JPH11158692A - Formation of bismuth titanate coating film - Google Patents
Formation of bismuth titanate coating filmInfo
- Publication number
- JPH11158692A JPH11158692A JP9322937A JP32293797A JPH11158692A JP H11158692 A JPH11158692 A JP H11158692A JP 9322937 A JP9322937 A JP 9322937A JP 32293797 A JP32293797 A JP 32293797A JP H11158692 A JPH11158692 A JP H11158692A
- Authority
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- Japan
- Prior art keywords
- bismuth
- peroxide
- film
- coating film
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、コンデンサ、圧電
素子、焦電センサ、強誘電性メモリ等に利用しうるチタ
ン酸ビスマス被膜の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a bismuth titanate film which can be used for capacitors, piezoelectric elements, pyroelectric sensors, ferroelectric memories and the like.
【０００２】[0002]
【従来の技術】従来より、チタン酸ビスマス被膜は産業
上有用な物質であり、コンデンサ、圧電素子、焦電セン
サ、強誘電性メモリ等への応用が検討されている。2. Description of the Related Art Conventionally, bismuth titanate coatings are industrially useful substances, and their application to capacitors, piezoelectric elements, pyroelectric sensors, ferroelectric memories and the like has been studied.
【０００３】このようなチタン酸ビスマス被膜の形成方
法は、スパッタリング法、真空蒸着法、ＣＶＤ法などの
乾式成膜法や、スプレイパイロリシス法、ゾル−ゲル
法、液相成長法などの湿式成膜法により基体上に成膜す
ることが試みられている。[0003] Such a bismuth titanate coating film is formed by a dry film forming method such as a sputtering method, a vacuum evaporation method or a CVD method, or a wet forming method such as a spray pyrolysis method, a sol-gel method or a liquid phase growth method. Attempts have been made to form a film on a substrate by a film method.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、従来の
スパッタリング法、真空蒸着法、ＣＶＤ法などの乾式成
膜法では、成膜装置が大掛かりで高価であり、また成膜
可能な基体面積が制限される、組成や膜厚制御が難し
い、複雑な形状には成膜が難しい等の欠点がある。However, in conventional dry film forming methods such as sputtering, vacuum evaporation, and CVD, the film forming apparatus is large and expensive, and the area of the substrate on which the film can be formed is limited. However, there are disadvantages such as difficulty in controlling the composition and film thickness, and difficulty in forming a film in a complicated shape.
【０００５】またスプレイパイロリシス法、ゾル−ゲル
法、液相成長法などの湿式成膜法においても、数百度の
高温加熱が必要となるため、耐熱性の弱い基板は使用で
きず、基板加熱用の機器が必要になり使用環境も限られ
てくるという問題があった。Further, even in a wet film forming method such as a spray pyrolysis method, a sol-gel method, or a liquid phase growth method, high-temperature heating of several hundred degrees is required, and a substrate having low heat resistance cannot be used. There is a problem that equipment for use is required and the use environment is limited.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上述の技
術的問題点に鑑みて鋭意研究を重ねた結果、基体上にチ
タン酸化物被膜を形成した後に、該チタン酸化物被膜を
ビスマス塩および過酸化物を含む水溶液中で陽極酸化す
ることにより、大掛かりな装置を必要とせず、大面積か
つ複雑形状の基体上にも、膜厚および組成の均一なチタ
ン酸ビスマス被膜を容易に得られる方法を見出し、本発
明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above technical problems, and as a result, after forming a titanium oxide film on a substrate, the titanium oxide film was By anodizing in an aqueous solution containing salts and peroxides, it is easy to obtain a bismuth titanate coating with a uniform thickness and composition on a large-area and complex-shaped substrate without requiring a large-scale apparatus. Thus, the present invention has been completed and the present invention has been completed.
【０００７】すなわち本発明は、基体上にチタン酸化物
被膜を形成する工程と、前記チタン酸化物被膜をビスマ
ス塩および過酸化物を含む水溶液中で陽極酸化する工程
とを含むことを特徴とする。That is, the present invention is characterized in that it comprises a step of forming a titanium oxide film on a substrate and a step of anodizing the titanium oxide film in an aqueous solution containing a bismuth salt and a peroxide. .
【０００８】本発明の製造方法における基体上のチタン
酸化物被膜の形成方法には、特に限定はない。例えば、
スパッタリング法、真空蒸着法、ＣＶＤ法などの乾式成
膜法、ゾル−ゲル法、電解析出法などの湿式成膜法で形
成したものを用いることができる。このうち、電解析出
法によるものが、成膜プロセスの低温下、容易さ、使用
装置の低価格化等の観点から望ましい。[0008] The method for forming the titanium oxide film on the substrate in the production method of the present invention is not particularly limited. For example,
A film formed by a dry film formation method such as a sputtering method, a vacuum evaporation method, or a CVD method, a sol-gel method, or a wet film formation method such as an electrolytic deposition method can be used. Among them, the one by the electrolytic deposition method is desirable from the viewpoints of low temperature, easiness of the film forming process, reduction of the cost of the used apparatus, and the like.
【０００９】また、使用するビスマス塩としても特に限
定はない。例えば、臭化ビスマス、塩化ビスマス、くえ
ん酸ビスマス、よう化ビスマス、硝酸ビスマス、りん酸
ビスマス、オキシ塩化ビスマス等が使用できる。さら
に、ビスマス金属、酸化ビスマス、水酸化ビスマス等を
酸性溶液中で溶解させたものも使用できる。The bismuth salt used is not particularly limited. For example, bismuth bromide, bismuth chloride, bismuth citrate, bismuth iodide, bismuth nitrate, bismuth phosphate, bismuth oxychloride and the like can be used. Furthermore, a solution in which bismuth metal, bismuth oxide, bismuth hydroxide, or the like is dissolved in an acidic solution can be used.
【００１０】使用する過酸化物も、特に限定はない。例
えば、過酸化水素、ペルオキソ硝酸、ペルオキソ一硫
酸、ペルオキソ二硫酸、ペルオキソ一硫酸ナトリウム、
ペルオキソ二硫酸ナトリウム、ペルオキソ一硫酸カリウ
ム、ペルオキソ二硫酸カリウム、ペルオキソ一炭酸ナト
リウム、ペルオキソ一炭酸カリウム、ペルオキソ二炭酸
ナトリウム、ペルオキソ二炭酸カリウム、ペルオキソ一
りん酸、ペルオキソ二りん酸、ペルオキソ一りん酸ナト
リウム、ペルオキソ二りん酸ナトリウム、ペルオキソ一
りん酸カリウム、ペルオキソ二りん酸カリウム、ペルオ
キソほう酸、ペルオキソほう酸ナトリウム等が使用でき
る。このうち、チタン酸ビスマス被膜への不純物の混入
を少なくできる点や入手しやすい点などから、過酸化水
素水を使用することが好都合である。The peroxide used is not particularly limited. For example, hydrogen peroxide, peroxonitrate, peroxomonosulfuric acid, peroxodisulfuric acid, sodium peroxomonosulfate,
Sodium peroxodisulfate, potassium peroxodisulfate, potassium peroxodisulfate, sodium peroxomonocarbonate, potassium peroxomonocarbonate, sodium peroxodicarbonate, potassium peroxodicarbonate, peroxomonophosphate, peroxodiphosphate, sodium peroxomonophosphate And sodium peroxodiphosphate, potassium peroxomonophosphate, potassium peroxodiphosphate, peroxoboric acid, sodium peroxoborate, and the like. Among them, it is convenient to use aqueous hydrogen peroxide because the contamination of the bismuth titanate film with impurities can be reduced, and it is easily available.
【００１１】本発明において、ビスマス塩、過酸化物
は、それぞれ一種類のものを用いてもよいし、複数のも
のを混合して用いても良い。なお、ビスマス塩は含むが
過酸化物を含まない溶液を用いた場合には、チタン酸化
物の溶解が起こりチタン酸ビスマス被膜は得られないこ
とが後述の比較実験から判明している。In the present invention, the bismuth salt and the peroxide may be used alone or in combination of two or more. It should be noted from a comparative experiment described below that when a solution containing a bismuth salt but not containing a peroxide was used, the titanium oxide was dissolved and a bismuth titanate coating could not be obtained.
【００１２】ビスマス塩および過酸化物の濃度は広い範
囲で使用可能であるが、低濃度すぎるとチタン酸化物の
溶解のみが生じるためチタン酸ビスマス被膜は得られ
ず、また高濃度すぎるとビスマス酸化物のみの生成とな
る傾向がある。このため通常、ビスマスイオンおよび過
酸化物イオンのそれぞれの濃度が、０．００１ｍｏｌ／
Ｌ〜１．０ｍｏｌ／Ｌ程度の範囲にあることが適当であ
り、特にそれぞれの濃度が０．１ｍｏｌ程度であること
が好ましい。The concentrations of the bismuth salt and the peroxide can be used in a wide range. However, if the concentration is too low, only the dissolution of the titanium oxide occurs, so that a bismuth titanate coating cannot be obtained. There is a tendency to produce only things. Therefore, the concentration of each of bismuth ions and peroxide ions is usually 0.001 mol /
The concentration is suitably in the range of about L to 1.0 mol / L, and particularly preferably, the concentration of each is about 0.1 mol.
【００１３】また、ビスマス塩および過酸化物を含む水
溶液の水温も、広い範囲で設定可能であるが、通常は２
０℃〜１００℃程度が適当であり、５０℃〜８０℃程度
が好ましい。さらに、水溶液のｐＨ範囲も広い範囲で設
定可能であるが、ｐＨ８〜１４の範囲であればよく、特
にｐＨ１０〜１３程度とすることが好ましい。この際、
ｐＨ３以上の水溶液では、ほとんどのビスマス塩が加水
分解し溶液が白濁してしまうため、場合によってはビス
マス錯体形成が必要である。この場合に使用する錯化剤
としては特に限定はなく、例えばエチレンジアミン四酢
酸塩、ニトリロ酢酸塩等が挙げられる。これらの錯化剤
は、一種類で用いても良いし、複数のものを混合して用
いても良い。The temperature of the aqueous solution containing the bismuth salt and the peroxide can be set in a wide range.
About 0 ° C to 100 ° C is appropriate, and about 50 ° C to 80 ° C is preferable. Further, the pH range of the aqueous solution can be set in a wide range, but may be in the range of pH 8 to 14, particularly preferably about pH 10 to 13. On this occasion,
In an aqueous solution having a pH of 3 or more, most of the bismuth salts are hydrolyzed and the solution becomes cloudy, so that it is necessary to form a bismuth complex in some cases. The complexing agent used in this case is not particularly limited, and examples thereof include ethylenediaminetetraacetate and nitriloacetate. One of these complexing agents may be used, or a plurality of them may be mixed and used.
【００１４】さらに、チタン酸化物被膜を形成する基体
に特に限定はない。例えば、銅、ニッケル、白金、金、
ステンレス鋼、チタンなどの金属材料、あるいは導電性
セラミックス材料、導電性ガラス材料等が挙げられる。
また、各種の絶縁体基体上に前述の導体を形成したもの
を用いても良い。基体は、陽極酸化を行う前に表面改
質、エッチング等の前処理を行っても良い。Further, the substrate on which the titanium oxide film is formed is not particularly limited. For example, copper, nickel, platinum, gold,
Examples thereof include metal materials such as stainless steel and titanium, conductive ceramic materials, and conductive glass materials.
In addition, those obtained by forming the above-described conductor on various insulating substrates may be used. The substrate may be subjected to a pretreatment such as surface modification and etching before the anodic oxidation.
【００１５】加えて、結晶性の向上、膜欠陥の補正、結
晶変態等の観点から、本発明によってチタン酸ビスマス
被膜を作製したのちに、熱処理を施すことも可能であ
る。In addition, from the viewpoints of improving crystallinity, correcting film defects, crystal transformation, and the like, it is also possible to perform a heat treatment after preparing the bismuth titanate coating according to the present invention.
【００１６】本発明において、チタン酸化物被膜の形成
された基体を陽極酸化する方法としては、通常の陽極酸
化法がいずれも採用できる。例えば、三極式の電解セル
を形成装置として用いた場合、作用電極電位は溶液中の
ビスマス塩および過酸化物濃度に応じて設定可能である
が、通常Ａｇ／ＡｇＣｌ電極基準で＋０．５〜＋０．６
Ｖ程度が適当であり、＋１．０〜＋５．０Ｖ程度が好ま
しい。In the present invention, as a method of anodizing the substrate on which the titanium oxide film is formed, any ordinary anodizing method can be adopted. For example, when a three-electrode electrolytic cell is used as a forming apparatus, the working electrode potential can be set according to the bismuth salt and peroxide concentrations in the solution, but is usually +0.5 to + based on the Ag / AgCl electrode. +0.6
About V is appropriate, and about +1.0 to +5.0 V is preferable.
【００１７】[0017]
【発明の実施の形態】以下、本発明に従って実施した実
験について説明する。なお、薬品はすべて試薬特級（ナ
カライテスク（株）製）を使用した。チタン酸ビスマス
被膜作成用基体（すなわち作用電極）としてはｓｕｓ３
０４（ニラコ（株）製）を用い、常法に従い脱脂処理を
行った。また、電解セルは通常用いられている三極式の
もの（対電極：Ｐｔ箔２０×３０×０．１ｍｍ、高純度
化学（株）製、参照電極：飽和ＫＣｌ入りＡｇ／ＡｇＣ
ｌ、堀場製作所（株）製、セル容量：３００ｍＬ）を使
用した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an experiment conducted according to the present invention will be described. In addition, all chemicals used reagent special grade (Nacalai Tesque Co., Ltd. product). Sus3 is used as a substrate for forming a bismuth titanate film (that is, a working electrode).
04 (manufactured by Niraco Co., Ltd.) and degreased according to a conventional method. The electrolytic cell is a commonly used three-electrode type (counter electrode: Pt foil 20 × 30 × 0.1 mm, manufactured by Kojundo Chemical Co., Ltd., reference electrode: Ag / AgC containing saturated KCl)
1, Horiba, Ltd., cell capacity: 300 mL) was used.
【００１８】[0018]
【実験例１】まず、先に準備したｓｕｓ３０４上に、高
周波スパッタリング法により膜厚０．５μｍのチタン酸
化物被膜を形成した。この際、ターゲットとして二酸化
チタン（純度９９．５％、高純度化学（株）製）を、形
成時の雰囲気ガスとしてアルゴンガス（純度９９．９９
９％、住友精化（株）製）を用い、チャンバー内真空度
３．０×１０-3Ｔｏｒｒ、投入電力量３００Ｗの条件と
した。Experimental Example 1 First, a titanium oxide film having a thickness of 0.5 μm was formed on the previously prepared sus304 by a high frequency sputtering method. At this time, titanium dioxide (purity 99.5%, manufactured by Kojundo Chemical Co., Ltd.) was used as a target, and argon gas (purity 99.99) was used as an atmosphere gas at the time of formation.
9%, manufactured by Sumitomo Seika Co., Ltd.), the conditions were as follows: the degree of vacuum in the chamber was 3.0 × 10 −3 Torr, and the input power was 300 W.
【００１９】次に、電解セルに下記の組成のチタン酸ビ
スマス被膜作成用水溶液を入れたあと、恒温槽中にセッ
トしたのち、以下の条件下で陽極酸化を行った。Next, an aqueous solution for forming a bismuth titanate coating having the following composition was put into an electrolytic cell, and then set in a thermostat, and then anodized under the following conditions.
【００２０】 塩化ビスマス ０．１ ｍｏｌ／Ｌ クエン酸三ナトリウム塩 ０．４ ｍｏｌ／Ｌ 過酸化水素水（３０重量％過酸化水素含有） ０．１ ｍｏｌ／Ｌ （２０重量％水酸化ナトリウム水溶液でｐＨ１１まで調整） 上記水溶液中で、液温を６０℃に保持し、＋２．０Ｖ、
９０分で陽極酸化を行ったところ、陽極酸化前には無色
透明であったチタン酸化物被膜が薄暗い黄色に着色され
た。この膜をＸ線回折法により測定したところ、チャー
トには結晶性チタン酸ビスマスおよびチタン金属箔に起
因するピークが認められた。Bismuth chloride 0.1 mol / L trisodium citrate 0.4 mol / L Hydrogen peroxide solution (containing 30% by weight of hydrogen peroxide) 0.1 mol / L (20% by weight aqueous sodium hydroxide solution) In the above aqueous solution, the solution temperature was maintained at 60 ° C., and +2.0 V
When anodic oxidation was performed for 90 minutes, the colorless and transparent titanium oxide film before anodic oxidation was colored dimly yellow. When this film was measured by an X-ray diffraction method, peaks attributable to crystalline bismuth titanate and titanium metal foil were recognized in the chart.
【００２１】[0021]
【実験例２】先に準備したｓｕｓ３０４上に、電解析出
法により膜厚０．４μｍのチタン酸化物被膜を形成し
た。この際、チタン酸化物被膜作成用の電解液には、三
塩化チタン、クエン酸、硝酸カリウム、過酸化水素をい
ずれも０．０１ｍｏｌ／Ｌ含むｐＨ６．０の水溶液を用
いた。Experimental Example 2 A 0.4 μm-thick titanium oxide film was formed on the previously prepared sus304 by electrolytic deposition. At this time, an aqueous solution having a pH of 6.0 containing 0.01 mol / L of titanium trichloride, citric acid, potassium nitrate, and hydrogen peroxide was used as an electrolyte for forming a titanium oxide film.
【００２２】次に、電解セルに下記の組成のチタン酸ビ
スマス被膜作成用水溶液を入れたあと、恒温槽中にセッ
トしたのち、以下の条件下で陽極酸化を行った。Next, an aqueous solution for forming a bismuth titanate film having the following composition was put into an electrolytic cell, and then set in a thermostat, and then anodized under the following conditions.
【００２３】 硝酸ビスマス ０．１ ｍｏｌ／Ｌ ニトリロ酢酸塩 ０．４ ｍｏｌ／Ｌ ペルオキソほう酸ナトリウム ０．１ ｍｏｌ／Ｌ （２０重量％水酸化ナトリウム水溶液でｐＨ１２まで調整） 上記水溶液中で、液温を７０℃に保持し、＋３．０Ｖ、
６０分で陽極酸化を行ったところ、陽極酸化前には無色
透明であったチタン酸化物被膜が薄暗い黄色に着色され
た。この膜を、実験例１と同様に、Ｘ線回折法により同
定したところチタン酸ビスマスであった。Bismuth nitrate 0.1 mol / L Nitriloacetate 0.4 mol / L Sodium peroxoborate 0.1 mol / L (adjusted to pH 12 with a 20 wt% aqueous sodium hydroxide solution) Hold at 70 ° C., + 3.0V,
When the anodization was performed for 60 minutes, the titanium oxide film that was colorless and transparent before the anodization was colored dim yellow. When this film was identified by X-ray diffraction in the same manner as in Experimental Example 1, it was bismuth titanate.
【００２４】[0024]
【実験例３】チタン酸化物被膜は、実験例２と同様の条
件で、電解析出法によりｓｕｓ３０４上に形成した。[Experimental Example 3] A titanium oxide film was formed on sus304 by electrolytic deposition under the same conditions as in Experimental Example 2.
【００２５】次に、電解セルに下記の組成のチタン酸ビ
スマス被膜作成用水溶液を入れたあと、恒温槽中にセッ
トしたのち、以下の条件下で陽極酸化を行った。Next, an aqueous solution for forming a bismuth titanate coating having the following composition was put into an electrolytic cell, and then set in a thermostat, and then anodized under the following conditions.
【００２６】 クエン酸ビスマス ０．０５ ｍｏｌ／Ｌ エチレンジアミン四酢酸二ナトリウム塩 ０．２ ｍｏｌ／Ｌ ペルオキソ二硫酸ナトリウム ０．０５ ｍｏｌ／Ｌ （２０重量％水酸化ナトリウム水溶液でｐＨ１０まで調整） 上記水溶液中で、液温を５０℃に保持し、＋４．０Ｖ、
６０分で陽極酸化を行ったところ、陽極酸化前には無色
透明であったチタン酸化物被膜が薄暗い黄色に着色され
た。この膜を、実験例１と同様に、Ｘ線回折法により同
定したところチタン酸ビスマスであった。Bismuth citrate 0.05 mol / L Disodium ethylenediaminetetraacetate 0.2 mol / L Sodium peroxodisulfate 0.05 mol / L (adjusted to pH 10 with 20% by weight aqueous sodium hydroxide solution) And the liquid temperature is maintained at 50 ° C.
When the anodization was performed for 60 minutes, the titanium oxide film that was colorless and transparent before the anodization was colored dim yellow. When this film was identified by X-ray diffraction in the same manner as in Experimental Example 1, it was bismuth titanate.
【００２７】[0027]
【比較例】チタン酸化物被膜は、実験例１と同条件で、
高周波スパッタリング法によりｓｕｓ３０４上に形成し
た。[Comparative Example] A titanium oxide film was prepared under the same conditions as in Experimental Example 1.
It was formed on sus304 by a high frequency sputtering method.
【００２８】次に、電解セルに過酸化物を除いた下記の
組成のチタン酸ビスマス被膜作成用水溶液を入れたあ
と、恒温槽中にセットしたのち、以下の条件下で陽極酸
化を行った。Next, after an aqueous solution for forming a bismuth titanate coating having the following composition excluding peroxides was put into the electrolytic cell, and set in a thermostat, anodization was performed under the following conditions.
【００２９】 塩化ビスマス ０．０５ ｍｏｌ／Ｌ エチレンジアミン四酢酸二ナトリウム塩 ０．２ ｍｏｌ／Ｌ （２０重量％水酸化ナトリウム水溶液でｐＨ１０まで調整） 上記水溶液中で、液温を５０℃に保持し、＋３．０Ｖ、
６０分で陽極酸化を行った。この陽極酸化の間に、ｓｕ
ｓ３０４上に形成されていたチタン酸化物被膜の一部が
剥離する現象が観察された。陽極酸化後、ｓｕｓ３０４
上の膜を、実施例１と同様に、Ｘ線回折法により同定し
たところ、チタン酸ビスマスに起因するピークは見られ
ず、チタン金属箔に起因するピークのみが認められた。Bismuth chloride 0.05 mol / L Ethylenediaminetetraacetic acid disodium salt 0.2 mol / L (adjusted to pH 10 with a 20 wt% aqueous sodium hydroxide solution) In the above aqueous solution, the liquid temperature was maintained at 50 ° C, + 3.0V,
Anodization was performed in 60 minutes. During this anodization, su
A phenomenon was observed in which a part of the titanium oxide film formed on s304 was peeled off. After anodic oxidation, sus304
When the upper film was identified by an X-ray diffraction method in the same manner as in Example 1, no peak due to bismuth titanate was found, and only a peak due to titanium metal foil was observed.
【００３０】[0030]
【発明の効果】このように本発明によれば、基体上にチ
タン酸化物被膜を形成したのちに、該被膜をビスマス塩
および過酸化物を含む水溶液中で陽極酸化することによ
り、大掛かりな装置を必要とせず、大面積および複雑形
状の基体上にも、膜厚および組成が均一なチタン酸ビス
マス被膜を容易に得ることが可能である。As described above, according to the present invention, after a titanium oxide film is formed on a substrate, the film is anodized in an aqueous solution containing a bismuth salt and a peroxide, whereby a large-scale apparatus is provided. It is possible to easily obtain a bismuth titanate coating having a uniform film thickness and composition even on a substrate having a large area and a complicated shape without the need for a thin film.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年７月２１日[Submission date] July 21, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１２】ビスマス塩および過酸化物の濃度は広い範
囲で使用可能であるが、低濃度すぎるとチタン酸化物の
溶解のみが生じるためチタン酸ビスマス被膜は得られ
ず、また高濃度すぎるとビスマス酸化物のみの生成とな
る傾向がある。このため通常、ビスマスイオンおよび過
酸化物イオンのそれぞれの濃度が、０．００１ｍｏｌ／
Ｌ〜１．０ｍｏｌ／Ｌ程度の範囲にあることが適当であ
り、特にそれぞれの濃度が０．１ｍｏｌ／Ｌ程度である
ことが好ましい。The concentrations of the bismuth salt and the peroxide can be used in a wide range. However, if the concentration is too low, only the dissolution of the titanium oxide occurs, so that a bismuth titanate coating cannot be obtained. There is a tendency to produce only things. Therefore, the concentration of each of bismuth ions and peroxide ions is usually 0.001 mol /
The concentration is suitably in the range of about L to 1.0 mol / L , and particularly preferably, each concentration is about 0.1 mol / L.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１６】本発明において、チタン酸化物被膜の形成
された基体を陽極酸化する方法としては、通常の陽極酸
化法がいずれも採用できる。例えば、三極式の電解セル
を形成装置として用いた場合、作用電極電位は溶液中の
ビスマス塩および過酸化物濃度に応じて設定可能である
が、通常Ａｇ／ＡｇＣｌ電極基準で＋０．５〜＋６．０
Ｖ程度が適当であり、＋１．０〜＋５．０Ｖ程度が好ま
しい。In the present invention, as a method of anodizing the substrate on which the titanium oxide film is formed, any ordinary anodizing method can be adopted. For example, when a three-electrode electrolytic cell is used as a forming apparatus, the working electrode potential can be set according to the bismuth salt and peroxide concentrations in the solution, but is usually +0.5 to + based on the Ag / AgCl electrode. +6.0
About V is appropriate, and about +1.0 to +5.0 V is preferable.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ２５Ｄ 9/06 Ｃ２５Ｄ 9/06 Ｈ０１Ｇ 4/10 Ｈ０１Ｇ 4/12 ３９７ 4/12 ３９７ 4/10 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C25D 9/06 C25D 9/06 H01G 4/10 H01G 4/12 397 4/12 397 4/10
Claims (3)
程と、 前記チタン酸化物被膜を、ビスマス塩および過酸化物を
含む水溶液中で陽極酸化する工程と、を含むことを特徴
とするチタン酸ビスマス被膜の形成方法。1. A titanium process comprising: forming a titanium oxide film on a substrate; and anodizing the titanium oxide film in an aqueous solution containing a bismuth salt and a peroxide. A method for forming a bismuth acid coating.
よって形成することを特徴とする請求項１記載のチタン
酸ビスマス被膜の形成方法。2. The method for forming a bismuth titanate coating according to claim 1, wherein the titanium oxide coating is formed by an electrolytic deposition method.
マス被膜が形成されたのちに、チタン酸ビスマス被膜に
熱処理を施す工程を有することを特徴とする請求項１ま
たは請求項２のいずれかに記載のチタン酸ビスマス被膜
の形成方法。3. The method according to claim 1, further comprising a step of subjecting the bismuth titanate coating to a heat treatment after the bismuth titanate coating is formed by the anodic oxidation step. A method for forming a bismuth titanate coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32293797A JP3921763B2 (en) | 1997-11-25 | 1997-11-25 | Method for forming bismuth titanate film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32293797A JP3921763B2 (en) | 1997-11-25 | 1997-11-25 | Method for forming bismuth titanate film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11158692A true JPH11158692A (en) | 1999-06-15 |
| JP3921763B2 JP3921763B2 (en) | 2007-05-30 |
Family
ID=18149305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32293797A Expired - Lifetime JP3921763B2 (en) | 1997-11-25 | 1997-11-25 | Method for forming bismuth titanate film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3921763B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238990A (en) * | 2006-03-07 | 2007-09-20 | Osaka City | Composition for electrolytically forming silver oxide film |
| JP2011516721A (en) * | 2008-02-28 | 2011-05-26 | コーニング インコーポレイテッド | Electrochemical methods for fabricating nanostructures |
| CN104131308A (en) * | 2014-07-24 | 2014-11-05 | 青岛农业大学 | Preparation method for bismuth tungstate |
| RU2614916C1 (en) * | 2016-04-05 | 2017-03-30 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for bismuth titanate thin layers production |
| CN114216949A (en) * | 2021-11-18 | 2022-03-22 | 佛山科学技术学院 | Screen printing electrode, manufacturing method and detection method thereof |
| CN114457358A (en) * | 2022-01-18 | 2022-05-10 | 安徽大学 | Bi/TiO2Series electrocatalytic materials, preparation method and application thereof |
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1997
- 1997-11-25 JP JP32293797A patent/JP3921763B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238990A (en) * | 2006-03-07 | 2007-09-20 | Osaka City | Composition for electrolytically forming silver oxide film |
| JP2011516721A (en) * | 2008-02-28 | 2011-05-26 | コーニング インコーポレイテッド | Electrochemical methods for fabricating nanostructures |
| CN104131308A (en) * | 2014-07-24 | 2014-11-05 | 青岛农业大学 | Preparation method for bismuth tungstate |
| RU2614916C1 (en) * | 2016-04-05 | 2017-03-30 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method for bismuth titanate thin layers production |
| CN114216949A (en) * | 2021-11-18 | 2022-03-22 | 佛山科学技术学院 | Screen printing electrode, manufacturing method and detection method thereof |
| CN114216949B (en) * | 2021-11-18 | 2023-08-08 | 佛山科学技术学院 | Screen printing electrode, manufacturing method and detection method thereof |
| CN114457358A (en) * | 2022-01-18 | 2022-05-10 | 安徽大学 | Bi/TiO2Series electrocatalytic materials, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| JP3921763B2 (en) | 2007-05-30 |
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