JPH0881222A - Titanium oxide film having modified surface, its production and photoelectron transfer element using the same film - Google Patents
Titanium oxide film having modified surface, its production and photoelectron transfer element using the same filmInfo
- Publication number
- JPH0881222A JPH0881222A JP7201775A JP20177595A JPH0881222A JP H0881222 A JPH0881222 A JP H0881222A JP 7201775 A JP7201775 A JP 7201775A JP 20177595 A JP20177595 A JP 20177595A JP H0881222 A JPH0881222 A JP H0881222A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- oxide film
- modified
- sensitizing dye
- film
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面改質された酸化チタ
ン膜およびその製造方法ならびにそれを用いた光電変換
素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-modified titanium oxide film, a method for producing the same, and a photoelectric conversion device using the same.
【０００２】[0002]
【従来の技術】酸化チタン膜は、酸化チタン粒子を支持
体に固着させたものであって、紫外線吸収材、光学材
料、電気・電子材料、光電変換材料、装飾用材料、触
媒、光触媒、触媒担体、吸着材、バイオリアクターなど
に有用なものである。2. Description of the Related Art A titanium oxide film is a film in which titanium oxide particles are fixed to a support, and is an ultraviolet absorber, an optical material, an electric / electronic material, a photoelectric conversion material, a decorative material, a catalyst, a photocatalyst, a catalyst. It is useful for carriers, adsorbents, bioreactors and the like.
【０００３】酸化チタン膜を製造するには、たとえば、
チタニウムイソプロポキサイドなどの有機チタン化合物
を含む溶液に支持体を浸漬し、引き上げた後、支持体を
高温に加熱して成膜する方法、高温の支持体表面に四塩
化チタンの蒸気を吹きつけて成膜する方法、高温の支持
体表面にチタニウムアセチルアセトナート、チタンアル
コキシドなどの有機チタン化合物を含む溶液を吹きつけ
て成膜する方法、酸化チタン粒子を支持体表面に付着さ
せる方法などが採られている。To manufacture a titanium oxide film, for example,
A method of forming a film by immersing the support in a solution containing an organic titanium compound such as titanium isopropoxide, pulling it up, then heating the support to a high temperature to form a film, spraying titanium tetrachloride vapor on the surface of the high-temperature support Film forming method, a method of spraying a solution containing an organotitanium compound such as titanium acetylacetonate or titanium alkoxide onto the surface of a high-temperature support to form a film, and a method of attaching titanium oxide particles to the surface of the support. Has been.
【０００４】[0004]
【発明が解決しようとする課題】酸化チタン膜の表面に
は、格子欠陥、不純物や水酸基が多く存在するため、そ
れらが障害となって充分満足できる特性が得られ難い。
たとえば、光電変換材料として用いる場合には、格子欠
陥、不純物や水酸基により表面準位が形成され暗電流が
増加し開放電圧が低下したり、増感色素を吸着させる際
には増感色素の吸着量が低下すると共に電子注入も阻害
され増感効率が低下したりする。また、触媒、光触媒、
吸着材などに用いる場合には、格子欠陥、不純物や水酸
基によりそれらの活性や吸着能が低下したりする。Since the surface of the titanium oxide film has many lattice defects, impurities and hydroxyl groups, it is difficult to obtain sufficiently satisfactory characteristics because they are obstacles.
For example, when used as a photoelectric conversion material, surface levels are formed by lattice defects, impurities, and hydroxyl groups, which increases dark current and lowers the open-circuit voltage. As the amount decreases, electron injection is also hindered and the sensitization efficiency decreases. Also, catalysts, photocatalysts,
When it is used as an adsorbent or the like, its activity or adsorbability may be reduced due to lattice defects, impurities or hydroxyl groups.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決するために種々検討した結果、（１）酸化チタン
膜をエッチング剤に接触させて、酸化チタン膜の表面を
エッチングすると、格子欠陥や不純物を減少させること
ができ、酸化チタン粒子をエッチング処理した後成膜す
る方法に比べ、酸化チタン膜の表面を効率よく、かつ、
容易に改質することができること、さらに鉱酸イオンが
水酸基と置換して水酸基の量を制御できること、（２）
前記のエッチング処理を行った後増感色素を吸着させる
と、増感色素の吸着量が増加すると共に増感効率が向上
することなどを見出し、本発明を完成した。As a result of various studies to solve the above problems, the present inventors have found that (1) when the titanium oxide film is brought into contact with an etching agent to etch the surface of the titanium oxide film, Lattice defects and impurities can be reduced, and the surface of the titanium oxide film can be efficiently and compared to a method of forming a film after etching the titanium oxide particles.
It can be easily modified, and the amount of hydroxyl groups can be controlled by substituting mineral acid ions with hydroxyl groups, (2)
The present invention has been completed by finding that adsorbing a sensitizing dye after performing the above-described etching treatment increases the adsorption amount of the sensitizing dye and improves the sensitizing efficiency.
【０００６】すなわち、本発明は、表面改質された酸化
チタン膜を提供することにある。また、本発明は、表面
改質された酸化チタン膜の製造方法を提供することにあ
る。さらに、本発明は、表面改質された酸化チタン膜を
電極として用いた光電変換素子を提供することにある。That is, the present invention is to provide a surface-modified titanium oxide film. The present invention also provides a method for producing a surface-modified titanium oxide film. Further, the present invention is to provide a photoelectric conversion element using a surface-modified titanium oxide film as an electrode.
【０００７】本発明において、酸化チタンとは、アナタ
ース型酸化チタン、ルチル型酸化チタン、ブルッカイト
型酸化チタン、無定形酸化チタン、メタチタン酸、オル
トチタン酸などの各種の酸化チタン、あるいは、水酸化
チタン、酸化チタン水和物を意味する。さらに、亜鉛や
ニオブなどの異種元素をドープしたり、表面に処理した
酸化チタンを含む。異種元素をドープしたり、表面処理
した酸化チタンを用いた酸化チタン膜をエッチング処理
すると、異種元素が溶出する際に酸化チタン膜の表面改
質が効率よく行われる。酸化チタンの粒子径は、支持体
との接着性を考慮すると、５〜１００ｎｍが好ましく、
１０〜５０ｎｍがより好ましく、１０〜３０ｎｍがもっ
とも好ましい。本発明において、酸化チタン膜とは、前
記の酸化チタンの粒子を支持体に付着したものである。
酸化チタン膜の結晶型は、アナタース型、ルチル型、あ
るいはそれらの混合物のいずれでもよく、用いる酸化チ
タン粒子の結晶型を適宜選択したり、支持体に付着する
際の焼成の条件などを適宜設定することにより任意に変
えることができる。また、酸化チタン膜の膜厚、透明
度、表面積で表される多孔度は、用いる酸化チタン懸濁
液の濃度や酸化チタン粒子の粒子径などの条件を適宜設
定することにより任意に変えることができる。酸化チタ
ン膜の膜厚は、０．５〜５０μｍ程度が好ましい。酸化
チタン膜の多孔度は、光電変換材料、触媒、光触媒、触
媒担体、吸着材などに用いる場合は特に、大きいものが
好ましく、支持体１ｃｍ2 あたりの酸化チタン膜の表面
積の値で表して、１０〜１００００ｃｍ2 程度が好まし
く、５０〜１００００ｃｍ2 がより好ましい。In the present invention, titanium oxide means various titanium oxides such as anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, or titanium hydroxide. , Means titanium oxide hydrate. Further, it includes titanium oxide whose surface is treated by doping with a different element such as zinc or niobium. When the titanium oxide film is doped with a different element or the surface of the titanium oxide film is etched, the surface of the titanium oxide film is efficiently modified when the different element is eluted. The particle size of titanium oxide is preferably 5 to 100 nm in consideration of the adhesiveness to the support,
10 to 50 nm is more preferable, and 10 to 30 nm is most preferable. In the present invention, the titanium oxide film is formed by adhering the particles of titanium oxide described above to a support.
The crystal form of the titanium oxide film may be either anatase type, rutile type, or a mixture thereof, and the crystal form of the titanium oxide particles to be used is appropriately selected, and the firing conditions when adhering to the support are appropriately set. Can be changed arbitrarily. Further, the film thickness of the titanium oxide film, the transparency, and the porosity represented by the surface area can be arbitrarily changed by appropriately setting conditions such as the concentration of the titanium oxide suspension used and the particle diameter of the titanium oxide particles. . The thickness of the titanium oxide film is preferably about 0.5 to 50 μm. The porosity of the titanium oxide film is preferably large, particularly when it is used for a photoelectric conversion material, a catalyst, a photocatalyst, a catalyst carrier, an adsorbent, etc., and is expressed by the value of the surface area of the titanium oxide film per 1 cm 2 of the support, 10~10000cm is preferably about 2, 50~10000cm 2 is more preferable.
【０００８】本発明において、酸化チタンを付着する支
持体は、使用目的、用途などに応じて材質、形状、大き
さなどを適宜選択することができる。材質としては、た
とえば、ガラス、金属、セラミックス、プラスチック
ス、木などが挙げられ、形状、大きさとしては、たとえ
ば、一枚の厚板、小さな断片、ビーズのような球状体な
どが挙げられる。In the present invention, the support to which titanium oxide is adhered can be appropriately selected in material, shape, size and the like according to the purpose of use and the intended use. Examples of the material include glass, metal, ceramics, plastics, wood, and the like, and examples of the shape and size include a single thick plate, a small piece, and a spherical body such as beads.
【０００９】本発明において、酸化チタン膜は通常の方
法によって得られたものを用いることができる。通常の
方法としては、たとえば、分解性有機チタン化合物を
支持体に吹き付け、あるいは、塗布して、分解する方
法、チタンアルコキシドやチタンアセトナートの溶液
に支持体を浸漬し、次いで、乾燥する方法、ハロゲン
化チタンや有機チタン化合物を蒸発させて、支持体に酸
化チタン粒子を沈着する方法、酸化チタンゾルを支持
体上でゲル化する方法、チタン化合物を、必要に応じ
核種子の存在下、加水分解または中和して得られる酸化
チタン粒子を支持体に吹き付け、あるいは塗布し、乾燥
し、必要に応じて焼成する方法、酸化チタン粒子をバ
インダーとともに支持体に吹き付け、あるいは塗布し、
乾燥する方法を用いることができる。本発明において
は、前記で得られた酸化チタン粒子を２００〜６００
℃の温度で焼成するか、あるいは、１００℃以上の温度
で水熱処理して酸化チタンの粒子を成長させた後、支持
体に吹き付け、あるいは、塗布し、次いで、乾燥し、焼
成する方法が、酸化チタン膜を支持体に強固に付着させ
ることができることから好ましい方法である。In the present invention, the titanium oxide film may be obtained by a usual method. As a usual method, for example, a method of spraying or decomposing a decomposable organic titanium compound on a support, a method of decomposing, a method of immersing the support in a solution of titanium alkoxide or titanium acetonate, and then drying, A method of evaporating a titanium halide or an organotitanium compound to deposit titanium oxide particles on a support, a method of gelating a titanium oxide sol on a support, and a titanium compound, if necessary, in the presence of nuclear seeds for hydrolysis. Or a method of spraying or coating the support with titanium oxide particles obtained by neutralization, followed by drying and baking as necessary, spraying or coating the support with titanium oxide particles together with a binder,
A method of drying can be used. In the present invention, the titanium oxide particles obtained above are used in an amount of 200 to 600
The method of firing at a temperature of ℃, or hydrothermal treatment at a temperature of 100 ℃ or more to grow particles of titanium oxide, then spraying or coating on a support, then drying and firing, This is a preferred method because the titanium oxide film can be firmly attached to the support.
【００１０】本発明は、酸化チタン膜をエッチング剤に
接触させて、酸化チタン膜の表面をエッチングしてな
る、表面改質された酸化チタン膜である。前記のエッチ
ング剤としては、硫酸、塩酸、次亜塩素酸、硝酸、フッ
酸などの鉱酸、または、フッ化アンモニウム、酸性フッ
化アンモニウムなどのアンモニウム塩、アミン塩などの
鉱酸の塩、あるいは、フッ化水素、フッ素、塩化水素な
どを用いることができる。本発明においては、鉱酸また
は鉱酸の塩が好ましく、特に、フッ酸、あるいは、フッ
化アンモニウム、酸性フッ化アンモニウムなどのフッ酸
の塩を用いると、エッチングにより格子欠陥や不純物を
減少させることができるとともに、酸化チタン膜の表面
に存在する水酸基がフッ素またはフッ素イオンで置換さ
れ、酸化チタン膜の表面にフッ素を結合させることがで
き、結合したフッ素は水分や汚れ成分などの付着を防止
できるため好ましい。The present invention is a surface-modified titanium oxide film obtained by bringing the titanium oxide film into contact with an etching agent to etch the surface of the titanium oxide film. Examples of the etching agent include sulfuric acid, hydrochloric acid, hypochlorous acid, nitric acid, hydrofluoric acid and other mineral acids, or ammonium salts such as ammonium fluoride and acidic ammonium fluoride, and salts of mineral acids such as amine salts, or , Hydrogen fluoride, fluorine, hydrogen chloride and the like can be used. In the present invention, a mineral acid or a salt of a mineral acid is preferable, and particularly, when a hydrofluoric acid or a salt of hydrofluoric acid such as ammonium fluoride or ammonium acid fluoride is used, lattice defects and impurities can be reduced by etching. At the same time, the hydroxyl groups present on the surface of the titanium oxide film are replaced with fluorine or fluorine ions, and the fluorine can be bonded to the surface of the titanium oxide film, and the bonded fluorine can prevent the adhesion of moisture and dirt components. Therefore, it is preferable.
【００１１】酸化チタン膜を前記のエッチング剤に接触
させるには、酸化チタン膜を液状のエッチング剤に浸漬
させたり、あるいは、酸化チタン膜にガス状のエッチン
グ剤を流したりして行うことができる。エッチング処理
の温度は適宜設定できるが、０〜１１０℃の温度、好ま
しくは室温〜８０℃の温度、より好ましくは室温〜６０
℃の温度である。また、エッチング処理の時間は適宜設
定できるが、０．０５〜４８時間、好ましくは０．１〜
１２時間、より好ましくは０．１〜５時間である。エッ
チング剤にはアンモニア、アミン類などの緩衝剤を添加
してもよい。鉱酸の水溶液を用いる場合の鉱酸の濃度は
好ましくは０．０００５〜２０規定、より好ましくは
０．００１〜１０規定、さらに好ましくは０．０１〜５
規定、もっとも好ましくは０．０１〜２規定である。前
記の鉱酸の濃度が０．０００５規定よりも低いと所望の
効果が得られ難いため好ましくなく、また、鉱酸の濃度
が２０規定より高いと酸化チタンの溶解が進み過ぎるた
め好ましくない。酸化チタン膜を液状のエッチング剤に
接触させた後、エッチング剤溶液を中和してもよい。こ
の中和により、エッチング剤溶液に存在するエッチング
されたチタン分を、酸化チタン膜の表面に再度析出させ
ることができる。The titanium oxide film can be brought into contact with the above-mentioned etching agent by immersing the titanium oxide film in a liquid etching agent or by flowing a gaseous etching agent into the titanium oxide film. . The temperature of the etching treatment can be set as appropriate, but it is 0 to 110 ° C, preferably room temperature to 80 ° C, and more preferably room temperature to 60.
The temperature is ° C. The time of the etching treatment can be set appropriately, but is 0.05 to 48 hours, preferably 0.1 to 48 hours.
It is 12 hours, more preferably 0.1 to 5 hours. A buffer such as ammonia or amines may be added to the etching agent. When using an aqueous solution of a mineral acid, the concentration of the mineral acid is preferably 0.0005 to 20 N, more preferably 0.001 to 10 N, and further preferably 0.01 to 5 N.
Specified, most preferably 0.01 to 2 stipulated. If the concentration of the mineral acid is lower than 0.0005N, the desired effect is difficult to obtain, which is not preferable, and if the concentration of the mineral acid is higher than 20N, the titanium oxide is excessively dissolved, which is not preferable. After the titanium oxide film is brought into contact with the liquid etching agent, the etching agent solution may be neutralized. By this neutralization, the etched titanium component existing in the etching agent solution can be re-precipitated on the surface of the titanium oxide film.
【００１２】エッチング処理した酸化チタン膜は、必要
に応じてエッチング剤から分離し、洗浄したり、乾燥し
たりしてもよい。さらに、表面改質された酸化チタン膜
を加熱するのが好ましい実施態様である。特に、酸化チ
タン膜をフッ酸、あるいは、フッ化アンモニウム、酸性
フッ化アンモニウムなどのフッ酸の塩に接触させて、該
酸化チタン膜を表面改質した場合は、酸化チタン膜の表
面に結合したフッ素は加熱により容易に除去することが
でき、フッ素を除去した酸化チタン膜は水分や汚れ成分
などが付着していない、大変活性な膜となる。加熱の温
度は４０〜１０００℃の範囲が好ましく、２００〜６０
０℃の範囲がより好ましい。加熱は、空気、酸素、窒
素、水素、アルゴン、ヘリウム、水蒸気などのガス雰囲
気下で行うことができるが、含有水分量の低い乾燥した
ガスの雰囲気下で行うのがよい。この加熱により、酸化
チタン膜の表面をより一層改質することができる。たと
えば、酸化チタン膜の表面に存在する水酸基などを除去
することができる。このようにして、表面が改質された
酸化チタン膜が得られる。The titanium oxide film subjected to the etching treatment may be separated from the etching agent and washed or dried, if necessary. Further, heating the surface-modified titanium oxide film is a preferred embodiment. In particular, when the titanium oxide film is surface-modified by bringing the titanium oxide film into contact with hydrofluoric acid or a salt of hydrofluoric acid such as ammonium fluoride or ammonium acid fluoride, the titanium oxide film is bonded to the surface of the titanium oxide film. Fluorine can be easily removed by heating, and the titanium oxide film from which fluorine has been removed becomes a very active film with no moisture or contaminants attached. The heating temperature is preferably in the range of 40 to 1000 ° C., and 200 to 60
The range of 0 ° C is more preferable. The heating can be carried out in a gas atmosphere of air, oxygen, nitrogen, hydrogen, argon, helium, steam or the like, but it is preferably carried out in a dry gas atmosphere having a low water content. By this heating, the surface of the titanium oxide film can be further modified. For example, it is possible to remove hydroxyl groups and the like existing on the surface of the titanium oxide film. In this way, a titanium oxide film having a modified surface is obtained.
【００１３】このようにして得られた表面が改質された
酸化チタン膜に増感色素を吸着させてもよい。本発明に
おいて、増感色素とは、可視光領域および／または赤外
光領域に吸収を持つ色素である。この増感色素として
は、金属錯体や有機色素を用いることができる。金属錯
体としては、銅フタロシアニン、チタニルフタロシアニ
ンなどの金属フタロシアニン、クロロフィルまたはその
誘導体、ヘミン、特開平１─２２０３８０号や特表平５
−５０４０２３号に記載のルテニウム、オスミウム、
鉄、および亜鉛の錯体が挙げられる。有機色素として
は、メタルフリーフタロシアニン、シアニン系色素、メ
ロシアニン系色素、キサンテン系色素、トリフェニルメ
タン系色素を用いることができる。シアニン系色素とし
ては、具体的には、ＮＫ３４２２、ＮＫ３２０３、ＮＫ
１１９４（いずれも日本感光色素研究所製）が挙げられ
る。メロシアニン系色素としては、具体的には、ＮＫ２
４２６、ＮＫ２５０１（いずれも日本感光色素研究所
製）が挙げられる。キサンテン系色素としては、具体的
には、ウラニン、エオシン、ローズベンガル、ローダミ
ンＢ、ジブロムフルオレセインが挙げられる。トリフェ
ニルメタン系色素としては、具体的には、マラカイトグ
リーン、クリスタルバイオレットが挙げられる。本発明
においては、前記の金属錯体が分光増感の効果や耐久性
に優れているため好ましい。また、増感色素の分子中に
カルボキシル基、ヒドロキシルアルキル基、ヒドロキシ
ル基、スルホン基、カルボキシアルキル基の官能基を有
するものが、酸化チタン膜への吸着が早いため好まし
い。本発明においては、これら増感色素の一種または二
種以上を用いることができる。A sensitizing dye may be adsorbed on the surface-modified titanium oxide film thus obtained. In the present invention, the sensitizing dye is a dye having absorption in the visible light region and / or the infrared light region. As this sensitizing dye, a metal complex or an organic dye can be used. Examples of the metal complex include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll or a derivative thereof, hemin, JP-A-1-220380 and Japanese Patent Publication No. H05-52035.
Ruthenium, osmium,
Complexes of iron and zinc are mentioned. As the organic dye, metal-free phthalocyanine, cyanine dye, merocyanine dye, xanthene dye, triphenylmethane dye can be used. Specific examples of cyanine dyes include NK3422, NK3203, and NK.
1194 (both manufactured by Japan Photosensitive Dye Research Institute) can be mentioned. Specific examples of the merocyanine dye include NK2
426 and NK2501 (both manufactured by Japan Photosensitive Dye Research Institute). Specific examples of the xanthene dyes include uranine, eosin, rose bengal, rhodamine B, and dibromofluorescein. Specific examples of triphenylmethane dyes include malachite green and crystal violet. In the present invention, the above metal complex is preferable because it is excellent in the effect of spectral sensitization and durability. Further, those having a functional group such as a carboxyl group, a hydroxylalkyl group, a hydroxyl group, a sulfone group, and a carboxyalkyl group in the molecule of the sensitizing dye are preferable because they are quickly adsorbed to the titanium oxide film. In the present invention, one kind or two or more kinds of these sensitizing dyes can be used.
【００１４】エッチング処理して得られた表面が改質さ
れた酸化チタン膜を増感色素に接触させて、酸化チタン
膜に増感色素を吸着させる。増感色素に接触させるに
は、表面が改質された酸化チタン膜を増感色素の溶液に
浸漬させたり、ガス状の増感色素を流したりして行うこ
とができる。本発明においては、エッチング処理した酸
化チタン膜を、増感色素を含有した液体に浸漬し、該液
体を加温すればより速やかに増感色素を吸着させること
ができる。前記の液体としては、使用する増感色素を溶
解するものであればよく、具体的には、水、アルコー
ル、トルエン、ジメチルホルムアミドを用いることがで
きる。加温する温度は、４０℃から前記の液体の沸点ま
での範囲が好ましく、６０℃から前記液体の沸点までの
範囲がより好ましく、（前記液体の沸点−１０℃）から
前記液体の沸点の範囲が最も好ましい。この加温では、
還流下行うのが好ましい。加温の時間は適宜設定するこ
とができるが、２分〜４８時間程度が適当である。この
ようにして得られた、増感色素を吸着させた酸化チタン
膜は、必要に応じて、増感色素の溶液から分離したり、
洗浄したり、乾燥あるいは蒸発乾固したりしてもよい。The surface-modified titanium oxide film obtained by the etching treatment is brought into contact with a sensitizing dye to adsorb the sensitizing dye to the titanium oxide film. The contact with the sensitizing dye can be carried out by immersing the surface-modified titanium oxide film in a solution of the sensitizing dye or flowing a gaseous sensitizing dye. In the present invention, the sensitizing dye can be adsorbed more quickly by immersing the etched titanium oxide film in a liquid containing the sensitizing dye and heating the liquid. The liquid may be any liquid that dissolves the sensitizing dye used, and specifically, water, alcohol, toluene, or dimethylformamide can be used. The temperature to be heated is preferably in the range of 40 ° C. to the boiling point of the liquid, more preferably in the range of 60 ° C. to the boiling point of the liquid, (boiling point of the liquid −10 ° C.) to the boiling point of the liquid. Is most preferred. With this heating,
It is preferably carried out under reflux. The heating time can be set as appropriate, but about 2 minutes to 48 hours is suitable. The titanium oxide film thus adsorbed with the sensitizing dye is, if necessary, separated from the solution of the sensitizing dye,
It may be washed, dried or evaporated to dryness.
【００１５】次に、本発明は、前記の表面改質された酸
化チタン膜を電極として備え、さらに、対電極を備え、
それらの間に電解質を封入してなる光電変換素子であ
る。本発明において、光電変換素子とは、電極間の電気
化学反応を利用して、光エネルギーを電気エネルギーに
変換する素子である。この光電変換素子に光を照射する
と、表面改質された酸化チタン膜の電極で電子が発生
し、電極間に設けられた電線を通って対電極に移動す
る。対電極に移動した電子は、電解質中を陰イオンとし
て移動する。このようにして光エネルギーを電気エネル
ギーに変換することができる。さらに、電解質中に酸化
還元対を存在させると、対電極に移動した電子は、酸化
還元対を構成する酸化体を還元する。その結果生じた還
元体は、酸化チタン膜の電極で酸化されて再び酸化体に
戻る。このようにして、酸化還元対を存在させた光電変
換素子は光エネルギーを継続して電気エネルギーに変換
することができ、太陽電池として利用できる。光電変換
素子に用いられる酸化チタン膜の電極は、光エネルギー
の利用効率を高めるため、増感色素を吸着させた酸化チ
タン膜を用いるのが好ましい。対電極としては、透明性
導電膜をコートしたガラス板などを用いることができ
る。電解質としては、リチウムイオンなどの陽イオンや
塩素イオンなどの陰イオンなど種々の電解質を用いるこ
とができる。電解質中に存在させる酸化還元対として
は、ヨウ素−ヨウ素化合物、臭素−臭素化合物などの酸
化還元対を用いることができる。Next, the present invention comprises the above-mentioned surface-modified titanium oxide film as an electrode, and further comprises a counter electrode,
It is a photoelectric conversion element in which an electrolyte is enclosed between them. In the present invention, the photoelectric conversion element is an element that converts light energy into electric energy by utilizing an electrochemical reaction between electrodes. When this photoelectric conversion element is irradiated with light, electrons are generated at the electrode of the surface-modified titanium oxide film and move to the counter electrode through the electric wire provided between the electrodes. The electrons that have moved to the counter electrode move as anions in the electrolyte. In this way, light energy can be converted into electrical energy. Furthermore, when a redox couple is present in the electrolyte, the electrons transferred to the counter electrode reduce the oxidant that constitutes the redox couple. The resulting reductant is oxidized at the electrode of the titanium oxide film and returns to the oxidant again. In this way, the photoelectric conversion element in which the redox couple is present can continuously convert light energy into electric energy and can be used as a solar cell. As the electrode of the titanium oxide film used for the photoelectric conversion element, it is preferable to use a titanium oxide film having a sensitizing dye adsorbed thereon in order to enhance the utilization efficiency of light energy. A glass plate or the like coated with a transparent conductive film can be used as the counter electrode. As the electrolyte, various electrolytes such as cations such as lithium ions and anions such as chlorine ions can be used. As the redox couple to be present in the electrolyte, a redox couple such as iodine-iodine compound or bromine-bromine compound can be used.
【００１６】[0016]
【実施例】以下に本発明の実施例を示すが、本発明はこ
れに限定されるものではない。 実施例１ 硫酸チタニルを熱加水分解して酸化チタンゾルを得た。
この酸化チタンゾルをアンモニアで中和したのち、濾過
し、洗浄し、次いで、４５０℃の温度で焼成して酸化チ
タンを得た。なお、この酸化チタンの粒子径は１５ｎｍ
であった。EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 Titanium oxide sol was obtained by thermally hydrolyzing titanyl sulfate.
The titanium oxide sol was neutralized with ammonia, filtered, washed, and then calcined at a temperature of 450 ° C. to obtain titanium oxide. The particle size of this titanium oxide is 15 nm.
Met.
【００１７】前記の酸化チタンを水に懸濁させて得られ
た液を導電性ガラス上に塗布した後、４５０℃の温度で
焼成して酸化チタン膜を得た。なお、この酸化チタン膜
は、膜厚１０μｍであり、支持体１ｃｍ2 あたり、１０
００ｃｍ2 の表面積を有していた。A liquid obtained by suspending the titanium oxide in water was coated on a conductive glass and then baked at a temperature of 450 ° C. to obtain a titanium oxide film. The titanium oxide film had a film thickness of 10 μm, and the film thickness was 10 μm per 1 cm 2 of the support.
It had a surface area of 00 cm 2 .
【００１８】得られた酸化チタン膜を、０．５規定のフ
ッ酸水溶液に１５分間浸漬してエッチング処理した後、
水溶液から取り出し、洗浄して、表面が改質された酸化
チタン膜を得た。The obtained titanium oxide film was immersed in a 0.5 N hydrofluoric acid aqueous solution for 15 minutes for etching treatment,
It was taken out of the aqueous solution and washed to obtain a surface-modified titanium oxide film.
【００１９】この表面が改質された酸化チタン膜に増感
色素としてＲｕ（II）（ビピリジン−ジカルボン酸）2
（イソチオシアン酸）2 で表されるルテニウム錯体を吸
着させて色素で増感された酸化チタン膜（試料Ａ）を得
た。Ru (II) (bipyridine-dicarboxylic acid) 2 was added as a sensitizing dye to the surface-modified titanium oxide film.
A ruthenium complex represented by (isothiocyanic acid) 2 was adsorbed to obtain a dye-sensitized titanium oxide film (Sample A).
【００２０】実施例２ 硫酸チタニルを熱加水分解して得られる酸化チタンゾル
のｐＨを硝酸で１．５に調節した後、オートクレーブに
入れ、１８０℃の温度で１３時間水熱処理を行い粒子成
長させた酸化チタンゾルを得た。なお、この酸化チタン
の粒子径は１６ｎｍであった。次いで、得られたゾルを
アンモニアで中和した後、濾過し、洗浄した。この酸化
チタン湿ケーキを水に懸濁させて得られた液を導電性ガ
ラス上に塗布した後、６００℃の温度で焼成して、酸化
チタン膜（試料１）を得た。Example 2 The pH of a titanium oxide sol obtained by thermal hydrolysis of titanyl sulfate was adjusted to 1.5 with nitric acid, then placed in an autoclave, and hydrothermally treated at 180 ° C. for 13 hours to grow particles. A titanium oxide sol was obtained. The particle size of this titanium oxide was 16 nm. Next, the obtained sol was neutralized with ammonia, filtered, and washed. A liquid obtained by suspending the titanium oxide wet cake in water was applied on a conductive glass and then baked at a temperature of 600 ° C. to obtain a titanium oxide film (Sample 1).
【００２１】得られた酸化チタン膜を、０．１規定の塩
酸水溶液に浸漬した後、還流下、１６時間エッチング処
理した後、水溶液から取り出し、洗浄して、表面が改質
された酸化チタン膜を得た。なお、この酸化チタン膜
は、膜厚１１μｍであり、支持体１ｃｍ2 あたり、１０
００ｃｍ2 の表面積を有していた。The obtained titanium oxide film was immersed in a 0.1 N hydrochloric acid aqueous solution, and then subjected to etching treatment under reflux for 16 hours, then taken out of the aqueous solution and washed to obtain a titanium oxide film having a surface modified. Got The titanium oxide film had a film thickness of 11 μm, and was 10 μm per 1 cm 2 of the support.
It had a surface area of 00 cm 2 .
【００２２】この表面が改質された酸化チタン膜に増感
色素としてＲｕ（II）（ビピリジン−ジカルボン酸）2
（イソチオシアン酸）2 で表されるルテニウム錯体を吸
着させて色素で増感された酸化チタン膜（試料Ｂ）を得
た。Ru (II) (bipyridine-dicarboxylic acid) 2 was added as a sensitizing dye to the surface-modified titanium oxide film.
A ruthenium complex represented by (isothiocyanic acid) 2 was adsorbed to obtain a dye-sensitized titanium oxide film (Sample B).
【００２３】実施例３ 実施例１で得られた酸化チタン膜を、０．５規定のフッ
酸水溶液に１５分間浸漬してエッチング処理した後、水
溶液から取り出し、洗浄し、酸素雰囲気中、５００℃で
１時間加熱して、表面が改質された酸化チタン膜を得
た。この表面が改質された酸化チタン膜を、Ｒｕ（II）
（ビピリジン−ジカルボン酸）2 （イソチオシアン酸）
2 で表されるルテニウム錯体増感色素のエタノール溶液
に浸漬させ、次いで、加温し、沸点の温度で加熱還流を
１５分間した後、酸化チタン膜を引き上げて、色素で増
感された酸化チタン膜（試料Ｃ）を得た。Example 3 The titanium oxide film obtained in Example 1 was immersed in a 0.5 N hydrofluoric acid aqueous solution for 15 minutes for etching treatment, then taken out of the aqueous solution and washed, and at 500 ° C. in an oxygen atmosphere. After heating for 1 hour, a surface-modified titanium oxide film was obtained. This surface-modified titanium oxide film is used for Ru (II)
(Bipyridine-dicarboxylic acid) 2 (isothiocyanic acid)
The ruthenium complex sensitizing dye represented by 2 is dipped in an ethanol solution, then heated and refluxed for 15 minutes at the boiling point temperature, and then the titanium oxide film is pulled up to obtain the dye-sensitized titanium oxide. A film (Sample C) was obtained.
【００２４】比較例１ 実施例２の試料１を比較試料として用いた。この試料１
に、実施例２と同様に増感色素を吸着させて色素で増感
された酸化チタン膜（試料Ｄ）を得た。Comparative Example 1 Sample 1 of Example 2 was used as a comparative sample. This sample 1
Then, a sensitizing dye was adsorbed in the same manner as in Example 2 to obtain a dye-sensitized titanium oxide film (Sample D).
【００２５】実施例１の試料Ａを用いた場合の増感色素
の吸着量は９１μｇ／ｃｍ2 であった。また、実施例２
の試料Ｂを用いた場合の増感色素の吸着量は８１μｇ／
ｃｍ2 であった。さらに、実施例３の試料Ｃを用いた場
合の増感色素の吸着量は１１０μｇ／ｃｍ2 であった。
一方、比較例１の試料Ｄを用いた場合の増感色素の吸着
量は６５μｇ／ｃｍ2 であった。The adsorption amount of the sensitizing dye when using the sample A of Example 1 was 91 μg / cm 2 . Example 2
Adsorption amount of the sensitizing dye when using the sample B of 81 μg /
cm 2 . Further, the adsorption amount of the sensitizing dye when using the sample C of Example 3 was 110 μg / cm 2 .
On the other hand, the adsorption amount of the sensitizing dye when using the sample D of Comparative Example 1 was 65 μg / cm 2 .
【００２６】次に、増感色素と酸化チタン膜の表面との
間の結合状態を調べるため、波数１２００〜２２００ｃ
ｍ-1の範囲でＩＲスペクトルを正反射法により測定し
た。使用した増感色素は−ＣＯＯＨを有しており、この
官能基を介して酸化チタン膜に吸着しているものと考え
られる。いずれの試料でも、−ＣＯＯＨに由来するＣ＝
Ｏ伸縮吸収帯とＯ−Ｃ−Ｏ逆対称伸縮吸収帯が観測され
た。しかしながら、実施例の試料（Ａ〜Ｃ）は、Ｃ＝Ｏ
伸縮吸収帯の強度がＯ−Ｃ−Ｏ逆対称伸縮吸収帯の強度
より強くなっていたが、比較例の試料Ｄは逆にＯ−Ｃ−
Ｏ逆対称伸縮吸収帯の強度が強くなっていた。このこと
から、実施例の試料では、エステル結合性が増大し、増
感色素と酸化チタン膜の表面との間の結合がより強固に
なっていると推察される。Next, in order to investigate the bonding state between the sensitizing dye and the surface of the titanium oxide film, the wave number of 1200 to 2200c.
The IR spectrum was measured by the specular reflection method in the range of m -1 . The sensitizing dye used has -COOH, and it is considered that it is adsorbed to the titanium oxide film via this functional group. In all samples, C = derived from -COOH
An O stretching absorption band and an O—C—O antisymmetric stretching absorption band were observed. However, the samples of the examples (AC) have C = O
The strength of the stretching absorption band was stronger than the strength of the O-C-O antisymmetric stretching absorption band.
The strength of the O antisymmetric stretch absorption band was increased. From this, it is assumed that in the samples of Examples, the ester bondability is increased, and the bond between the sensitizing dye and the surface of the titanium oxide film is stronger.
【００２７】以上のことから、本発明のエッチング処理
を施した酸化チタン膜は、比較例に比し、増感色素の吸
着量が増加し、しかも、増感色素の結合強度が強固にな
っていることから、酸化チタン膜の表面が改質され、表
面活性が向上していることがわかった。さらに、エッチ
ング処理を施した後加熱をすると、より一層表面活性が
向上することがわかった。これらのことから、本発明の
酸化チタン膜は、表面での反応性が重要な触媒、光触
媒、触媒担体、吸着材または光電変換素子として有用で
あることがわかった。From the above, the titanium oxide film subjected to the etching treatment of the present invention has an increased adsorption amount of the sensitizing dye and a stronger bonding strength of the sensitizing dye, as compared with the comparative example. Therefore, it was found that the surface of the titanium oxide film was modified and the surface activity was improved. Further, it was found that the surface activity is further improved by heating after the etching treatment. From these facts, it was found that the titanium oxide film of the present invention is useful as a catalyst, a photocatalyst, a catalyst carrier, an adsorbent or a photoelectric conversion element whose surface reactivity is important.
【００２８】次に、前記実施例および比較例で得られた
試料（Ａ、Ｂ、ＣおよびＤ）の各々と対電極用透明導電
性ガラスとを重ね合わせ、その間にヨウ素−ヨウ化物イ
オンを酸化還元対とする電解液を入れ、これらの側面を
樹脂で封入した後、リード線を取り付けて、光電変換素
子を得た。前記の光電変換素子に、ＡＭ１．５の波長分
布で、照射強度１００Ｗ／ｍ2 の光を照射して、電流−
電圧特性を測定した。Next, each of the samples (A, B, C and D) obtained in the above Examples and Comparative Examples and the transparent conductive glass for the counter electrode were superposed, and iodine-iodide ions were oxidized between them. After putting an electrolytic solution as a reducing pair and encapsulating these side surfaces with a resin, a lead wire was attached to obtain a photoelectric conversion element. The photoelectric conversion element was irradiated with light having an AM1.5 wavelength distribution and an irradiation intensity of 100 W / m 2 to obtain a current-
The voltage characteristics were measured.
【００２９】実施例１の試料Ａを用いた場合は、短絡電
流が１．４２ｍＡ／ｃｍ2 であり、変換効率が６．３％
であった。また、実施例２の試料Ｂを用いた場合は、短
絡電流が１．３５ｍＡ／ｃｍ2 であり、変換効率が５．
４％であった。さらに、実施例３の試料Ｃを用いた場合
は、短絡電流が１．５１ｍＡ／ｃｍ2 であり、変換効率
が６．３％であった。これに対して、比較例１の試料Ｄ
を用いた場合は、短絡電流が１．１８ｍＡ／ｃｍ2 であ
り、変換効率が４．６％であった。When the sample A of Example 1 was used, the short-circuit current was 1.42 mA / cm 2 , and the conversion efficiency was 6.3%.
Met. Moreover, when the sample B of Example 2 was used, the short-circuit current was 1.35 mA / cm 2 and the conversion efficiency was 5.
4%. Furthermore, when the sample C of Example 3 was used, the short-circuit current was 1.51 mA / cm 2 and the conversion efficiency was 6.3%. On the other hand, sample D of Comparative Example 1
When was used, the short-circuit current was 1.18 mA / cm 2 and the conversion efficiency was 4.6%.
【００３０】さらに、前記の光電変換素子に、波長５３
０ｎｍの単色光を強度が約２０ｍＷ／ｃｍ2 となるよう
に照射して、その際、光電変換素子から発せられるフォ
トルミネッセンスの強度を測定した。この測定では、発
せられたフォトルミネッセンスをダブルモノクロメータ
で波長６００ｎｍから１０００ｎｍの範囲で分光し、そ
の光強度を光電子倍増管により検出した。実施例の試料
を用いた場合のフォトルミネッセンス強度は、比較例１
の試料Ｄを用いた場合の半分以下であった。フォトルミ
ネッセンスは、増感色素が光を吸収して励起した際に生
じる電子が酸化チタン膜に注入されなかった場合に、失
活する過程で発せられる。このことから、実施例の試料
を用いた光電変換素子のほうが、比較例１の試料を用い
たものより、増感に有効な色素の割合が多いことがわか
った。Further, a wavelength of 53 is added to the photoelectric conversion element.
The monochromatic light of 0 nm was irradiated so that the intensity was about 20 mW / cm 2, and at that time, the intensity of photoluminescence emitted from the photoelectric conversion element was measured. In this measurement, the emitted photoluminescence was dispersed by a double monochromator in the wavelength range of 600 nm to 1000 nm, and the light intensity was detected by a photomultiplier tube. The photoluminescence intensity when the sample of the example is used is the comparative example 1.
It was less than half of the case of using the sample D. Photoluminescence is generated in the process of deactivation when electrons generated when the sensitizing dye absorbs light and is excited are not injected into the titanium oxide film. From this, it was found that the photoelectric conversion element using the sample of the example had a larger proportion of the dye effective for sensitization than the photoelectric conversion element using the sample of the comparative example 1.
【００３１】以上のことから、本発明のエッチング処理
した後増感色素を吸着させた酸化チタン膜は、比較例に
比し、有効に増感に寄与する増感色素の吸着量が増し、
それを電極として用いると光電変換特性が向上すること
から、太陽電池などの光電変換素子、光化学電池、電気
化学電極などの電極として有用であることがわかった。
また、本発明の、表面改質された酸化チタン膜を電極と
して用いてなる光電変換素子は、優れた電流−電圧特性
を有することから、太陽電池などの光電変換素子として
有用であることがわかった。From the above, the titanium oxide film of the present invention, to which the sensitizing dye has been adsorbed after the etching treatment, has an increased adsorption amount of the sensitizing dye which contributes to the sensitization effectively, as compared with the comparative example.
Since the photoelectric conversion characteristics are improved when it is used as an electrode, it was found to be useful as an electrode such as a photoelectric conversion element such as a solar cell, a photochemical cell, and an electrochemical electrode.
Further, the photoelectric conversion element of the present invention, which uses the surface-modified titanium oxide film as an electrode, has excellent current-voltage characteristics, and is therefore useful as a photoelectric conversion element such as a solar cell. It was
【００３２】[0032]
【発明の効果】本発明は、酸化チタン膜をエッチング剤
に接触させて、該酸化チタン膜の表面をエッチングして
なることを特徴とする表面改質された酸化チタン膜であ
って、紫外線吸収材、光学材料、電気・電子材料、光電
変換材料、装飾用材料、触媒、光触媒、触媒担体、吸着
材、バイオリアクターなどに有用なものであり、工業用
途に限らず、一般家庭用としても種々の用途に適用する
ことができるなど有用なものである。また、本発明は、
表面改質された酸化チタン膜の製造方法であって、優れ
た特性を有する酸化チタン膜を簡便に製造することがで
きるなど有用な方法である。さらに、本発明は、表面改
質された酸化チタン膜を電極として用いてなる光電変換
素子であって、優れた光電変換特性を有し、しかも、廉
価に製造できることなどから、太陽電池などに有用なも
のである。The present invention is a surface-modified titanium oxide film, characterized in that the surface of the titanium oxide film is etched by bringing the titanium oxide film into contact with an etching agent. Materials, optical materials, electric / electronic materials, photoelectric conversion materials, decorative materials, catalysts, photocatalysts, catalyst carriers, adsorbents, bioreactors, etc., and are not limited to industrial applications, but also for general household use. It is useful as it can be applied to. Also, the present invention
The method is a method for producing a surface-modified titanium oxide film, and is a useful method in which a titanium oxide film having excellent characteristics can be easily produced. Further, the present invention is a photoelectric conversion device using a surface-modified titanium oxide film as an electrode, which has excellent photoelectric conversion characteristics and can be manufactured at low cost, and thus is useful for solar cells and the like. It is something.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｍ 14/00 Ｐ // Ｇ０３Ｇ 5/09 １０１ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location H01M 14/00 P // G03G 5/09 101
Claims (9)
て、該酸化チタン膜の表面をエッチングしてなることを
特徴とする表面改質された酸化チタン膜。1. A surface-modified titanium oxide film, characterized in that the surface of the titanium oxide film is etched by bringing the titanium oxide film into contact with an etching agent.
であることを特徴とする請求項１に記載の表面改質され
た酸化チタン膜。2. The surface-modified titanium oxide film according to claim 1, wherein the etching agent is a mineral acid and / or a salt thereof.
項２に記載の表面改質された酸化チタン膜。3. The surface-modified titanium oxide film according to claim 2, wherein the mineral acid is hydrofluoric acid.
１ｃｍ2 あたり酸化チタン膜の表面積が１０〜１０００
０ｃｍ2 である酸化チタン膜を用いることを特徴とする
請求項１に記載の表面改質された酸化チタン膜。4. The titanium oxide film on the support has a surface area of the titanium oxide film of 10 to 1000 per cm 2 of the support.
The surface-modified titanium oxide film according to claim 1, wherein a titanium oxide film having a size of 0 cm 2 is used.
化チタン膜の表面に、さらに増感色素を吸着してなるこ
とを特徴とする表面改質された酸化チタン膜。5. A surface-modified titanium oxide film, which is obtained by further adsorbing a sensitizing dye on the surface of the etched titanium oxide film according to claim 1.
て、該酸化チタン膜の表面をエッチングし、次いで、得
られた酸化チタン膜を加熱することを特徴とする表面改
質された酸化チタン膜の製造方法。6. A surface-modified titanium oxide film, characterized in that the titanium oxide film is brought into contact with an etching agent to etch the surface of the titanium oxide film, and then the obtained titanium oxide film is heated. Manufacturing method.
て、該酸化チタン膜の表面をエッチングし、次いで、得
られた酸化チタン膜を増感色素を含有した液体に浸漬
し、該液体を加温して、該酸化チタン膜の表面に増感色
素を吸着させることを特徴とする表面改質された酸化チ
タン膜の製造方法。7. A titanium oxide film is brought into contact with an etching agent to etch the surface of the titanium oxide film, and then the obtained titanium oxide film is immersed in a liquid containing a sensitizing dye, and the liquid is added. A method for producing a surface-modified titanium oxide film, which comprises heating to adsorb a sensitizing dye on the surface of the titanium oxide film.
て、該酸化チタン膜の表面をエッチングし、次いで、得
られた酸化チタン膜を加熱し、さらに、得られた酸化チ
タン膜を増感色素を含有した液体に浸漬し、該液体を加
温して、該酸化チタン膜の表面に増感色素を吸着させる
ことを特徴とする表面改質された酸化チタン膜の製造方
法。8. A titanium oxide film is brought into contact with an etching agent to etch the surface of the titanium oxide film, the obtained titanium oxide film is then heated, and the obtained titanium oxide film is further sensitized with a dye. A method for producing a surface-modified titanium oxide film, which comprises immersing the surface of the titanium oxide film in a liquid containing, and adsorbing a sensitizing dye on the surface of the titanium oxide film.
の、または、請求項６ないし８のいずれか１項に記載の
製造方法によって得られる表面改質された酸化チタン膜
を電極として備え、さらに、対電極を備え、それらの間
に電解質を封入してなることを特徴とする光電変換素
子。9. A surface-modified titanium oxide film obtained by the manufacturing method according to any one of claims 1 to 5 or any one of claims 6 to 8 as an electrode. A photoelectric conversion element comprising: a counter electrode; and an electrolyte enclosed between them.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7201775A JP2824749B2 (en) | 1994-07-15 | 1995-07-13 | Surface-modified titanium oxide film, method for producing the same, and photoelectric conversion element using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18665994 | 1994-07-15 | ||
| JP6-186659 | 1994-07-15 | ||
| JP7201775A JP2824749B2 (en) | 1994-07-15 | 1995-07-13 | Surface-modified titanium oxide film, method for producing the same, and photoelectric conversion element using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0881222A true JPH0881222A (en) | 1996-03-26 |
| JP2824749B2 JP2824749B2 (en) | 1998-11-18 |
Family
ID=26503898
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7201775A Expired - Lifetime JP2824749B2 (en) | 1994-07-15 | 1995-07-13 | Surface-modified titanium oxide film, method for producing the same, and photoelectric conversion element using the same |
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Cited By (18)
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|---|---|---|---|---|
| WO1999063614A1 (en) * | 1998-05-29 | 1999-12-09 | Catalysts & Chemicals Industries Co., Ltd. | Method of manufacturing photoelectric cell and oxide semiconductor for photoelectric cell |
| JP2000277786A (en) * | 1999-03-24 | 2000-10-06 | Fuji Photo Film Co Ltd | Photovoltaic power generator |
| JP2002246620A (en) * | 2001-02-13 | 2002-08-30 | Fuji Photo Film Co Ltd | Photoelectric conversion element and photocell and method of manufacturing them |
| WO2006134939A1 (en) | 2005-06-14 | 2006-12-21 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| JP2007534169A (en) * | 2004-04-22 | 2007-11-22 | コミツサリア タ レネルジー アトミーク | Method for producing photosensitive semiconductor thin film |
| JP2009064782A (en) * | 2008-10-02 | 2009-03-26 | Sharp Corp | Manufacturing method of semiconductor for photoelectric conversion material |
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| US7817942B2 (en) | 2007-05-11 | 2010-10-19 | Sharp Kabushiki Kaisha | Image forming apparatus and image forming method which utilize a wet developer solution |
| EP2302650A2 (en) | 2009-09-28 | 2011-03-30 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| EP2306479A2 (en) | 2009-09-28 | 2011-04-06 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| US7977570B2 (en) | 2005-05-24 | 2011-07-12 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| US8022293B2 (en) | 2004-09-08 | 2011-09-20 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectic conversion devices |
| US8227690B2 (en) | 2003-03-14 | 2012-07-24 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| JP2012146631A (en) * | 2010-12-20 | 2012-08-02 | Peccell Technologies Inc | Method of manufacturing photoelectric conversion element, photoelectric conversion element and photocell |
| US8338701B2 (en) | 2001-07-06 | 2012-12-25 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| US8735720B2 (en) | 2006-03-02 | 2014-05-27 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| WO2014129575A1 (en) | 2013-02-22 | 2014-08-28 | 富士フイルム株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element and dye-sensitized solar cell |
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| JPS5983935A (en) * | 1982-06-25 | 1984-05-15 | Daicel Chem Ind Ltd | Treatment of titanium oxide film |
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| JPS5542265A (en) * | 1978-09-22 | 1980-03-25 | Teijin Ltd | Titanium oxide film treating method |
| JPS5983935A (en) * | 1982-06-25 | 1984-05-15 | Daicel Chem Ind Ltd | Treatment of titanium oxide film |
Cited By (21)
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| WO1999063614A1 (en) * | 1998-05-29 | 1999-12-09 | Catalysts & Chemicals Industries Co., Ltd. | Method of manufacturing photoelectric cell and oxide semiconductor for photoelectric cell |
| JP2000277786A (en) * | 1999-03-24 | 2000-10-06 | Fuji Photo Film Co Ltd | Photovoltaic power generator |
| JP2002246620A (en) * | 2001-02-13 | 2002-08-30 | Fuji Photo Film Co Ltd | Photoelectric conversion element and photocell and method of manufacturing them |
| US8338700B2 (en) | 2001-07-06 | 2012-12-25 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| US8338701B2 (en) | 2001-07-06 | 2012-12-25 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| US8227690B2 (en) | 2003-03-14 | 2012-07-24 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| JP2007534169A (en) * | 2004-04-22 | 2007-11-22 | コミツサリア タ レネルジー アトミーク | Method for producing photosensitive semiconductor thin film |
| US8022293B2 (en) | 2004-09-08 | 2011-09-20 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectic conversion devices |
| US7977570B2 (en) | 2005-05-24 | 2011-07-12 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| US8022294B2 (en) | 2005-06-14 | 2011-09-20 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| WO2006134939A1 (en) | 2005-06-14 | 2006-12-21 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| US8735720B2 (en) | 2006-03-02 | 2014-05-27 | Nippon Kayaku Kabushiki Kaisha | Dye-sensitized photoelectric conversion device |
| US7817942B2 (en) | 2007-05-11 | 2010-10-19 | Sharp Kabushiki Kaisha | Image forming apparatus and image forming method which utilize a wet developer solution |
| JP2009064782A (en) * | 2008-10-02 | 2009-03-26 | Sharp Corp | Manufacturing method of semiconductor for photoelectric conversion material |
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
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