光触媒含有層の感度を上昇させることが可能となり、上記パターン形成工程を効率よく行うことが可能となるのである。
【０１７９】
ここで、エネルギー照射に際してのエネルギーの照射量は、光触媒含有層表面に存在する不純物が、光触媒含有層中の光触媒の作用により分解除去されるのに必要な照射量とする。
【０１８０】
またこの際、光触媒含有層を加熱しながらエネルギー照射してもよい。これにより、光触媒の感度を上昇させることが可能となり、効率的な洗浄を行うことができる。具体的には３０℃〜８０℃の範囲内で加熱することが好ましい。
【０１８１】
照射されるエネルギーの種類等は、上述したパターン形成工程のエネルギー照射の項で説明したものと同様であるので、ここでの説明は省略する。
【０１８２】
（液体による洗浄による方法）
次に、液体により洗浄をする方法について説明する。
【０１８３】
本方法によれば、上述した光触媒含有層製造後に残存する不純物、光触媒含有層の表面に付着した不純物を、液体で洗い流すことにより、不純物を除去するのである。この液体で洗い流す場合、液体に不純物を溶解させて除去してもよく、また液体を流す圧力で不純物を除去してもよい。
【０１８４】
本実施態様で洗浄に用いられる液体としては、上記光触媒含有層の表面を洗い流すことが可能な液体であれば、特に限定されるものではなく、有機溶媒等であってもよいが、特に水であることが好ましい。上記液体が水であれば、廃液の処理等も容易であり、また特別の装置も必要としないことから、コストや製造効率等の面から好ましく、また、後述する第四実施態様のエネルギー照射時に水が存在することにより、光触媒の高感度化をはかる場合にも用いることが可能であることからも好ましい。
【０１８５】
液体による洗浄の方法として具体的には、洗浄器具が直接接触しない非接触洗浄方法を用いることが可能であり、具体的には、スピン洗浄および超音波洗浄等により行うことができる。また、この際使用される液体は、上述した中でも純水であることが好ましい。
【０１８６】
２．第二実施態様
次に、本発明の第二実施態様について説明する。
【０１８７】
本発明のパターン形成体の製造方法における第二実施態様は、光触媒の作用により特性が変化する特性変化層と、光触媒を含有する光触媒含有層および基材を有する光触媒含有層側基板とを、上記光触媒含有層および上記特性変化層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、特性の異なる部位からなるパターンを形成するパターン形成工程を有するパターン形成体の製造方法であって、上記間隙中に酸素を所定の濃度で存在させることにより、光触媒反応の高感度化を行うものである。
【０１８８】
このような本実施態様のパターン形成体の製造方法は、例えば図１に示すように、基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、光触媒含有層側基板３のうち基材４上に形成された光触媒を含有する光触媒含有層５とを、所定の間隔をおいて対向するように配置し、この間隙中の酸素濃度が所定の濃度となるように調整し、フォトマスク６を用いてエネルギー７をパターン状に照射するパターン形成工程を有する製造方法である。エネルギー照射時に、光触媒含有層および特性変化層の間の酸素濃度が上記範囲内であることにより、光触媒の効果が向上し、短時間で特性変化層の特性を変化させることが可能となるのである。これは、酸素が光触媒反応により還元され、その量が多くなると有機物を分解するスーパーオキサイドアニオン等の活性酸素種の生成が促進されるからである。以下、これらについて説明する。
【０１８９】
本実施態様におけるエネルギー照射は、上述した光触媒含有層および特性変化層を２００μｍ以下の間隙をおいて配置した後、所定の方向から行うが、このエネルギー照射時に、光触媒含有層と特性変化層との間隙中の酸素濃度が２０ｍｏｌ％以上、好ましくは５０ｍｏｌ％以上とするものである。エネルギー照射時に上記間隙内の酸素濃度を上記範囲内とすることにより、上記間隙中の酸素により光触媒の効果が高められ、より効率的に特性変化層の特性を変化させることが可能となるのである。
【０１９０】
上記間隙中の酸素濃度を上記範囲内とする方法としては、エネルギー照射を酸素濃度が上記範囲内である雰囲気下としたチャンバー内で行う方法と、上記間隙中に上記間隙中に酸素濃度が上記範囲内であるガスを導入する方法が挙げられる。
【０１９１】
なお、本実施態様における特性変化層、光触媒含有層、光触媒含有層と特性変化層との間隙、照射するエネルギー、エネルギー照射方法等については、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０１９２】
３．第三実施態様
次に、本発明の第三実施態様について説明する。
【０１９３】
本発明のパターン形成体の製造方法における第三実施態様は、光触媒の作用により特性が変化する特性変化層と、光触媒を含有する光触媒含有層および基材を有する光触媒含有層側基板とを、上記光触媒含有層および上記特性変化層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、特性の異なる部位からなるパターンを形成するパターン形成工程を有するパターン形成体の製造方法であって、上記間隙中の相対湿度を所定の濃度とすることにより、光触媒反応を高感度化させるものである。
【０１９４】
本実施態様のパターン形成体の製造方法は、例えば図１に示すように、基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、光触媒含有層側基板３のうち基材４上に形成された光触媒を含有する光触媒含有層５とを、所定の間隔をおいて対向するように配置し、この間隙中の相対湿度を所定の濃度となるように調整し、フォトマスク６を用いてエネルギー７をパターン状に照射するパターン形成工程を有する製造方法である。エネルギー照射時に、光触媒含有層および特性変化層の間の相対湿度が所定の濃度であることにより、光触媒を高感度化させることができ、短時間で特性変化層の特性を変化させることが可能となるのである。これは、水が光触媒反応により酸化され、その量が多くなると有機物を分解するヒドロキシラジカル等の活性酸素種の生成が促進されることによるものである。以下、これらについて説明する。
【０１９５】
本実施態様のエネルギー照射は、上述した光触媒含有層および特性変化層を２００μｍ以下の間隙をおいて配置した後、所定の方向から行うが、このエネルギー照射時に、光触媒含有層と特性変化層との間隙中の相対湿度が１０％以上、好ましくは７０％以上とするものである。エネルギー照射時に上記間隙内の相対湿度を上記範囲内とすることにより、上記間隙中の水分により光触媒の効果が高められ、より効率的に特性変化層の特性を変化させることが可能となるのである。
【０１９６】
なお、本実施態様においては、相対湿度が上記の範囲であれば、特に空気の組成等は限定されるものではなく、酸素濃度が高いものであってもよい。
【０１９７】
上記間隙中の相対湿度を上記範囲内とする方法としては、エネルギー照射を相対湿度が上記範囲内である雰囲気下としたチャンバー内で行う方法と、上記間隙中に上記間隙中に相対湿度が上記範囲内であるガスを導入する方法が挙げられる。
【０１９８】
本実施態様における特性変化層、光触媒含有層、光触媒含有層と特性変化層との間隙、照射するエネルギー、エネルギー照射方法等については、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０１９９】
４．第四実施態様
次に、本発明の第四実施態様について説明する。
【０２００】
本発明のパターン形成体の製造方法における第四実施態様は、光触媒の作用により特性が変化する特性変化層と、光触媒を含有する光触媒含有層および基材を有する光触媒含有層側基板とを、上記光触媒含有層および上記特性変化層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、特性の異なる部位からなるパターンを形成するパターン形成工程を有するパターン形成体の製造方法であって、上記エネルギー照射前に上記特性変化層および上記光触媒含有層の少なくとも一方に水を吸着させる処理を行うことにより、光触媒の高感度化を図るものである。
【０２０１】
本実施態様のパターン形成体の製造方法は、例えば図１に示すように、基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、光触媒含有層側基板３のうち基材４上に形成された光触媒を含有する光触媒含有層５とを、所定の間隔をおいて対向するように配置し、フォトマスク６を用いてエネルギー７をパターン状に照射するパターン形成工程を有する製造方法であるが、このエネルギー７の照射前に、上記特性変化層２または光触媒含有層５の少なくともどちらか一方の表面に、水を吸着させる処理を行う方法である。上記エネルギー照射前に、光触媒含有層または特性変化層の間の少なくともどちらかの表面に一方に水を吸着させることにより、光触媒を高感度化させることができ、短時間で特性変化層の特性を変化させることが可能となるのである。以下、これらについて説明する。
【０２０２】
本実施態様のエネルギー照射は、上述した光触媒含有層および特性変化層を２００μｍ以下の間隙をおいて配置した後、所定の方向から行うが、このエネルギー照射時に、光触媒含有層と特性変化層の少なくともどちらか一方の表面に水が吸着している状態で行う。ここで、本実施態様に用いられる水は純水であることが好ましい。
【０２０３】
具体的に上記特性変化層または光触媒含有層の表面に水を吸着させる処理方法としては、スプレーによる塗布、浸漬等が挙げられる。
【０２０４】
また、上記水は、上述した第一実施態様で述べたような光触媒含有層を洗浄した際に付着した水であってもよく、一般的にパターン形成工程前に光触媒含有層または特性変化層を洗浄する際に付着した水であってもよい。この場合、改めて表面に水を導入する必要性がなく、製造効率やコストの面からも好ましい。
【０２０５】
ここで、本実施態様における特性変化層および光触媒含有層、エネルギー照射時の光触媒含有層と特性変化層との間隙や、照射するエネルギー、エネルギー照射方法等については、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０２０６】
５．第五実施態様
次に、本発明の第五実施態様について説明する。
【０２０７】
本発明のパターン形成体の製造方法における第五実施態様は、光触媒の作用により特性が変化する特性変化層と、光触媒を含有する光触媒含有層および基材を有する光触媒含有層側基板とを、上記光触媒含有層および上記特性変化層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、特性の異なる部位からなるパターンを形成するパターン形成工程を有するパターン形成体の製造方法であって、上記エネルギー照射をエキシマーランプによる照射とすることにより、光触媒反応の高感度化を図るものである。
【０２０８】
このような、本実施態様のパターン形成体の製造方法は、例えば図１に示すように、基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、光触媒含有層側基板３のうち基材４上に形成された光触媒を含有する光触媒含有層５とを、所定の間隔をおいて対向するように配置し、フォトマスク６を用いてエネルギー７をパターン状に照射するパターン形成工程を有する製造方法であるが、このエネルギー７の照射を、高感度化のために、エキシマーランプにより行う方法である。以下、この方法について説明する。
【０２０９】
本実施態様のエネルギー照射は、上述した光触媒含有層および特性変化層を２００μｍ以下の間隙をおいて配置した後、エキシマーランプにより所定の方向からエネルギーの照射を行う。エキシマーランプは、１７２ｎｍという短波長の光を放出することから、上記エネルギー照射を、エキシマーランプにより行うことにより、エネルギー照射による光触媒含有層の作用だけでなく、エキシマーランプから放出される短波長の高いエネルギーが上記特性変化層中の有機物を直接分解等する効果も得られ、より効率的にパターン形成体を形成することが可能となる。
【０２１０】
ここで、本実施態様においては、上記光触媒含有層および特性変化層の間隙を０．０１μｍ〜５０μｍの間隙をおいて行うことが好ましい。エキシマーランプから放出される光は、空気中の酸素に吸収される性質があることから、上記間隙を上記範囲内で行うことにより、効率より特性変化層の特性を変化させることが可能となるからである。
【０２１１】
なお、本実施態様に用いられる特性変化層および光触媒含有層については、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０２１２】
６．第六実施態様
次に、本発明の第六実施態様について説明する。
【０２１３】
本発明のパターン形成体の製造方法における第六実施態様は、光触媒の作用により特性が変化する特性変化層と、光触媒を含有する光触媒含有層および基材を有する光触媒含有層側基板とを、上記光触媒含有層および上記特性変化層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、特性の異なる部位からなるパターンを形成するパターン形成工程を有するパターン形成体の製造方法であって、上記光触媒含有層に第２の成分としての金属元素が含有されており、この金属元素を鉄および鉄よりイオン化傾向の小さい金属から選択される少なくとも一種の金属元素とすることにより、光触媒反応の高感度化を達成するものである。
【０２１４】
本実施態様のパターン形成体の製造方法は、例えば図１に示すように、基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、光触媒含有層側基板３のうち基材４上に形成された光触媒を含有する光触媒含有層５とを、所定の間隔をおいて対向するように配置し、フォトマスク６を用いてエネルギー７をパターン状に照射するパターン形成工程を有する製造方法であるが、上記光触媒含有層に、第２の成分として、金属元素が含有されていることを特徴とする方法である。上記光触媒含有層中の金属元素の作用により、光触媒を活性化させ、高感度化することが可能となり、特性変化層の特性を効率的に向上させることが可能となるのである。
【０２１５】
以下、本実施態様に用いられる光触媒含有層について説明する。
【０２１６】
本実施態様に用いられる光触媒含有層は、上記第一実施態様の光触媒含有層の項で説明した光触媒含有層中に第２の成分としての金属元素を含有させたものである。ここで、この第２の成分としての金属元素とは、上記光触媒として投入された金属元素とは異なる金属元素であることを意味するものであり、かつ特性変化層上の特性を変化させる速度を向上させる機能を有する金属元素を示すものである。
【０２１７】
本実施態様に用いられる金属元素の種類としては、特に限定されるものでなく、上述したように特性変化層上の特性を変化させる速度を向上させる機能を有するものであれば、特に限定されるものではないが、鉄および鉄よりイオン化傾向の小さい金属を一種以上含有することが好ましい。また、具体的に金属元素として、鉄（Ｆｅ）、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、プラチナ（Ｐｔ）が挙げられ、中でも製造コストや効率の面から銅（Ｃｕ）であることが好ましい。
【０２１８】
このような金属元素の光触媒含有層中での状態は、金属微粒子等の金属として存在していても、また金属塩化物、金属酸化物等の金属化合物として存在していても、さらには金属イオンとして存在していてもよく、光触媒の作用による光触媒含有層上の濡れ性を変化させる速度を向上させる機能を有する状態であれば特に限定されるものではない。
【０２１９】
本実施態様においては、上記光触媒に対する第２の成分としての金属元素のモル比は、光触媒を１とした場合、０．００００１〜０．０５の範囲内、特に０．００００５〜０．００５の範囲内であることが好ましい。
【０２２０】
この金属元素の光触媒含有層への導入方法としては、光触媒含有層を形成する塗工液中に上記金属元素の塩を溶解させ、基材上に塗布後乾燥させる方法、または光触媒含有層表面に上記金属イオンを含有する塗工液を塗り、この光触媒含有層にエネルギーを照射することにより、光触媒の作用により金属イオンを還元し、光触媒含有層の表面に析出させる方法等を挙げることが可能である。
【０２２１】
なお、本実施態様における特性変化層、エネルギー照射時の光触媒含有層と特性変化層との間隙や、照射するエネルギー、エネルギー照射方法等については、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０２２２】
７．第七実施態様
本発明の第七実施態様について説明する。
【０２２３】
本発明のパターン形成体の製造方法における第七実施態様は、光触媒の作用により特性が変化する特性変化層と、光触媒を含有する光触媒含有層および基材を有する光触媒含有層側基板とを、上記光触媒含有層および上記特性変化層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、特性の異なる部位からなるパターンを形成するパターン形成工程を有するパターン形成体の製造方法であって、上記光触媒含有層を波長２５４ｎｍの光を所定の量透過させる膜厚の層とし、かつ上記エネルギー照射を光触媒含有層側基板から行うことにより、光触媒反応の高感度化を図るものである。
【０２２４】
このような、本実施態様のパターン形成体の製造方法は、例えば図１に示すように、基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、光触媒含有層側基板３のうち基材４上に形成された光触媒を含有する光触媒含有層５とを、所定の間隔をおいて対向するように配置し、フォトマスク６を用いてエネルギー７をパターン状に照射するパターン形成工程を有する製造方法であるが、上記光触媒含有層５が、波長２５４ｎｍの光を所定の量透過させる膜厚の層であり、かつ上記エネルギー照射が光触媒含有層側基板から行われるパターン形成体の製造方法である。これにより、光触媒含有層を高感度化させることが可能となり、効率よく特性変化層の特性を変化させることが可能となるのである。
【０２２５】
上記光触媒含有層が、具体的には波長２５４ｎｍの光を５％〜９０％、好ましくは３０％〜８０％透過させる膜厚の層であることが好ましい。
【０２２６】
光触媒含有層は、通常膜厚が厚くなることにより、低波長側（高エネルギー側）の光の透過率が低下する。これにより、上記光触媒含有層に、上記光触媒含有層側基板側からエネルギーを照射した際に、光触媒含有層表面の光触媒の活性化に寄与するエネルギー量が減少する。このエネルギー量が減少する原因としては、光触媒含有層内部に、光触媒が多量に存在すると、光触媒による光の散乱や吸収が行われ、光触媒含有層表面に到達するエネルギーが減少するのである。また、上記波長の透過率が、上記範囲より大きい場合には、光触媒含有層中に含有される光触媒の量や濃度が少なく、エネルギー照射により光触媒が活性化されても、特性変化層の特性を十分に変化させることが困難となり、製造効率やコストの面から好ましくないからである。
【０２２７】
ここで、照射されたエネルギーにより励起されて特性変化層の特性変化に寄与する光触媒は、光触媒含有層表面近傍に存在する光触媒のみであることから、本実施態様においては、このような２５４ｎｍという低波長の光の透過率が上記範囲内である膜厚の層とすることにより、低波長側の光のエネルギーの多くが光触媒含有層の表面に到達し、光触媒が活性化され、効率よくパターン形成体を製造することが可能となるのである。
【０２２８】
なお、光の透過率は、紫外可視分光光度計ＵＶ３１００ＰＣ 島津製作所で測定した値である。
【０２２９】
本実施態様のパターン形成体の製造方法における特性変化層、エネルギー照射時の光触媒含有層と特性変化層との間隙や、照射するエネルギー、エネルギー照射方法等については、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０２３０】
８．第八実施態様
次に、本発明の第八実施態様について説明する。
【０２３１】
本発明のパターン形成体の製造方法における第八実施態様は、光触媒の作用により特性が変化する特性変化層と、光触媒を含有する光触媒含有層および基材を有する光触媒含有層側基板とを、上記光触媒含有層および上記特性変化層が２００μｍ以下となるように間隙をおいて配置した後、エネルギーを照射し、特性の異なる部位からなるパターンを形成するパターン形成工程を有するパターン形成体の製造方法であって、上記光触媒が可視光応答化されたものとすることにより、光触媒反応の高感度化を図るものである。
【０２３２】
このような本実施態様のパターン形成体の製造方法は、例えば図１に示すように、基板１上に形成された光触媒の作用により特性が変化する特性変化層２と、光触媒含有層側基板３のうち基材４上に形成された光触媒を含有する光触媒含有層５とを、所定の間隔をおいて対向するように配置し、フォトマスク６を用いてエネルギー７をパターン状に照射するパターン形成工程を有する製造方法であるが、上記光触媒含有層５に含有される光触媒が、可視光応答化されたものであるパターン形成体の製造方法である。
【０２３３】
本実施態様でいう可視光応答化とは、通常可視光のエネルギーでは励起されない光触媒を、可視光のエネルギーによっても励起されるようにすることをいう。
【０２３４】
本実施態様において、光触媒が可視光応答化されたものであることにより、照射されるエネルギーの可視光領域のエネルギーによっても、光触媒を励起させることが可能となることから、効率よく特性変化層の特性を変化させることが可能となるのである。
【０２３５】
本実施態様に使用する光触媒としては、光半導体として知られる例えば二酸化チタン（ＴｉＯ_２）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ_２）、チタン酸ストロンチウム（ＳｒＴｉＯ_３）、酸化タングステン（ＷＯ_３）、酸化ビスマス（Ｂｉ_２Ｏ_３）、および酸化鉄（Ｆｅ_２Ｏ_３）を挙げることができ、これらから選択して１種または２種以上を混合して用いることができる。
【０２３６】
光触媒の可視光応答化の方法としては、上記の光触媒中への金属イオンのドーピングや、上記光触媒の窒化処理等を挙げることが可能であるが、本発明においては、酸化チタン（ＴｉＯ_２）が窒化処理されたものであることが好ましい。
【０２３７】
酸化チタン（ＴｉＯ_２）は、窒化処理をすることにより、酸化チタン（ＴｉＯ_２）のバンドギャップの内側に新しいエネルギー準位が形成され、バンドギャップが狭くなる。その結果、通常酸化チタン（ＴｉＯ_２）の励起波長は３８０ｎｍであるが、その励起波長より長波長の可視光によっても、励起されることが可能となるのである。これにより、種々の光源によるエネルギー照射の可視光領域の波長も酸化チタン（ＴｉＯ_２）の励起に寄与させることが可能となることから、光触媒含有層側基板を高感度化させることが可能となり、効率よくパターン形成体を製造することが可能となるのである。
【０２３８】
ここで、本実施態様でいう酸化チタンの窒化処理とは、酸化チタン（ＴｉＯ_２）の結晶の酸素サイトの一部を窒素原子での置換する処理や、酸化チタン（ＴｉＯ_２）結晶の格子間に窒素原子をドーピングする処理、または酸化チタン（ＴｉＯ_２）結晶の多結晶集合体の粒界に窒素原子を配する処理等をいう。
【０２３９】
ここで、酸化チタン（ＴｉＯ_２）の窒化処理方法は、特に限定されるものではなく、例えば、結晶性酸化チタンの微粒子をアンモニア雰囲気下で７００℃の熱処理により、窒素をドーピングし、この窒素のドーピングされた微粒子と、無機バインダや溶媒等を用いて、分散液とする。この分散液を基材上に塗布し、その後乾燥させ、１５０℃の熱処理により安定化させる方法等が挙げられる。
【０２４０】
本実施態様のパターン形成体の製造方法における特性変化層、エネルギー照射時の光触媒含有層と特性変化層との間隙や、照射するエネルギー、エネルギー照射方法等については、上記第一実施態様と同様であるので、ここでの説明は省略する。
【０２４１】
９．その他
本発明においては、パターン形成体製造時に上記第一実施態様から第八実施態様までのそれぞれの実施態様をそれぞれ個別に行ってもよいが、上記実施態様を二つ、またはそれ以上の複数の実施態様組み合わせてパターン形成体の製造を行ってもよい。
【０２４２】
Ｂ．パターン形成体製造用光触媒含有層側基板
本発明のパターン形成体製造用光触媒含有層側基板は、高感度化の種類により、３つの実施態様がある。以下、各態様について説明する。
【０２４３】
（１）第一実施態様
本発明のパターン形成体製造用光触媒含有層側基板の第一実施態様は、基材と、上記基材上に形成された光触媒および金属元素を含有する光触媒含有層とを有するパターン形成体製造用光触媒含有層側基板であって、上記金属元素として具体的には、鉄および鉄よりイオン化傾向の小さい金属を一種以上含有することにより、光触媒含有層の高感度化をはかるものである。
【０２４４】
このような本実施態様のパターン形成体製造用光触媒含有層側基板は、光触媒含有層中に上記の金属元素を含有していることにより、パターン形成体を製造する際に、光触媒の活性が高く、光触媒含有層を高感度化することが可能であり、効率よくパターン形成体を製造することが可能となるのである。具体的に金属元素として、鉄および鉄よりイオン化傾向の小さい金属を一種以上含有することが好ましい。また、具体的に金属元素として、鉄（Ｆｅ）、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、プラチナ（Ｐｔ）が挙げられ、中でも製造コストや効率の面から銅（Ｃｕ）であることが好ましい。
【０２４５】
本実施態様におけるパターン形成体製造用光触媒含有層側基板の基材および光触媒は、上記パターン形成体の製造方法の第一実施態様における光触媒含有層側基板の項で述べたものと同様であるので、ここでの説明は省略する。
【０２４６】
また、本実施態様のパターン形成体製造用光触媒含有層側基板の製造方法は、上記パターン形成体の製造方法の第一実施態様および第六実施態様で述べた方法と同様であるので、ここでの説明は省略する。
【０２４７】
さらに、本実施態様のパターン形成体製造用光触媒含有層側基板は、上述したパターン形成体の製造方法の第六実施態様だけでなく、他の全ての実施態様においても、使用することが可能である。
【０２４８】
（２）第二実施態様
本発明のパターン形成体製造用光触媒含有層側基板における第二実施態様は、基材と、上記基材上に形成された光触媒を含有する光触媒含有層とを有するパターン形成体製造用光触媒含有層側基板であって、上記光触媒含有層が波長２５４ｎｍの光を５％〜９０％、好ましくは３０％〜８０％透過させる膜厚の層とすることにより、光触媒含有層の高感度化を図るものである。
【０２４９】
このような本実施態様のパターン形成体製造用光触媒含有層側基板は、光触媒含有層が上記波長の光を上記範囲内透過させる膜厚の層であることにより、低波長側の光のエネルギーも光触媒含有層の表面の光触媒の活性化に寄与させることが可能となり、光触媒含有層を高感度化させることができ、効率よくパターン形成体を製造することが可能となるのである。
【０２５０】
ここで、光の透過率は、上記パターン形成体の製造方法で述べた方法により測定した値である。
【０２５１】
また、本実施態様におけるパターン形成体製造用光触媒含有層側基板の基材および光触媒は、上記本発明のパターン形成体の製造方法の第一実施態様における光触媒含有層側基板の項で述べたものと同様であるので、ここでの説明は省略する。
【０２５２】
さらに、本実施態様のパターン形成体製造用光触媒含有層側基板の製造方法は、上記パターン形成体の製造方法の第一実施態様で述べたものと同様であるので、ここでの説明は省略する。
【０２５３】
さらにまた、本実施態様のパターン形成体製造用光触媒含有層側基板は、上述したパターン形成体の製造方法の第七実施態様だけでなく、他の全ての実施態様においても、使用することが可能である。
【０２５４】
（３）第三実施態様
次に、本発明の第三実施態様について説明する。本発明のパターン形成体製造用光触媒含有層側基板の第三実施態様は、基材と、上記基材上に形成された光触媒を含有する光触媒含有層とを有するパターン形成体製造用光触媒含有層側基板であって、上記光触媒が可視光応答化されたものであることを特徴とするものである。
【０２５５】
本実施態様のパターン形成体製造用光触媒含有層側基板は、光触媒が可視光応答化されていることにより、照射されるエネルギーのうち、高波長側の可視光によっても、光触媒が励起されるのである。これにより、励起される光触媒の量が増加することから、光触媒を高感度化させることが可能となり、短時間で効率よくパターン形成体を製造することが可能となるのである。
【０２５６】
これらの光触媒の可視光応答化の具体的な方法としては、光触媒含有層中への金属イオンのドーピングや、光触媒の窒化処理等が挙げられるが、本実施態様における光触媒の可視光応答化は、酸化チタン（ＴｉＯ_２）の窒化処理であることが好ましい。
【０２５７】
酸化チタン（ＴｉＯ_２）は、窒化処理をすることにより、酸化チタン（ＴｉＯ_２）のバンドギャップの内側に新しいエネルギー準位が形成され、バンドギャップが
狭くなる。その結果、通常酸化チタン（ＴｉＯ_２）の励起波長は３８０ｎｍであるが、その励起波長より長波長の可視光によっても、励起されることが可能となるのである。
【０２５８】
これにより、種々の光源によるエネルギー照射の可視光領域の波長も励起に寄与させることが可能となることから、光触媒含有層側基板を高感度化させることが可能となり、効率よくパターン形成体を製造することが可能となるのである。
【０２５９】
なお、無機バインダや溶媒、基材、光触媒含有層の製造方法等は、上述した「Ａ．パターン形成体の製造方法」の第一実施態様および第八実施態様で説明したものと同様であるので、ここでの説明は省略する。
【０２６０】
また、本実施態様のパターン形成体製造用光触媒含有層側基板は、上述したパターン形成体の製造方法の第八実施態様だけでなく、他の全ての実施態様においても、使用することが可能である。
【０２６１】
なお、本実施態様は、上記実施形態に限定されるものではない。上記実施形態は、例示であり、本実施態様の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本実施態様の技術的範囲に包含される。
【０２６２】
【実施例】
以下に実施例および比較例を示して、本実施態様をさらに具体的に説明する。
【０２６３】
[実施例１]（第一実施態様）
１．光触媒含有層側基板の形成
テトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し、２４時間攪拌した。次に、この溶液０．１ｇと光触媒無機コーティング剤（石原産業（株）製 ＳＴ−Ｋ０３）５０ｇとを混合し、１時間常温で撹拌した。これをイソプロピルアルコールにより２倍に希釈し光触媒含有層用組成物とした。この光触媒含有層用組成物を１００μｍのライン＆スペースのパターンが形成されたフォトマスク基板上に、スピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、厚さ０．１５μｍの光触媒含有層を形成した。このとき、光触媒含有層の透過率は、２５４ｎｍで３０％であった。
【０２６４】
２．濡れ性変化層の形成
フルオロアルキルシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８２３３）０．４ｇとテトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し８時間攪拌した。これをイソプロピルアルコールにより１００倍に希釈し濡れ性変化層用組成物とした。次に、透明基板上に、上記濡れ性変化層用組成物をスピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、濡れ性変化層（厚み０．１μｍ）を形成した。
【０２６５】
３．光触媒層不純物除去工程
前記光触媒含有層側基板に光触媒含有層側から超高圧水銀ランプ（波長３６５ｎｍ ４０ｍＷ／ｃｍ^２）により６０分間露光し、表面の不純物を除去した。
【０２６６】
４．パターン形成工程
前記光触媒含有層側基板と前記濡れ性変化層とを５０μｍのギャップを設けて配置し、フォトマスク側から超高圧水銀ランプ（波長２５４ｎｍ １０ｍＷ／ｃｍ^２）露光した。このとき、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのに３０秒かかった。
【０２６７】
[比較例１]
光触媒層不純物除去工程を行わずに実施例１同様パターン形成を行ったところ、親液性領域が水の接触角で１０°以下になるのに２４０秒かかった。
【０２６８】
[実施例２]（第二実施態様）
１．光触媒含有層側基板の形成
テトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し、２４時間攪拌した。次に、この溶液０．１ｇと光触媒無機コーティング剤（石原産業（株）製 ＳＴ−Ｋ０３）５０ｇとを混合し、１時間常温で撹拌した。これをイソプロピルアルコールにより２倍に希釈し光触媒含有層用組成物とした。この光触媒含有層用組成物を１００μｍでライン＆スペースのパターンが形成されたフォトマスク基板上に、スピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、厚さ０．１５μｍの光触媒含有層を形成した。
【０２６９】
２．濡れ性変化層の形成
フルオロアルキルシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８２３３）０．４ｇとテトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し８時間攪拌した。これをイソプロピルアルコールにより１００倍に希釈し濡れ性変化層用組成物とした。次に、透明基板上に、上記濡れ性変化層用組成物をスピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、濡れ性変化層（厚み０．１μｍ）を形成した。
【０２７０】
３．光触媒層不純物除去工程
前記光触媒含有層側基板に光触媒含有層側から超高圧水銀ランプ（波長３６５ｎｍ ４０ｍＷ／ｃｍ^２）により６０分間露光し、表面の不純物を除去した。
【０２７１】
４．パターン形成工程
前記光触媒含有層側基板と前記濡れ性変化層とを５０μｍのギャップを設けてガラス製のチャンバー内に配置し、９３％の酸素ガスにより置換した後、フォトマスク側から超高圧水銀ランプ（波長２５４ｎｍ １０ｍＷ／ｃｍ^２）露光した。
【０２７２】
このとき、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのに２５秒かかった。
【０２７３】
[実施例３]（第二実施態様）
チャンバー内を２０％の酸素ガス（窒素ガス約８０％）により置換した以外は、上記実施例２と同様にパターン形成を行ったところ、親液性領域が水の接触角で１０°以下になるのに４０秒かかった。
【０２７４】
[比較例２]
チャンバー内を１０％の酸素ガス（窒素ガス約９０％）により置換した以外は、上記実施例２と同様にパターン形成を行ったところ、親液性領域が水の接触角で１０°以下になるのに１８０秒かかった。
【０２７５】
[実施例４]（第三実施態様）
１．光触媒含有層側基板の形成
テトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し、２４時間攪拌した。次に、この溶液０．１ｇと光触媒無機コーティング剤（石原産業（株）製 ＳＴ−Ｋ０３）５０ｇとを混合し、１時間常温で撹拌した。これをイソプロピルアルコールにより２倍に希釈し光触媒含有層用組成物とした。この光触媒含有層用組成物を１００μｍでライン＆スペースのパターンが形成されたフォトマスク基板上に、スピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、厚さ０．１５μｍの光触媒含有層を形成した。
【０２７６】
２．濡れ性変化層の形成
フルオロアルキルシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８２３３）０．４ｇとテトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し８時間攪拌した。次に、これをイソプロピルアルコールにより１００倍に希釈し濡れ性変化層用組成物とした。この濡れ性変化層用組成物を透明基板上に、スピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、濡れ性変化層（厚み０．１μｍ）を形成した。
【０２７７】
３．光触媒層不純物除去工程
前記光触媒含有層側基板に光触媒含有層側から超高圧水銀ランプ（波長３６５ｎｍ ４０ｍＷ／ｃｍ^２）により６０分間露光し、表面の不純物を除去した。
【０２７８】
４．パターン形成工程
湿度７０％の環境下で前記光触媒含有層側基板と前記濡れ性変化層とを５０μｍのギャップを設けて配置し、フォトマスク側から超高圧水銀ランプ（波長２５４ｎｍ １０ｍＷ／ｃｍ^２）露光した。このとき、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのに２０秒かかった。
【０２７９】
[実施例５]（第三実施態様）
湿度１０％の環境とした以外は、上記実施例４と同様にパターン形成を行ったところ、親液性領域が水の接触角で１０°以下になるのに４５秒かかった。
【０２８０】
[比較例３]
湿度５％の環境とした以外は、実施例４と同様にパターン形成を行ったところ、親液性領域が水の接触角で１０°以下になるのに１２０秒かかった。
【０２８１】
[実施例６]（第四実施態様）
光触媒層不純物除去工程を行った光触媒含有層側基板を５分間純水に浸漬し、引き上げた後、空気ブローにて表面を乾燥した以外は、実施例１と同様にパターン形成を行ったところ、親液性領域が水の接触角で１０°以下になるのに１５秒かかった。
【０２８２】
[実施例７]（第五実施態様）
パターン形成工程において、エキシマランプ（１７２ｎｍ １０ｍＷ／ｃｍ^２）を使用た以外は、実施例１と同様にパターン形成を行った。このとき、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのに１０秒かかった。
【０２８３】
[実施例８]（第六実施態様）
１．光触媒含有層側基板の形成
テトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し、２４時間攪拌した。次に、この溶液０．１ｇと光触媒無機コーティング剤（石原産業（株）製 ＳＴ−Ｋ０３）５０ｇとを混合し、１時間常温で撹拌した。これに、表１に示す各種金属化合物をモル比で酸化チタン１に対して０．０００５添加した。これをイソプロピルアルコールにより２倍に希釈し光触媒含有層用組成物とした。この光触媒含有層用組成物を１００μｍでライン＆スペースのパターンが形成されたフォトマスク基板上に、スピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、厚さ０．１５μｍの光触媒含有層を形成した。
【０２８４】
２．濡れ性変化層の形成
フルオロアルキルシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８２３３）０．４ｇとテトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し８時間攪拌した。これをイソプロピルアルコールにより１００倍に希釈し濡れ性変化層用組成物とした。次に、この濡れ性変化層用組成物を透明基板上に、スピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、濡れ性変化層（厚み０．１μｍ）を形成した。
【０２８５】
３．光触媒層不純物除去工程
前記光触媒含有層側基板に光触媒含有層側から超高圧水銀ランプ（波長３６５ｎｍ ４０ｍＷ／ｃｍ^２）により６０分間露光し、表面の不純物を除去した。
【０２８６】
４．パターン形成工程
前記光触媒含有層側基板と前記濡れ性変化層とを５０μｍのギャップを設けて配置し、フォトマスク側から超高圧水銀ランプ（波長２５４ｎｍ １０ｍＷ／ｃｍ^２）露光した。このとき、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのにかかった時間を表１に示す。
【０２８７】
【表１】

【０２８８】
[実施例９]（第七実施態様）
光触媒層の２５４ｎｍの透過率が８０％になるように膜厚を薄くした以外は、実施１と同様にパターン形成を行ったところ、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのに２０秒かかった。
【０２８９】
[比較例４]
光触媒層の２５４ｎｍの透過率が３％、９５％になるように膜厚を設定した以外は、実施例１と同様にパターン形成を行ったところ、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのにそれぞれ、８０秒、６０秒かかった。
【０２９０】
[実施例１０]（第八実施態様）
１．光触媒含有層側基板の形成
酸化チタン粉末（石原産業（株）製 ＳＴ−０１）をアンモニア雰囲気７００℃で熱処理し、窒素を含有させた酸化チタン粉末を作製した。次に、テトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し、２４時間攪拌した。この溶液とイソプロピルアルコールと前記酸化チタン粉末とを混合し光触媒含有層用組成物とした。この光触媒含有層用組成物を１００μｍでライン＆スペースのパターンが形成されたフォトマスク基板上に、スピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、厚さ０．２５μｍの光触媒含有層を形成した。
【０２９１】
２．濡れ性変化層の形成
フルオロアルキルシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８２３３）０．４ｇとテトラメトキシシラン（ＧＥ東芝シリコーン（株）製 ＴＳＬ８１１４）５ｇと０．０５規定塩酸２．５ｇとを混合し８時間攪拌した。これをイソプロピルアルコールにより１００倍に希釈し濡れ性変化層用組成物とした。次に、透明基板上に、前記濡れ性変化層用組成物をスピンコーターにより塗布し、その後、１５０℃で１０分間の乾燥処理を行うことにより、濡れ性変化層（厚み０．１μｍ）を形成した。
【０２９２】
３．光触媒層不純物除去工程
前記光触媒含有層側基板に光触媒含有層側から超高圧水銀ランプ（波長３６５ｎｍ ４０ｍＷ／ｃｍ^２）により６０分間露光し、表面の不純物を除去した。
【０２９３】
４．パターン形成工程
前記光触媒含有層側基板と前記濡れ性変化層とを５０μｍのギャップを設けて配置し、フォトマスク側から超高圧水銀ランプ（波長２５４ｎｍ １０ｍＷ／ｃｍ^２）露光した。
【０２９４】
このとき、濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのに６０秒かかった。
【０２９５】
[比較例５]
窒素化処理しない酸化チタン粉末を使用した以外は、実施例９同様にパターン形成を行ったところ濡れ性変化層上に１００μｍのライン＆スペースで水の接触角が１０°以下の親液性領域を形成するのに９０秒かかった。
【０２９６】
【発明の効果】
本発明によれば、上記パターン形成工程前に、上記光触媒含有層不純物除去工程を行い、例えば光触媒含有層側基板製造時に光触媒含有層表面に存在する不純物等を除去する。これにより、光触媒含有層が露出し、目的とするパターンを高精細に形成することが可能となるのである。また、光触媒含有層の感度が向上することから、短時間のエネルギー照射で特性変化層の特性を変化させることが可能となり、効率よくパターン形成体を製造でき、製造コスト的にも有利なパターン形成体とすることが可能となる。
【図面の簡単な説明】
【図１】本発明のパターン形成工程の一例を示すである。
【図２】本発明の光触媒含有層側基板の一例を示す断面図である。
【図３】本発明の光触媒含有層側基板の他の例を示す断面図である。
【図４】本発明の光触媒含有層側基板の他の例を示す断面図である。
【図５】本発明の光触媒含有層側基板の他の例を示す断面図である。
【図６】本発明の光触媒含有層側基板の他の例を示す断面図である。
【符号の説明】
１…基板
２…特性変化層
３…光触媒含有層側基板
４…基材
５…光触媒含有層
６…フォトマスク
７…エネルギー
８…遮光部
９…プライマー層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a pattern forming body having a pattern with different characteristics on the surface, which can be used for various applications including color filters, for example.
[0002]
[Prior art]
Conventionally, various methods for producing a pattern forming body for forming various patterns such as designs, images, characters, and circuits on a substrate have been produced.
[0003]
As such a high-definition pattern forming body, a pattern forming body using a photocatalyst by the present inventors and a manufacturing method thereof have been proposed (Japanese Patent Laid-Open No. 2000-249821). According to this, since it is possible to obtain a pattern formed body on which patterns having different characteristics are formed by pattern exposure, the pattern formed body can be obtained easily and accurately. Since various functional elements can be manufactured by utilizing the difference in characteristics of pattern forming bodies having patterns having different characteristics, functional elements such as color filters and microlenses can be efficiently and high-quality. There is an effect that it can be obtained.
[0004]
However, the above-described pattern forming body changes the characteristics of the portion irradiated with energy by using the action of the photocatalyst to form patterns having different characteristics. It takes a certain amount of time to generate. If this time can be shortened, further efficiency can be achieved.
[0005]
In order to obtain a functional element with high accuracy, it is preferable to form a large characteristic difference on the pattern forming body. However, such a large characteristic difference is allowed within a predetermined time allowed for efficiency. In order to form it, it is necessary to improve the rate of change of critical surface tension due to exposure on the surface of the pattern forming body.
[0006]
[Problems to be solved by the invention]
From the above, it is desired to provide an efficient manufacturing method of a pattern forming body in which patterns having different characteristics are formed.
[0007]
[Means for solving the problems]
  According to the present invention, the photocatalyst-containing layer includes a photo-catalyst-containing layer side substrate having a photo-catalyst-containing layer and a photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a photocatalyst-containing layer. And the characteristic change layerIs in close contact, orA pattern forming body manufacturing method comprising a pattern forming step of forming a pattern having different characteristics by irradiating energy after being arranged with a gap of 200 μm or less, before the pattern forming step And a photocatalyst-containing layer impurity removal step of decomposing and removing impurities on the surface of the photocatalyst-containing layer or washing with a liquid.
[0008]
According to the present invention, the photocatalyst-containing layer impurity removal step is performed before the pattern formation step, and for example, impurities present on the surface of the photocatalyst-containing layer when the photocatalyst-containing layer side substrate is manufactured, or adhere to the surface during use or storage. Impurities are removed. As a result, the photocatalyst of the photocatalyst-containing layer is exposed on the surface, the sensitivity can be increased, and the target pattern can be formed with high definition. In addition, since the sensitivity of the photocatalyst-containing layer is improved, it is possible to change the characteristics of the property-changing layer by short-time energy irradiation, and it is possible to efficiently produce a pattern forming body, which is advantageous in terms of manufacturing cost. The body can be made.
[0009]
In the invention described in claim 1, as described in claim 2, the photocatalyst-containing layer impurity removing step irradiates the photocatalyst-containing layer with energy, thereby causing impurities on the surface of the photocatalyst-containing layer. And the photocatalyst-containing layer impurity removal step may be a step of washing impurities on the surface of the photocatalyst-containing layer with a liquid. This is because the foreign matters and impurities present on the surface of the photocatalyst containing layer can be removed by a method of irradiating the photocatalyst containing layer with energy and decomposing it by the action of the photocatalyst, or a method of washing with a liquid.
[0010]
  Further, according to the present invention, the photocatalyst-containing layer includes a photo-catalyst-containing layer side substrate having a photo-catalyst-containing layer and a base material having a photo-catalyst-containing layer and a photo-catalyst-containing layer. Layer and topThe characteristic change layer is in close contact, or 200A method for producing a pattern forming body having a pattern forming process in which a pattern having different characteristics is formed by irradiating energy after being arranged with a gap so as to be less than or equal to μm, the oxygen concentration in the gap Is 20 mol% or more, and provides the manufacturing method of the pattern formation body characterized by the above-mentioned.
[0011]
According to the present invention, in the pattern formation step, the presence of oxygen in the above-mentioned range between the photocatalyst-containing layer and the characteristic change layer makes it possible to enhance the effect of the photocatalyst, and the characteristic of the characteristic change layer Thus, it becomes possible to efficiently manufacture a pattern-formed body having changed.
[0012]
  According to the present invention, the photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a photocatalyst-containing layer side substrate having a photocatalyst-containing layer and a base material, wherein the photocatalyst-containing layer side substrate has a photocatalyst-containing layer. Contained layer and characteristic change layerIs in close contact, orA method for producing a pattern forming body having a pattern forming step of forming a pattern having different characteristics after irradiating energy after being arranged with a gap of 200 μm or less, wherein the relative humidity in the gap is Is within the range of 10% or more.
[0013]
According to the present invention, the effect of the photocatalyst can be enhanced by the presence of water vapor having a concentration in the above range between the photocatalyst-containing layer and the characteristic change layer in the pattern formation step. It becomes possible to efficiently manufacture a pattern-formed body having changed characteristics.
[0014]
  Further, according to the present invention, the photocatalyst-containing layer side substrate having the photocatalyst-containing layer and the photocatalyst-containing layer side substrate having the photocatalyst-containing layer and the base material, wherein the photocatalyst-containing layer side substrate has a photocatalyst-containing layer. Contained layer and characteristic change layerIs in close contact, orA pattern forming body manufacturing method comprising a pattern forming step of forming a pattern having different characteristics by irradiating energy after being arranged with a gap of 200 μm or less, before the energy irradiation. Provided is a method for producing a pattern forming body, characterized in that a treatment for adsorbing water on at least one of a characteristic change layer and the photocatalyst containing layer is performed.
[0015]
According to the present invention, in the pattern formation step, it is possible to improve the sensitivity of the photocatalyst by adsorbing water on the surface of either the characteristic change layer or the photocatalyst-containing layer. Thus, it becomes possible to efficiently manufacture a pattern-formed body having changed.
[0016]
  Further, according to the present invention, the photocatalyst containing layer side substrate having the photocatalyst-containing layer and the photocatalyst-containing layer side substrate having the photocatalyst-containing layer and the base material, wherein the photocatalyst-containing layer side substrate has a photocatalyst-containing layer. Contained layer and characteristic change layerIs in close contact, orA method of manufacturing a pattern forming body having a pattern forming step of forming a pattern having different characteristics by irradiating energy after being arranged with a gap of 200 μm or less, wherein the energy irradiation is an excimer lamp. There is provided a method for producing a pattern-formed body, characterized in that the irradiation is carried out by.
[0017]
According to the present invention, when the energy irradiation is performed by the excimer lamp, the characteristics of the property change layer are changed by the action of the photocatalyst, and at the same time, the energy irradiated by the excimer lamp is directly in the property change layer. Since the organic group is decomposed and the like, the pattern forming body can be performed with higher definition and higher sensitivity.
[0018]
  Further, according to the present invention, as described in claim 8, the characteristic changing layer whose characteristics are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the base material, Layer and the property change layerIs in close contact, orA pattern forming body manufacturing method comprising a pattern forming step of forming a pattern having different characteristics by irradiating energy after being arranged with a gap of 200 μm or less. Provided is a method for producing a pattern forming body, which contains at least one metal element selected from iron and a metal having a lower ionization tendency than iron. To do.
[0019]
According to the present invention, by containing a metal element as the second component in the photocatalyst-containing layer, the photocatalyst in the photocatalyst-containing layer is activated, and the characteristics of the characteristic change layer can be changed in a short time. This is because the manufacturing efficiency of the pattern forming body is improved.
[0020]
  Further, according to the present invention, as described in claim 9, the photocatalyst-containing layer comprises a photo-catalyst-containing layer side substrate having a photo-catalyst-containing layer and a base material having a photo-catalyst-containing layer and a photo-catalyst-containing layer. Layer and the property change layerIs in close contact, orA method for producing a pattern forming body having a pattern forming step in which a pattern having different characteristics is formed by irradiating energy after being arranged with a gap of 200 μm or less, wherein the photocatalyst-containing layer has a wavelength Provided is a method for producing a pattern forming body, which is a layer having a film thickness that transmits 5% to 90% of light at 254 nm, and the energy irradiation is performed from a photocatalyst-containing layer side substrate.
[0021]
According to the present invention, the photocatalyst-containing layer has a film thickness that allows the light having the wavelength to pass within the above range, so that the energy on the low wavelength side of the irradiated energy also reaches the surface of the photocatalyst-containing layer. Thus, the photocatalyst can be more activated, and the characteristics of the characteristic change layer can be changed efficiently.
[0022]
  Further, according to the present invention, as described in claim 10, the property changing layer whose property is changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the substrate are contained in the photocatalyst-containing layer. Layer and the property change layerIs in close contact, orA method for producing a pattern forming body having a pattern forming step in which a pattern having different characteristics is formed by irradiating energy after being arranged with a gap of 200 μm or less, wherein the photocatalyst has a visible light response Provided is a method for producing a pattern forming body, characterized in that
[0023]
According to the present invention, since the photocatalyst is made to be visible light responsive, the photocatalyst is also excited by visible light when irradiated with energy. It can be changed.
[0024]
In the invention described in claim 10, as described in claim 11, the photocatalyst is made of titanium oxide (TiO 2).₂) Is preferably nitrided. Titanium oxide (TiO₂This is because the nitriding-treated material is efficiently excited by visible light, so that it becomes possible to more efficiently produce a pattern forming body in which the properties of the property changing layer have changed.
[0025]
In the invention according to any one of claims 1 to 11, as described in claim 12, it is preferable that the characteristic change layer is formed on a substrate.
[0026]
In the present invention, the property change layer may have a self-supporting property and may not require a substrate. However, a material having a good property change sensitivity usually has a self-supporting property. There are few things and it is often necessary to form a coating film on a substrate. Therefore, as described above, it is preferable to use the characteristic change layer formed on the substrate.
[0027]
In the invention according to any one of claims 1 to 12, as described in claim 13, the photocatalyst-containing layer is formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. It is preferable that it is the layer formed. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to form a uniform and homogeneous layer with less irregularities on the surface, and the characteristics of the characteristic change layer can be changed uniformly. Because.
[0028]
In the invention according to any one of claims 1 to 12, as described in claim 14, the photocatalyst-containing layer is preferably a layer having a photocatalyst and a binder. This is because, when the photocatalyst-containing layer has a binder, the production becomes easy, and as a result, the pattern forming body can be produced at low cost.
[0029]
In the invention according to any one of claims 1 to 14, as described in claim 15, the photocatalyst is made of titanium oxide (TiO 2).₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃It is preferable that it is 1 type, or 2 or more types of substances selected from the above, and as described in claim 16, the photocatalyst is titanium oxide (TiO 2).₂) Is preferable. This is because titanium dioxide is effective as a photocatalyst because of its high band gap energy, is chemically stable, has low toxicity, and is easily available.
[0030]
In the invention according to any one of claims 1 to 16, as described in claim 17, the energy irradiation is preferably performed while heating the photocatalyst-containing layer. This is because the photocatalyst is activated by heating the photocatalyst-containing layer, and the characteristics of the characteristic change layer can be changed in a short time.
[0031]
In the invention according to any one of claims 1 to 17, as described in claim 18, energy irradiation is performed with the photocatalyst-containing layer on the surface of the characteristic change layer with a gap. In doing so, the distance between the photocatalyst-containing layer and the surface of the characteristic change layer is preferably in the range of 0.2 μm to 10 μm. This is because, when the gap is within the above range, the characteristics of the characteristic change layer can be changed more effectively.
[0032]
In the invention according to any one of claims 1 to 18, it is preferable that the characteristic change layer is a layer that does not contain a photocatalyst as described in claim 19. This is because the pattern forming body can be a pattern forming body that is not affected by the photocatalyst over time.
[0033]
In the invention according to any one of claims 1 to 19, as described in claim 20, the characteristic change layer is irradiated with energy by the action of the photocatalyst in the photocatalyst-containing layer. It is preferable that the wettability changing layer changes wettability so that the contact angle with the liquid is lowered. Since the property change layer is a wettability change layer, and the property change layer is a wettability change layer, the region irradiated with energy is made lyophilic and the region not irradiated with energy is repelled. This is because a liquid region can be formed, and a functional part or the like can be easily formed on the pattern forming body by utilizing the difference in wettability.
[0034]
In the invention described in claim 20, as described in claim 21, the contact angle with the liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° or more in a portion where energy is not irradiated. It is preferable that the angle is 9 ° or less in the portion irradiated with energy. When a functional part or the like is formed on the pattern, the liquid repellency is insufficient when the contact angle with the liquid of the part of the wettability changing layer that is not irradiated with energy is 10 ° or less. This is because, when the contact angle between the energy-irradiated portion and the liquid is 10 ° or more, there is a possibility that the spread of the functional part forming composition such as ink may be inferior.
[0035]
In the invention described in claim 20 or claim 21, as described in claim 22, the wettability changing layer is preferably a layer containing an organopolysiloxane. In the present invention, the properties required for the wettability changing layer are lyophobic when not irradiated with energy, and lyophilic by the action of the photocatalyst in the photocatalyst-containing layer that comes into contact when irradiated with energy. The characteristic is. This is because it is preferable to use organopolysiloxane as a material for imparting such characteristics to the wettability changing layer.
[0036]
In the invention described in claim 22, as described in claim 23, the organopolysiloxane is preferably an organopolysiloxane containing a fluoroalkyl group. This is because if it contains a fluoroalkyl group, the difference in wettability between the energy-irradiated portion and the energy-unirradiated portion can be increased.
[0037]
In the invention described in claim 22 or claim 23, as described in claim 24, the organopolysiloxane is Y_nSiX_(4-n)Wherein 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 or a halogen, and n is an integer from 0 to 3. It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolyzed condensate or cohydrolyzed condensate of the silicon compound. This is because by using such an organopolysiloxane, it is possible to exhibit the characteristics against the change in wettability as described above.
[0038]
In the invention according to any one of claims 20 to 24, as described in claim 25, the wettability changing layer may be self-supporting. If the wettability changing layer has a self-supporting property, it is not necessary to use a substrate or the like. For example, if a commercially available resin film is used, a functional element can be easily manufactured.
[0039]
In the invention according to any one of claims 1 to 19, as described in claim 26, the characteristic change layer is irradiated with energy by the action of the photocatalyst in the photocatalyst-containing layer. It is preferable that the layer be decomposed and removed when it is removed. This is because when the characteristic change layer is a decomposition removal layer, it is possible to form a pattern having irregularities on the surface of the decomposition removal layer by energy irradiation.
[0040]
In the invention described in claim 26, as described in claim 27, the contact angle of the liquid with respect to the decomposition / removal layer is the contact angle of the liquid with respect to the substrate exposed when the decomposition / removal layer is decomposed / removed. It is preferable that it is different. A pattern in which a functional part can be more easily formed in the pattern part by utilizing the difference in wettability, because the contact angle between the decomposition removal layer and the liquid is different from the contact angle with the liquid on the substrate. This is because a formed body can be obtained.
[0041]
In the invention described in claim 26 or claim 27, as described in claim 28, the decomposition / removal layer is any of a self-assembled monolayer, a Langmuir-Blodgett film, and an alternately adsorbed film. It is preferable that This is because, when the decomposition removal layer is the above film, a uniform film having no defects can be formed.
[0042]
In the invention according to any one of claims 26 to 28, as described in claim 29, the wettability on the substrate is a contact angle with a liquid having a surface tension of 40 mN / m. It is preferably 9 ° or less and 10 ° or more on the decomposition removal layer. When the wettability on the decomposition / removal layer and the substrate is within the above range, the region where the energy is irradiated and the substrate is exposed is a lyophilic region, the energy is not irradiated, and the region where the decomposition / removal layer remains This is because the liquid repellent region can be used, and the functional portion can be easily formed in the pattern portion by utilizing the difference in wettability.
[0043]
The present invention also provides a photocatalyst-containing layer side substrate for producing a pattern forming body, comprising: a base material; and a photocatalyst-containing layer containing a photocatalyst and a metal element formed on the base material. A photocatalyst-containing layer side substrate for producing a pattern forming body is provided, wherein the metal element is at least one metal element selected from iron and a metal having a lower ionization tendency than iron.
[0044]
According to the present invention, a photocatalyst-containing layer-side substrate for producing a pattern forming body having a high photocatalytic activity can be obtained by containing the metal element in the photocatalyst-containing layer. It is possible to produce a high-definition pattern forming body using the containing layer side substrate.
[0045]
The present invention also provides a photocatalyst-containing layer side substrate for producing a pattern forming body, comprising a base material and a photocatalyst-containing layer containing a photocatalyst formed on the base material, as described in claim 31. The photocatalyst-containing layer side substrate for producing a pattern forming body is provided, wherein the photocatalyst-containing layer is a layer having a film thickness that transmits 5% to 90% of light having a wavelength of 254 nm.
[0046]
According to the present invention, since the photocatalyst-containing layer has a film thickness that allows the light having the above wavelength to pass within the above range, it is possible to transmit the energy on the low wavelength side of the irradiated energy. This is because a photocatalyst-containing layer-side substrate for producing a pattern-forming body that can form a pattern well can be obtained.
[0047]
Moreover, the present invention is a photocatalyst containing layer side substrate for producing a pattern forming body, comprising a base material and a photocatalyst containing layer containing a photocatalyst formed on the base material, as described in claim 32, Provided is a photocatalyst-containing layer side substrate for producing a pattern forming body, characterized in that the photocatalyst is responsive to visible light.
[0048]
According to the present invention, by making the photocatalyst responsive to visible light, it is possible to use the energy on the high wavelength side of the irradiated energy for excitation of the photocatalyst, and to form a pattern efficiently. A photocatalyst-containing layer side substrate for producing a pattern forming body can be obtained.
[0049]
In the invention described in claim 32, as described in claim 33, the photocatalyst is made of titanium oxide (TiO 2).₂) Is preferably nitrided. The photocatalyst is titanium oxide (TiO₂This is because nitriding treatment) can be efficiently excited by visible light and is preferable from the viewpoint of manufacturing efficiency and cost.
[0050]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a method for producing a patterned product and a photocatalyst-containing layer side substrate for producing the patterned product. Each of these will be described below.
[0051]
A. Method for producing pattern forming body
The method for producing a pattern forming body of the present invention has eight embodiments, all of which aim to increase sensitivity. Each embodiment will be described below.
[0052]
1. First embodiment
In the first embodiment of the present invention, for the purpose of increasing the sensitivity of a photocatalyst-containing layer, a property-changing layer whose properties are changed by the action of the photocatalyst, a photocatalyst-containing layer containing a photocatalyst, and a photocatalyst-containing layer-side substrate having a substrate, Of the pattern forming body having a pattern forming step of forming a pattern composed of portions having different characteristics by irradiating energy after arranging the photocatalyst-containing layer and the characteristic change layer so as to be 200 μm or less. A method for producing a photocatalyst-containing layer with high sensitivity by having a photocatalyst-containing layer impurity removal step of decomposing and removing impurities on the surface of the photocatalyst-containing layer or washing with a liquid before the pattern forming step. is there.
[0053]
For example, as shown in FIG. 1, the method for producing a pattern forming body according to this embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1, and a photocatalyst-containing layer side substrate. 3, a photocatalyst-containing layer 5 containing a photocatalyst formed on the substrate 4 is disposed so as to face each other at a predetermined interval, and a pattern is irradiated with energy 7 using a photomask 6 Although it is a manufacturing method which has a formation process, before this pattern formation process, it has the photocatalyst content layer impurity removal process which decomposes | disassembles the impurity of the surface of the said photocatalyst content layer 5, or wash | cleans with a liquid.
[0054]
By performing this photocatalyst-containing layer impurity removal step, for example, it is possible to remove impurities present on the surface of the photocatalyst-containing layer during production of the photocatalyst-containing layer side substrate, impurities that adhere to the surface during use or storage, and the like. It is possible to expose the photocatalyst in the containing layer to the surface. This makes it possible to increase the sensitivity of the photocatalyst-containing layer and to form a target pattern with high definition. In addition, since impurities on the surface and the like are removed, the sensitivity of the photocatalyst containing layer is improved, and the characteristics of the characteristic change layer can be changed by short-time energy irradiation.
[0055]
Hereinafter, each step will be described.
[0056]
(1) Pattern formation process
For example, as shown in FIG. 1, the pattern forming process of this embodiment includes a characteristic changing layer 2 whose characteristics change by the action of a photocatalyst formed on the substrate 1, and a substrate 4 on the photocatalyst containing layer side substrate 3. The photocatalyst containing layer 5 containing the photocatalyst formed in the step is disposed so as to face each other with a predetermined interval, and the photomask 6 is used to irradiate energy 7 in a pattern. Hereinafter, each of these configurations will be described.
[0057]
(Characteristic change layer)
First, the characteristic change layer in this embodiment will be described. The characteristic change layer of the present embodiment is not particularly limited as long as the characteristic changes by the action of the photocatalyst containing layer described later, and for example, a polymer material such as polyolefin such as polyethylene or polypropylene is used. As a characteristic change layer, the layer irradiated with energy improves the adhesion with various substances by introducing a polar group by the action of the photocatalyst or making the surface rough. Also good. By making the property-changing layer an adhesive-changing layer whose adhesiveness changes in this way, it becomes possible to form a pattern with good adhesiveness by energy irradiation, and a functional part can be easily formed on the pattern formation body. Because it becomes possible to do.
[0058]
In addition, the characteristic change layer in the present embodiment may be self-supporting or non-self-supporting. The term “having self-supporting property” as used in the present embodiment means that it can exist in a tangible state without other supporting materials. When the characteristic change layer has self-supporting properties, it is not necessary to form the characteristic change layer on a substrate described later, and a commercially available resin film can be used, which is advantageous in terms of cost. It can be said.
[0059]
However, the characteristic change layer formed of a material whose characteristics change significantly is usually less self-supporting material. In such a non-self-supporting material, the characteristic change layer is formed on the substrate. It is necessary. Further, by forming the characteristic change layer on the substrate, the strength and the like are increased, and it can be used as various pattern forming bodies.
[0060]
As a method of forming the above-described property change layer on the substrate, it may be formed by a dry method, that is, a vacuum deposition method or the like, or by a wet method, that is, a method such as a spin coating method or a dip coating method. It may be formed.
[0061]
As described above, the characteristic change layer is not particularly limited as long as it has various characteristics that change due to the action of the photocatalyst. However, in this embodiment, the characteristic change layer changes the wettability due to the action of the photocatalyst. Two cases are particularly obtained: a wettability changing layer in which a pattern due to wettability is formed, and a case in which the characteristic changing layer is a decomposition removing layer in which a pattern due to unevenness is formed by being decomposed and removed by the action of a photocatalyst. This is preferable because the effectiveness of this embodiment is derived from the relationship of functional elements and the like.
[0062]
The characteristic change layer used in the present embodiment is not particularly limited as long as the characteristic change layer is changed by the action of the photocatalyst as described above. In particular, a layer not containing the photocatalyst is preferable. . If the photocatalyst is not included in the wettability changing layer in this way, there is no need to worry about the effect of the photocatalyst over time when used as a functional element, and it can be used without problems for a long time. That's why. Hereinafter, the wettability changing layer and the decomposition removal layer will be described.
[0063]
a. Wetting change layer
The wettability changing layer in the present embodiment is not particularly limited as long as the wettability of the surface is changed by the action of the photocatalyst. A layer whose wettability changes so that the contact angle with the liquid on the surface of the layer decreases is preferable.
[0064]
In this way, by using a wettability changing layer in which the wettability changes so that the contact angle with the liquid decreases by energy irradiation, the wettability can be easily changed to a pattern by performing energy irradiation in a pattern. It becomes possible to form a pattern of a lyophilic region having a small contact angle with the liquid, and a functional element can be easily formed by attaching, for example, a functional part forming composition to the lyophilic region. Therefore, it is possible to obtain a pattern forming body that can efficiently produce a functional element.
[0065]
Here, the lyophilic region is a region having a small contact angle with the liquid, for example, a region having good wettability with respect to the functional part forming composition or the like. The liquid repellent region is a region having a large contact angle with the liquid, and refers to a region having poor wettability with respect to the above-described functional part forming composition.
[0066]
In the present embodiment, when the contact angle with the liquid in the adjacent region is 1 ° or more lower than the contact angle with the liquid in the adjacent region, the liquid is When the contact angle is higher by 1 ° or more, the liquid-repellent region is set.
[0067]
Here, the liquid having a surface tension equivalent to the surface tension of the functional part-forming composition to be applied thereafter is a property of the lyophilic region formed by the energy irradiation and the liquid repellent region not irradiated with energy. It is preferable that the pattern is formed from a lyophilic region and a liquid-repellent region that differ by at least 1 ° or more, preferably 5 ° or more, particularly 10 ° or more.
[0068]
Further, the wettability changing layer has a contact angle with a liquid with a surface tension of 40 mN / m of 10 ° or more, preferably a liquid with a surface tension of 30 mN / m, in a portion not irradiated with energy, that is, in a water-repellent region. It is preferable to exhibit wettability with a contact angle of 10 ° or more, particularly 10 ° or more with a liquid having a surface tension of 20 mN / m. This is because the portion that is not irradiated with energy is a portion that requires liquid repellency in this embodiment, and therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient, and the above functionality This is because the part forming composition may remain, which is not preferable.
[0069]
Further, the wettability changing layer has a contact angle with a liquid that is lowered when irradiated with energy, and a contact angle with a liquid with a surface tension of 40 mN / m is 9 ° or less, preferably with a liquid with a surface tension of 50 mN / m. A layer having an angle of 10 ° or less, particularly a contact angle with a liquid having a surface tension of 60 mN / m is preferably 10 ° or less. If the contact angle with the liquid in the energy-irradiated portion, that is, the lyophilic region is high, the spread of the composition for forming the functional part in this part may be inferior, resulting in problems such as lack of the functional part. Because there is a possibility.
[0070]
In addition, the contact angle with the liquid here is measured using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions (from the microsyringe to the liquid. 30 seconds after dropping), and the result was obtained or the result was graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.
[0071]
Further, when the wettability changing layer as described above is used in the present embodiment, fluorine is contained in the wettability changing layer, and the fluorine content on the surface of the wettability changing layer is more than the wettability changing layer. The wettability changing layer may be formed so that when the energy is irradiated, the photocatalyst acts to reduce the energy compared to before the energy irradiation.
[0072]
In the wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy. Here, fluorine has an extremely low surface energy. Therefore, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than the surrounding surface forms a pattern of the lyophilic region in the liquid repellent region.
[0073]
Therefore, when such a wettability changing layer is used, a pattern of the lyophilic region can be easily formed in the lyophobic region by irradiating the pattern with energy. Therefore, it is possible to easily form a functional part only, and a functional element with good quality can be obtained at low cost.
[0074]
As described above, the fluorine content contained in the wettability changing layer containing fluorine is not irradiated with energy in the lyophilic region having a low fluorine content formed by energy irradiation. When the fluorine content of the part is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.
[0075]
By setting it within such a range, it is possible to make a great difference in wettability between the energy irradiated portion and the energy non-irradiated portion. Therefore, by forming the functional part in such a wettability changing layer, it becomes possible to accurately form the functional part only in the lyophilic region where the fluorine content is reduced, and the functional element can be accurately formed. Because it can be obtained. This rate of decrease is based on weight.
[0076]
The fluorine content in such a wettability changing layer can be measured by various commonly used methods. For example, X-ray photoelectron spectroscopy (ESCA) (Electron Spectroscopy, ESCA) Spectroscopy for Chemical Analysis)), and any method capable of quantitatively measuring the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry.
[0077]
The material used for such a wettability changing layer is a material whose wettability changing layer has the characteristics described above, that is, a material whose wettability is changed by the photocatalyst in the photocatalyst-containing layer that is contacted by energy irradiation, and deteriorated by the action of the photocatalyst The main chain is not particularly limited as long as it has a main chain that is difficult to be decomposed. For example, (1) an organo group that exhibits high strength by hydrolysis and polycondensation of chloro or alkoxysilane by sol-gel reaction or the like Examples include polysiloxanes and (2) organopolysiloxanes such as organopolysiloxanes crosslinked with reactive silicones having excellent water and oil repellency.
[0078]
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 the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. 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.
[0079]
In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof 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.
[0080]
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si CH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;and
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃.
[0081]
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-irradiated portion of the wettability changing layer is greatly improved. For example, the pixel portion when the functional element is a color filter The function of preventing the adhesion of the composition for forming a functional part such as an ink for coloring is developed.
[0082]
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0083]
[Chemical 1]

[0084]
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 preferably a methyl group because the surface energy becomes the smallest, and the methyl group is preferably 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.
[0085]
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.
[0086]
In this embodiment, various materials such as organopolysiloxane can be used in the wettability changing layer as described above. However, as described above, it is possible to include fluorine in the wettability changing layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing layer.
[0087]
The wettability changing layer in this embodiment 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.
[0088]
In addition to the above surfactants, 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, etc. Can be contained.
[0089]
Such a wettability changing layer can be formed by preparing a coating solution by dispersing the above-described components in a solvent together with other additives as necessary, and coating the coating solution on a substrate. . 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 or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0090]
In this embodiment, the thickness of the wettability changing layer is preferably 0.001 μm to 1 μm, particularly preferably in the range of 0.01 to 0.1 μm, in consideration of the wettability change rate due to the photocatalyst. It is.
[0091]
Further, as described above, the wettability changing layer of the present embodiment may be a material having self-supporting property. As the material having self-supporting property, a material obtained by forming the above-described material has self-supporting property. This can be used as long as it has, for example, polyethylene, polycarbonate, polypropylene, polystyrene, polyester, polyvinyl fluoride, acetal resin, nylon, ABS, PTFE, methacrylic resin, phenol resin, polyfluoride Examples thereof include vinylidene, polyoxymethylene, polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, and silicone.
[0092]
b. Decomposition removal layer
Next, the decomposition removal layer will be described. The decomposition / removal layer used in this embodiment is not particularly limited as long as the decomposition / removal layer of the portion irradiated with energy is decomposed and removed by the action of the photocatalyst in the photocatalyst-containing layer when irradiated with energy. It is not a thing.
[0093]
As described above, since the portion irradiated with energy 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.
[0094]
This decomposition / removal layer is oxidatively decomposed and vaporized by the action of the photocatalyst by energy irradiation, and is therefore removed without any special post-treatment such as development / washing process. Depending on the material, a cleaning process or the like may be performed.
[0095]
In addition, the decomposition / removal layer used in this embodiment not only forms irregularities, but the decomposition / removal layer preferably has a higher contact angle with the liquid than the substrate surface. As a result, the decomposition / removal layer can be decomposed and removed, and the region where the substrate is exposed can be defined as a lyophilic region, and the region where the decomposition / removal layer remains can be defined as a lyophobic region, thereby forming various patterns. This is because it becomes easy.
[0096]
Here, the characteristics of the lyophilic region, which is the region where the substrate is exposed by the energy irradiation, and the liquid repellent region, which is the region composed of the remaining decomposition-removed layer that has not been irradiated with the energy, form a functional part to be subsequently applied. In a pattern formed from a lyophilic region and a liquid repellent region that differ by at least 1 ° or more, preferably 5 ° or more, particularly 10 ° or more in the contact angle with respect to a liquid having a surface tension equivalent to the surface tension of the composition for use. Preferably there is.
[0097]
Further, the contact angle with the liquid on the surface of the decomposition removal layer of the present embodiment is such that the contact angle with the liquid having a surface tension of 40 mN / m is 10 ° or more, preferably 10 ° with the liquid having a surface tension of 30 mN / m. As described above, it is particularly preferable that the contact angle with a liquid having a surface tension of 20 mN / m exhibits a value of 10 ° or more.
[0098]
In this embodiment, when the characteristic change layer is a decomposition removal layer, the substrate described later is preferably lyophilic, specifically, as a contact angle with a liquid having a surface tension of 40 mN / m. The contact angle with a liquid having a surface tension of 40 mN / m is more preferably 5 ° or less, and particularly preferably 1 ° or less.
[0099]
Since the wettability of the decomposition removal layer and the substrate is within the above range, the region where the substrate is exposed can be made a lyophilic region, and the region where the decomposition removal layer remains can be made a liquid repellent region. This is because a simple pattern can be easily formed. Here, the contact angle with the liquid is a value measured by the method described above.
[0100]
In this case, the substrate described later may be surface-treated so that the surface becomes lyophilic. Examples of the surface treatment so that the surface of the material becomes lyophilic include lyophilic surface treatment by plasma treatment using argon or water, and the lyophilic layer formed on the substrate is as follows: For example, a silica film by a sol-gel method of tetraethoxysilane can be used. In this embodiment, the portion where the substrate is usually exposed is defined as the lyophilic region.
[0101]
Specific examples of the film that can be used for the above-described decomposition removal layer include a film made of a fluorine-based or hydrocarbon-based resin having liquid repellency. These fluorine-based and hydrocarbon-based resins are not particularly limited as long as they have liquid repellency, and these resins are dissolved in a solvent, for example, a general composition such as a spin coating method. It can be formed by a film method.
[0102]
Moreover, in this embodiment, it is possible to form a film without defects by using a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Blodgett film, an alternating adsorption film, and the like. Therefore, it can be said that it is more preferable to use such a film forming method.
[0103]
Here, the self-assembled monomolecular film, the Langmuir-Blodgett film, and the alternately adsorbed film used in this embodiment will be specifically described.
[0104]
(I) Self-assembled monolayer
Although the inventors do not know the existence of an official definition of self-assembled monolayer, a commentary on what is generally recognized as a self-assembled membrane is, for example, a review by Abraham Ulman. “Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996) is excellent. Referring to this review article, a self-assembled monolayer can be said to be a monolayer formed as a result of adsorbing and binding (self-organizing) appropriate molecules to the appropriate substrate surface. Examples of materials capable of forming a self-assembled film include surfactant molecules such as fatty acids, organosilicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. And organic phosphoric acid molecules. The common commonality of the molecular structure is that there is a functional group that has a relatively long alkyl chain and that interacts with the substrate surface at one molecular end. The portion of the alkyl chain is a source of intermolecular force when molecules are packed two-dimensionally. However, the example shown here has the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain part having an oxyethylene chain, or a fluorocarbon chain. Self-assembled monolayers composed of various molecules such as those of complex type chains have been reported. There is also a composite type self-assembled monolayer composed of a plurality of molecular species. In addition, recently, a polymer having a plurality of functional groups (which may have one functional group) or a linear polymer (which may have a branched structure) as represented by dendrimers has been developed. One formed on the surface of the substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In the present embodiment, these are also included in the self-assembled monolayer.
[0105]
(Ii) Langmuir-Blodgett membrane
If the Langmuir-Blodgett film used in this embodiment is formed on a substrate, there is no significant difference in form from the above-described self-assembled monolayer. It can be said that the Langmuir-Blodgett film is characterized by its formation method and the advanced two-dimensional molecular packing properties (high orientation and high order). That is, in general, Langmuir-Blodgett film-forming molecules are first developed on the gas-liquid interface, and the developed film is condensed by the trough to change into a highly packed condensed film. In practice, this is transferred to a suitable substrate for use. It is possible to form a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. Further, not only low molecules but also polymers and colloidal particles can be used as the film material. Recent examples of the application of various materials are described in detail in the review by Tokuharu Miyashita et al. “Prospects for Nanotechnology for the Creation of Soft Nanodevices” Polymer Vol. 50, September, 644-647 (2001).
[0106]
(Iii) Alternate adsorption film
Alternating adsorption film (Layer-by-Layer Self-Assembled Film) is generally laminated by adsorbing and bonding at least two materials with positive or negative functional groups sequentially onto the substrate. It is a film | membrane formed by doing. Since a material having a large number of functional groups has many advantages such as increased strength and durability of the membrane, recently, an ionic polymer (polymer electrolyte) is often used as a material. Further, particles having surface charges such as proteins, metals and oxides, so-called “colloid particles” are also frequently used as film-forming substances. More recently, membranes that actively utilize weaker interactions than ionic bonds such as hydrogen bonds, coordination bonds, and hydrophobic interactions have been reported. A relatively recent example of alternating adsorption films is slightly biased towards materials with electrostatic interaction as the driving force, but a review by Paula T. Hammond “Recent Explorations in Electrostatic Multilayer Thin Film Assembly” Current Opinion in Colloid & Interface Science, 4, 430-442 (2000). The alternate adsorption film can be described by taking the simplest process as an example, by repeating the adsorption-washing of a material having a positive (negative) charge-adsorption-washing of a material having a negative (positive) charge a predetermined number of times. It is a film to be formed. As with Langmuir-Blodgett membranes, no development-condensation-transfer operations are required. Further, as apparent from the difference in these production methods, the alternate adsorption film generally does not have a two-dimensional high orientation / high order like the Langmuir-Blodgett film. However, the alternate adsorption film and its manufacturing method have advantages over conventional film formation methods, such as the ability to easily form a dense film without defects and the ability to form even fine irregular surfaces, tube inner surfaces, and spherical surfaces. Have many.
[0107]
Further, the thickness of the decomposition / removal layer is not particularly limited as long as it is a thickness that can be decomposed and removed by energy irradiated in an energy irradiation step described later. The specific film thickness varies greatly depending on the type of energy to be irradiated, the material of the decomposition removal layer, and the like, but is generally within the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0.001. It is preferable to be within the range of 1 μm.
[0108]
c. substrate
Next, the substrate in this embodiment will be described. In the present embodiment, when the characteristic change layer is a material having no self-supporting property or a decomposition removal layer, for example, as shown in FIG. 1, the characteristic change layer 2 is provided on the substrate 1.
[0109]
The substrate is not particularly limited as long as the above-described characteristic change layer is formed. Even if the substrate has flexibility according to the use of the functional element, the substrate is flexible. It may be a thing which does not have.
[0110]
In addition, the material and the like are not particularly limited, and various materials can be used as necessary. Specific examples include metals such as glass, aluminum, and alloys thereof, plastics, woven fabrics, and nonwoven fabrics.
[0111]
(Photocatalyst containing layer side substrate)
Next, the photocatalyst containing layer side substrate used in this embodiment will be described. For example, as shown in FIG. 1, the photocatalyst-containing layer side substrate 3 used in the method for producing a functional element of this embodiment has at least a base material 4 and a photocatalyst-containing layer 5, and usually the base material 4. A thin film-like photocatalyst containing layer 5 formed by a predetermined method is formed thereon. The photocatalyst-containing layer side substrate may be a substrate having a light-shielding portion formed in a pattern, and a substrate having a primer layer formed between the light-shielding portion and the photocatalyst-containing layer is also used. be able to. Hereinafter, each of these configurations will be described.
[0112]
a. Photocatalyst containing layer
The photocatalyst-containing layer used in the present embodiment is not particularly limited as long as the photocatalyst in the photocatalyst-containing layer changes the characteristics of the target characteristic change layer. It may be configured, or may be formed with a photocatalyst alone. Further, the surface characteristics may be particularly lyophilic or lyophobic.
[0113]
The photocatalyst containing layer used in the present embodiment may be one in which the photocatalyst containing layer 5 is formed on the entire surface of the base material 4 of the photocatalyst containing layer side substrate 3 as shown in FIG. For example, as shown in FIG. 3, the photocatalyst containing layer 5 may be formed on the pattern on the base material 4 of the photocatalyst containing layer side substrate 3.
[0114]
By forming the photocatalyst-containing layer in a pattern in this way, as described in the energy irradiation step described later, when the photocatalyst-containing layer is arranged at a predetermined interval from the characteristic change layer and irradiated with energy, It is not necessary to perform pattern irradiation using a photomask or the like, and by irradiating the entire surface, a pattern with changed characteristics can be formed on the characteristic change layer.
[0115]
The photocatalyst-containing layer patterning method is not particularly limited, but can be performed by, for example, a photolithography method.
[0116]
In addition, since the characteristics of only the part on the characteristic change layer facing the photocatalyst containing layer actually change, the energy irradiation direction is such that the part where the photocatalyst containing layer and the characteristic change layer face is irradiated with energy. As long as it irradiates, it may irradiate from what direction, and also has the advantage that irradiation energy is not limited to parallel things, such as parallel light.
[0117]
Thus, the action mechanism of the photocatalyst represented by titanium dioxide as described later in the photocatalyst-containing layer is not necessarily clear, but the carrier generated by light irradiation reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of organic matter. In this embodiment, it is considered that this carrier acts on the compound in the characteristic change layer disposed in the vicinity of the photocatalyst containing layer.
[0118]
As a photocatalyst used in this embodiment, for example, titanium dioxide (TiO 2) known as an optical semiconductor.₂), 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.
[0119]
In this embodiment, 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 anatase type and rutile type, and both can be used in this embodiment, but anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0120]
Examples of such anatase type titanium dioxide include hydrochloric acid peptizer 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.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.
[0121]
The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst having a size of 20 nm or less.
[0122]
The photocatalyst-containing layer in this embodiment may be formed of a photocatalyst alone as described above, or may be formed by mixing with a binder.
[0123]
In the case of a photocatalyst-containing layer composed only of a photocatalyst, the efficiency with respect to the change in characteristics on the characteristic change layer is improved, which is advantageous in terms of cost such as shortening the processing time. On the other hand, in the case of a photocatalyst-containing layer comprising a photocatalyst and a binder, there is an advantage that the formation of the photocatalyst-containing layer is easy.
[0124]
Examples of a method for forming a photocatalyst-containing layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst-containing layer by a vacuum film-forming method, it is possible to obtain a photocatalyst-containing layer that is a uniform film and contains only the photocatalyst, which can uniformly change the characteristics on the characteristic change layer. Since it is possible and consists only of a photocatalyst, it is possible to change the characteristics on the characteristic change layer more efficiently than in the case of using a binder.
[0125]
In addition, as another example of a method for forming a photocatalyst-containing layer comprising only a photocatalyst, for example, when the photocatalyst is titanium dioxide, a method of forming amorphous titania on a substrate and then changing the phase to crystalline titania by firing. Etc. 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. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0126]
Moreover, when using a binder, what has the high bond energy that the main frame | skeleton of a binder is not decomposed | disassembled by photoexcitation of said photocatalyst is preferable, for example, organopolysiloxane etc. can be mentioned.
[0127]
When organopolysiloxane is used as a binder in this way, the photocatalyst-containing layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. It can be formed by applying this coating solution on a substrate. 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 or bead coating. When an ultraviolet curable component is contained as the binder, the photocatalyst-containing layer can be formed by irradiating ultraviolet rays and performing a curing treatment.
[0128]
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 halogen, methoxy group, ethoxy group, or acetyl group, a hydrolyzate thereof, silanol, or a polysiloxane having an average molecular weight of 3000 or less.
[0129]
Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, and hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst-containing layer can be formed by dehydration-condensation polymerization. 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.
[0130]
When the binder is used, the content of the photocatalyst in the photocatalyst containing layer can be set in the range of 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.
[0131]
In addition to the photocatalyst and the binder, the photocatalyst containing layer can 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.
[0132]
In addition to the above surfactants, the photocatalyst-containing 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. It can be included.
[0133]
b. Base material
Next, the base material of the photocatalyst containing layer side substrate in this embodiment will be described. In this embodiment, for example, as shown in FIG. 2A, the photocatalyst containing layer side substrate 3 has at least a base material 4 and a photocatalyst containing layer 5 formed on the base material 4. Under the present circumstances, the material which comprises the base material used is suitably selected by the irradiation direction of the energy in the energy irradiation process mentioned later, whether the functional element obtained requires transparency, etc.
[0134]
As will be described later, a light shielding part is formed in a predetermined pattern in advance on the photocatalyst containing layer side substrate, and when forming a pattern using this light shielding part, as shown in FIG. When forming a pattern on the photocatalyst containing layer side substrate 3 side using the photomask 7, it is necessary to irradiate energy from the photocatalyst containing layer side substrate 3 side. In such a case, the base material 4 needs to have transparency.
[0135]
On the other hand, it is also possible to irradiate energy by arranging a photomask on the characteristic change layer side. In such a case, the transparency of the substrate is not particularly required.
[0136]
The base material used in this embodiment may be a flexible material such as a resinous film, or may be a non-flexible material such as a glass substrate. This is appropriately selected depending on the energy irradiation method in the energy irradiation step described later.
[0137]
Thus, the base material used for the photocatalyst-containing layer side substrate in this embodiment is not particularly limited in material, but in this embodiment, the photocatalyst-containing layer side substrate is used repeatedly. For this reason, a material having a predetermined strength and having a surface with good adhesion to the photocatalyst containing layer is preferably used. Specific examples include glass, ceramic, metal, and plastic.
[0138]
An anchor layer may be formed on the substrate in order to improve the adhesion between the substrate surface and the photocatalyst containing layer. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0139]
c. Shading part
Next, the light shielding part of the photocatalyst containing layer side substrate in this embodiment will be described. As the photocatalyst-containing layer side substrate used in the present embodiment, a substrate having a light shielding part formed in a pattern may be used. By using the photocatalyst containing layer side substrate having the light shielding portion in this way, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy in a pattern. Therefore, since alignment between the photocatalyst-containing layer side substrate and the photomask is not necessary, it is possible to use a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.
[0140]
The photocatalyst-containing layer side substrate having such a light shielding part can be made into the following two embodiments depending on the formation position of the light shielding part.
[0141]
One example is an embodiment in which a light shielding part 8 is formed on a base material 4 of a photocatalyst containing layer side substrate 3 and a photocatalyst containing layer 5 is formed on the light shielding part 8 as shown in FIG. The other is an embodiment in which the photocatalyst containing layer 5 is formed on the base material 4 of the photocatalyst containing layer side substrate 3 and the light shielding part 8 is formed thereon as shown in FIG.
[0142]
In any embodiment, as compared with the case where a photomask is used, the light-shielding portion is disposed in the vicinity of the portion where the photocatalyst-containing layer and the characteristic change layer are located with a gap. Since it is possible to reduce the influence of energy scattering, the energy pattern irradiation can be performed very accurately.
[0143]
Furthermore, in the embodiment in which the light shielding part is formed on the photocatalyst containing layer, when the photocatalyst containing layer and the characteristic change layer are arranged with a predetermined gap, the thickness of the light shielding part is set to the width of the gap. By matching, the light-shielding part can be used as a spacer for maintaining a certain gap.
[0144]
That is, when the photocatalyst containing layer and the characteristic change layer are arranged in contact with each other with a predetermined gap, the light shielding part and the characteristic change layer are arranged in close contact with each other, It becomes possible to make the gap accurate, and by irradiating energy from the photocatalyst containing layer side substrate in this state, it becomes possible to form a pattern on the characteristic change layer with high accuracy.
[0145]
The method for forming such a light-shielding part is not particularly limited, and is appropriately selected and used depending on the characteristics of the surface where the light-shielding part is formed, the shielding property against the required energy, and the like.
[0146]
As a method for forming the light shielding part of this embodiment, a thin metal film such as chromium having a thickness of about 1000 to 2000 mm is formed by, for example, a sputtering method or a vacuum deposition method, and the thin film is patterned. The method etc. can be mentioned.
[0147]
The light shielding part may be a layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments and organic pigments are contained in a resin binder. In the present embodiment, this resinous light shielding part. Part. The thickness of such a resinous light-shielding part can be set within a range of 0.5 to 10 μm, and can generally be higher than when a metal thin film is used.
[0148]
Also, the resin binder used may be one or a mixture of two or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, photosensitive resin, An O / W emulsion type resin composition, for example, an emulsion of reactive silicone can be used. As a method for patterning such a resinous light shielding part, a generally used method such as a photolithography method or a printing method can be used.
[0149]
In the above description, the two positions of the light shielding portion between the base material and the photocatalyst containing layer and the surface of the photocatalyst containing layer have been described. However, the photocatalyst containing layer of the base material is formed. It is also possible to adopt a mode in which a light shielding portion is formed on the surface on the non-side. In this aspect, for example, a case where the photomask is attached to the surface to be attachable and detachable can be considered, and it can be suitably used when the functional element is changed in a small lot.
[0150]
d. Primer layer
Next, the primer layer used for the photocatalyst containing layer side substrate of this embodiment will be described. In this embodiment, as described above, when the light-shielding portion is formed in a pattern on the substrate and the photocatalyst-containing layer is formed thereon to form the photocatalyst-containing layer side substrate, the light-shielding portion and the photocatalyst are contained. A primer layer may be formed between the layers.
[0151]
Although the action and function of this primer layer are not necessarily clear, by forming a primer layer between the light shielding part and the photocatalyst containing layer, the primer layer inhibits the characteristic change of the characteristic change layer due to the action of the photocatalyst. It is considered to exhibit a function to prevent diffusion of impurities such as light shielding portions and openings from between the light shielding portions, which are factors, particularly residues generated when patterning the light shielding portions, impurities such as metals and metal ions. . Therefore, by forming the primer layer, the characteristic change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0152]
In this embodiment, the primer layer prevents impurities present in the openings formed between the light shielding portions as well as the light shielding portions from affecting the action of the photocatalyst. It is preferable that it is formed over the entire light shielding part.
[0153]
FIG. 6 shows an example of the photocatalyst containing layer side substrate on which such a primer layer is formed. A primer layer 9 is formed on the surface of the substrate 4 on which the light shielding portion 8 is formed of the substrate 4 on which the light shielding portion 8 of the photocatalyst containing layer side substrate 3 is formed, and the photocatalyst containing layer 5 is formed on the surface of the primer layer 9. Is formed.
[0154]
The primer layer in this embodiment is not particularly limited as long as the primer layer is formed so that the light shielding portion of the photocatalyst containing layer side substrate and the photocatalyst containing layer are not in contact with each other.
[0155]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of amorphous silica is represented by the general formula SiX.₄X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, and a hydrolyzate thereof, silanol, or polysiloxane having an average molecular weight of 3000 or less is preferable.
[0156]
The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.
[0157]
(Energy irradiation)
In this embodiment, the photocatalyst-containing layer and the characteristic change layer described above are arranged with a gap of 200 μm or less, and then energy is irradiated from a predetermined direction. At this time, the photocatalyst-containing layer and the characteristic change layer may be adhered to each other.
[0158]
In the present embodiment, the gap has a very good pattern accuracy, a high photocatalyst sensitivity, and therefore a good characteristic change efficiency, and particularly within the range of 0.2 μm to 10 μm, preferably 1 μm to 5 μm. It is preferable to be within the range. Such a gap range is particularly effective for a small-area characteristic change layer capable of controlling the gap with high accuracy.
[0159]
On the other hand, when processing a characteristic change layer having a large area of, for example, 300 mm × 300 mm, a fine gap as described above is formed between the photocatalyst containing layer side substrate and the characteristic change layer without contact. It is extremely difficult to do. Therefore, when the characteristic change layer has a relatively large area, the gap is preferably in the range of 10 to 100 μm, particularly in the range of 50 to 75 μm. By setting the gap within such a range, there is no problem of pattern accuracy deterioration such as blurring of the pattern or problems such as deterioration of photocatalyst sensitivity and deterioration of efficiency of characteristic change. This is because there is an effect that unevenness of the characteristic change on the layer does not occur.
[0160]
Thus, when irradiating energy on the characteristic change layer having a relatively large area, the setting of the gap in the positioning device between the photocatalyst containing layer side substrate and the characteristic change layer in the energy irradiation device is within the range of 10 μm to 200 μm, In particular, it is preferable to set within a range of 25 μm to 75 μm. By setting the set value within such a range, it is possible to arrange the photocatalyst-containing layer side substrate and the characteristic change layer without contact with each other without causing a significant decrease in pattern accuracy and a significant deterioration in the sensitivity of the photocatalyst. Because it becomes possible.
[0161]
As described above, by disposing the photocatalyst-containing layer and the surface of the characteristic change layer at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, if the interval between the photocatalyst containing layer and the characteristic change layer is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the characteristic change rate may be slowed down. It is not preferable. In addition, it is not preferable that the active oxygen species generated are difficult to reach the characteristic change layer, and in this case, the change speed of the characteristic may be slowed, if the interval is arranged away from the above range.
[0162]
In this embodiment, such an arrangement state with a gap need only be maintained at least during energy irradiation.
[0163]
An example of a method for uniformly forming such an extremely narrow gap and arranging the photocatalyst-containing layer and the characteristic change layer is a method using a spacer. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not affected by the photocatalyst action on the surface of the characteristic change layer. It is possible to form a predetermined pattern on the characteristic change layer.
[0164]
In this embodiment, such a spacer may be formed as one member, but for simplification of the process, etc., as described in the column of the photocatalyst containing layer side substrate, It is preferable to form on the surface of the photocatalyst containing layer. In the above description of the photocatalyst-containing layer side substrate preparation step, the light shielding portion has been described. However, in this embodiment, such a spacer protects the surface so that the photocatalytic action does not reach the surface of the property change layer. Since it only needs to have an action, it may be formed of a material that does not have a function of shielding the energy to be irradiated.
[0165]
The energy irradiation (exposure) referred to in the present embodiment is a concept including irradiation of any energy ray that can change the characteristics of the surface of the characteristic change layer by the photocatalyst-containing layer, and is limited to irradiation with visible light. Is not to be done.
[0166]
Usually, the wavelength of light used for such energy irradiation is set in the range of 400 nm or less, preferably in the range of 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.
[0167]
Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0168]
In addition to the method of performing pattern irradiation through a photomask using the light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.
[0169]
Here, the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for the property change layer surface to change the property of the property change layer surface by the action of the photocatalyst in the photocatalyst containing layer.
[0170]
Further, at this time, it is preferable in that the photocatalyst-containing layer is irradiated with energy while heating, so that the sensitivity can be increased and the characteristic can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0171]
The energy irradiation direction in this embodiment may be from the photocatalyst-containing layer side substrate side or from the characteristic change layer side. Here, when the light-shielding part is formed on the photocatalyst containing layer side substrate, it is necessary to irradiate energy from the photocatalyst containing layer side substrate side, and in this case, the energy applied to the photocatalyst containing layer side substrate It must be transparent to it. In this case, when the light-shielding part is formed on the photocatalyst-containing layer and the photocatalyst-containing layer side light-shielding part is used so as to function as a spacer as described above, the energy irradiation direction is the photocatalyst-containing layer. It may be from the side substrate side or from the characteristic change layer side.
[0172]
Furthermore, the energy irradiation direction in the case where the photocatalyst-containing layer is formed in a pattern may be irradiated from any direction as long as energy is applied to a portion where the photocatalyst-containing layer and the property change layer are in contact with each other. Similarly, in the case of using the above-described spacer, irradiation may be performed from any direction as long as energy is applied to the contact portion. Here, when using a photomask, it is necessary to irradiate energy from the side where the photomask is arranged.
[0173]
When the energy irradiation as described above is completed, the photocatalyst-containing layer side substrate is separated from the arrangement position with the characteristic change layer, and a pattern forming body in which the characteristic of the characteristic change layer is changed can be obtained.
[0174]
(2) Photocatalyst-containing layer impurity removal step
Next, the photocatalyst containing layer impurity removal step in this embodiment will be described.
[0175]
The photocatalyst-containing layer impurity removal step of the present embodiment is, for example, as shown in FIG. 1, in the photocatalyst-containing layer side substrate 3 containing the base material 4 and the photocatalyst-containing layer 5 described above. This is a step of removing impurities from the photocatalyst-containing layer 5 that contribute to the change. By performing this photocatalyst-containing layer impurity removal step before the above-described pattern forming step, for example, when forming the above-mentioned photocatalyst-containing layer side substrate, impurities present on the surface of the photocatalyst-containing layer, or on the surface during use or storage It is possible to remove adhering impurities and the like, and the photocatalyst in the photocatalyst-containing layer is exposed on the surface. Thereby, it is possible to increase the sensitivity of the photocatalyst-containing layer, and it is possible to improve the sensitivity of the photocatalyst-containing layer in the pattern forming step described above, and the high-definition pattern forming body in which the characteristics of the characteristic change layer are changed. Can be manufactured.
[0176]
In the present embodiment, as a method for removing impurities from the photocatalyst-containing layer, a method of decomposing and removing the impurities on the surface of the photocatalyst-containing layer by irradiating energy or a method of cleaning the surface of the photocatalyst-containing layer with a liquid is used. Is possible. This is because the impurities are usually hydrocarbon-based coatings and the like, and can be removed by a method in which the photocatalyst-containing layer is irradiated with energy and decomposed by the action of the photocatalyst or a method of washing with a liquid. Hereinafter, each of these methods will be described.
[0177]
(Method by disassembly and removal)
First, a method for decomposing and removing impurities on the surface of the photocatalyst containing layer by irradiating the photocatalyst containing layer with energy will be described.
[0178]
According to this method, the photocatalyst-containing layer is activated by irradiating energy to the photocatalyst-containing layer, and the impurities present on the surface of the photocatalyst-containing layer after the production of the photocatalyst-containing layer described above, or impurities that adhere to the surface during use or storage Etc. are decomposed, and the photocatalyst in the photocatalyst-containing layer is exposed on the surface. Thereby, the sensitivity of the photocatalyst-containing layer can be increased, and the pattern forming step can be performed efficiently.
[0179]
Here, the energy irradiation amount at the time of energy irradiation is an irradiation amount necessary for the impurities present on the surface of the photocatalyst containing layer to be decomposed and removed by the action of the photocatalyst in the photocatalyst containing layer.
[0180]
At this time, energy may be irradiated while heating the photocatalyst-containing layer. As a result, the sensitivity of the photocatalyst can be increased, and efficient cleaning can be performed. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0181]
The type of energy to be irradiated and the like are the same as those described in the section of energy irradiation in the pattern forming process described above, and a description thereof will be omitted here.
[0182]
(Method by washing with liquid)
Next, a method for cleaning with a liquid will be described.
[0183]
According to this method, impurities remaining after manufacturing the photocatalyst containing layer and impurities adhering to the surface of the photocatalyst containing layer are washed away with a liquid to remove the impurities. In the case of washing with this liquid, the impurities may be removed by dissolving them in the liquid, or the impurities may be removed by the pressure at which the liquid flows.
[0184]
The liquid used for washing in this embodiment is not particularly limited as long as it is a liquid that can wash away the surface of the photocatalyst-containing layer, and may be an organic solvent or the like. Preferably there is. If the liquid is water, it is easy to treat the waste liquid and does not require a special device, which is preferable in terms of cost, production efficiency, and the like. The presence of water is also preferable because it can be used to increase the sensitivity of the photocatalyst.
[0185]
Specifically, it is possible to use a non-contact cleaning method in which the cleaning tool does not come in direct contact with the liquid cleaning method. Specifically, the cleaning can be performed by spin cleaning, ultrasonic cleaning, or the like. Moreover, it is preferable that the liquid used in this case is pure water among the above-mentioned.
[0186]
2. Second embodiment
Next, a second embodiment of the present invention will be described.
[0187]
In the second embodiment of the method for producing a patterned body of the present invention, the property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the base material, A method for producing a pattern forming body having a pattern forming process in which a photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less and then irradiated with energy to form a pattern composed of parts having different characteristics. Thus, the sensitivity of the photocatalytic reaction is increased by allowing oxygen to exist in the gap at a predetermined concentration.
[0188]
For example, as shown in FIG. 1, the method for producing a pattern forming body of this embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1, and a photocatalyst-containing layer side substrate 3. Among them, the photocatalyst containing layer 5 containing the photocatalyst formed on the substrate 4 is arranged so as to be opposed to each other with a predetermined interval, and the oxygen concentration in the gap is adjusted to be a predetermined concentration. , A manufacturing method having a pattern forming step of irradiating energy 7 in a pattern using a photomask 6. When the energy is irradiated, the oxygen concentration between the photocatalyst-containing layer and the characteristic change layer is within the above range, so that the effect of the photocatalyst is improved and the characteristic of the characteristic change layer can be changed in a short time. . This is because oxygen is reduced by the photocatalytic reaction, and when the amount increases, the generation of active oxygen species such as superoxide anion that decomposes organic matter is promoted. Hereinafter, these will be described.
[0189]
The energy irradiation in this embodiment is performed from a predetermined direction after the photocatalyst-containing layer and the characteristic change layer described above are arranged with a gap of 200 μm or less. During this energy irradiation, the photocatalyst-containing layer and the characteristic change layer The oxygen concentration in the gap is 20 mol% or more, preferably 50 mol% or more. By setting the oxygen concentration in the gap within the above range at the time of energy irradiation, the effect of the photocatalyst is enhanced by the oxygen in the gap, and the characteristics of the characteristic change layer can be changed more efficiently. .
[0190]
As a method for setting the oxygen concentration in the gap within the above range, energy irradiation is performed in a chamber in an atmosphere where the oxygen concentration is in the above range, and the oxygen concentration in the gap is set in the gap. The method which introduce | transduces the gas which is in the range is mentioned.
[0191]
The characteristic change layer, the photocatalyst containing layer, the gap between the photocatalyst containing layer and the characteristic change layer, the irradiation energy, the energy irradiation method, and the like in this embodiment are the same as those in the first embodiment. Description is omitted.
[0192]
3. Third embodiment
Next, a third embodiment of the present invention will be described.
[0193]
In the third embodiment of the method for producing a pattern-formed body of the present invention, the property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the substrate are described above. A method for producing a pattern forming body having a pattern forming process in which a photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less and then irradiated with energy to form a pattern composed of parts having different characteristics. Thus, the photocatalytic reaction is made highly sensitive by setting the relative humidity in the gap to a predetermined concentration.
[0194]
For example, as shown in FIG. 1, the pattern forming body manufacturing method according to the present embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1 and a photocatalyst-containing layer side substrate 3. A photocatalyst-containing layer 5 containing a photocatalyst formed on the material 4 is arranged so as to face each other at a predetermined interval, and the relative humidity in this gap is adjusted to a predetermined concentration, and a photomask 6 is a manufacturing method having a pattern forming step of irradiating energy 7 in a pattern using 6. At the time of energy irradiation, the relative humidity between the photocatalyst containing layer and the characteristic change layer is a predetermined concentration, so that the photocatalyst can be made highly sensitive and the characteristics of the characteristic change layer can be changed in a short time. It becomes. This is because water is oxidized by the photocatalytic reaction, and when the amount increases, the generation of active oxygen species such as hydroxy radicals that decompose organic substances is promoted. Hereinafter, these will be described.
[0195]
The energy irradiation of this embodiment is performed from a predetermined direction after the photocatalyst-containing layer and the characteristic change layer described above are arranged with a gap of 200 μm or less. At the time of this energy irradiation, the photocatalyst-containing layer and the characteristic change layer The relative humidity in the gap is 10% or more, preferably 70% or more. By making the relative humidity in the gap within the above range during energy irradiation, the effect of the photocatalyst is enhanced by the moisture in the gap, and the characteristics of the characteristic change layer can be changed more efficiently. .
[0196]
In the present embodiment, as long as the relative humidity is in the above range, the composition of air is not particularly limited, and the oxygen concentration may be high.
[0197]
As a method for setting the relative humidity in the gap within the above range, energy irradiation is performed in a chamber in an atmosphere in which the relative humidity is in the above range, and the relative humidity in the gap is set in the gap. The method which introduce | transduces the gas which is in the range is mentioned.
[0198]
Since the characteristic change layer, the photocatalyst containing layer, the gap between the photocatalyst containing layer and the characteristic change layer, the energy to be irradiated, the energy irradiation method, and the like in this embodiment are the same as those in the first embodiment, the description here Omitted.
[0199]
4). Fourth embodiment
Next, a fourth embodiment of the present invention will be described.
[0200]
In the fourth embodiment of the method for producing a pattern forming body of the present invention, the property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the base material are described above. A method for producing a pattern forming body having a pattern forming process in which a photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less and then irradiated with energy to form a pattern composed of parts having different characteristics. In addition, the sensitivity of the photocatalyst is increased by performing a process of adsorbing water on at least one of the characteristic change layer and the photocatalyst containing layer before the energy irradiation.
[0201]
For example, as shown in FIG. 1, the pattern forming body manufacturing method according to the present embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1 and a photocatalyst-containing layer side substrate 3. The photocatalyst containing layer 5 containing the photocatalyst formed on the material 4 is disposed so as to be opposed to each other with a predetermined interval, and a pattern forming step is performed in which energy 7 is irradiated in a pattern using a photomask 6. Although it is a manufacturing method, it is the method of performing the process which makes water adsorb | suck to the surface of at least any one of the said characteristic change layer 2 or the photocatalyst containing layer 5 before irradiation of this energy 7. FIG. Prior to the energy irradiation, by adsorbing water to at least one of the surfaces between the photocatalyst-containing layer or the property change layer, the photocatalyst can be made highly sensitive, and the property of the property change layer can be improved in a short time. It is possible to change. Hereinafter, these will be described.
[0202]
The energy irradiation of this embodiment is performed from a predetermined direction after the above-described photocatalyst-containing layer and the characteristic change layer are arranged with a gap of 200 μm or less. At the time of this energy irradiation, at least the photocatalyst-containing layer and the characteristic change layer It is performed with water adsorbed on either surface. Here, the water used in the present embodiment is preferably pure water.
[0203]
Specifically, examples of the treatment method for adsorbing water on the surface of the property change layer or the photocatalyst-containing layer include application by spraying and immersion.
[0204]
Further, the water may be water adhering to the photocatalyst containing layer as described in the first embodiment, and generally the photocatalyst containing layer or the characteristic change layer is formed before the pattern forming step. It may be water adhering at the time of washing. In this case, there is no need to introduce water to the surface again, which is preferable from the viewpoint of manufacturing efficiency and cost.
[0205]
Here, the characteristic change layer and the photocatalyst containing layer, the gap between the photocatalyst containing layer and the characteristic change layer at the time of energy irradiation, the irradiation energy, the energy irradiation method, and the like are the same as in the first embodiment. Since there is, explanation here is omitted.
[0206]
5). Fifth embodiment
Next, a fifth embodiment of the present invention will be described.
[0207]
In the fifth embodiment of the method for producing a pattern-formed body of the present invention, the property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the base material are as described above. A method for producing a pattern forming body having a pattern forming process in which a photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less and then irradiated with energy to form a pattern composed of parts having different characteristics. Therefore, the sensitivity of the photocatalytic reaction is increased by using the excimer lamp as the energy irradiation.
[0208]
For example, as shown in FIG. 1, the method for producing a pattern forming body according to this embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1, and a photocatalyst-containing layer side substrate. 3, a photocatalyst-containing layer 5 containing a photocatalyst formed on the substrate 4 is disposed so as to face each other at a predetermined interval, and a pattern is irradiated with energy 7 using a photomask 6 Although it is a manufacturing method which has a formation process, it is a method which performs irradiation of this energy 7 with an excimer lamp for high sensitivity. Hereinafter, this method will be described.
[0209]
In the energy irradiation of the present embodiment, the above-described photocatalyst-containing layer and the characteristic change layer are arranged with a gap of 200 μm or less, and then energy is irradiated from a predetermined direction by an excimer lamp. Since the excimer lamp emits light with a short wavelength of 172 nm, by performing the energy irradiation with the excimer lamp, not only the action of the photocatalyst containing layer due to the energy irradiation but also the short wavelength emitted from the excimer lamp is high. The effect that energy decomposes the organic substance in the characteristic change layer directly is also obtained, and the pattern forming body can be formed more efficiently.
[0210]
Here, in this embodiment, it is preferable that the gap between the photocatalyst-containing layer and the characteristic change layer is 0.01 μm to 50 μm. Since the light emitted from the excimer lamp has the property of being absorbed by oxygen in the air, it is possible to change the characteristics of the characteristic change layer more efficiently by performing the gap within the above range. It is.
[0211]
In addition, about the characteristic change layer and photocatalyst containing layer used for this embodiment, since it is the same as that of the said 1st embodiment, description here is abbreviate | omitted.
[0212]
6). Sixth embodiment
Next, a sixth embodiment of the present invention will be described.
[0213]
In a sixth embodiment of the method for producing a pattern forming body of the present invention, the property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the substrate are the above-mentioned A method for producing a pattern forming body having a pattern forming process in which a photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less and then irradiated with energy to form a pattern composed of parts having different characteristics. The photocatalyst-containing layer contains a metal element as the second component, and the metal element is at least one metal element selected from iron and a metal having a smaller ionization tendency than iron, thereby providing a photocatalyst. Higher sensitivity of the reaction is achieved.
[0214]
For example, as shown in FIG. 1, the pattern forming body manufacturing method according to the present embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1 and a photocatalyst-containing layer side substrate 3. The photocatalyst containing layer 5 containing the photocatalyst formed on the material 4 is disposed so as to be opposed to each other with a predetermined interval, and a pattern forming step is performed in which energy 7 is irradiated in a pattern using a photomask 6. Although it is a manufacturing method, it is a method characterized in that the photocatalyst-containing layer contains a metal element as the second component. By the action of the metal element in the photocatalyst-containing layer, the photocatalyst can be activated and enhanced in sensitivity, and the characteristics of the characteristic change layer can be improved efficiently.
[0215]
Hereinafter, the photocatalyst containing layer used in this embodiment will be described.
[0216]
The photocatalyst-containing layer used in this embodiment is a layer containing a metal element as the second component in the photocatalyst-containing layer described in the section of the photocatalyst-containing layer of the first embodiment. Here, the metal element as the second component means that the metal element is different from the metal element introduced as the photocatalyst, and the speed at which the characteristics on the characteristic change layer are changed. The metal element which has the function to improve is shown.
[0217]
The type of the metal element used in the present embodiment is not particularly limited as long as it has a function of improving the speed of changing the characteristics on the characteristic change layer as described above. Although it is not a thing, it is preferable to contain 1 or more types of metals with a smaller ionization tendency than iron and iron. Specific examples of metal elements include iron (Fe), copper (Cu), silver (Ag), gold (Au), and platinum (Pt). Among these, copper (Cu) is used from the viewpoint of manufacturing cost and efficiency. Preferably there is.
[0218]
The state of such a metal element in the photocatalyst-containing layer may exist as a metal such as a metal fine particle, or as a metal compound such as a metal chloride or a metal oxide. It is not particularly limited as long as it has a function of improving the speed of changing the wettability on the photocatalyst containing layer by the action of the photocatalyst.
[0219]
In this embodiment, the molar ratio of the metal element as the second component to the photocatalyst is within a range of 0.00001 to 0.05, particularly within a range of 0.00005 to 0.005, assuming that the photocatalyst is 1. It is preferable to be within.
[0220]
As a method for introducing the metal element into the photocatalyst-containing layer, the salt of the metal element is dissolved in a coating solution for forming the photocatalyst-containing layer, and is applied to a substrate and then dried, or on the surface of the photocatalyst-containing layer. By applying a coating solution containing the above metal ions and irradiating the photocatalyst containing layer with energy, it is possible to reduce the metal ions by the action of the photocatalyst and deposit it on the surface of the photocatalyst containing layer. is there.
[0221]
The characteristic change layer, the gap between the photocatalyst containing layer and the characteristic change layer at the time of energy irradiation, the energy to be irradiated, the energy irradiation method, and the like are the same as those in the first embodiment. Description of is omitted.
[0222]
7. Seventh embodiment
A seventh embodiment of the present invention will be described.
[0223]
In the seventh embodiment of the method for producing a pattern forming body of the present invention, the property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the base material, A method for producing a pattern forming body having a pattern forming process in which a photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less and then irradiated with energy to form a pattern composed of parts having different characteristics. Thus, the photocatalyst-containing layer is formed to have a film thickness that allows a predetermined amount of light having a wavelength of 254 nm to pass therethrough, and the energy irradiation is performed from the photocatalyst-containing layer side substrate, thereby increasing the sensitivity of the photocatalytic reaction. .
[0224]
For example, as shown in FIG. 1, the method for producing a pattern forming body according to this embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1, and a photocatalyst-containing layer side substrate. 3, a photocatalyst-containing layer 5 containing a photocatalyst formed on the substrate 4 is disposed so as to face each other at a predetermined interval, and a pattern is irradiated with energy 7 using a photomask 6 A pattern forming body in which the photocatalyst-containing layer 5 is a layer having a film thickness that transmits a predetermined amount of light having a wavelength of 254 nm, and the energy irradiation is performed from the photocatalyst-containing layer side substrate. It is a manufacturing method. This makes it possible to increase the sensitivity of the photocatalyst-containing layer and to change the characteristics of the characteristic change layer efficiently.
[0225]
Specifically, the photocatalyst-containing layer is preferably a layer having a film thickness that allows light having a wavelength of 254 nm to pass through 5% to 90%, preferably 30% to 80%.
[0226]
In the photocatalyst-containing layer, the transmittance of light on the low wavelength side (high energy side) decreases as the film thickness usually increases. Thereby, when the said photocatalyst containing layer is irradiated with energy from the said photocatalyst containing layer side board | substrate side, the energy amount which contributes to activation of the photocatalyst on the photocatalyst containing layer surface reduces. The cause of the decrease in the amount of energy is that if a large amount of photocatalyst is present in the photocatalyst containing layer, light is scattered or absorbed by the photocatalyst, and the energy reaching the surface of the photocatalyst containing layer is reduced. In addition, when the transmittance of the wavelength is larger than the above range, the amount and concentration of the photocatalyst contained in the photocatalyst containing layer is small, and even if the photocatalyst is activated by energy irradiation, the characteristics of the property changing layer are improved. This is because it is difficult to change the temperature sufficiently, which is not preferable in terms of manufacturing efficiency and cost.
[0227]
Here, since the photocatalyst that is excited by the irradiated energy and contributes to the characteristic change of the characteristic change layer is only the photocatalyst existing in the vicinity of the surface of the photocatalyst containing layer, in the present embodiment, such a low photocatalyst of 254 nm is used. By making the layer with a light transmittance of the wavelength within the above range, much of the energy of light on the low wavelength side reaches the surface of the photocatalyst containing layer, the photocatalyst is activated, and the pattern is formed efficiently The body can be manufactured.
[0228]
The light transmittance is a value measured by an ultraviolet-visible spectrophotometer UV3100PC Shimadzu Corporation.
[0229]
The characteristic change layer, the gap between the photocatalyst containing layer and the characteristic change layer at the time of energy irradiation, the energy to be irradiated, the energy irradiation method, etc. in the manufacturing method of the pattern formed body of this embodiment are the same as in the first embodiment. Since there is, explanation here is omitted.
[0230]
8). Eighth embodiment
Next, an eighth embodiment of the present invention will be described.
[0231]
In an eighth embodiment of the method for producing a pattern forming body of the present invention, the property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst-containing layer containing the photocatalyst, and the photocatalyst-containing layer side substrate having the base material, A method for producing a pattern forming body having a pattern forming process in which a photocatalyst-containing layer and the characteristic change layer are arranged with a gap so as to be 200 μm or less and then irradiated with energy to form a pattern composed of parts having different characteristics. Therefore, by making the photocatalyst responsive to visible light, the sensitivity of the photocatalytic reaction is increased.
[0232]
For example, as shown in FIG. 1, the method for producing a pattern forming body of this embodiment includes a characteristic changing layer 2 whose characteristics are changed by the action of a photocatalyst formed on the substrate 1, and a photocatalyst-containing layer side substrate 3. The photocatalyst containing layer 5 containing the photocatalyst formed on the substrate 4 is disposed so as to face the photocatalyst 6 at a predetermined interval, and the pattern 7 is irradiated with energy 7 in a pattern using the photomask 6. Although it is a manufacturing method which has a process, it is a manufacturing method of the pattern formation body by which the photocatalyst contained in the said photocatalyst content layer 5 made visible light response.
[0233]
The visible light response in the present embodiment means that a photocatalyst that is not normally excited by visible light energy is also excited by visible light energy.
[0234]
In this embodiment, since the photocatalyst is made to be visible light responsive, the photocatalyst can be excited by the energy in the visible light region of the irradiated energy. It is possible to change the characteristics.
[0235]
As a photocatalyst used in this embodiment, for example, titanium dioxide (TiO 2) known as an optical semiconductor.₂), 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.
[0236]
Examples of the method of making the photocatalyst responsive to visible light include doping of metal ions into the photocatalyst and nitriding treatment of the photocatalyst. In the present invention, titanium oxide (TiO₂) Is preferably nitrided.
[0237]
Titanium oxide (TiO₂) By nitriding, titanium oxide (TiO 2)₂), A new energy level is formed inside the band gap, and the band gap becomes narrower. As a result, normal titanium oxide (TiO₂) Is 380 nm, but it can be excited even by visible light having a longer wavelength than the excitation wavelength. As a result, the wavelength in the visible light region of energy irradiation by various light sources is also changed to titanium oxide (TiO 2).₂), It is possible to increase the sensitivity of the photocatalyst-containing layer side substrate, and it is possible to efficiently produce a pattern forming body.
[0238]
Here, the nitriding treatment of titanium oxide referred to in this embodiment is titanium oxide (TiO 2).₂) Treatment of replacing part of the oxygen sites of the crystal with nitrogen atoms, and titanium oxide (TiO₂) Treatment of doping nitrogen atoms between crystal lattices, or titanium oxide (TiO₂) A treatment of arranging nitrogen atoms at the grain boundaries of a polycrystalline aggregate of crystals.
[0239]
Here, titanium oxide (TiO₂) Is not particularly limited. For example, crystalline titanium oxide fine particles are doped with nitrogen by a heat treatment at 700 ° C. in an ammonia atmosphere, and the nitrogen-doped fine particles and an inorganic binder are added. Or a solvent to obtain a dispersion. For example, a method of applying this dispersion on a substrate, drying it, and stabilizing it by heat treatment at 150 ° C. can be mentioned.
[0240]
The characteristic change layer, the gap between the photocatalyst containing layer and the characteristic change layer at the time of energy irradiation, the energy to be irradiated, the energy irradiation method, etc. in the manufacturing method of the pattern formed body of this embodiment are the same as in the first embodiment. Since there is, explanation here is omitted.
[0241]
9. Other
In the present invention, each of the embodiments from the first embodiment to the eighth embodiment may be performed individually at the time of pattern formation, but the above embodiments may be performed in two or more. You may manufacture a pattern formation body combining an aspect.
[0242]
B. Photocatalyst-containing layer side substrate for pattern formation production
The photocatalyst-containing layer side substrate for producing a patterned body of the present invention has three embodiments depending on the type of sensitivity enhancement. Hereinafter, each aspect will be described.
[0243]
(1) First embodiment
1st embodiment of the photocatalyst containing layer side board | substrate for pattern formation object manufacture of this invention is a pattern formation object manufacture which has a base material and the photocatalyst content layer containing the photocatalyst and metal element which were formed on the said base material. In the photocatalyst-containing layer side substrate, specifically, the photocatalyst-containing layer is made highly sensitive by containing at least one kind of metal having a lower ionization tendency than iron and iron as the metal element.
[0244]
Such a photocatalyst containing layer side substrate for producing a pattern forming body according to the present embodiment contains the above metal element in the photocatalyst containing layer, so that the photocatalytic activity is high when producing the pattern forming body. It is possible to increase the sensitivity of the photocatalyst-containing layer, and it is possible to efficiently produce a pattern-formed body. Specifically, it is preferable to contain at least one metal having a smaller ionization tendency than iron and iron as the metal element. Specific examples of metal elements include iron (Fe), copper (Cu), silver (Ag), gold (Au), and platinum (Pt). Among these, copper (Cu) is used from the viewpoint of manufacturing cost and efficiency. Preferably there is.
[0245]
Since the base material and the photocatalyst of the photocatalyst containing layer side substrate for producing a pattern forming body in this embodiment are the same as those described in the section of the photocatalyst containing layer side substrate in the first embodiment of the pattern forming body producing method, Explanation here is omitted.
[0246]
Further, the method for producing the photocatalyst-containing layer side substrate for producing the pattern forming body of the present embodiment is the same as the method described in the first embodiment and the sixth embodiment of the pattern forming body manufacturing method, so here Description of is omitted.
[0247]
Furthermore, the photocatalyst-containing layer side substrate for producing a patterned product of this embodiment can be used not only in the sixth embodiment of the method for producing a patterned product described above, but also in all other embodiments. is there.
[0248]
(2) Second embodiment
The second embodiment of the photocatalyst-containing layer side substrate for producing a pattern-forming body of the present invention is a photocatalyst-containing layer for producing a pattern-forming body having a base material and a photocatalyst-containing layer containing a photocatalyst formed on the base material. The photocatalyst-containing layer is a side substrate, and the photocatalyst-containing layer has a film thickness that allows light having a wavelength of 254 nm to pass through 5% to 90%, preferably 30% to 80%, thereby increasing the sensitivity of the photocatalyst-containing layer. It is.
[0249]
Such a photocatalyst-containing layer side substrate for producing a pattern forming body of this embodiment has a film thickness that allows the photocatalyst-containing layer to transmit light having the above wavelength within the above range, so that light energy on the low wavelength side is also reduced. This makes it possible to contribute to the activation of the photocatalyst on the surface of the photocatalyst-containing layer, to increase the sensitivity of the photocatalyst-containing layer, and to efficiently produce a pattern forming body.
[0250]
Here, the light transmittance is a value measured by the method described in the method for manufacturing the pattern forming body.
[0251]
Moreover, the base material and photocatalyst of the photocatalyst containing layer side substrate for pattern forming body production in this embodiment are those described in the section of the photocatalyst containing layer side substrate in the first embodiment of the method for producing a pattern forming body of the present invention. The description here is omitted.
[0252]
Furthermore, since the manufacturing method of the photocatalyst containing layer side substrate for pattern forming body manufacture of this embodiment is the same as that described in the first embodiment of the pattern forming body manufacturing method, description thereof is omitted here. .
[0253]
Furthermore, the photocatalyst-containing layer side substrate for producing a patterned product of this embodiment can be used not only in the seventh embodiment of the method for producing a patterned product described above, but also in all other embodiments. It is.
[0254]
(3) Third embodiment
Next, a third embodiment of the present invention will be described. The third embodiment of the photocatalyst-containing layer side substrate for producing a pattern-forming body of the present invention is a photocatalyst-containing layer for producing a pattern-forming body having a base material and a photocatalyst-containing layer containing a photocatalyst formed on the base material. It is a side substrate, wherein the photocatalyst is made visible light responsive.
[0255]
Since the photocatalyst-containing layer side substrate for producing a pattern forming body according to this embodiment has a photocatalyst that has been made to respond to visible light, the photocatalyst is excited by visible light on the high wavelength side of the irradiated energy. is there. As a result, the amount of the photocatalyst to be excited increases, so that the photocatalyst can be made highly sensitive and a pattern forming body can be produced efficiently in a short time.
[0256]
Specific methods of making these photocatalysts visible light responsive include metal ion doping in the photocatalyst-containing layer, photocatalytic nitriding treatment, etc. Titanium oxide (TiO₂) Nitriding treatment.
[0257]
Titanium oxide (TiO₂) Is a titanium oxide (TiO2) by nitriding.₂) A new energy level is formed inside the band gap,
Narrow. As a result, normal titanium oxide (TiO₂) Is 380 nm, but it can be excited even by visible light having a longer wavelength than the excitation wavelength.
[0258]
As a result, the wavelength in the visible light region of energy irradiation by various light sources can also contribute to excitation, so the photocatalyst-containing layer side substrate can be made highly sensitive, and a pattern formed body can be produced efficiently. It becomes possible to do.
[0259]
In addition, since the manufacturing method of an inorganic binder, a solvent, a base material, a photocatalyst containing layer, etc. are the same as what was demonstrated by the 1st embodiment and 8th embodiment of "A. manufacturing method of a pattern formation body" mentioned above. Explanation here is omitted.
[0260]
Moreover, the photocatalyst-containing layer side substrate for producing a pattern forming body according to this embodiment can be used not only in the eighth embodiment of the method for producing a pattern forming body described above but also in all other embodiments. is there.
[0261]
In addition, this embodiment is not limited to the said embodiment. The above embodiment is an exemplification, and any structure that has substantially the same configuration as the technical idea described in the claims of the present embodiment and has the same effect can be used. It is included in the technical scope of this embodiment.
[0262]
【Example】
The present embodiment will be described more specifically with reference to the following examples and comparative examples.
[0263]
[Example 1] (First embodiment)
1. Formation of photocatalyst containing layer side substrate
Tetramethoxysilane (GE Toshiba Silicones Co., Ltd. TSL8114) 5g and 0.05N hydrochloric acid 2.5g were mixed and stirred for 24 hours. Next, 0.1 g of this solution and 50 g of a photocatalytic inorganic coating agent (ST-K03 manufactured by Ishihara Sangyo Co., Ltd.) were mixed and stirred at room temperature for 1 hour. This was diluted 2 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer. This photocatalyst-containing layer composition was applied onto a photomask substrate on which a 100 μm line and space pattern was formed, using a spin coater, and then subjected to a drying treatment at 150 ° C. for 10 minutes to obtain a thickness of 0. A 15 μm photocatalyst-containing layer was formed. At this time, the transmittance of the photocatalyst-containing layer was 30% at 254 nm.
[0264]
2. Formation of wettability changing layer
0.4 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd. TSL8233), 5 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd. TSL8114) and 2.5 g of 0.05 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 100 times with isopropyl alcohol to obtain a wettability changing layer composition. Next, the wettability changing layer composition is applied onto a transparent substrate by a spin coater, and then dried at 150 ° C. for 10 minutes to form a wettability changing layer (thickness 0.1 μm). did.
[0265]
3. Photocatalyst layer impurity removal process
An ultrahigh pressure mercury lamp (wavelength 365 nm 40 mW / cm) from the photocatalyst containing layer side to the photocatalyst containing layer side substrate.²) For 60 minutes to remove impurities on the surface.
[0266]
4). Pattern formation process
The photocatalyst-containing layer side substrate and the wettability changing layer are arranged with a gap of 50 μm, and an ultrahigh pressure mercury lamp (wavelength 254 nm, 10 mW / cm from the photomask side).²) Exposed. At this time, it took 30 seconds to form a lyophilic region having a contact angle of water of 10 ° or less with a 100 μm line and space on the wettability changing layer.
[0267]
[Comparative Example 1]
When pattern formation was carried out in the same manner as in Example 1 without performing the photocatalyst layer impurity removal step, it took 240 seconds for the lyophilic region to be 10 ° or less in water contact angle.
[0268]
[Example 2] (Second embodiment)
1. Formation of photocatalyst containing layer side substrate
Tetramethoxysilane (GE Toshiba Silicones Co., Ltd. TSL8114) 5g and 0.05N hydrochloric acid 2.5g were mixed and stirred for 24 hours. Next, 0.1 g of this solution and 50 g of a photocatalytic inorganic coating agent (ST-K03 manufactured by Ishihara Sangyo Co., Ltd.) were mixed and stirred at room temperature for 1 hour. This was diluted 2 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer. This photocatalyst-containing layer composition was applied to a photomask substrate on which a line and space pattern was formed at 100 μm by a spin coater, and then dried at 150 ° C. for 10 minutes to obtain a thickness of 0. A 15 μm photocatalyst-containing layer was formed.
[0269]
2. Formation of wettability changing layer
0.4 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd. TSL8233), 5 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd. TSL8114) and 2.5 g of 0.05 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 100 times with isopropyl alcohol to obtain a wettability changing layer composition. Next, the wettability changing layer composition is applied onto a transparent substrate by a spin coater, and then dried at 150 ° C. for 10 minutes to form a wettability changing layer (thickness 0.1 μm). did.
[0270]
3. Photocatalyst layer impurity removal process
An ultrahigh pressure mercury lamp (wavelength 365 nm 40 mW / cm) from the photocatalyst containing layer side to the photocatalyst containing layer side substrate.²) For 60 minutes to remove impurities on the surface.
[0271]
4). Pattern formation process
The photocatalyst-containing layer side substrate and the wettability changing layer were placed in a glass chamber with a gap of 50 μm, replaced with 93% oxygen gas, and then an ultrahigh pressure mercury lamp (wavelength 254 nm) from the photomask side. 10 mW / cm²) Exposed.
[0272]
At this time, it took 25 seconds to form a lyophilic region having a water contact angle of 10 ° or less on a wettability changing layer with a line and space of 100 μm.
[0273]
[Example 3] (Second embodiment)
Except that the inside of the chamber was replaced with 20% oxygen gas (nitrogen gas about 80%), pattern formation was performed in the same manner as in Example 2 described above. As a result, the lyophilic region was 10 ° or less in water contact angle. It took 40 seconds.
[0274]
[Comparative Example 2]
Except that the inside of the chamber was replaced with 10% oxygen gas (about 90% nitrogen gas), pattern formation was performed in the same manner as in Example 2 described above. As a result, the lyophilic region was 10 ° or less in water contact angle. It took 180 seconds.
[0275]
[Example 4] (Third embodiment)
1. Formation of photocatalyst containing layer side substrate
Tetramethoxysilane (GE Toshiba Silicones Co., Ltd. TSL8114) 5g and 0.05N hydrochloric acid 2.5g were mixed and stirred for 24 hours. Next, 0.1 g of this solution and 50 g of a photocatalytic inorganic coating agent (ST-K03 manufactured by Ishihara Sangyo Co., Ltd.) were mixed and stirred at room temperature for 1 hour. This was diluted 2 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer. This photocatalyst-containing layer composition was applied to a photomask substrate on which a line and space pattern was formed at 100 μm by a spin coater, and then dried at 150 ° C. for 10 minutes to obtain a thickness of 0. A 15 μm photocatalyst-containing layer was formed.
[0276]
2. Formation of wettability changing layer
0.4 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd. TSL8233), 5 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd. TSL8114) and 2.5 g of 0.05 N hydrochloric acid were mixed and stirred for 8 hours. Next, this was diluted 100 times with isopropyl alcohol to obtain a wettability changing layer composition. The wettability changing layer composition was applied onto a transparent substrate by a spin coater, and then dried at 150 ° C. for 10 minutes to form a wettability changing layer (thickness 0.1 μm).
[0277]
3. Photocatalyst layer impurity removal process
An ultrahigh pressure mercury lamp (wavelength 365 nm 40 mW / cm) from the photocatalyst containing layer side to the photocatalyst containing layer side substrate.²) For 60 minutes to remove impurities on the surface.
[0278]
4). Pattern formation process
In a 70% humidity environment, the photocatalyst-containing layer side substrate and the wettability changing layer are arranged with a gap of 50 μm, and an ultrahigh pressure mercury lamp (wavelength 254 nm, 10 mW / cm from the photomask side).²) Exposed. At this time, it took 20 seconds to form a lyophilic region having a contact angle of water of 10 ° or less with a 100 μm line and space on the wettability changing layer.
[0279]
[Example 5] (Third embodiment)
When pattern formation was performed in the same manner as in Example 4 except that the environment was set to a humidity of 10%, it took 45 seconds for the lyophilic region to be 10 ° or less at the water contact angle.
[0280]
[Comparative Example 3]
When pattern formation was performed in the same manner as in Example 4 except that the environment was set to a humidity of 5%, it took 120 seconds for the lyophilic region to be 10 ° or less in water contact angle.
[0281]
[Example 6] (Fourth embodiment)
When the photocatalyst-containing layer side substrate subjected to the photocatalyst layer impurity removal step was immersed in pure water for 5 minutes and pulled up, and then the surface was dried by air blow, the pattern was formed in the same manner as in Example 1, It took 15 seconds for the lyophilic region to be 10 ° or less in water contact angle.
[0282]
[Example 7] (Fifth embodiment)
In the pattern formation process, an excimer lamp (172 nm, 10 mW / cm²) Was used in the same manner as in Example 1 except that. At this time, it took 10 seconds to form a lyophilic region having a contact angle of water of 10 ° or less with a 100 μm line and space on the wettability changing layer.
[0283]
[Example 8] (Sixth embodiment)
1. Formation of photocatalyst containing layer side substrate
Tetramethoxysilane (GE Toshiba Silicones Co., Ltd. TSL8114) 5g and 0.05N hydrochloric acid 2.5g were mixed and stirred for 24 hours. Next, 0.1 g of this solution and 50 g of a photocatalytic inorganic coating agent (ST-K03 manufactured by Ishihara Sangyo Co., Ltd.) were mixed and stirred at room temperature for 1 hour. To this, various metal compounds shown in Table 1 were added in a molar ratio of 0.0005 to titanium oxide 1. This was diluted 2 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer. This photocatalyst-containing layer composition was applied to a photomask substrate on which a line and space pattern was formed at 100 μm by a spin coater, and then dried at 150 ° C. for 10 minutes to obtain a thickness of 0. A 15 μm photocatalyst-containing layer was formed.
[0284]
2. Formation of wettability changing layer
0.4 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd. TSL8233), 5 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd. TSL8114) and 2.5 g of 0.05 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 100 times with isopropyl alcohol to obtain a wettability changing layer composition. Next, this wettability changing layer composition is applied on a transparent substrate by a spin coater, and then dried at 150 ° C. for 10 minutes to form a wettability changing layer (thickness 0.1 μm). did.
[0285]
3. Photocatalyst layer impurity removal process
An ultrahigh pressure mercury lamp (wavelength 365 nm 40 mW / cm) from the photocatalyst containing layer side to the photocatalyst containing layer side substrate.²) For 60 minutes to remove impurities on the surface.
[0286]
4). Pattern formation process
The photocatalyst-containing layer side substrate and the wettability changing layer are arranged with a gap of 50 μm, and an ultrahigh pressure mercury lamp (wavelength 254 nm, 10 mW / cm from the photomask side).²) Exposed. Table 1 shows the time taken to form a lyophilic region having a water contact angle of 10 ° or less on a wettability changing layer with a line and space of 100 μm.
[0287]
[Table 1]

[0288]
[Example 9] (Seventh embodiment)
Except that the film thickness was reduced so that the transmittance of 254 nm of the photocatalyst layer was 80%, pattern formation was performed in the same manner as in Example 1, and the contact angle of water with a 100 μm line and space on the wettability changing layer Took 20 seconds to form a lyophilic region of 10 ° or less.
[0289]
[Comparative Example 4]
A pattern was formed in the same manner as in Example 1 except that the film thickness was set so that the transmittance at 254 nm of the photocatalyst layer was 3% and 95%. As a result, a 100 μm line and space were formed on the wettability changing layer. It took 80 seconds and 60 seconds to form a lyophilic region having a water contact angle of 10 ° or less, respectively.
[0290]
[Example 10] (Eighth embodiment)
1. Formation of photocatalyst containing layer side substrate
Titanium oxide powder (ST-01 manufactured by Ishihara Sangyo Co., Ltd.) was heat-treated in an ammonia atmosphere at 700 ° C. to produce titanium oxide powder containing nitrogen. Next, 5 g of tetramethoxysilane (GE Toshiba Silicones Co., Ltd. TSL8114) and 2.5 g of 0.05 N hydrochloric acid were mixed and stirred for 24 hours. This solution, isopropyl alcohol, and the titanium oxide powder were mixed to obtain a composition for a photocatalyst-containing layer. This photocatalyst-containing layer composition was applied to a photomask substrate on which a line and space pattern was formed at 100 μm by a spin coater, and then dried at 150 ° C. for 10 minutes to obtain a thickness of 0. A 25 μm photocatalyst-containing layer was formed.
[0291]
2. Formation of wettability changing layer
0.4 g of fluoroalkylsilane (GE Toshiba Silicone Co., Ltd. TSL8233), 5 g of tetramethoxysilane (GE Toshiba Silicone Co., Ltd. TSL8114) and 2.5 g of 0.05 N hydrochloric acid were mixed and stirred for 8 hours. This was diluted 100 times with isopropyl alcohol to obtain a wettability changing layer composition. Next, the wettability changing layer composition is applied on a transparent substrate with a spin coater, and then dried at 150 ° C. for 10 minutes to form a wettability changing layer (thickness 0.1 μm). did.
[0292]
3. Photocatalyst layer impurity removal process
An ultrahigh pressure mercury lamp (wavelength 365 nm 40 mW / cm) from the photocatalyst containing layer side to the photocatalyst containing layer side substrate.²) For 60 minutes to remove impurities on the surface.
[0293]
4). Pattern formation process
The photocatalyst-containing layer side substrate and the wettability changing layer are arranged with a gap of 50 μm, and an ultrahigh pressure mercury lamp (wavelength 254 nm, 10 mW / cm from the photomask side).²) Exposed.
[0294]
At this time, it took 60 seconds to form a lyophilic region having a water contact angle of 10 ° or less with a 100 μm line and space on the wettability changing layer.
[0295]
[Comparative Example 5]
A pattern was formed in the same manner as in Example 9 except that titanium oxide powder not subjected to nitrogenation treatment was used. It took 90 seconds to form.
[0296]
【The invention's effect】
According to the present invention, before the pattern formation step, the photocatalyst-containing layer impurity removal step is performed to remove, for example, impurities present on the surface of the photocatalyst-containing layer when the photocatalyst-containing layer side substrate is manufactured. As a result, the photocatalyst-containing layer is exposed, and a target pattern can be formed with high definition. In addition, since the sensitivity of the photocatalyst-containing layer is improved, it is possible to change the characteristics of the property-changing layer by short-time energy irradiation, and it is possible to efficiently produce a pattern forming body, which is advantageous in terms of manufacturing cost. The body can be made.
[Brief description of the drawings]
FIG. 1 shows an example of a pattern forming process of the present invention.
FIG. 2 is a cross-sectional view showing an example of the photocatalyst-containing layer side substrate of the present invention.
FIG. 3 is a cross-sectional view showing another example of the photocatalyst-containing layer side substrate of the present invention.
FIG. 4 is a cross-sectional view showing another example of the photocatalyst-containing layer side substrate of the present invention.
FIG. 5 is a cross-sectional view showing another example of the photocatalyst-containing layer side substrate of the present invention.
FIG. 6 is a cross-sectional view showing another example of the photocatalyst containing layer side substrate of the present invention.
[Explanation of symbols]
1 ... Board
2. Characteristics change layer
3 ... Photocatalyst containing layer side substrate
4 ... Base material
5 ... Photocatalyst containing layer
6 ... Photomask
7 ... Energy
8 ... Shading part
9 ... Primer layer

Claims (22)

The property changing layer whose properties are changed by the action of the photocatalyst, the photocatalyst containing layer containing the photocatalyst, and the photocatalyst containing layer side substrate having the base material are in close contact with each other, or the photocatalyst containing layer and the property changing layer are 200 μm or less A method for producing a pattern forming body having a pattern forming step of forming a pattern having portions having different characteristics by irradiating energy after being arranged with a gap therebetween, wherein the photocatalyst is formed before the pattern forming step. A photocatalyst-containing layer impurity removing step for decomposing or removing impurities on the surface of the containing layer, and a light-shielding portion is formed on the photocatalyst-containing layer side substrate; A method for producing a pattern forming body, wherein energy is irradiated from the substrate side. The method for producing a pattern forming body according to claim 1, wherein the photocatalyst-containing layer side substrate has a primer layer between the photocatalyst-containing layer and the light shielding part. The photocatalyst-containing layer an impurity removal step, by irradiating energy to the photocatalyst-containing layer, as claimed in claim 1 or claim 2, characterized in that a step of decomposing and removing impurities of the photocatalyst-containing layer surface A manufacturing method of a pattern formation object. Method for manufacturing a patterned member according to claim 1 or claim 2, wherein the photocatalyst-containing layer an impurity removal step, the impurities of the photocatalyst-containing layer surface is a step of washing with a liquid. The method for producing a pattern forming body according to any one of claims 1 to 4 , wherein the characteristic change layer is formed on a substrate. The pattern forming body according to any one of claims 1 to 5, wherein the photocatalyst-containing layer is a layer formed by depositing a photocatalyst on a substrate by a vacuum film-forming method. Manufacturing method. The said photocatalyst containing layer is a layer which has a photocatalyst and a binder, The manufacturing method of the pattern formation body in any one of Claim 1-5 characterized by the above-mentioned. The photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxide. iron (Fe 2 _{O 3)} 1 type or method of manufacturing a patterned member according to any one of claims of claims 1 to 7, characterized in that the two or more substances selected from. The method for producing a pattern forming body according to claim 8, wherein the photocatalyst is titanium oxide (TiO ₂ ). The method for producing a pattern forming body according to any one of claims 1 to 9 , wherein the energy irradiation is performed while heating the photocatalyst-containing layer. When the surface of the property change layer is irradiated with energy with the photocatalyst-containing layer in a gap, the distance between the photocatalyst-containing layer and the property change layer surface should be within a range of 0.2 μm to 10 μm. method for manufacturing a patterned member according to any one of claims of claims 1 to 10, characterized in. The method for producing a pattern forming body according to any one of claims 1 to 11 , wherein the characteristic change layer is a layer not containing a photocatalyst. The characteristic change layer is a wettability change layer in which wettability is changed by an action of a photocatalyst in the photocatalyst-containing layer so that a contact angle with a liquid decreases when irradiated with energy. method for manufacturing a patterned member according to any of claims from claim 1 to claim 12. The contact angle with a liquid having a surface tension of 40 mN / m on the wettability changing layer is 10 ° or more in a portion not irradiated with energy and 9 ° or less in a portion irradiated with energy. Item 14. A method for producing a pattern formed body according to Item 13 . The method for producing a pattern forming body according to claim 13 or 14 , wherein the wettability changing layer is a layer containing an organopolysiloxane. The method for producing a pattern forming body according to claim 15 , wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The organopolysiloxane is Y _n SiX _(4-n) (where Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, and X represents an alkoxyl group or a halogen. 16. n is an integer from 0 to 3.) It is an organopolysiloxane which is one or two or more hydrolytic condensates or cohydrolytic condensates of a silicon compound represented by formula ( 15 ). Or the manufacturing method of the pattern formation body of Claim 16 . The method for producing a pattern forming body according to any one of claims 13 to 17, wherein the wettability changing layer has a self-supporting property. The claim according to any one of claims 1 to 18 , wherein the characteristic change layer is a decomposition removal layer that is decomposed and removed when irradiated with energy by the action of a photocatalyst in the photocatalyst-containing layer. The manufacturing method of the pattern formation body of description. 20. The pattern forming body according to claim 19 , wherein the contact angle of the liquid with respect to the decomposition removal layer is different from the contact angle of the liquid with respect to the substrate exposed when the decomposition removal layer is decomposed and removed. Production method. 21. The pattern forming body manufacturing method according to claim 19 or 20 , wherein the decomposition removal layer is any of a self-assembled monomolecular film, a Langmuir-Blodgett film, and an alternating adsorption film. Wettability on the substrate, the surface tension 40 mN / m or less of 9 ° as the contact angle with a liquid, and claim 21 claim 19, wherein the at 10 ° or more in the decomposition removal layer The manufacturing method of the pattern formation body in any one of the preceding claims.

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