JP2004018913A

JP2004018913A - Liquid for forming transparent conductive film and method for manufacturing substrate coated with transparent conductive film using the same

Info

Publication number: JP2004018913A
Application number: JP2002173692A
Authority: JP
Inventors: Yasuhiro Seta; 瀬田　康弘; Hideaki Gondaira; 権平　英昭; Shigeo Yamada; 山田　茂男; Hiroyuki Kanda; 神田　広行
Original assignee: Nippon Soda Co Ltd
Current assignee: Nippon Soda Co Ltd
Priority date: 2002-06-14
Filing date: 2002-06-14
Publication date: 2004-01-22

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid for forming a transparent conductive film which forms the transparent conductive film showing an extremely uniform sheet-resistance and transparency, and a method for manufacturing a substrate coated with the transparent conductive film. <P>SOLUTION: The liquid contains an indium compound of the formula: In(R<SP>1</SP>COCHCOR<SP>2</SP>)<SB>3</SB>(wherein R<SP>1</SP>and R<SP>2</SP>are each independently a 1-10C alkyl group or a phenyl group) and a tin compound of the formula: (R<SP>3</SP>)<SB>2</SB>Sn(OR<SP>4</SP>)<SB>2</SB>(wherein R<SP>3</SP>is a 1-10C alkyl group; and R<SP>4</SP>is a 1-10C alkyl group or a 1-10C acyl group). The liquid is used in the method for manufacturing the substrate. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は、透明導電膜形成液、及び前記透明導電膜形成液を用いた透明導電膜付基体の製造方法に関する。
【０００２】
【従来の技術】
透明導電膜（ＩＴＯ膜）は、その優れた透明性と導電性を利用して、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、面発熱体、タッチパネル電極、太陽電池等に広く利用されている。
透明導電膜は、このように広い分野で利用されるものであるため、使用目的によって種々のシート抵抗値及び透明度を有するものが要求される。例えば、フラットパネルディスプレイ用の透明導電膜の場合、低抵抗かつ高透過率の膜であることが要求され、タッチパネル用の透明導電膜では、高抵抗かつ高透過率の膜であることが要求される。特に、近年開発されて市場の伸びが期待されているペン入力タッチパネル用の透明導電膜は、高い位置認識精度が要求されることから、シート抵抗値が２００〜３０００Ω／□といった高抵抗の膜であることが求められている。ここで、シート抵抗値は比抵抗／導電膜の膜厚で求められる値である。
【０００３】
上記のような所望のシート抵抗値を有する透明導電膜を形成する方法としては、例えば、特開２００１−３５２７３号公報及び特開２００２−１３３９５６号公報に、スパッタ法、電子ビーム法、イオンプレーティング法又は化学的気相成長法により透明導電膜を形成した後、透明導電膜を所定の濃度の有機溶剤の存在下に加熱処理する方法が記載されている。かかる公報においては、透明導電膜を形成するための原材料について、インジウム化合物としてインジウムトリスアセチルアセトナート、インジウムトリスベンゾイルメタネート、三塩化インジウム、硝酸インジウム、インジウムトリイソプロポキシド等が例示されており、スズ化合物として塩化第２スズ、ジメチルスズジクロライド、ジブチルスズジクロライド、テトラブチルスズ、スタニアスオクトエート、ジブチルスズマレエート、ジブチルスズアセテート、ジブチルスズビスアセチルアセトナート等が例示されている。
【０００４】
しかしながら、上記公報においては、所望の抵抗値を有する透明導電膜を得るための方法が記載されているのであって、インジウム化合物とスズ化合物についての好ましい組み合わせの検討や、その特定の組み合わせとの関係における透明導電膜のシート抵抗値及び透明性の均一性について検討されていない。本発明者らは、将来的な透明導電膜、特にＩＴＯ膜の用途の広がり等を考慮して、シート抵抗値及び透明性の均一性の更なる向上について検討した。
【０００５】
【発明が解決しようとする課題】
本発明は、かかる実状に鑑みてなされたものであり、本発明の課題は、シート抵抗値及び透明性において極めて均一な透明導電膜を形成することのできる透明導電膜形成液、及びシート抵抗値及び透明性において極めて均一な透明導電膜を有する透明導電膜付基体の製造方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、より均一な膜質の透明導電膜を形成すべく鋭意研究を重ねた結果、透明導電膜を形成するための透明導電膜形成液に含まれるインジウム化合物として後記式〔１〕で表されるインジウム化合物を用い、スズ化合物として後記式〔２〕で表されるスズ化合物を用いることにより、より均一な膜質の透明導電膜を形成することができることを見い出し、本発明を完成するに至った。
【０００７】
すなわち本発明は、式〔１〕
Ｉｎ（Ｒ^１ＣＯＣＨＣＯＲ^２）_３　〔１〕
（式中、Ｒ^１及びＲ^２は、それぞれ独立して炭素数１〜１０のアルキル基又はフェニル基を表す。）で表されるインジウム化合物と、式〔２〕
（Ｒ^３）_２Ｓｎ（ＯＲ^４）_２　〔２〕
（式中、Ｒ^３は炭素数１〜１０のアルキル基を表し、Ｒ^４は炭素数１〜１０のアルキル基又は炭素数１〜１０のアシル基を表す。）で表されるスズ化合物とを含有することを特徴とする透明導電膜形成液（請求項１）や、式〔１〕で表されるインジウム化合物が、インジウムトリスアセチルアセトナートであることを特徴とする請求項１に記載の透明導電膜形成液（請求項２）や、式〔２〕で表されるスズ化合物が、ジ−ｎ−ブチルスズジアセテートであることを特徴とする請求項１又は２に記載の透明導電膜形成液（請求項３）や、式〔１〕で表されるインジウム化合物中のＩｎが、質量で、式〔２〕で表されるスズ化合物中のＳｎより多く含有されていることを特徴とする請求項１〜３のいずれかに記載の透明導電膜形成液（請求項４）や、式〔２〕で表されるスズ化合物中のＳｎが、質量比で、式〔１〕で表されるインジウム化合物中のＩｎ１に対して０．００１〜０．５含有されていることを特徴とする請求項４に記載の透明導電膜形成液（請求項５）に関する。
【０００８】
また本発明は、基体上に、直接又は中間膜を介して透明導電膜を形成して透明導電膜付基体を製造する方法であって、前記基体又は中間膜上に、式〔１〕で表されるインジウム化合物と、式〔２〕で表されるスズ化合物とを含有する透明導電膜形成液を用いて化学的熱分解法により透明導電膜を形成することを特徴とする透明導電膜付基体の製造方法（請求項６）や、式〔２〕で表されるスズ化合物中のＳｎが、質量比で、式〔１〕で表されるインジウム化合物中のＩｎ１に対して０．００１〜０．５含有されていることを特徴とする請求項６に記載の透明導電膜付基体の製造方法（請求項７）や、化学的熱分解法が、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に堆積させる方法であることを特徴とする請求項６又は７に記載の透明導電膜付基体の製造方法（請求項８）や、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に堆積させる方法が、パイロゾルプロセス法であることを特徴とする請求項８に記載の透明導電膜付基体の製造方法（請求項９）や、基体が、ガラス基板であることを特徴とする請求項６〜９のいずれかに記載の透明導電膜付基体の製造方法（請求項１０）に関する。
【０００９】
【発明の実施の形態】
本発明の透明導電膜形成液は、式〔１〕
Ｉｎ（Ｒ^１ＣＯＣＨＣＯＲ^２）_３　〔１〕
で表されるインジウム化合物と、式〔２〕
（Ｒ^３）_２Ｓｎ（ＯＲ^４）_２　〔２〕
で表されるスズ化合物とを含有することを特徴とする。
式〔１〕中、Ｒ^１及びＲ^２は、それぞれ独立して炭素数１〜１０のアルキル基又はフェニル基を表し、具体的には、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ターシャリブチル基等が挙げられる。これらの中でも、式〔１〕で表されるインジウム化合物としては、インジウムトリスアセチルアセトナート（Ｉｎ（ＣＨ_３ＣＯＣＨＣＯＣＨ_３）_３）であることが特に好ましい。
【００１０】
式〔２〕中、Ｒ^３は炭素数１〜１０のアルキル基を表し、Ｒ^４は炭素数１〜１０のアルキル基又は炭素数１〜１０のアシル基を表す。具体的に、Ｒ^３としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ターシャリブチル基が挙げられ、Ｒ^４としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ターシャリブチル基のアルキル基、アセチル基、プロピオニル基等のアシル基が挙げられる。これらの中でも、式〔２〕で表されるスズ化合物としては、ジ−ｎ−ブチルスズジアセテート（（ｎ−Ｂｕ）_２Ｓｎ（ＯＣＯＣＨ_３）_２）であることが特に好ましい。
【００１１】
透明導電膜形成液を用いて透明導電膜を形成する場合においては、透明導電膜形成液に含有されるインジウム化合物とスズ化合物の熱分解温度がより近い方が、両者が均一に拡散して均一な膜質を形成することができると考えられる。本発明の透明導電膜形成液においては、式〔１〕で表わされるインジウム化合物と式〔２〕で表わされるスズ化合物は熱分解温度が近く、具体的にはインジウムトリスアセチルアセトナートは３２０℃近辺で、ジ−ｎ−ブチルスズジアセテートは３６０℃近辺である。
【００１２】
したがって、本発明の透明導電膜形成液を用いて透明導電膜を形成する場合において、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に堆積させる場合には、式〔１〕で表されるインジウム化合物と式〔２〕で表されるスズ化合物とが、所定温度のもとでほぼ同時に熱分解を起こすことで両者が均一に拡散して堆積（蒸着）すると考えられ、膜質の極めて均一な膜を形成して、極めて均一な導電性及び透明性を保有する透明導電膜を形成することができる。また、透明導電膜形成液をコーティングした後、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に固定する場合には、コーティング後の乾燥及び／又は焼成において、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物が、所定温度のもとでほぼ同時に熱分解を起こして均一に拡散して基体又は中間膜上に固定されると考えられ、膜質の極めて均一な膜を形成して、極めて均一な導電性及び透明性を保有する透明導電膜を形成することができる。また、本発明の透明導電膜形成液を用いて形成した膜は、導電性及び透明性に優れているので、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、面発熱体、タッチパネル電極、太陽電池等に広く利用することができる。
【００１３】
本発明の透明導電膜形成液は、式〔１〕で表されるインジウム化合物と、式〔２〕で表されるスズ化合物を含有すれば特に制限されるものではないが、式〔１〕で表されるインジウム化合物中のＩｎが、質量で、式〔２〕で表されるスズ化合物中のＳｎより多く含有されていること（形成される透明導電膜がＩＴＯ膜であること）が好ましく、式〔２〕で表されるスズ化合物中のＳｎが、質量比で、式〔１〕で表されるインジウム化合物中のＩｎ１に対して０．００１〜０．５含有されていることがより好ましく、０．０５〜０．３５含有されていることがさらに好ましい。
上記質量比の範囲で式〔１〕で表されるインジウム化合物と式〔２〕で表されるスズ化合物を含有することにより、透明度及び抵抗値の均一性に優れた透明導電膜の形成が可能となって、かかる抵抗値を有する透明導電膜は、例えば、タッチパネル用の透明電極として特に有用である。
【００１４】
本発明の透明導電膜形成液は、式〔１〕で表されるインジウム化合物を含有するが、他のインジウム化合物を併用することもできる。併用するインジウム化合物としては、熱分解して酸化インジウムとなるものが好ましく、例えば、三塩化インジウム（ＩｎＣｌ_３）、硝酸インジウム（Ｉｎ（ＮＯ_３）_３）、インジウムトリイソプロポキシド（Ｉｎ（ＯｉＰｒ）_３）等が挙げられる。
他のインジウム化合物を併用する場合、式〔１〕で表されるインジウム化合物は、全インジウム化合物中、８０質量％以上含有されていることが好ましく、９０質量％以上含有されていることがより好ましく、９５質量％以上含有されていることがさらに好ましく、式〔１〕で表されるインジウム化合物がより多く含有されているほど好ましい。
【００１５】
本発明の透明導電膜形成液は、式〔２〕で表されるスズ化合物を含有するが、他のスズ化合物を併用することもできる。併用するスズ化合物としては、熱分解して酸化第２スズとなるものが好ましく、例えば、塩化第２スズ、ジメチルスズジクロライド、ジブチルスズジクロライド、テトラブチルスズ、スタニアスオクトエート（Ｓｎ（ＯＣＯＣ_７Ｈ_１５）_２）、ジブチルスズマレエート、ジブチルスズビスアセチルアセトナート等を挙げることができる。
他のスズ化合物を併用する場合、式〔２〕で表されるスズ化合物は、全スズ化合物中、８０質量％以上含有されていることが好ましく、９０質量％以上含有されていることがより好ましく、９５質量％以上含有されていることがさらに好ましく、式〔２〕で表されるスズ化合物がより多く含有されているほど好ましい。
【００１６】
また、本発明の透明導電膜形成液は、前記式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物に加えて、第３成分として、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等の周期律表第２族元素、Ｓｃ、Ｙ等の第３族元素、Ｌａ、Ｃｅ、Ｎｄ、Ｓｍ、Ｇｄ等のランタノイド、Ｔｉ、Ｚｒ、Ｈｆ等の第４族元素、Ｖ、Ｎｂ、Ｔａ等の第５族元素、Ｃｒ、Ｍｏ、Ｗ等の第６族元素、Ｍｎ等の第７族元素、Ｃｏ等の第９族元素、Ｎｉ、Ｐｄ、Ｐｔ等の第１０族元素、Ｃｕ、Ａｇ等の第１１族元素、Ｚｎ、Ｃｄ等の第１２族元素、Ｂ、Ａｌ、Ｇａ等の第１３族元素、Ｓｉ、Ｇｅ、Ｐｂ等の第１４族元素、Ｐ、Ａｓ、Ｓｂ等の第１５族元素、Ｓｅ、Ｔｅ等の第１６族元素等からなる単体若しくはこれらの化合物を含有することも好ましい。
これらの元素の添加割合は、インジウムに対して、０．０５〜２０原子％程度が好ましく、添加元素によって添加割合は異なり、目的とする抵抗値にあった元素及び添加量を適宜選定することができる。
【００１７】
本発明の透明導電膜形成液に用いられる有機溶媒としては、アセチルアセトン、アセトン、メチルイソブチルケトン、ジエチルケトン等のケトン系溶媒、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール系溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、メチルセルソルブ、テトラヒドロフラン等のエーテル系溶媒、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素類等を挙げることができる。
これらの有機溶媒の種類及び添加量は、透明導電膜のシート抵抗値の設定値等に依存し、透明導電膜の種類、透明導電膜の膜厚、用いる有機溶媒の種類、加熱温度、加熱時間等により適宜定めることができる。例えば、他の条件を同一にして、より熱分解しやすい有機溶媒を多量に添加することにより、シート抵抗値をより低くすることができる。以上のようにして、用いる有機溶媒の種類、添加量及び加熱温度を適宜選択・設定することにより、所望のシート抵抗値を有する透明導電膜を得ることができる。
【００１８】
以下、本発明の透明導電膜付基体の製造方法について説明する。
本発明の透明導電膜付基体の製造方法は、基体上に、直接又は中間膜を介して透明導電膜を形成して透明導電膜付基体を製造する方法であって、前記基体又は中間膜上に、式〔１〕で表されるインジウム化合物と式〔２〕で表されるスズ化合物とを含有する透明導電膜形成液を用いて化学的熱分解法により透明導電膜を形成することを特徴とする。即ち、上記透明導電膜形成液を用いて化学的熱分解法により透明導電膜を形成することを特徴とする。
【００１９】
ここで、前記化学的熱分解法とは、透明導電膜形成液に含有される式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に堆積させる方法、並びに透明導電膜形成液をコーティングした後、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に固定する方法をいい、例えば、スプレー法、ディップコーティング法、スピンコート法、ＬＢ法、ゾル−ゲル法、液相エピタキシー法、熱ＣＶＤ法、プラズマＣＶＤ法、ＭＯＣＶＤ法、パイロゾルプロセス法、（超音波霧化による常圧ＣＶＤ法）、ＳＰＤ法、Ｃａｔ−ＣＶＤ法等のＣＶＤ法（ｃｈｅｍｉｃａｌ　ｖａｐｏｒ　ｄｅｐｏｓｉｔｉｏｎ）等が挙げられ、これらの中でもパイロゾルプロセス法を用いることが特に好ましい。パイロゾルプロセス法を用いることにより、より均一な膜質を有する透明導電膜を製造することができる。
【００２０】
本発明の透明導電膜付基体の製造方法によれば、熱分解温度が近い式〔１〕で表されるインジウム化合物と式〔２〕で表されるスズ化合物が、所定温度のもとで均一に拡散し、均一な膜質の透明導電膜を形成することができる。具体的には、透明導電膜形成液中の式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に堆積させる場合には、式〔１〕で表されるインジウム化合物と式〔２〕で表されるスズ化合物とが、所定温度のもとでほぼ同時に熱分解を起こすことで両者が均一に拡散して堆積（蒸着）すると考えられ、膜質の極めて均一な膜を形成して、極めて均一な導電性及び透明性を保有する透明導電膜を形成することができる。また、透明導電膜形成液をコーティングした後、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を熱により分解させて基体又は中間膜上に固定する場合には、コーティング後の乾燥及び／又は焼成において、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物が、所定温度のもとでほぼ同時に熱分解を起こして均一に拡散して基体又は中間膜上に固定されると考えられ、膜質の極めて均一な膜を形成して、極めて均一な導電性及び透明性を保有する透明導電膜を形成することができる。
【００２１】
また、本発明の透明導電膜付基体の製造方法により製造された透明導電膜は導電性及び透明性に優れているので、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、面発熱体、タッチパネル電極、太陽電池等に広く利用することができる。さらに、本発明の透明導電膜付基体の製造方法においては、成膜の一般的手法である化学的熱分解法を用いることによって簡便に均質な膜を形成することができる。
【００２２】
前記中間膜は、一層の膜であってもよく、二層以上の膜であってもよい。かかる中間膜としては、例えば、酸化シリコン膜、有機ポリシラン化合物から形成されるポリシラン膜、ＭｇＦ_２膜、ＣａＦ_２膜、ＳｉＯ_２とＴｉＯ_２の複合酸化物膜等を挙げることができる。これらの中間膜は、例えば、基板としてソーダーガラスを用いる場合のＮａイオンの拡散防止の為に形成される。また、透明導電膜と異なる屈折率、好ましくは低屈折率の下地膜を形成することによって、反射防止或いは透明性を向上させることもできる。これらの膜は、一般に知られている成膜方法、例えば、スパッタ法、ＣＶＤ法、スプレー法、ディップ法等により形成することができ、膜厚としては、特に制限されるものではないが、通常２０〜２００ｎｍ程度である。
【００２３】
前記基体としては、シート状（基板）、ハニカム状、ファイバー状、ビーズ状、発泡状やそれらが集積したもの等であってもよく、透明導電膜形成液の成分が熱分解を起こす温度で耐熱性を有するものであれば特に制限されるものではないが、例えば、ガラス基板、セラミックス基板、金属基板等を挙げることができる。これらのうち、本発明の透明導電膜付基体の製造方法においてはガラス基板を用いるのが好ましい。ガラス基板としては、例えば、ケイ酸ガラス（石英ガラス）、ケイ酸アルカリガラス、ソーダ石灰ガラス、カリ石灰ガラス、鉛ガラス、バリウムガラス、ホウケイ酸ガラス等を挙げることができる。
【００２４】
なお、本発明の透明導電膜付基体の製造方法において形成する透明導電膜の膜厚としては、特に制限されるものではなく、その用途等によって適宜選定すればよいが、シート抵抗値が３０Ω／□以下のＩＴＯ膜を形成する場合には、一般に８０ｎｍ以上であり、シート抵抗値が６０〜２００Ω／□のＩＴＯ膜を形成する場合には、一般に３０ｎｍ程度であり、シート抵抗値が２００〜３０００Ω／□のＩＴＯ膜を形成する場合には、一般に１０〜２５ｎｍである。
【００２５】
また、本発明の透明導電膜付基体の製造方法において、上記パイロゾルプロセス法を用いる場合には、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を有機溶媒に溶解させた透明導電膜形成液を超音波によるアトマイジング法を利用して、粒状の比較的そろった微小な小液滴からなるエアロゾルにし、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物が熱分解を起こして酸化インジウム及び酸化第２スズを形成し得る温度、例えば、３００〜８００℃の均一な温度に管理した加熱炉内の基体上に供給して、式〔１〕で表されるインジウム化合物及び式〔２〕で表されるスズ化合物を加熱炉内で気化させ気相状態から基体上で反応させて透明導電膜を形成する。
【００２６】
【実施例】
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。
［実施例１］
インジウムトリスアセチルアセトナート（Ｉｎ（ＡｃＡｃ）_３）をアセチルアセトンにモル濃度で０．２ｍｏｌ／Ｌになるように溶解して黄色透明溶液を得た。この溶液にＳｎ／Ｉｎ＝５質量％となるようにスズ化合物としてジ−ｎ−ブチルスズジアセテートを加えたＩＴＯ膜形成液（透明導電膜形成液）を調製した。
このＩＴＯ膜形成液を用いてパイロゾルプロセス法により、ＩＴＯ膜形成液の霧化による化学的熱分解量を調整しながら、ガラス基板上に厚さ２０ｎｍのＩＴＯ膜を形成し、無色透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板（透明導電膜付基体）を得た。
【００２７】
［実施例２］
上記実施例１と同様にして、ガラス基板上に厚さ４０ｎｍのＩＴＯ膜を形成し、透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板を得た。
［実施例３］
上記実施例１と同様にして、ガラス基板上に厚さ２００ｎｍのＩＴＯ膜を形成し、透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板を得た。
【００２８】
［比較例１］
インジウムトリスアセチルアセトナート（Ｉｎ（ＡｃＡｃ）_３）をアセチルアセトンにモル濃度で０．２ｍｏｌ／Ｌになるように溶解して黄色透明溶液を得た。この溶液にＳｎ／Ｉｎ＝５質量％となるようにスズ化合物としてトリ−ｎ−オクチルスズオキサイドを加えたＩＴＯ膜形成液を調製した。
このＩＴＯ膜形成液を用いてパイロゾルプロセス法により、ＩＴＯ膜形成液の霧化による化学的熱分解量を調整しながら、ガラス基板上に厚さ３０ｎｍのＩＴＯ膜を形成し、黄色味を帯びた透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板を製造した。
【００２９】
＜評価＞
上記実施例１〜３及び比較例１に係るＩＴＯ膜付ガラス基板の比抵抗値をロレスタ（三菱化学社製）を用いて測定し、シート抵抗値を算出した。なお、シート抵抗値は、比抵抗／導電膜の膜厚で求められる値である。また、実施例１〜３及び比較例１に係るＩＴＯ膜付ガラス基板の任意に選ばれた部分ａ〜ｃ（３箇所）について５５０ｎｍの波長における光透過率を磁気分光光度計（日立製作所製）を用いて測定した。さらに、実施例１〜３及び比較例１に係るＩＴＯ膜付ガラス基板のＩＴＯ膜の深さ方向でのインジウムとスズの含有量をＥＳＣＡで測定した。
シート抵抗値の測定結果を下記表１に示し、光透過率の測定結果を下記表２に示す。また、実施例１〜３に係るＩＴＯ膜付ガラス基板についてのＥＳＣＡによる測定結果を図１に示す。
【００３０】
【表１】

【００３１】
【表２】

【００３２】
（結果）
表１から明らかなように、本発明の透明導電膜付基体の製造方法により、膜厚を変化させることによって、シート抵抗値が１０〜５００Ω／□のＩＴＯ膜付基体を製造することができ、種々の用途に対応した所望のシート抵抗値のＩＴＯ膜を有するＩＴＯ膜付基体を得ることができることが明らかとなった。
また、表２から明らかなように、本発明に係る実施例１〜３のＩＴＯ膜付ガラス基板は、それぞれ、任意の部分において光透過率がほぼ等しく、膜の透明度が均一なことが明らかとなった。
【００３３】
また、図１から明らかなように、本発明に係る実施例１〜３のＩＴＯ膜付ガラス基板においては、スズの含有率がほぼ一定しており、膜の表面及び内部でインジウムとスズが均一に分散した膜が形成されたことが明らかになった。一方、比較例１に係るＩＴＯ膜付基体においては、ＥＳＣＡの測定によってスズは検出されず、スズは単に熱分解されただけでインジウムと共に膜になっていないことが明らかとなった。
【００３４】
【発明の効果】
本発明の透明導電膜形成液によれば、シート抵抗値、透明性、及び透明導電膜の深さ方向でのインジウムとスズの分布において、極めて均一な透明導電膜を形成することができる。また、本発明の透明導電膜付基体の製造方法によれば、シート抵抗値、透明性、及び透明導電膜の深さ方向でのインジウムとスズの分布において極めて均一な透明導電膜を有する膜付基体を製造することができる。
【図面の簡単な説明】
【図１】本発明の透明導電膜付基体（実施例のＩＴＯ膜付ガラス基板）についてのＥＳＣＡによる測定結果を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a liquid for forming a transparent conductive film and a method for producing a substrate with a transparent conductive film using the liquid for forming a transparent conductive film.
[0002]
[Prior art]
BACKGROUND ART Transparent conductive films (ITO films) are widely used in liquid crystal displays, electroluminescent displays, surface heating elements, touch panel electrodes, solar cells, and the like, utilizing their excellent transparency and conductivity.
Since the transparent conductive film is used in such a wide field, it is required to have various sheet resistance values and transparency depending on the purpose of use. For example, a transparent conductive film for a flat panel display is required to have a low resistance and a high transmittance, and a transparent conductive film for a touch panel is required to have a high resistance and a high transmittance. You. In particular, a transparent conductive film for pen input touch panels, which has been developed in recent years and is expected to grow in the market, requires high position recognition accuracy, and is a high-resistance film having a sheet resistance value of 200 to 3000 Ω / □. There is a demand. Here, the sheet resistance value is a value determined by specific resistance / film thickness of the conductive film.
[0003]
As a method of forming a transparent conductive film having a desired sheet resistance value as described above, for example, JP-A-2001-35273 and JP-A-2002-133956 disclose a sputtering method, an electron beam method, and an ion plating method. A method is described in which after a transparent conductive film is formed by a method or a chemical vapor deposition method, the transparent conductive film is subjected to a heat treatment in the presence of a predetermined concentration of an organic solvent. In this publication, as a raw material for forming a transparent conductive film, indium compounds such as indium trisacetylacetonate, indium trisbenzoylmethanate, indium trichloride, indium nitrate, and indium triisopropoxide are exemplified. Examples of the tin compound include stannic chloride, dimethyltin dichloride, dibutyltin dichloride, tetrabutyltin, staniasoctoate, dibutyltin maleate, dibutyltin acetate, dibutyltin bisacetylacetonate, and the like.
[0004]
However, the above publication describes a method for obtaining a transparent conductive film having a desired resistance value, and studies a preferable combination of an indium compound and a tin compound, and describes a relationship between the indium compound and the tin compound. No studies have been made on the uniformity of the sheet resistance and the transparency of the transparent conductive film in the above. The present inventors have studied further improvement of the sheet resistance value and the uniformity of the transparency in consideration of the future application of the transparent conductive film, particularly the ITO film, and the like.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a transparent conductive film forming liquid capable of forming a transparent conductive film having extremely uniform sheet resistance and transparency, and a sheet resistance value. Another object of the present invention is to provide a method of manufacturing a substrate with a transparent conductive film having a transparent conductive film which is extremely uniform in transparency.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to form a transparent conductive film having a more uniform film quality. As a result, the indium compound contained in the transparent conductive film forming liquid for forming the transparent conductive film is represented by the following formula [1]. By using an indium compound represented by the formula (1), and using a tin compound represented by the following formula [2] as a tin compound, it has been found that a transparent conductive film having more uniform film quality can be formed. Reached.
[0007]
That is, the present invention relates to formula [1]
In (R ¹ COCHCOR ² ) ₃ [1]
(Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group), and an indium compound represented by the formula [2]:
(R ³ ) ₂ Sn (OR ⁴ ) ₂ [2]
(Wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms). The transparent conductive film forming liquid (claim 1) characterized in that the indium compound represented by the formula [1] or indium trisacetylacetonate is indium trisacetylacetonate. 3. The transparent conductive film forming liquid according to claim 1, wherein the conductive film forming liquid (claim 2) or the tin compound represented by the formula [2] is di-n-butyltin diacetate. (Claim 3) The invention is characterized in that In in the indium compound represented by the formula [1] is contained more in mass than Sn in the tin compound represented by the formula [2]. The liquid for forming a transparent conductive film according to any one of claims 1 to 3 (claim 4) Or that Sn in the tin compound represented by the formula [2] is contained in a mass ratio of 0.001 to 0.5 with respect to In1 in the indium compound represented by the formula [1]. A liquid for forming a transparent conductive film according to claim 4 (claim 5).
[0008]
The present invention also relates to a method for producing a substrate with a transparent conductive film by forming a transparent conductive film directly or via an intermediate film on a substrate, wherein the substrate or the intermediate film is represented by the formula [1]. A transparent conductive film formed by a chemical thermal decomposition method using a transparent conductive film forming solution containing an indium compound to be produced and a tin compound represented by the formula [2]. And Sn in the tin compound represented by the formula [2] is 0.001 to 0 in mass ratio to In1 in the indium compound represented by the formula [1]. The method for producing a substrate with a transparent conductive film according to claim 6, wherein the indium compound represented by the formula [1] The tin compound represented by the formula [2] is decomposed by heat and deposited on a substrate or an intermediate film. The method for producing a substrate with a transparent conductive film according to claim 6 or 7, wherein the indium compound represented by the formula [1] and the indium compound represented by the formula [2] are provided. 9. The method for producing a substrate with a transparent conductive film according to claim 8, wherein the method of decomposing the tin compound by heat and depositing it on the substrate or the intermediate film is a pyrosol process method. Further, the present invention relates to a method for producing a substrate with a transparent conductive film according to any one of claims 6 to 9, wherein the substrate is a glass substrate.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The liquid for forming a transparent conductive film of the present invention has the formula [1]
In (R ¹ COCHCOR ² ) ₃ [1]
An indium compound represented by the formula [2]:
(R ³ ) ₂ Sn (OR ⁴ ) ₂ [2]
And a tin compound represented by the formula:
In Formula [1], R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and specifically, for example, a methyl group, an ethyl group, an n-propyl group, -Butyl group, tertiary butyl group and the like. Among these, the indium compound represented by the formula [1] is particularly preferably indium trisacetylacetonate (In (CH ₃ COCHCOCH ₃ ) ₃ ).
[0010]
In the formula [2], R ³ represents an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms. Specifically, examples of R ³ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tertiary butyl group, and examples of R ⁴ include a methyl group, an ethyl group, and an n- An acyl group such as an alkyl group such as a propyl group, an n-butyl group and a tertiary butyl group, an acetyl group and a propionyl group is exemplified. Among these, the tin compounds represented by the formula (2), particularly preferably di -n- butyl tin diacetate _{((n-Bu) 2 Sn} (OCOCH 3) 2).
[0011]
In the case of forming a transparent conductive film using the transparent conductive film forming solution, the closer the thermal decomposition temperature of the indium compound and the tin compound contained in the transparent conductive film forming solution, the more uniform the two are diffused and uniform. It is considered that a good film quality can be formed. In the transparent conductive film forming solution of the present invention, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] have close thermal decomposition temperatures, and specifically, indium trisacetylacetonate has a temperature of around 320 ° C. The di-n-butyltin diacetate is around 360 ° C.
[0012]
Therefore, when a transparent conductive film is formed using the transparent conductive film forming liquid of the present invention, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] are decomposed by heat to form a substrate. Alternatively, when deposited on an intermediate film, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] undergo thermal decomposition almost simultaneously at a predetermined temperature, whereby Is considered to be uniformly diffused and deposited (deposited), so that a film having extremely uniform film quality can be formed, and a transparent conductive film having extremely uniform conductivity and transparency can be formed. In addition, after coating the transparent conductive film forming solution, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] are decomposed by heat and fixed on a substrate or an intermediate film. In the drying and / or baking after coating, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] are thermally decomposed almost simultaneously at a predetermined temperature and diffuse uniformly. It is considered that the film is fixed on the substrate or the intermediate film, and a film having extremely uniform film quality can be formed, and a transparent conductive film having extremely uniform conductivity and transparency can be formed. Further, since the film formed using the transparent conductive film forming solution of the present invention has excellent conductivity and transparency, it is widely used for liquid crystal displays, electroluminescence displays, surface heating elements, touch panel electrodes, solar cells, and the like. be able to.
[0013]
The transparent conductive film forming solution of the present invention is not particularly limited as long as it contains an indium compound represented by the formula [1] and a tin compound represented by the formula [2]. It is preferable that the In in the indium compound represented by mass contains more In by mass than the Sn in the tin compound represented by the formula [2] (the formed transparent conductive film is an ITO film), More preferably, Sn in the tin compound represented by the formula [2] is contained in a mass ratio of 0.001 to 0.5 with respect to In1 in the indium compound represented by the formula [1]. , 0.05 to 0.35.
By containing the indium compound represented by the formula [1] and the tin compound represented by the formula [2] in the above range of the mass ratio, it is possible to form a transparent conductive film excellent in uniformity of transparency and resistance value. Thus, a transparent conductive film having such a resistance value is particularly useful, for example, as a transparent electrode for a touch panel.
[0014]
The liquid for forming a transparent conductive film of the present invention contains the indium compound represented by the formula [1], but other indium compounds may be used in combination. As the indium compound to be used in combination, a compound which is thermally decomposed to indium oxide is preferable. For example, indium trichloride (InCl ₃ ), indium nitrate (In (NO ₃ ) ₃ ), indium triisopropoxide (In (OiPr)) ₃ ) and the like.
When another indium compound is used in combination, the indium compound represented by the formula [1] is preferably contained in an amount of 80% by mass or more, more preferably 90% by mass or more in all the indium compounds. , 95% by mass or more, and more preferably the indium compound represented by the formula [1].
[0015]
The liquid for forming a transparent conductive film of the present invention contains a tin compound represented by the formula [2], but another tin compound may be used in combination. As the tin compound to be used in combination, a compound which is thermally decomposed into stannic oxide is preferable. For example, stannic chloride, dimethyltin dichloride, dibutyltin dichloride, tetrabutyltin, staniasoctoate (Sn (OCOC ₇ H ₁₅ )) ₂ ), dibutyltin maleate, dibutyltin bisacetylacetonate and the like.
When another tin compound is used in combination, the tin compound represented by the formula [2] is preferably contained in an amount of at least 80% by mass, more preferably at least 90% by mass of all the tin compounds. , 95% by mass or more, and more preferably the tin compound represented by the formula [2].
[0016]
Further, the liquid for forming a transparent conductive film of the present invention contains Mg, Ca, Sr, and Ba as a third component in addition to the indium compound represented by the formula [1] and the tin compound represented by the formula [2]. Group 3 elements such as Sc, Y, lanthanoids such as La, Ce, Nd, Sm, and Gd; Group 4 elements such as Ti, Zr, and Hf; V, Nb, and Ta Group 5 element such as Cr, Mo, W, etc., Group 7 element such as Mn, Group 9 element such as Co, Group 10 element such as Ni, Pd, Pt, Cu, Ag Group 11 elements such as Zn, Cd, etc., Group 13 elements such as B, Al, Ga, etc., Group 14 elements such as Si, Ge, Pb, etc., and Group 15 elements such as P, As, Sb, etc. It is also preferable to contain a simple substance composed of a Group 16 element, a Group 16 element such as Se or Te, or a compound thereof.
The addition ratio of these elements is preferably about 0.05 to 20 atomic% with respect to indium. The addition ratio differs depending on the added element, and the element and the addition amount suitable for the target resistance value can be appropriately selected. it can.
[0017]
Examples of the organic solvent used in the transparent conductive film forming liquid of the present invention include acetylacetone, acetone, methyl isobutyl ketone, ketone solvents such as diethyl ketone, methanol, ethanol, propanol, isopropanol, alcohol solvents such as butanol, ethyl acetate, and the like. Ester solvents such as butyl acetate, ether solvents such as methylcellosolve and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane. Can be.
The type and addition amount of these organic solvents depend on the set value of the sheet resistance value of the transparent conductive film, and the like, the type of the transparent conductive film, the thickness of the transparent conductive film, the type of the organic solvent used, the heating temperature, and the heating time. Can be determined as appropriate. For example, the sheet resistance can be further reduced by adding a large amount of an organic solvent which is more easily thermally decomposed under the same other conditions. As described above, a transparent conductive film having a desired sheet resistance value can be obtained by appropriately selecting and setting the type, the addition amount, and the heating temperature of the organic solvent to be used.
[0018]
Hereinafter, a method for producing the substrate with a transparent conductive film of the present invention will be described.
The method for producing a substrate with a transparent conductive film according to the present invention is a method for producing a substrate with a transparent conductive film by forming a transparent conductive film directly or via an intermediate film on the substrate. A transparent conductive film is formed by a chemical pyrolysis method using a transparent conductive film forming solution containing an indium compound represented by the formula [1] and a tin compound represented by the formula [2]. And That is, a transparent conductive film is formed by a chemical thermal decomposition method using the above-mentioned transparent conductive film forming liquid.
[0019]
Here, the chemical pyrolysis method means that an indium compound represented by the formula [1] and a tin compound represented by the formula [2] contained in the transparent conductive film forming solution are decomposed by heat to form a substrate or A method of depositing on an intermediate film, and a method of coating a transparent conductive film forming solution, and then thermally decomposing an indium compound represented by the formula [1] and a tin compound represented by the formula [2] to form a substrate or an intermediate film. It refers to a method of fixing on the top, for example, spray method, dip coating method, spin coating method, LB method, sol-gel method, liquid phase epitaxy method, thermal CVD method, plasma CVD method, MOCVD method, pyrosol process method, (Atmospheric pressure CVD method by ultrasonic atomization), CVD method (chemical vapor deposition) such as SPD method, Cat-CVD method and the like. It is particularly preferred to use a pyrolytic sol process method. By using the pyrosol process method, a transparent conductive film having more uniform film quality can be manufactured.
[0020]
According to the method for producing a substrate with a transparent conductive film of the present invention, the indium compound represented by the formula [1] and the tin compound represented by the formula [2], which have similar thermal decomposition temperatures, are uniformly formed at a predetermined temperature. And a transparent conductive film having uniform film quality can be formed. Specifically, when the indium compound represented by the formula [1] and the tin compound represented by the formula [2] in the transparent conductive film forming liquid are thermally decomposed and deposited on a substrate or an intermediate film, When the indium compound represented by the formula [1] and the tin compound represented by the formula [2] undergo thermal decomposition almost simultaneously at a predetermined temperature, they are uniformly diffused and deposited (evaporated). It is considered that a film having extremely uniform film quality can be formed, and a transparent conductive film having extremely uniform conductivity and transparency can be formed. In addition, after coating the transparent conductive film forming solution, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] are decomposed by heat and fixed on a substrate or an intermediate film. In the drying and / or baking after coating, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] are thermally decomposed almost simultaneously at a predetermined temperature and diffuse uniformly. It is considered that the film is fixed on the substrate or the intermediate film, and a film having extremely uniform film quality can be formed, and a transparent conductive film having extremely uniform conductivity and transparency can be formed.
[0021]
Further, since the transparent conductive film produced by the method for producing a substrate with a transparent conductive film of the present invention has excellent conductivity and transparency, it can be used for liquid crystal displays, electroluminescent displays, surface heating elements, touch panel electrodes, solar cells, and the like. Can be widely used. Further, in the method for producing a substrate with a transparent conductive film of the present invention, a uniform film can be easily formed by using a chemical pyrolysis method which is a general method of film formation.
[0022]
The intermediate film may be a one-layer film or a two-layer or more film. Examples of such an intermediate film include a silicon oxide film, a polysilane film formed from an organic polysilane compound, an MgF ₂ film, a CaF ₂ film, and a composite oxide film of SiO ₂ and TiO ₂ . These intermediate films are formed, for example, to prevent diffusion of Na ions when soda glass is used as the substrate. Further, by forming a base film having a refractive index different from that of the transparent conductive film, preferably a low refractive index, the antireflection or the transparency can be improved. These films can be formed by a generally known film forming method, for example, a sputtering method, a CVD method, a spray method, a dipping method, and the like. The thickness is not particularly limited, but is usually It is about 20 to 200 nm.
[0023]
The substrate may be a sheet (substrate), a honeycomb, a fiber, a bead, a foam, or a combination thereof, and is heat-resistant at a temperature at which a component of the transparent conductive film forming liquid thermally decomposes. The material is not particularly limited as long as it has properties, and examples thereof include a glass substrate, a ceramics substrate, and a metal substrate. Among them, a glass substrate is preferably used in the method for producing a substrate with a transparent conductive film of the present invention. Examples of the glass substrate include silicate glass (quartz glass), alkali silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass, and borosilicate glass.
[0024]
The thickness of the transparent conductive film formed in the method for producing a substrate with a transparent conductive film of the present invention is not particularly limited, and may be appropriately selected depending on the application and the like. When forming an ITO film of □ or less, it is generally 80 nm or more, and when forming an ITO film having a sheet resistance of 60 to 200 Ω / □, it is generally about 30 nm and the sheet resistance is 200 to 3000 Ω. When an ITO film of // is formed, the thickness is generally 10 to 25 nm.
[0025]
In the method for producing a substrate with a transparent conductive film according to the present invention, when the above-mentioned pyrosol process method is used, the indium compound represented by the formula [1] and the tin compound represented by the formula [2] are mixed with an organic solvent. The transparent conductive film forming liquid dissolved in the aerosol is formed into an aerosol composed of fine particles that are relatively uniform and granular using an atomizing method by ultrasonic waves, and the indium compound represented by the formula [1] and the formula [ 2] is supplied to a substrate in a heating furnace controlled to a temperature at which indium oxide and stannic oxide can be formed by thermal decomposition of the tin compound, for example, a uniform temperature of 300 to 800 ° C. The indium compound represented by the formula [1] and the tin compound represented by the formula [2] are vaporized in a heating furnace and reacted from a gaseous phase on a substrate to form a transparent conductive film.
[0026]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the technical scope of the present invention is not limited to these examples.
[Example 1]
Indium trisacetylacetonate (In (AcAc) ₃ ) was dissolved in acetylacetone at a molar concentration of 0.2 mol / L to obtain a yellow transparent solution. An ITO film forming solution (transparent conductive film forming solution) was prepared by adding di-n-butyltin diacetate as a tin compound to this solution so that Sn / In = 5% by mass.
A 20 nm thick ITO film is formed on a glass substrate by a pyrosol process method using the ITO film forming solution while controlling the amount of chemical thermal decomposition caused by atomization of the ITO film forming solution. A glass substrate with an ITO film (a substrate with a transparent conductive film) having a film was obtained.
[0027]
[Example 2]
An ITO film having a thickness of 40 nm was formed on a glass substrate in the same manner as in Example 1 to obtain a glass substrate with an ITO film having a transparent ITO film.
[Example 3]
A 200-nm-thick ITO film was formed on a glass substrate in the same manner as in Example 1 to obtain a glass substrate with an ITO film having a transparent ITO film.
[0028]
[Comparative Example 1]
Indium trisacetylacetonate (In (AcAc) ₃ ) was dissolved in acetylacetone at a molar concentration of 0.2 mol / L to obtain a yellow transparent solution. An ITO film forming solution was prepared by adding tri-n-octyltin oxide as a tin compound to this solution so that Sn / In = 5% by mass.
A 30 nm thick ITO film is formed on a glass substrate by adjusting the amount of chemical thermal decomposition by atomization of the ITO film forming solution by a pyrosol process method using the ITO film forming solution, and has a yellow tint. A glass substrate with an ITO film having a transparent ITO film was manufactured.
[0029]
<Evaluation>
The specific resistance of the glass substrate with the ITO film according to Examples 1 to 3 and Comparative Example 1 was measured using Loresta (manufactured by Mitsubishi Chemical Corporation), and the sheet resistance was calculated. Note that the sheet resistance value is a value determined by the specific resistance / the thickness of the conductive film. In addition, the light transmittance at a wavelength of 550 nm of the arbitrarily selected portions a to c (three places) of the glass substrates with the ITO film according to Examples 1 to 3 and Comparative Example 1 was measured using a magnetic spectrophotometer (manufactured by Hitachi, Ltd.) It measured using. Furthermore, the content of indium and tin in the depth direction of the ITO film of the glass substrate with the ITO film according to Examples 1 to 3 and Comparative Example 1 was measured by ESCA.
Table 1 below shows the measurement results of the sheet resistance value, and Table 2 below shows the measurement results of the light transmittance. FIG. 1 shows the results of ESCA measurement on the glass substrates with ITO films according to Examples 1 to 3.
[0030]
[Table 1]

[0031]
[Table 2]

[0032]
(result)
As is clear from Table 1, by changing the film thickness by the method for producing a substrate with a transparent conductive film of the present invention, a substrate with an ITO film having a sheet resistance value of 10 to 500 Ω / □ can be produced. It has been clarified that an ITO film-coated substrate having an ITO film having a desired sheet resistance value corresponding to various uses can be obtained.
Further, as is clear from Table 2, it is clear that the glass substrates with the ITO films of Examples 1 to 3 according to the present invention have almost the same light transmittance in any part and uniform film transparency. became.
[0033]
Also, as is clear from FIG. 1, in the glass substrates with the ITO film of Examples 1 to 3 according to the present invention, the tin content is almost constant, and indium and tin are uniform on the surface and inside of the film. It was clarified that a film dispersed in was formed. On the other hand, in the substrate with an ITO film according to Comparative Example 1, tin was not detected by ESCA measurement, and it was revealed that tin was simply thermally decomposed and did not form a film with indium.
[0034]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to the transparent conductive film formation liquid of this invention, a very uniform transparent conductive film can be formed in sheet resistance value, transparency, and distribution of indium and tin in the depth direction of a transparent conductive film. Further, according to the method for producing a substrate with a transparent conductive film of the present invention, a film having a transparent conductive film which is extremely uniform in sheet resistance, transparency, and distribution of indium and tin in the depth direction of the transparent conductive film is provided. A substrate can be manufactured.
[Brief description of the drawings]
FIG. 1 is a view showing the results of ESCA measurement on a substrate with a transparent conductive film of the present invention (glass substrate with an ITO film in Examples).

Claims

Equation [1]
In (R ¹ COCHCOR ² ) ₃ [1]
(Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group), and an indium compound represented by the formula [2]:
(R ³ ) ₂ Sn (OR ⁴ ) ₂ [2]
(Wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms). A liquid for forming a transparent conductive film, comprising:

The transparent conductive film forming liquid according to claim 1, wherein the indium compound represented by the formula (1) is indium trisacetylacetonate.

3. The transparent conductive film forming solution according to claim 1, wherein the tin compound represented by the formula [2] is di-n-butyltin diacetate.

The In in the indium compound represented by the formula (1) is contained in a larger amount than the Sn in the tin compound represented by the formula (2) by mass. 4. The liquid for forming a transparent conductive film according to item 1.

Sn in the tin compound represented by the formula [2] is contained in a mass ratio of 0.001 to 0.5 with respect to In1 in the indium compound represented by the formula [1]. The liquid for forming a transparent conductive film according to claim 4.

A method for producing a substrate with a transparent conductive film by forming a transparent conductive film directly or via an intermediate film on a substrate,
On the substrate or the intermediate film, the formula [1]
In (R ¹ COCHCOR ² ) ₃ [1]
(Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group), and an indium compound represented by the formula [2]:
(R ³ ) ₂ Sn (OR ⁴ ) ₂ [2]
(Wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms, and R ⁴ represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms). A method for producing a substrate with a transparent conductive film, wherein a transparent conductive film is formed by a chemical pyrolysis method using a transparent conductive film forming solution contained therein.

Sn in the tin compound represented by the formula [2] is contained in a mass ratio of 0.001 to 0.5 with respect to In1 in the indium compound represented by the formula [1]. The method for producing a substrate with a transparent conductive film according to claim 6.

The chemical pyrolysis method is a method in which an indium compound represented by the formula [1] and a tin compound represented by the formula [2] are decomposed by heat and deposited on a substrate or an intermediate film. A method for producing a substrate with a transparent conductive film according to claim 6.

The method wherein the method of decomposing the indium compound represented by the formula [1] and the tin compound represented by the formula [2] by heat and depositing them on a substrate or an intermediate film is a pyrosol process method. Item 10. The method for producing a substrate with a transparent conductive film according to Item 8.

The method for producing a substrate with a transparent conductive film according to any one of claims 6 to 9, wherein the substrate is a glass substrate.