JP4081625B2 - Preparation method of transparent zinc oxide film - Google Patents
Preparation method of transparent zinc oxide film Download PDFInfo
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- JP4081625B2 JP4081625B2 JP18829298A JP18829298A JP4081625B2 JP 4081625 B2 JP4081625 B2 JP 4081625B2 JP 18829298 A JP18829298 A JP 18829298A JP 18829298 A JP18829298 A JP 18829298A JP 4081625 B2 JP4081625 B2 JP 4081625B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、液晶ディスプレイの透明電極、太陽電池用などの透明半導体電極などとして有用な透明酸化亜鉛皮膜の作製方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
酸化亜鉛は、ウルツ鉱構造を有する禁制帯巾３．３ｅＶの酸化物半導体であり、圧電効果、導電効果並びに発光効果にも優れた特性を有し、資源的にも豊富である。この酸化亜鉛膜は、表面弾性波素子、透明導電膜、センサー及び光触媒へ応用されている。現在、酸化亜鉛膜は、化学蒸着（ＣＶＤ）法、スパッタリング法並びにモレキュラービームエピタクシー（ＭＢＥ）法などの乾式法や、ゾル−ゲル法、液相成長法などの湿式法による作製が検討されている。しかし、乾式法では、製膜雰囲気の制御のための真空排気装置やガス導入装置、プラズマ発生のための高周波電源や機材加熱及び駆動装置が必要であり、一般的に製膜は４００℃以上で行われる。また、上記湿式法においても、結晶性酸化物膜を得るためには、製膜後、４００℃以上の加熱が必要である。
【０００３】
そこで、近年、硝酸亜鉛とジメチルアミンボラン（ＤＭＡＢ）を用いた無電解法と電解法を併用することにより、不導体上に電気伝導性の優れた酸化亜鉛を作製させる方法が報告されている（第１２回回路実装学術講演大会講演予稿集第１２１頁，１９９８年３月９日発行）。この方法は、不導体上に水溶液から電気伝導性の優れた酸化亜鉛膜を作製させる方法であり、乾式法で必要とする設備を必要とせず、また高温での加熱を必要としない。
【０００４】
しかしながら、報告されている方法では、電気伝導性の優れた酸化亜鉛膜は作製することはできるが、光学的透明性に優れた酸化亜鉛膜を作製することは困難である。従って、酸化亜鉛膜を産業的に使用できるものにするためには、透明性と電気伝導性に優れた酸化亜鉛膜の作製が必要である。
【０００５】
本発明は、上記要望に応えるためになされたもので、電気伝導性と透明性の優れた湿式めっき法による酸化亜鉛皮膜の作製方法を提供することを目的とする。
【０００６】
【課題を解決するための手段及び発明の実施の形態】
本発明は、上記目的を達成するため、
請求項１：
光学的透明性を有する不導体基材を銀イオンを含有する活性化剤で触媒化処理した後、酸化亜鉛析出溶液に浸漬して無電解法により上記基材上に酸化亜鉛皮膜を形成し、更に上記酸化亜鉛析出溶液で該酸化亜鉛皮膜を陰極として電解して、厚さ０．０１μｍ以上の透明酸化亜鉛皮膜を形成することを特徴とする透明酸化亜鉛皮膜の作製方法、
請求項２：
上記基材を２価の錫イオンを含むセンシタイジング溶液でセンシタイジング処理した後、上記銀イオンを含有する活性化剤で触媒化処理を施すようにした請求項１記載の作製方法、
請求項３：
活性化剤で触媒処理した後、強酸溶液への浸漬処理を行い、その後酸化亜鉛析出溶液への浸漬処理を行うようにした請求項２記載の作製方法
を提供する。
【０００７】
即ち、本発明者らは、無電解法で酸化亜鉛皮膜を作製させる際の触媒付与工程を検討することにより、酸化亜鉛皮膜の透明度の向上を図った結果、電気導電性が向上すると共に、光学的透明性に優れた酸化亜鉛皮膜が得られることを見出し、本発明を完成するに至った。これらが向上した理由は、銀触媒はＰｄ触媒に比べて、緻密なＺｎＯの初期析出ができ、その上に緻密なＺｎＯが成長するので、透明性が向上すると共に、導電性も向上するものと考えられる。
【０００８】
本発明で使用したガラス上の銀触媒の一例をＥＳＣＡで分析したところ、酸化銀と２酸化錫が認められた。一方、Ｐｄ触媒の場合は、酸化Ｐｄと２酸化錫が認められた。また、これら触媒の付着状態をＡＦＭ（原子間力顕微鏡）で観察したところ、銀触媒はＰｄ触媒と比較して、より緻密で凹凸の少ない付着の仕方をしていることが判明した。このように、銀触媒による触媒の分散性、均一性の向上が酸化亜鉛の光学的、電気的性質の改善に大きく寄与していると考えられる。これらの触媒機構は不明であるが、酸化銀は次工程で使用するジメチルアミンボラン等の還元剤によって還元され、金属になるのかもしれない。
【０００９】
以下、本発明につき更に詳しく説明する。
本発明に係る酸化亜鉛皮膜の作製方法は、上述したように、光学的透明性を有する不導体基材を銀イオンを含有する活性化剤で触媒化処理した後、酸化亜鉛析出溶液に浸漬して無電解法により上記基材上に酸化亜鉛皮膜を形成し、更に上記酸化亜鉛析出溶液で該酸化亜鉛皮膜を陰極として電解して、透明酸化亜鉛皮膜を形成するもので、この場合、上記基材を２価の錫イオンを含むセンシタイジング溶液でセンシタイジング処理した後、上記銀イオンを含有する活性化剤で触媒化処理を施すことが好ましい。また、活性化剤による処理の後、アクセレレータ処理（強酸溶液への浸漬処理）を行うことが好ましい。
【００１０】
ここで、上記基材としては、ガラスや、ポリカーボネート、ポリエチレンテレフタレート等の透明プラスチックフィルムなどが挙げられる。
【００１１】
これらの基材を処理して酸化亜鉛皮膜を形成する場合、以下の処理工程１）〜８）で行うことが好ましい。
【００１２】
１）洗 浄：ガラスのような素材を清浄にする。公知の脱脂剤水溶液、有機溶剤などが使用でき、公知の処理条件で処理することができる。
２）表面調整：公知の表面調整剤を使用して、素材表面に電荷を付与する。
３）センシタイジング：公知の錫イオンを含有する溶液に浸漬して、センシタイジングを行う。
４）アクチベーティング：銀イオンを主として含む活性化剤で活性化を行う。
５）アクセレレータ処理：強酸溶液による浸漬処理を行う。
６）上記の３），４），５）工程を必要により数回繰り返してもよい。
７）無電解ＺｎＯ膜作製
８）電解ＺｎＯ膜作製
【００１３】
この場合、上記表面調整剤としては、主成分としてカチオン界面活性剤あるいはカチオン性高分子化合物を１〜５０ｇ／Ｌ含有する水溶液を使用することができ、１０〜６０℃で１〜１０分間浸漬処理することができる。
【００１４】
また、上記センシタイジング処理に用いるセンシタイジング溶液としては、ＳｎＣｌ2、ＳｎＳＯ4等の２価の錫塩を塩酸、硫酸等の酸溶液に溶解した、２価の錫イオンを１〜５０ｇ／Ｌ含有し、ｐＨが１〜３である溶液を使用し、１０〜６０℃で１〜１０分間浸漬処理することが好ましい。
【００１５】
本発明において、上記工程４）で用いる銀イオンを含む活性化剤としては、銀イオン濃度０．０００１〜０．５モル／Ｌ、特に０．００１〜０．１モル／Ｌであるものが好ましい。この場合、銀イオンを与える銀塩の例としては、硫酸銀、亜硫酸銀、チオ硫酸銀、過塩素酸銀、メタンスルホン酸銀などが使用できるが、特に限定はない。上記銀イオンを主成分とする溶液には、２価の金属イオンを混合することで活性化の性能を向上することができる。この例としては、Ｎｉイオン、Ｃｏイオン、鉄イオン、亜鉛イオン、銅イオンなどが好適に使用できる。この向上機構は不明であるが、次工程で使用する無電解めっきの還元剤によってこれらの金属イオンが還元されて金属になるかもしれない。これらの使用濃度は上記銀イオンと同様である。なお、上記金属イオンに対する対アニオンは、硫酸イオン、ハロゲン化物イオン、メタンスルホン酸イオン等が好適に使用されるが、特に限定はない。また、ｐＨは５〜１１程度が適当である。
【００１６】
本発明の銀を主成分とする溶液の液温は広い範囲で設定できるが、通常は１５〜６０℃とすることが好ましい。また、これらの活性化液への浸漬処理時間も適宜選択できるが、数秒〜数分間が好適である。
【００１７】
本発明では、銀を主成分とする溶液を活性化剤として用いることにより、電気伝導性を損なうことなく、透明性に優れた酸化亜鉛皮膜を作製することができる。
【００１８】
上記工程５）で使用する強酸溶液としては、ホウフッ酸、塩酸、メタンスルホン酸、硫酸等の強酸を１〜２００ｇ／Ｌ、特に１０〜１００ｇ／Ｌ水に溶解した溶液を使用することができる。この場合、浸漬温度は１０〜６０℃、特に１５〜３５℃、浸漬時間は０．１〜３０分間、特に０．５〜５分間とすることができる。このアクセレレータ処理を行うことにより、透明性を更に向上させることができ、生成酸化亜鉛の物性を高めることができる。その理由は必ずしも明らかではないが、上記センシタイジング、アクチベーティングの工程で生じた２酸化錫を溶解するためと考えられる。なお、上記３），４）の工程だけでも十分な透明性を与えるので、工程５）は都合により省略してもよいが、この工程５）を使用すると透明性はより向上する。
【００１９】
上記工程７）で使用する酸化亜鉛析出溶液としては、ＺｎＯを作製できる液であればよく、特に制限されないが、硝酸亜鉛等の亜鉛塩０．０１〜０．５モル／Ｌ、好ましくは０．０５〜０．２モル／Ｌと、ジメチルアミンボラン等のボラン系還元剤、その他の還元剤を０．００１〜０．５モル／Ｌ、好ましくは０．０１〜０．２モル／Ｌ、特に０．０３〜０．１モル／Ｌ含有するｐＨ４〜９程度、特にｐＨ６．５程度の処理液を好適に用いることができ、１０〜８０℃で５〜１２０分間浸漬処理する方法が採用し得る。
【００２０】
最適な無電解めっき液としては、Ｚｎ（ＮＯ3）2０．１モル／Ｌと、ジメチルアミンボラン０．０３モル／Ｌを含有するｐＨ６．５の処理液を用いることがよい。この組成から得られた酸化亜鉛皮膜は、粒子径が小さくなり、Ｃ軸配向（０００１）し、ボイドが減少するので、透明性、導電性が向上する。
【００２１】
また、工程８）においては、上記工程７）と同様の処理液を使用し得、工程７）で得られた無電解酸化亜鉛皮膜を陰極とし、亜鉛、カーボン、白金等を陽極として、上記酸化亜鉛皮膜１ｃｍ2あたり０．１〜２０クーロン、好ましくは１〜１０クーロン通電して、０．０１μｍ以上、好ましくは０．０５〜５μｍ、更に好ましくは０．１〜２μｍの厚さに形成すればよい。なお、めっき温度としては１０〜８０℃程度とすることができる。
【００２２】
上記方法で得られた酸化亜鉛皮膜は、厚さ０．０１μｍ以上において、吸光光度計で可視部の透過度を測定した場合、６０％以上、特に６０〜９５％程度の透過度を示す。また、その比抵抗は四探針法で測定した場合、０．２Ω・ｃｍ以下、特に０．０００１〜０．２Ω・ｃｍである。
【００２３】
本発明の酸化亜鉛皮膜は、電気導電性、透明性に優れているため、液晶ディスプレイの透明電極、太陽電池用の透明半導体電極などとして有効に用いられる。
【００２４】
【発明の効果】
本発明によれば、電気導電性と透明性の優れた酸化亜鉛皮膜を作製できる。
【００２５】
【実施例】
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００２６】
〔実施例１〕
ガラスをアセトンで洗浄し、下記表面調整剤溶液に２０℃で５分間浸漬後、水洗を行い、次いで下記センシタイジング溶液で２０℃で１分間センシタイズした後、下記銀塩活性化溶液を用いて２０℃で１分間活性化処理した。この上に、下記に示す酸化亜鉛析出溶液に６５℃で３０分間浸漬して、無電解法でＺｎＯを析出させた。更に、このＺｎＯ析出物を陰極とし、亜鉛板を陽極とし、上記酸化亜鉛析出溶液中で６５℃，３０分間，１ｃｍ2あたり４クーロンの通電化処理を行い、電解して、ＺｎＯを成長させた。
【００２７】
得られたＺｎＯ皮膜の厚さは約１μｍであり、その光透過率、比抵抗を測定した。結果を表１に示す。なお、光透過率は吸光光度法により、比抵抗は四探針法により測定した。
【００２８】
表面調整剤溶液
上村工業株式会社製 スルカップＣＤ−２０２ ５０ ｍＬ／Ｌ
センシタイジング溶液
ＳｎＣｌ2・２Ｈ2Ｏ １５ ｇ／Ｌ
濃塩酸 １５ ｍＬ／Ｌ
銀塩活性化溶液
ＡｇＮＯ3 １．５ ｇ／Ｌ
ＮｉＳＯ4・６Ｈ2Ｏ ０．３ ｇ／Ｌ
ｐＨ ７
酸化亜鉛析出溶液
Ｚｎ（ＮＯ3）2 ０．１ モル／Ｌ
ジメチルアミンボラン ０．０３ モル／Ｌ
ｐＨ ６．５
【００２９】
〔実施例２〕
実施例１において、銀塩活性化溶液による処理後、ホウフッ酸５０ｇ／Ｌの強酸溶液を用いて２０℃で１分間アクセレレータ処理を行い、次いで酸化亜鉛析出溶液による処理を行った以外は、実施例１と同様にしてＺｎＯ皮膜を得た。
【００３０】
〔比較例〕
実施例１において、銀塩活性化溶液の代わりに下記パラジウム活性化溶液を用いて、２０℃，１分間の活性化処理を行った以外は実施例１と同様に操作した。
【００３１】
得られたＺｎＯ皮膜（厚さ１μｍ）の光透過率及び比抵抗の測定結果を表１に示す。
【００３２】
パラジウム活性化液
ＰｄＣｌ2 １ ｇ／Ｌ
濃塩酸 １ ｍＬ／Ｌ
【００３３】
【表１】
表１の結果より、本発明法により透明性、導電性が非常に改善されたＺｎＯ皮膜を形成し得ることが認められる。[0001]
BACKGROUND OF THE INVENTION
The present invention is a transparent electrode of a liquid crystal display, to a method for manufacturing a transparent semiconductor electrode such as a useful transparent zinc oxide skin layer, such as for solar cells.
[0002]
[Prior art and problems to be solved by the invention]
Zinc oxide is an oxide semiconductor with a forbidden band width of 3.3 eV having a wurtzite structure, has excellent characteristics in terms of piezoelectric effect, conductive effect and light emitting effect, and is abundant in resources. This zinc oxide film is applied to surface acoustic wave elements, transparent conductive films, sensors, and photocatalysts. At present, preparation of zinc oxide films by dry methods such as chemical vapor deposition (CVD), sputtering, and molecular beam epitaxy (MBE), and wet methods such as sol-gel method and liquid phase growth method are under consideration. Yes. However, the dry method requires an evacuation device and gas introduction device for controlling the film forming atmosphere, a high-frequency power source for generating plasma, and equipment heating and driving devices. Generally, film formation is performed at 400 ° C. or higher. Done. Also in the above wet method, in order to obtain a crystalline oxide film, heating at 400 ° C. or higher is necessary after film formation.
[0003]
Therefore, in recent years, there has been reported a method of producing zinc oxide having excellent electrical conductivity on a non-conductor by using both an electroless method using zinc nitrate and dimethylamine borane (DMAB) and an electrolytic method ( (Proceedings of the 12th Circuit Implementation Academic Lecture Conference, page 121, published March 9, 1998). This method is a method for producing a zinc oxide film having excellent electrical conductivity from an aqueous solution on a nonconductor, and does not require equipment required for the dry method, and does not require heating at a high temperature.
[0004]
However, although the reported method can produce a zinc oxide film having excellent electrical conductivity, it is difficult to produce a zinc oxide film having excellent optical transparency. Therefore, in order to make the zinc oxide film usable industrially, it is necessary to produce a zinc oxide film excellent in transparency and electrical conductivity.
[0005]
The present invention has been made in order to meet the demands, and an object thereof is to provide a manufacturing method of the zinc oxide skin layer by the electric conductivity and transparency of the excellent wet plating method.
[0006]
Means for Solving the Problem and Embodiment of the Invention
In order to achieve the above object, the present invention
Claim 1 :
After catalyzing a non-conductive base material having optical transparency with an activator containing silver ions, a zinc oxide film is formed on the base material by an electroless method by dipping in a zinc oxide deposition solution, A method for producing a transparent zinc oxide film, wherein the zinc oxide film is electrolyzed with the zinc oxide deposition solution as a cathode to form a transparent zinc oxide film having a thickness of 0.01 μm or more;
Claim 2 :
The method according to claim 1 , wherein the substrate is subjected to a sensitizing treatment with a sensitizing solution containing divalent tin ions, and then subjected to a catalytic treatment with an activator containing the silver ions.
Claim 3 :
The preparation method according to claim 2 , wherein after the catalyst treatment with the activator, the immersion treatment in a strong acid solution is performed, and then the immersion treatment in the zinc oxide deposition solution is performed.
[0007]
That is, as a result of improving the transparency of the zinc oxide film by examining the catalyst application step when the zinc oxide film is produced by an electroless method, the present inventors have improved electrical conductivity and optical properties. The present inventors have found that a zinc oxide film excellent in mechanical transparency can be obtained. The reason for these improvements is that the silver catalyst can deposit dense ZnO early compared to the Pd catalyst, and the dense ZnO grows thereon, so that the transparency is improved and the conductivity is also improved. Conceivable.
[0008]
When an example of the silver catalyst on the glass used in the present invention was analyzed by ESCA, silver oxide and tin dioxide were found. On the other hand, in the case of a Pd catalyst, Pd oxide and tin dioxide were observed. Further, when the adhesion state of these catalysts was observed with an AFM (Atomic Force Microscope), it was found that the silver catalyst had a denser and less uneven surface as compared with the Pd catalyst. Thus, it is considered that the improvement of the dispersibility and uniformity of the catalyst by the silver catalyst greatly contributes to the improvement of the optical and electrical properties of zinc oxide. Although the mechanism of these catalysts is unknown, silver oxide may be reduced to a metal by a reducing agent such as dimethylamine borane used in the next step.
[0009]
Hereinafter, the present invention will be described in more detail.
As described above, the method for producing a zinc oxide film according to the present invention comprises catalyzing a non-conductive substrate having optical transparency with an activator containing silver ions, and then immersing it in a zinc oxide deposition solution. A zinc oxide film is formed on the substrate by an electroless method, and the zinc oxide film is electrolyzed with the zinc oxide deposition solution as a cathode to form a transparent zinc oxide film. The material is preferably sensitized with a sensitizing solution containing divalent tin ions, and then subjected to a catalytic treatment with an activator containing silver ions. Moreover, it is preferable to perform an accelerator process (immersion process to a strong acid solution) after the process by an activator.
[0010]
Here, as said base material, transparent plastic films, such as glass, a polycarbonate, a polyethylene terephthalate, etc. are mentioned.
[0011]
When these base materials are processed to form a zinc oxide film, it is preferable to perform the following processing steps 1) to 8).
[0012]
1) Cleaning: Clean materials such as glass. A known degreasing agent aqueous solution, an organic solvent or the like can be used, and the treatment can be performed under known treatment conditions.
2) Surface conditioning: Charge is imparted to the surface of the material using a known surface conditioning agent.
3) Sensitizing: It is immersed in a solution containing a known tin ion to perform sensitizing.
4) Activating: Activation is performed with an activator mainly containing silver ions.
5) Accelerator treatment: An immersion treatment with a strong acid solution is performed.
6) The above steps 3), 4) and 5) may be repeated several times as necessary.
7) Electroless ZnO film preparation 8) Electrolytic ZnO film preparation
In this case, as the surface conditioner, an aqueous solution containing 1 to 50 g / L of a cationic surfactant or a cationic polymer compound as a main component can be used, and immersion treatment is performed at 10 to 60 ° C. for 1 to 10 minutes. can do.
[0014]
In addition, as a sensitizing solution used for the sensitizing treatment, a divalent tin salt such as SnCl 2 or SnSO 4 dissolved in an acid solution such as hydrochloric acid or sulfuric acid is used in an amount of 1 to 50 g / It is preferable to use a solution containing L and having a pH of 1 to 3, and immersing at 10 to 60 ° C. for 1 to 10 minutes.
[0015]
In the present invention, the activator containing silver ions used in the above step 4) is preferably one having a silver ion concentration of 0.0001 to 0.5 mol / L, particularly 0.001 to 0.1 mol / L. . In this case, examples of the silver salt that gives silver ions include silver sulfate, silver sulfite, silver thiosulfate, silver perchlorate, and silver methanesulfonate, but are not particularly limited. The activation performance can be improved by mixing divalent metal ions in the solution containing silver ions as a main component. As this example, Ni ion, Co ion, iron ion, zinc ion, copper ion, etc. can be used conveniently. Although this improvement mechanism is unknown, these metal ions may be reduced to metals by the electroless plating reducing agent used in the next step. These use concentrations are the same as those of the silver ions. In addition, although the sulfate ion, halide ion, methanesulfonate ion, etc. are used suitably as a counter anion with respect to the said metal ion, there is no limitation in particular. Moreover, about 5-11 is suitable for pH.
[0016]
The solution temperature of the silver-based solution of the present invention can be set in a wide range, but it is usually preferably 15 to 60 ° C. Moreover, the immersion treatment time in these activation liquids can be appropriately selected, but several seconds to several minutes are preferable.
[0017]
In the present invention, by using a solution containing silver as a main component as an activator, a zinc oxide film having excellent transparency can be produced without impairing electrical conductivity.
[0018]
As the strong acid solution used in the above step 5), a solution obtained by dissolving a strong acid such as borofluoric acid, hydrochloric acid, methanesulfonic acid, sulfuric acid or the like in 1 to 200 g / L, particularly 10 to 100 g / L water can be used. In this case, the immersion temperature can be 10 to 60 ° C., particularly 15 to 35 ° C., and the immersion time can be 0.1 to 30 minutes, particularly 0.5 to 5 minutes. By performing this accelerator treatment, the transparency can be further improved and the physical properties of the generated zinc oxide can be enhanced. Although the reason is not necessarily clear, it is considered to dissolve tin dioxide generated in the sensitizing and activating processes. In addition, since sufficient transparency is given only by the steps 3) and 4), the step 5) may be omitted for convenience. However, when this step 5) is used, the transparency is further improved.
[0019]
The zinc oxide deposition solution used in the above step 7) is not particularly limited as long as it is a solution capable of producing ZnO, but is 0.01 to 0.5 mol / L of zinc salt such as zinc nitrate, preferably 0.8. 05-0.2 mol / L, borane-based reducing agents such as dimethylamine borane, and other reducing agents are 0.001-0.5 mol / L, preferably 0.01-0.2 mol / L, especially A treatment liquid containing about 0.03 to 0.1 mol / L of pH about 4 to 9, particularly about pH 6.5 can be suitably used, and a method of immersion treatment at 10 to 80 ° C. for 5 to 120 minutes can be adopted. .
[0020]
As an optimal electroless plating solution, it is preferable to use a pH 6.5 treatment solution containing Zn (NO 3 ) 2 0.1 mol / L and dimethylamine borane 0.03 mol / L. The zinc oxide film obtained from this composition has a small particle size, C-axis orientation (0001), and voids are reduced, so that transparency and conductivity are improved.
[0021]
In step 8), the same treatment solution as in step 7) can be used. The electroless zinc oxide film obtained in step 7) is used as a cathode, and zinc, carbon, platinum, etc. are used as an anode, and the above oxidation is performed. If it forms 0.1-20 coulombs per 1 cm < 2 > of zinc membranes, Preferably it is 1-10 coulombs, and it forms in the thickness of 0.01 micrometer or more, Preferably it is 0.05-5 micrometers, More preferably, it is 0.1-2 micrometers. Good. The plating temperature can be about 10 to 80 ° C.
[0022]
The zinc oxide film obtained by the above method exhibits a transmittance of 60% or more, particularly about 60 to 95%, when the transmittance of the visible part is measured with an absorptiometer at a thickness of 0.01 μm or more. Further, the specific resistance is 0.2Ω · cm or less, particularly 0.0001 to 0.2Ω · cm, when measured by the four-probe method.
[0023]
Since the zinc oxide film of the present invention is excellent in electrical conductivity and transparency, it is effectively used as a transparent electrode for liquid crystal displays, a transparent semiconductor electrode for solar cells, and the like.
[0024]
【The invention's effect】
According to the present invention, a zinc oxide film having excellent electrical conductivity and transparency can be produced.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0026]
[Example 1]
The glass is washed with acetone, immersed in the following surface conditioner solution at 20 ° C. for 5 minutes, washed with water, then sensitized with the following sensitizing solution at 20 ° C. for 1 minute, and then the following silver salt activation solution is used. Activation treatment was performed at 20 ° C. for 1 minute. On this, it immersed in the zinc oxide precipitation solution shown below at 65 degreeC for 30 minute (s), and ZnO was deposited by the electroless method. Further, the ZnO precipitate was used as a cathode, the zinc plate was used as an anode, energization treatment was carried out at 4 ° C. per 1 cm 2 at 65 ° C. for 30 minutes in the zinc oxide precipitation solution, and electrolyzed to grow ZnO. .
[0027]
The thickness of the obtained ZnO film was about 1 μm, and its light transmittance and specific resistance were measured. The results are shown in Table 1. The light transmittance was measured by an absorptiometric method, and the specific resistance was measured by a four probe method.
[0028]
Surface conditioning agent solution Urumura Kogyo Co., Ltd. Sulcup CD-202 50 mL / L
Sensitizing solution SnCl 2 · 2H 2 O 15 g / L
Concentrated hydrochloric acid 15 mL / L
Silver salt activation solution AgNO 3 1.5 g / L
NiSO 4 · 6H 2 O 0.3 g / L
pH 7
Zinc oxide precipitation solution Zn (NO 3 ) 2 0.1 mol / L
Dimethylamine borane 0.03 mol / L
pH 6.5
[0029]
[Example 2]
In Example 1, the treatment with the silver salt activation solution was followed by the accelerator treatment with a strong acid solution of 50 g / L borofluoric acid at 20 ° C. for 1 minute, and then the treatment with the zinc oxide precipitation solution. In the same manner as in Example 1, a ZnO film was obtained.
[0030]
[Comparative Example]
In Example 1, the same operation as in Example 1 was carried out except that the following palladium activation solution was used instead of the silver salt activation solution and the activation treatment was carried out at 20 ° C. for 1 minute.
[0031]
Table 1 shows the measurement results of light transmittance and specific resistance of the obtained ZnO film (thickness: 1 μm).
[0032]
Palladium activation solution PdCl 2 1 g / L
Concentrated hydrochloric acid 1 mL / L
[0033]
[Table 1]
From the results shown in Table 1, it can be seen that a ZnO film having greatly improved transparency and conductivity can be formed by the method of the present invention.
Claims (3)
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| JP4742607B2 (en) * | 2005-02-18 | 2011-08-10 | 大日本印刷株式会社 | Porous material |
| JP4686234B2 (en) * | 2005-03-31 | 2011-05-25 | 大日本印刷株式会社 | Method for producing metal oxide film |
| JP2008244467A (en) * | 2007-02-28 | 2008-10-09 | Sharp Corp | Metal compound film, method of forming same, and base for forming metal compound film |
| JP5295751B2 (en) | 2008-12-25 | 2013-09-18 | 大日本スクリーン製造株式会社 | Zinc oxide film forming method and zinc oxide film forming apparatus |
| JP2011159729A (en) * | 2010-01-29 | 2011-08-18 | Fujifilm Corp | Method of forming conductive zinc oxide laminated film, and method of manufacturing photoelectric conversion element |
| JP2011176283A (en) | 2010-01-29 | 2011-09-08 | Fujifilm Corp | Manufacturing method of photoelectric conversion element |
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