JP2014011022A - Method of forming porous metal oxide semiconductor film for photoelectric cell, and photoelectric cell - Google Patents

Method of forming porous metal oxide semiconductor film for photoelectric cell, and photoelectric cell Download PDF

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JP2014011022A
JP2014011022A JP2012146834A JP2012146834A JP2014011022A JP 2014011022 A JP2014011022 A JP 2014011022A JP 2012146834 A JP2012146834 A JP 2012146834A JP 2012146834 A JP2012146834 A JP 2012146834A JP 2014011022 A JP2014011022 A JP 2014011022A
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metal oxide
semiconductor film
oxide semiconductor
porous metal
organic group
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Hidemaru Miya
英丸 宮
Atsushi Tanaka
田中　　敦
Takayoshi Mizuno
隆喜 水野
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JGC Catalysts and Chemicals Ltd
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    • 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
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    • 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
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Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a photoelectric cell capable of achieving a predetermined photoelectric conversion efficiency from the beginning of operation start.SOLUTION: A method of manufacturing a porous metal oxide semiconductor film for a photoelectric cell includes following steps of (b) to (d): (b) applying porous metal oxide semiconductor film formation coating consisting of metal oxide particles and dispersion medium on an electrode layer provided on a substrate; (c) performing drying and/or heating treatment; and (d) introducing at least one kind of organic group chosen from an acyl group, an aroyl group, and a carboxylate group, to the porous metal oxide semiconductor film.

Description

稼働開始当初からほぼ所定の光電変換効率を達成しうる光電気セルの製造方法を提供する。   Provided is a photoelectric cell manufacturing method capable of achieving a predetermined photoelectric conversion efficiency from the beginning of operation.

高バンドギャップを有する金属酸化物半導体材料が光電変換材料、光触媒材料等の他光センサーや蓄電材料（バッテリー）等に用いられている。
このうち、光電変換材料は光エネルギーを電気エネルギーとして連続して取り出せる材料であり、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材料である。このような光電変換材料に光を照射すると、一方の電極側で電子が発生し、対電極に移動し、対電極に移動した電子は、電解質中をイオンとして移動して一方の電極に戻る。このエネルギー変換は連続であるため、たとえば、太陽電池などに利用されている。 Metal oxide semiconductor materials having a high band gap are used for other optical sensors such as photoelectric conversion materials and photocatalyst materials, power storage materials (batteries), and the like.
Among these, the photoelectric conversion material is a material that can continuously extract light energy as electric energy, and is a material that converts light energy into electric energy using an electrochemical reaction between electrodes. When such a photoelectric conversion material is irradiated with light, electrons are generated on one electrode side, move to the counter electrode, and the electrons moved to the counter electrode move as ions in the electrolyte and return to the one electrode. Since this energy conversion is continuous, it is used, for example, for solar cells.

一般的な太陽電池は、先ず透明性導電膜を形成したガラス板などの支持体上に光電変換材料用半導体の膜を形成して電極とし、次に、対電極として別の透明性導電膜を形成したガラス板などの支持体を備え、これらの電極間に電解質を封入して構成されている。   In general solar cells, a semiconductor film for a photoelectric conversion material is first formed on a support such as a glass plate on which a transparent conductive film is formed, and then another transparent conductive film is used as a counter electrode. A support such as a formed glass plate is provided, and an electrolyte is sealed between these electrodes.

光電変換材料用半導体に吸着した光増感材に例えば太陽光を照射すると、光増感材は可視領域の光を吸収して励起する。この励起によって発生する電子は半導体に移動し、次いで、透明導電性ガラス電極に移動し、２つの電極を接続する導線を通って対電極に移動し、対電極に移動した電子は電解質中の酸化還元系を還元する。一方、半導体に電子を移動させた光増感材は、酸化体の状態になっているが、この酸化体は電解質中の酸化還元系によって還元され、元の状態に戻る。このようにして電子が連続的に流れ、光電変換材料は太陽電池として機能する。   When the photosensitizer adsorbed on the photoelectric conversion material semiconductor is irradiated with, for example, sunlight, the photosensitizer absorbs light in the visible region and is excited. The electrons generated by this excitation move to the semiconductor, then move to the transparent conductive glass electrode, move to the counter electrode through the conducting wire connecting the two electrodes, and the electrons transferred to the counter electrode are oxidized in the electrolyte. Reduce the reduction system. On the other hand, the photosensitizer that has moved electrons to the semiconductor is in an oxidant state, but this oxidant is reduced by the redox system in the electrolyte and returns to its original state. In this way, electrons flow continuously, and the photoelectric conversion material functions as a solar cell.

この光電変換材料としては、半導体表面に可視光領域に吸収を持つ分光増感色素を吸着させたものが用いられている。たとえば、特開平１−２２０３８０号公報（特許文献１）には、金属酸化物半導体の表面に、ルテニウム錯体などの遷移金属錯体からなる分光増感色素層を有する太陽電池が記載されている。また、特表平５−５０４０２３号公報（特許文献２）には、金属イオンでドープした酸化チタン半導体層の表面に、ルテニウム錯体などの遷移金属錯体からなる分光増感色素層を有する太陽電池が記載されている。   As this photoelectric conversion material, a material obtained by adsorbing a spectral sensitizing dye having absorption in the visible light region on the semiconductor surface is used. For example, JP-A-1-220380 (Patent Document 1) describes a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a metal oxide semiconductor. Japanese Patent Application Laid-Open No. 5-504023 (Patent Document 2) discloses a solar cell having a spectral sensitizing dye layer made of a transition metal complex such as a ruthenium complex on the surface of a titanium oxide semiconductor layer doped with metal ions. Have been described.

特開平１−２２０３８０号公報Japanese Patent Laid-Open No. 1-220380 特表平５−５０４０２３号公報Japanese National Patent Publication No. 5-504023

しかしながら、従来の太陽電池では、使用開始時の光電変換効率が低く、所定の光電変換効率に達するまでに長時間を要するという問題点があった。また、製品は直ちに使用することができず、あらかじめ所定の光電変換効率に達するまで稼働させたのち、性能を確認して出荷するなど、生産効率が十分ではなかった。   However, the conventional solar cell has a problem that the photoelectric conversion efficiency at the start of use is low, and it takes a long time to reach a predetermined photoelectric conversion efficiency. In addition, the product cannot be used immediately, and the production efficiency is not sufficient, for example, the product is operated until the predetermined photoelectric conversion efficiency is reached in advance and then the performance is confirmed before shipping.

上記問題点に鑑み本発明者等は鋭意検討した結果、多孔質金属酸化物半導体膜に、アシル基、アロイル基、カルボキシレート基を導入することで、稼働開始当初からほぼ所定の光電変換効率を達成できることを見出して本発明を完成するに至った。   In view of the above problems, the present inventors have conducted intensive studies, and as a result, by introducing acyl groups, aroyl groups, and carboxylate groups into the porous metal oxide semiconductor film, almost predetermined photoelectric conversion efficiency has been achieved from the beginning of operation. The inventors have found that this can be achieved and have completed the present invention.

本発明によれば、光電気セル用多孔質金属酸化物半導体膜に特定の有機基を導入しているので、稼働開始当初から高い光電変換効率を保持する光電気セル用が得られる。この光電気セルは直ちに使用することが可能であり、出荷における性能確認も容易となり、出荷までの時間を著しく短縮できる。   According to the present invention, since a specific organic group is introduced into the porous metal oxide semiconductor film for photoelectric cells, a photoelectric cell having high photoelectric conversion efficiency from the beginning of operation can be obtained. This photoelectric cell can be used immediately, facilitates performance confirmation in shipment, and can significantly shorten the time to shipment.

本発明の光電気セルの１例を示す概略断面図である。It is a schematic sectional drawing which shows one example of the photoelectric cell of this invention.

以下、先ず、本発明に係る光電気セル用多孔質金属酸化物半導体膜の製造方法について具体的に説明する。   Hereinafter, first, the manufacturing method of the porous metal oxide semiconductor film for photoelectric cells according to the present invention will be specifically described.

[光電気セル用多孔質金属酸化物半導体膜の製造方法]
本発明は、下記の工程（ｂ）〜（ｄ）からなる光電気セル用多孔質金属酸化物半導体膜の製造方法である；
（ｂ）基板上の電極層上に金属酸化物粒子と分散媒とからなる多孔質金属酸化物半導体膜形成用塗料を塗布し、
（ｃ）乾燥および／または加熱処理したのち、
（ｄ）多孔質金属酸化物半導体膜にアシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を導入する。 [Method for producing porous metal oxide semiconductor film for photoelectric cell]
The present invention is a method for producing a porous metal oxide semiconductor film for photoelectric cells comprising the following steps (b) to (d);
(B) Applying a coating for forming a porous metal oxide semiconductor film comprising metal oxide particles and a dispersion medium on the electrode layer on the substrate;
(C) After drying and / or heat treatment,
(D) At least one organic group selected from an acyl group, an aroyl group, and a carboxylate group is introduced into the porous metal oxide semiconductor film.

基板としては光電気セルに使用される基板が使用される。具体的にはガラス基板、ＰＥＴ等の有機ポリマー基板等の透明絶縁性基板、金属チタン、金属アルミニウム、金属銅、金属ニッケルなどの導電性基板を使用することができる。   As the substrate, a substrate used in a photoelectric cell is used. Specifically, a transparent insulating substrate such as a glass substrate or an organic polymer substrate such as PET, or a conductive substrate such as metal titanium, metal aluminum, metal copper, or metal nickel can be used.

基板表面には、電極層が形成されている。電極層としては、特に制限されるものでなく、白金、ロジウム、ルテニウム金属、ルテニウム酸化物等の電極材料、酸化錫、Ｓｂ、ＦまたはＰがドーピングされた酸化錫、Ｓｎおよび／またはＦがドーピングされた酸化インジウム、酸化アンチモン、酸化亜鉛などの導電性酸化材料からなる電極や、前記導電性材料表面をメッキあるいは蒸着した電極、カーボン電極など従来公知の電極を用いることができる。   An electrode layer is formed on the substrate surface. The electrode layer is not particularly limited, and electrode materials such as platinum, rhodium, ruthenium metal, ruthenium oxide, tin oxide doped with tin oxide, Sb, F or P, Sn and / or F are doped. Conventionally known electrodes such as an electrode made of a conductive oxide material such as indium oxide, antimony oxide, and zinc oxide, an electrode obtained by plating or vapor-depositing the surface of the conductive material, and a carbon electrode can be used.

このような電極層は、基板上に直接コーティング、メッキあるいは蒸着させて、導電性材料を熱分解法、ＣＤＶ法等の従来公知の方法により導電層を形成した後、必要に応じて、該導電層上に前記電極材料をメッキあるいは蒸着するなど従来公知の方法により形成することができる。   Such an electrode layer is formed by coating, plating, or vapor-depositing directly on a substrate to form a conductive layer by a conventionally known method such as a thermal decomposition method or a CDV method, and then, if necessary, the conductive layer. The electrode material can be formed on the layer by a conventionally known method such as plating or vapor deposition.

電極層自体の抵抗値は、各々１００Ω／ｃｍ2以下であることが好ましい。電極層の抵抗値が１００Ω／ｃｍ2を超えて高くなると光電変換効率が低くなることがある。
あらかじめ、電極層表面には、酸化チタン薄膜が形成されていてもよい。（酸化チタン薄膜形成（ａ））
電極層上に酸化チタン薄膜を形成する。 The resistance value of the electrode layer itself is preferably 100 Ω / cm 2 or less. When the resistance value of the electrode layer exceeds 100 Ω / cm 2 , the photoelectric conversion efficiency may be lowered.
A titanium oxide thin film may be formed on the electrode layer surface in advance. (Titanium oxide thin film formation (a))
A titanium oxide thin film is formed on the electrode layer.

酸化チタン薄膜が形成されていると、光電気セルを構成したときに、暗電流の抑制、電子の再結合の抑制をすることができ光電変換効率を向上させることができる。
酸化チタン薄膜は膜厚が７０ｎｍ以下、さらには４０ｎｍ以下の範囲にあることが好ましい。酸化チタン薄膜の膜厚が厚すぎると、エネルギー障壁が大きくなりすぎて電子の移動が抑制され、逆に光電変換効率が低下することがある。 When the titanium oxide thin film is formed, when a photoelectric cell is formed, dark current can be suppressed and recombination of electrons can be suppressed, and photoelectric conversion efficiency can be improved.
The titanium oxide thin film preferably has a thickness in the range of 70 nm or less, more preferably 40 nm or less. If the titanium oxide thin film is too thick, the energy barrier becomes too large and the movement of electrons is suppressed, and conversely, the photoelectric conversion efficiency may decrease.

このような酸化チタン薄膜は、電極層上にペルオキシチタン酸水溶液、あるいは四塩化チタン等のチタン塩化合物の水溶液を、(A)スピンコート法、(B)ディップコート法、(C)フレキソ印刷法、(D)ロールコーター法、(E)電気泳動法から選ばれる１種以上の方法で塗布し、乾燥し、硬化させることにより形成することができる。   Such a titanium oxide thin film is obtained by applying a peroxytitanic acid aqueous solution or an aqueous solution of a titanium salt compound such as titanium tetrachloride on the electrode layer, (A) spin coating method, (B) dip coating method, (C) flexographic printing method. It can be formed by coating, drying and curing by one or more methods selected from (D) roll coater method and (E) electrophoresis method.

なお、スパッタリングなどの方法でも、緻密な酸化チタン薄膜を得ることは可能であるが、緻密すぎて電子の移動を阻害したり、後に形成する多孔質金属酸化物半導体膜との密着性が不充分となることがある。   It is possible to obtain a dense titanium oxide thin film even by a method such as sputtering, but it is too dense to inhibit the movement of electrons or has insufficient adhesion to a porous metal oxide semiconductor film to be formed later. It may become.

酸化チタン薄膜の形成に用いるペルオキシチタン酸水溶液あるいはチタン塩化合物水溶液の濃度はＴiＯ2として０．１〜２．０質量％、さらには０．３〜１．０質量％の範囲にあることが好ましい。水溶液の濃度が薄いと、所望の膜厚の酸化チタン薄膜が得られないことがあり、繰返し塗布、乾燥を行う必要が生じる。水溶液の濃度が高いと、乾燥時にクラックが生じたり、緻密な膜を形成できないことがあり、暗電流の抑制、電子の再結合の抑制効果が得られないことがある。 The concentration of the peroxytitanic acid aqueous solution or the titanium salt compound aqueous solution used for forming the titanium oxide thin film is preferably 0.1 to 2.0% by mass, more preferably 0.3 to 1.0% by mass as TiO 2. . When the concentration of the aqueous solution is low, a titanium oxide thin film having a desired film thickness may not be obtained, and it is necessary to repeatedly apply and dry. If the concentration of the aqueous solution is high, cracks may occur during drying, or a dense film may not be formed, and the effect of suppressing dark current and recombination of electrons may not be obtained.

また、ペルオキシチタン酸水溶液あるいはチタン塩化合物水溶液は増粘剤を含んでいてもよく、増粘剤としてはエチレングリコール、ポリエチレングリコール、ポリビニルピロリドン、ヒドロキシプロピルセルロース、ポリアクリル酸、エチルセルロース、ポリビニルアルコール、メタノール、エタノール、イソプロピルアルコール、ノルマルブタノール、ターシャリーブタノール等が含まれていてもよい。このような増粘剤が含まれていると、水溶液の粘度が高くなり、これにより均一に塗布することができ、クラックのない均一な膜厚の酸化チタン薄膜が得られ、下層の電極層との密着性の高い酸化チタン薄膜を得ることができる。
乾燥処理のみでも硬化するが、さらに必要に応じて紫外線を照射し、ついで加熱処理によってアニーリングすることもできる。 Further, the peroxytitanic acid aqueous solution or the titanium salt compound aqueous solution may contain a thickener, and examples of the thickener include ethylene glycol, polyethylene glycol, polyvinyl pyrrolidone, hydroxypropyl cellulose, polyacrylic acid, ethyl cellulose, polyvinyl alcohol, and methanol. , Ethanol, isopropyl alcohol, normal butanol, tertiary butanol and the like may be contained. When such a thickener is contained, the viscosity of the aqueous solution is increased, whereby it can be applied uniformly, and a titanium oxide thin film having a uniform thickness without cracks can be obtained. A titanium oxide thin film with high adhesion can be obtained.
Although it hardens | cures only by a drying process, it can also irradiate with an ultraviolet-ray as needed and can also anneal by heat processing.

塗布（ｂ）
本発明に用いる多孔質金属酸化物半導体膜形成用塗料は金属酸化物粒子と分散媒とからなる。 Application (b)
The coating material for forming a porous metal oxide semiconductor film used in the present invention comprises metal oxide particles and a dispersion medium.

本発明に用いる金属酸化物粒子としては、酸化チタン粒子、酸化亜鉛粒子、酸化錫等のバンドギャップの高い従来公知の酸化物粒子を用いることができる。
なかでも、酸化チタン粒子は後述する特定の有機基が結合しやすく、このため稼働開始当初からほぼ所定の高い光電変換効率を有する光電気セルが得られるので好適に用いることができる。 As the metal oxide particles used in the present invention, conventionally known oxide particles having a high band gap such as titanium oxide particles, zinc oxide particles, and tin oxide can be used.
Among them, the titanium oxide particles can be preferably used because specific organic groups described later are easily bonded to the titanium oxide particles, and thus a photoelectric cell having a predetermined high photoelectric conversion efficiency can be obtained from the beginning of operation.

金属酸化物粒子の平均粒子径は、５〜３０００ｎｍ、さらには１０〜２０００ｎｍの範囲にあることが好ましい。平均粒子径が低いものは得ることが困難であり、得られたとしても結晶性が低く、また、粒子が焼結しやすくなるため、それにともない形成後の半導体膜を加熱処理した際に温度によっては有機基が脱離しやすくなることがあり、定常状態になる時間を充分短縮できない場合がある。平均粒子径が大きすぎても膜強度が低くなったり、比表面積の低下に伴い、光増感材の吸着量が不充分となるため光電変換効率が不充分となることがある。   The average particle diameter of the metal oxide particles is preferably in the range of 5 to 3000 nm, more preferably 10 to 2000 nm. It is difficult to obtain a product having a low average particle size, and even if obtained, the crystallinity is low, and the particles are easily sintered. In some cases, the organic group is likely to be eliminated, and the time for steady state cannot be sufficiently shortened. If the average particle size is too large, the film strength may be lowered, or the amount of adsorption of the photosensitizer may be insufficient due to a decrease in specific surface area, resulting in insufficient photoelectric conversion efficiency.

本発明では、これらの粒子の平均粒子径は、粒子の透過型電子顕微鏡写真（ＴＥＭ）を撮影し、任意の粒子１００個について粒子径を測定し、その平均値として求める。
本発明で酸化チタン粒子を使用する場合、結晶性はアナタース型酸化チタン、ブルッカイト型酸化チタン、ルチル型酸化チタンであることが好ましい。 In the present invention, the average particle size of these particles is determined by taking a transmission electron micrograph (TEM) of the particles, measuring the particle size of 100 arbitrary particles, and obtaining the average value.
When titanium oxide particles are used in the present invention, the crystallinity is preferably anatase type titanium oxide, brookite type titanium oxide, or rutile type titanium oxide.

分散媒としては、前記有機化合物を除く従来公知の水、アルコール類、グリコール類、エーテル類、テレピン類からなる群選ばれる１種または２種以上が用いられる。
具体的には、アルコール類としてはメタノール、エタノール、イソプロピルアルコール、ブタノール等、グリコール類としてエチレングリコール、プロピレングリコール等、エーテル類としてはブチルカルビトール、ブチルカルビトールアセテート等、テレピン類としては、テルピネオール、ジヒドロターピネオール、ターピノーレン等およびこれらの混合物が挙げられる。 As the dispersion medium, one or two or more kinds selected from the group consisting of conventionally known water, alcohols, glycols, ethers, and terpines excluding the organic compounds are used.
Specifically, methanol, ethanol, isopropyl alcohol, butanol and the like as alcohols, ethylene glycol and propylene glycol as glycols, butyl carbitol and butyl carbitol acetate as ethers, terpineol as terpines, Examples include dihydroterpineol, terpinolene, and the like and mixtures thereof.

スクリーン印刷法ではテルピネオール、ブチルカルビトール等の溶媒に分散させた塗料が好適に用いられる。また、速乾性が要求される印刷方法では、水とメタノール、エタノール、イソプロピルアルコール、ブタノール等の比較的低沸点のアルコール類を含む水性分散媒が用いられ、これらは前記酸化チタン粒子、後述する必要に応じて用いる増粘剤とを均一に分散あるいは溶解できるとともに、基材に酸化チタン粒子層を形成した後、乾燥する際に分散媒が蒸発しやすいので好適に用いることができる。   In the screen printing method, a paint dispersed in a solvent such as terpineol or butyl carbitol is preferably used. Further, in a printing method that requires quick drying, an aqueous dispersion medium containing water and relatively low boiling point alcohols such as methanol, ethanol, isopropyl alcohol, and butanol is used. The thickener used according to the above can be uniformly dispersed or dissolved, and after the titanium oxide particle layer is formed on the substrate, the dispersion medium easily evaporates during drying, so that it can be suitably used.

本発明の塗料には増粘剤が含まれていてもよく、増粘剤としては、ポリエチレングリコール、ポリビニルピロリドン、ヒドロキシプロピルセルロース、ポリアクリル酸、エチルセルロース、メチルセルロース、カルボキシメチルメチルセルロース、ポリビニルアルコール、アクリル樹脂、ケトン樹脂、メラミン樹脂等が挙げられる。このような増粘剤が多孔質金属酸化物半導体膜形成用塗料中に含まれていると、塗料の粘度が高くなり、これにより均一に塗布することができ、所定の多孔質金属酸化物半導体膜を得ることができる。   The paint of the present invention may contain a thickener. Examples of the thickener include polyethylene glycol, polyvinyl pyrrolidone, hydroxypropyl cellulose, polyacrylic acid, ethyl cellulose, methyl cellulose, carboxymethyl methyl cellulose, polyvinyl alcohol, and acrylic resin. , Ketone resin, melamine resin and the like. When such a thickening agent is contained in the coating material for forming a porous metal oxide semiconductor film, the viscosity of the coating material is increased, whereby a uniform coating can be achieved, and a predetermined porous metal oxide semiconductor is provided. A membrane can be obtained.

多孔質金属酸化物半導体膜形成用塗料中の増粘剤の濃度は増粘剤の種類によっても異なるが、増粘剤を含む場合、固形分として１．０〜４０質量％、さらには４．０〜１０質量％の範囲にあることが好ましい。増粘剤が少ないと効果が不充分でとなることがあるが、多すぎても塗布性が低下するとともに、得られる半導体膜の強度が不充分となり、さらに増粘剤の完全な除去が困難となり、充分な光電変換効率の向上効果が得られないことがある。   The concentration of the thickener in the coating material for forming a porous metal oxide semiconductor film varies depending on the type of the thickener, but when it contains a thickener, it is 1.0 to 40% by mass as a solid content, and further 4. It is preferable that it exists in the range of 0-10 mass%. If the amount of the thickener is small, the effect may be insufficient. However, if the amount is too large, the coatability is lowered, the strength of the resulting semiconductor film is insufficient, and further, it is difficult to completely remove the thickener. Thus, there may be a case where a sufficient photoelectric conversion efficiency improvement effect cannot be obtained.

前記多孔質金属酸化物半導体膜形成用塗料にはペルオキシチタン酸が含まれていてもよい。このようなペルオキシチタン酸はバインダー成分として機能し、緻密で強度に優れ、光増感剤の吸着量が多く、電子移動性に優れた多孔質金属酸化物半導体膜が得られ、この結果光電変換効率が向上するという効果が達成される。ペルオキソチタン酸は、半導体膜中ではバインダーの酸化チタンとなる。塗料中のペルオキシチタン酸の使用量は酸化チタンとして金属酸化物粒子の１〜３０質量％、さらには２〜１５質量％の範囲にあることが好ましい。   The porous metal oxide semiconductor film-forming coating material may contain peroxytitanic acid. Such peroxytitanic acid functions as a binder component, and a porous metal oxide semiconductor film that is dense and excellent in strength, has a large amount of adsorption of a photosensitizer, and has excellent electron mobility is obtained. The effect of improved efficiency is achieved. Peroxotitanic acid becomes titanium oxide as a binder in the semiconductor film. The amount of peroxytitanic acid used in the paint is preferably 1 to 30% by mass, more preferably 2 to 15% by mass of the metal oxide particles as titanium oxide.

ペルオキシチタン酸の使用量が少ないと、場合によって、後述する酸化チタン薄膜との密着性、半導体膜の強度や、光増感材の吸着量、光電変換効率などが不充分となることがある。ペルオキシチタン酸を多くしても、前記効果が更に向上することもなく、光電変換効率が低下することがある。   If the amount of peroxytitanic acid used is small, the adhesion to the titanium oxide thin film described later, the strength of the semiconductor film, the adsorption amount of the photosensitizer, the photoelectric conversion efficiency, etc. may be insufficient in some cases. Even if the amount of peroxytitanic acid is increased, the above effect is not further improved, and the photoelectric conversion efficiency may be lowered.

このような、多孔質金属酸化物半導体膜形成用塗料を電極層上または電極層上の酸化チタン薄膜上に塗布し、乾燥した後紫外線照射により硬化、あるいは加熱硬化するとともにアニーリングして形成する。   Such a coating material for forming a porous metal oxide semiconductor film is applied on the electrode layer or the titanium oxide thin film on the electrode layer, dried, cured by ultraviolet irradiation, or cured by heating and annealing.

塗布方法はディップ法、スピナー法、ロールコーター法、フレキソ印刷、スクリーン印刷法等が好適である。   As a coating method, a dip method, a spinner method, a roll coater method, flexographic printing, a screen printing method, and the like are suitable.

乾燥・加熱処理（ｃ）
前記の方法で塗布した塗膜を、乾燥および／または加熱処理して多孔質金属酸化物半導体膜を形成する。 Drying / heating treatment (c)
The coating film applied by the above method is dried and / or heat-treated to form a porous metal oxide semiconductor film.

乾燥は分散媒を除去できる温度であればよく、従来公知の方法を採用することができ、風乾することも可能であるが、通常５０〜２００℃で０．２〜５時間程度乾燥する。
ついで、加熱処理することができるが、通常、１００〜７００℃、さらには３００〜６００℃で概ね０．５〜４８時間処理する。 The drying may be performed at a temperature at which the dispersion medium can be removed, and a conventionally known method can be adopted. Air drying can also be performed, but drying is usually performed at 50 to 200 ° C. for about 0.2 to 5 hours.
Then, although heat treatment can be performed, the treatment is usually performed at 100 to 700 ° C., and further at 300 to 600 ° C. for approximately 0.5 to 48 hours.

加熱処理温度が高すぎると、基板あるいは基板上の電極層が劣化する場合があり、また、多孔質金属酸化物半導体膜を構成する金属酸化物粒子の種類、粒子径によっては半導体膜の比表面積、多孔性が低下し、光増感材の吸着量が不十分となり光電変換効率が不十分となる場合がある。   If the heat treatment temperature is too high, the substrate or the electrode layer on the substrate may deteriorate, and the specific surface area of the semiconductor film depends on the type and particle diameter of the metal oxide particles constituting the porous metal oxide semiconductor film. In some cases, the porosity decreases, the amount of adsorption of the photosensitizer becomes insufficient, and the photoelectric conversion efficiency becomes insufficient.

このようにして得られた多孔質金属酸化物半導体膜の膜厚は０．１〜５０μｍの範囲にあることが好ましい。また、多孔質金属酸化物半導体膜の細孔容積は０．１０〜０．８０ｍｌ／ｇ、さらには０．２０〜０．６５ｍｌ／ｇの範囲にある。本発明の方法において、上記の範囲内で細孔容積を多くするには、加熱温度を低くしたり、金属酸化物粒子の粒径を大きくすればよい。逆に細孔容積を少なくするには、加熱温度を高めたり、粒子径の小さい粒子を使用すればよい。細孔容積が小さいと、増感色素の吸着が不十分となったり、電解質の拡散性が低下してバックカレントを引き起こすことがあり、変換効率が不充分となることがある。また細孔容積が大きすぎても金属酸化物半導体膜の強度が不充分となることがある。通常、半導体膜は、５〜50nm程度の細孔を有し、光電気セルでは、かかる細孔に、光増感材を吸着している。   The film thickness of the porous metal oxide semiconductor film thus obtained is preferably in the range of 0.1 to 50 μm. The pore volume of the porous metal oxide semiconductor film is in the range of 0.10 to 0.80 ml / g, and further 0.20 to 0.65 ml / g. In the method of the present invention, in order to increase the pore volume within the above range, the heating temperature may be lowered or the particle size of the metal oxide particles may be increased. Conversely, in order to reduce the pore volume, the heating temperature may be increased or particles having a small particle diameter may be used. When the pore volume is small, the adsorption of the sensitizing dye may be insufficient, or the diffusibility of the electrolyte may be lowered to cause back current, resulting in insufficient conversion efficiency. Further, even if the pore volume is too large, the strength of the metal oxide semiconductor film may be insufficient. Usually, a semiconductor film has pores of about 5 to 50 nm, and in a photoelectric cell, a photosensitizer is adsorbed in these pores.

有機基導入（ｄ）
前記の方法で得られた多孔質金属酸化物半導体膜にアシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を導入する。 Introduction of organic group (d)
At least one organic group selected from an acyl group, an aroyl group, and a carboxylate group is introduced into the porous metal oxide semiconductor film obtained by the above method.

アシル基はＲＣＯ−（Ｒは炭素数１〜１０の炭化水素基）で表され、アセチル基（ＣＨ3ＣＯ−）、Ｃ2Ｈ5ＣＯ−、Ｃ3Ｈ7ＣＯ−等が挙げられる。
アロイル基はＡｒＣＯ−（Ａｒは芳香族炭化水素基）で表されるが、Ｃ6Ｈ5ＣＯ−等が挙げられる。）
カルボキシレート基は上記アシル基（ＲＣＯ−）、アロイル基（ＡｒＣＯ−）がさらに酸素原子を含むＲＣＯＯ−（アシルオキシ基）、ＡｒＣＯＯ−（アロイルオキシ基）で表される有機基が挙げられる。 Acyl group is represented by RCO- (R is a hydrocarbon group having 1 to 10 carbon atoms), an acetyl group (CH 3 CO -), C 2 H 5 CO-, include C 3 H 7 CO- like.
The aroyl group is represented by ArCO— (Ar is an aromatic hydrocarbon group), and examples thereof include C 6 H 5 CO—. )
Examples of the carboxylate group include organic groups represented by the above-mentioned acyl group (RCO-), aroyl group (ArCO-) further containing an oxygen atom, RCOO- (acyloxy group), and ArCOO- (aroyloxy group).

このような有機基を含むことで、吸着させる光増感色素との親和性が高くなり、稼働開始当初からほぼ所定の光電変換効率を達成できる。
アシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を多孔質金属酸化物半導体膜に導入することのできる有機化合物としては、アシル基、アロイル基、カルボキシレート基を有する有機化合物が挙げられる。たとえば、アセチルアセトン、3-メチル2,4ペンタジオン、3-プロピル-2,4-ベンタジオン、安息香酸、フタル酸、3-フェニル-2,4ペンタジオン、酢酸、マレイン酸、酒石酸、マロン酸、コハク酸等およびこれらの混合物が挙げられる。 By including such an organic group, the affinity with the photosensitizing dye to be adsorbed is increased, and almost predetermined photoelectric conversion efficiency can be achieved from the beginning of operation.
Examples of the organic compound that can introduce at least one organic group selected from an acyl group, an aroyl group, and a carboxylate group into the porous metal oxide semiconductor film include an organic compound having an acyl group, an aroyl group, and a carboxylate group Is mentioned. For example, acetylacetone, 3-methyl 2,4 pentadione, 3-propyl-2,4-bentadione, benzoic acid, phthalic acid, 3-phenyl-2,4 pentadione, acetic acid, maleic acid, tartaric acid, malonic acid, succinic acid, etc. And mixtures thereof.

有機化合物の使用量は、多孔質金属酸化物半導体膜中の有機基の含有量が炭素換算で５０〜２０００重量ｐｐｍ、好ましくは１００〜１０００重量ｐｐｍの範囲となる量である。   The amount of the organic compound used is such that the organic group content in the porous metal oxide semiconductor film is in the range of 50 to 2000 ppm by weight, preferably 100 to 1000 ppm by weight in terms of carbon.

多孔質金属酸化物半導体膜中の有機基の含有量が少なすぎると、多孔質金属酸化物半導体膜に吸着する光増感剤に対して極微量であるため、光増感剤との相互作用が弱いためか、光電気セルの定常状態になるのに時間を要する場合がある。一方、多孔質金属酸化物半導体膜形成時に高温で焼成することから、過剰に導入することは困難であり、得られたとしてもさらに初期性能を向上させる効果が得られておらず、光増感剤の吸着を阻害するためか、変換効率が低下する場合がある。   If the content of the organic group in the porous metal oxide semiconductor film is too small, the amount of the organic group is extremely small compared to the photosensitizer adsorbed on the porous metal oxide semiconductor film. It may take time to reach the steady state of the photoelectric cell because of weakness. On the other hand, since it is baked at a high temperature during the formation of the porous metal oxide semiconductor film, it is difficult to introduce excessively, and even if obtained, the effect of further improving the initial performance has not been obtained, and photosensitization In some cases, the conversion efficiency may be reduced to inhibit the adsorption of the agent.

なお、多孔質金属酸化物半導体膜中の有機基の含有量は、最終的に加熱処理して得られた多孔質金属酸化物半導体膜の炭素の量を測定し、炭素換算として規定している。また、有機基の同定は赤外分光法により行なう。なお、かかる有機基は後記する有機化合物がそのまま存在しているのではなく、金属酸化物粒子(酸化チタン粒子)の表面ＯＨ基と反応して結合した状態となっているものと考えられる。これはＩＲによって確認できる。
このような有機基導入方法としては、下記（ｄ1）または（ｄ2）であることが好ましい。 Note that the organic group content in the porous metal oxide semiconductor film is defined as carbon conversion by measuring the amount of carbon in the porous metal oxide semiconductor film finally obtained by heat treatment. . The organic group is identified by infrared spectroscopy. In addition, it is considered that such an organic group is in a state in which an organic compound described later does not exist as it is, but reacts with and binds to a surface OH group of metal oxide particles (titanium oxide particles). This can be confirmed by IR.
Such an organic group introduction method is preferably the following (d 1 ) or (d 2 ).

工程（ｄ 1 ）
多孔質金属酸化物半導体膜にアシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を含む有機化合物を吸収させ、ついで、１００〜７００℃、好ましくは３００〜６００℃で加熱処理する。
吸収方法としては、多孔質金属酸化物半導体膜に前記有機化合物の溶液を前記含有量となるように吸収させる。 Step (d 1 )
The porous metal oxide semiconductor film is allowed to absorb an organic compound containing at least one organic group selected from an acyl group, an aroyl group, and a carboxylate group, and then heat-treated at 100 to 700 ° C., preferably 300 to 600 ° C. To do.
As an absorption method, a solution of the organic compound is absorbed in the porous metal oxide semiconductor film so as to have the content.

工程（ｄ 2 ）
多孔質金属酸化物半導体膜を、１００〜７００℃、好ましくは３００〜６００℃で加熱しながら、アシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を含む有機化合物を多孔質金属酸化物半導体膜と接触させる。 Step (d 2 )
While heating a porous metal oxide semiconductor film at 100 to 700 ° C., preferably 300 to 600 ° C., an organic compound containing at least one organic group selected from an acyl group, an aroyl group, and a carboxylate group is porous. Contact with the metal oxide semiconductor film.

具体的には、多孔質金属酸化物半導体膜付基材を所定の温度に維持しながら、有機化合物溶液を供給し、気化させながら有機化合物のガスと接触させる。なお、有機化合物のガスは単独で供給してもよく、窒素等の不活性ガスと混合して供給することもできる。このときも、有機化合物の使用量は、前記含有量となる量である。   Specifically, the organic compound solution is supplied while maintaining the substrate with the porous metal oxide semiconductor film at a predetermined temperature, and is brought into contact with the gas of the organic compound while being vaporized. Note that the organic compound gas may be supplied alone or mixed with an inert gas such as nitrogen. Also at this time, the amount of the organic compound used is the amount corresponding to the content.

酸化チタン処理
前記工程（ｃ）または（ｄ）の後、以下の酸化チタン処理を行ってもよい。
酸化チタン処理は、多孔質金属酸化物半導体膜（有機基導入後でもよい）にチタン化合物を塗布・吸収させ、ついで、２００〜７００℃、好ましくは３００〜６００℃で加熱処理する。この処理により、多孔質金属酸化物半導体膜上に、酸化チタン薄膜を形成する。 Titanium oxide treatment After the step (c) or (d), the following titanium oxide treatment may be performed.
In the titanium oxide treatment, a porous metal oxide semiconductor film (which may be after the introduction of an organic group) is coated and absorbed with a titanium compound, and then heat-treated at 200 to 700 ° C., preferably 300 to 600 ° C. By this treatment, a titanium oxide thin film is formed on the porous metal oxide semiconductor film.

チタン化合物は、ペルオキシチタン酸水溶液あるいはチタン塩水溶液等のチタン化合物である。ペルオキシチタン酸水溶液あるいはチタン塩化合物水溶液の濃度はＴiＯ2として０．１〜２．０質量％、さらには０．３〜１．０質量％の範囲にあることが好ましい。水溶液の濃度が薄いと所望の膜厚の酸化チタン薄膜が得られないことがあり、繰返し塗布、乾燥を行う必要が生じる。水溶液の濃度が高いと、乾燥時にクラックが生じたり、緻密な膜を形成できないことがあり、暗電流の抑制、電子の再結合の抑制効果が得られないことがある。 The titanium compound is a titanium compound such as a peroxytitanic acid aqueous solution or a titanium salt aqueous solution. The concentration of the peroxytitanic acid aqueous solution or the titanium salt compound aqueous solution is preferably 0.1 to 2.0% by mass, more preferably 0.3 to 1.0% by mass as TiO 2 . If the concentration of the aqueous solution is low, a titanium oxide thin film having a desired film thickness may not be obtained, and it becomes necessary to repeatedly apply and dry the titanium oxide thin film. If the concentration of the aqueous solution is high, cracks may occur during drying, or a dense film may not be formed, and the effect of suppressing dark current and recombination of electrons may not be obtained.

酸化チタン処理における酸化チタン処理量は、ＴｉＯ2として多孔質金属酸化物半導体膜の０．１〜５０質量％、さらには０．５〜２０質量％の範囲にあることが好ましい。
酸化チタン処理量が少ないと十分な暗電流の抑制、電子の再結合の抑制効果が得られない場合があり、酸化チタン処理量が多いと金属酸化物微粒子層の比表面積が小さくなり、このため光増感剤の吸着量が不十分となり、光電変換効率が不十分となることがある。 Titanium oxide treated amount of the titanium oxide process, 0.1 to 50% by weight of the porous metal oxide semiconductor film as TiO 2, more preferably in the range of 0.5 to 20 mass%.
If the amount of titanium oxide treatment is small, sufficient dark current suppression and electron recombination suppression effects may not be obtained. If the amount of titanium oxide treatment is large, the specific surface area of the metal oxide fine particle layer becomes small. The adsorption amount of the photosensitizer may be insufficient, and the photoelectric conversion efficiency may be insufficient.

また、加熱処理温度が低いと、チタン化合物が酸化チタンに変わらず、また、緻密な膜を形成できないことがあり、暗電流の抑制、電子の再結合の抑制効果が充分得られない場合がある。加熱処理温度が高すぎても、基板あるいは基板上の電極層が劣化する場合があり、また、多孔質金属酸化物半導体膜を構成する金属酸化物粒子の種類、粒子径によっては半導体膜の比表面積、多孔性が低下し、光増感材の吸着量が不十分となり光電変換効率が不十分となる場合がある。   In addition, when the heat treatment temperature is low, the titanium compound does not change to titanium oxide, and a dense film may not be formed, and the effect of suppressing dark current and suppressing recombination of electrons may not be sufficiently obtained. . Even if the heat treatment temperature is too high, the substrate or the electrode layer on the substrate may deteriorate, and the ratio of the semiconductor film depends on the type and particle size of the metal oxide particles constituting the porous metal oxide semiconductor film. In some cases, the surface area and the porosity are lowered, the adsorption amount of the photosensitizer is insufficient, and the photoelectric conversion efficiency is insufficient.

また、上記酸化チタン処理および前記有機基導入処理(d)の代わりに、前記乾燥・加熱処理（ｃ）の後、前記特定の有機基を含む有機化合物とチタン化合物の双方を用いて、酸化チタン処理と有機基導入を同時に行ってもよい。すなわち、多孔質金属酸化物半導体膜にチタン化合物およびアシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を含む有機化合物を服務溶液を塗布・吸収させ、ついで、１００〜７００℃、好ましくは３００〜６００℃で加熱処理して酸化チタン処理する。この工程では、チタン化合物と特定の有機基を含む有機化合物の双方を服務溶液を用いることから、酸化チタン処理と有機基の導入を同時に行うことができる。   Further, instead of the titanium oxide treatment and the organic group introduction treatment (d), after the drying / heating treatment (c), both the organic compound containing the specific organic group and the titanium compound are used, and titanium oxide is used. Treatment and organic group introduction may be performed simultaneously. That is, a porous metal oxide semiconductor film is coated and absorbed with a customary solution containing a titanium compound and an organic compound containing at least one organic group selected from an acyl group, an aroyl group, and a carboxylate group, and then 100 to 700 ° C. The titanium oxide treatment is preferably performed by heat treatment at 300 to 600 ° C. In this step, since both the titanium compound and the organic compound containing a specific organic group are used as the service solution, the titanium oxide treatment and the introduction of the organic group can be performed simultaneously.

いずれの場合も、チタン化合物の使用量は、最終的に得られる多孔質金属酸化物半導体膜中の有機基の含有量が炭素換算で５０〜２０００重量ｐｐｍ、さらには１００〜１０００重量ｐｐｍの範囲となる量である。
つぎに、本発明に係る光電気セルについて説明する。 In any case, the amount of the titanium compound used is such that the content of the organic group in the finally obtained porous metal oxide semiconductor film is in the range of 50 to 2000 ppm by weight in terms of carbon, and further 100 to 1000 ppm by weight. This is the amount.
Next, the photoelectric cell according to the present invention will be described.

[光電気セル]
本発明に係る光電気セルは、
表面に電極層(1)を有し、かつ該電極層(1)表面に光増感材を吸着した多孔質金属酸化物半導体膜(1)が形成されてなる基板(1)と、表面に電極層(2)を有する基板(2)とが、
前記電極層(1)および電極層(2)が対向するように配置してなり、
多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質層を設けてなる光電気セルにおいて、
該多孔質金属酸化物半導体膜(1)が請求項１〜１０のいずれかに記載の光電気セル用多孔質金属酸化物半導体膜の製造方法で得られたことを特徴としている。 [Photoelectric cell]
The photovoltaic cell according to the present invention comprises:
A substrate (1) having an electrode layer (1) on the surface and a porous metal oxide semiconductor film (1) having a photosensitizer adsorbed on the surface of the electrode layer (1); A substrate (2) having an electrode layer (2),
The electrode layer (1) and the electrode layer (2) are arranged so as to face each other,
In the photoelectric cell comprising an electrolyte layer between the porous metal oxide semiconductor film (1) and the electrode layer (2),
The porous metal oxide semiconductor film (1) is obtained by the method for producing a porous metal oxide semiconductor film for photoelectric cells according to any one of claims 1 to 10.

本発明によって得られる光電気セルとしては、たとえば、図１に示すものが挙げられる。
図１は、本発明によって得られる光電気セルの１例を示す概略断面図であり、表面に電極層(1)を有し、必要に応じて該電極層(1)上に酸化チタン薄膜(1)を有し、電極層(1)上、あるいは酸化チタン薄膜(1)上に光増感材を吸着した多孔質金属酸化物半導体膜(1)が形成されてなる基板(1)と、表面に電極層(2)を有する基板(2)とが、前記電極層(1)および電極層(2)が対向するように配置してなり、多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質が封入されている。 As a photoelectric cell obtained by the present invention, for example, the one shown in FIG.
FIG. 1 is a schematic cross-sectional view showing an example of a photoelectric cell obtained by the present invention, which has an electrode layer (1) on the surface, and a titanium oxide thin film (on the electrode layer (1) if necessary). A substrate (1) having a porous metal oxide semiconductor film (1) formed by adsorbing a photosensitizer on an electrode layer (1) or a titanium oxide thin film (1), The substrate (2) having the electrode layer (2) on the surface is disposed so that the electrode layer (1) and the electrode layer (2) face each other, and the porous metal oxide semiconductor film (1) and the electrode An electrolyte is enclosed between the layer (2).

図１中、１は電極層(1)、２は半導体膜(1)、３は電極層(2)、４は電解質層(2)、５は基板(1)、６は基板(2)を示す。
なお、本発明によって得られる光電気セルは図示した光電気セルに限定されるものではなく、半導体膜を２層以上有し、この間に別の電極層および電解質層を設けた光電気セルであってもよい。 In FIG. 1, 1 is an electrode layer (1), 2 is a semiconductor film (1), 3 is an electrode layer (2), 4 is an electrolyte layer (2), 5 is a substrate (1), and 6 is a substrate (2). Show.
The photoelectric cell obtained by the present invention is not limited to the illustrated photoelectric cell, and is a photoelectric cell having two or more semiconductor films and another electrode layer and electrolyte layer interposed therebetween. May be.

基板
一方の基板としてはガラス基板、ＰＥＴ等の有機ポリマー基板等の透明でかつ絶縁性を有する基板を用いることができる。
他の一方の基板としては使用に耐える強度を有していれば特に制限はなく、ガラス基板、ＰＥＴ等の有機ポリマー基板等の絶縁性基板の他に、金属チタン、金属アルミニウム、金属銅、金属ニッケルなどの導電性基板を使用することができる。
また、基板は少なくとも一方が透明であればよい。また双方の基板が透明であってもよい。通常、光の入射側に透明な基板を用いる。 As the one substrate, a transparent and insulating substrate such as a glass substrate or an organic polymer substrate such as PET can be used.
The other substrate is not particularly limited as long as it has enough strength to withstand use. In addition to insulating substrates such as glass substrates and organic polymer substrates such as PET, metal titanium, metal aluminum, metal copper, metal A conductive substrate such as nickel can be used.
Further, it is sufficient that at least one of the substrates is transparent. Further, both substrates may be transparent. Usually, a transparent substrate is used on the light incident side.

電極層
基板表面に形成された電極層としては、特に制限されるものでなく、白金、ロジウム、ルテニウム金属、ルテニウム酸化物等の電極材料、酸化錫、Ｓｂ、ＦまたはＰがドーピングされた酸化錫、Ｓｎおよび／またはＦがドーピングされた酸化インジウム、酸化アンチモン、酸化亜鉛などの導電性酸化材料からなる電極や、前記導電性材料表面をメッキあるいは蒸着した電極、カーボン電極など従来公知の電極を用いることができる。 The electrode layer formed on the surface of the electrode layer substrate is not particularly limited, and electrode materials such as platinum, rhodium, ruthenium metal and ruthenium oxide, tin oxide, tin oxide doped with Sb, F or P Conventionally known electrodes such as an electrode made of a conductive oxide material such as indium oxide, antimony oxide, and zinc oxide doped with Sn, / and F, an electrode obtained by plating or vapor-depositing the surface of the conductive material, and a carbon electrode are used. be able to.

なお、光の入射側の透明基板表面には透明電極層を形成し、該透明電極層は、上記の導電材料のうち、酸化錫、Ｓｂ、ＦまたはＰがドーピングされた酸化錫、Ｓｎおよび／またはＦがドーピングされた酸化インジウム、酸化アンチモン、酸化亜鉛、白金、ロジウム、ルテニウム金属などの貴金属などの電極を使用することができる。   A transparent electrode layer is formed on the surface of the transparent substrate on the light incident side, and the transparent electrode layer includes tin oxide, Sn and / or doped with tin oxide, Sb, F, or P among the above conductive materials. Alternatively, an electrode such as a noble metal such as indium oxide, antimony oxide, zinc oxide, platinum, rhodium, or ruthenium metal doped with F can be used.

なお、２つの基板は、双方とも透明基板であってもよく、また基板上に形成される電極層は、双方とも透明電極であってもよい。さらに、２つの基板は同じものであってもよく、電極層も同じものであってもよい。なお通常、光の入射側に透明電極を設ける。   The two substrates may both be transparent substrates, and the electrode layers formed on the substrates may both be transparent electrodes. Further, the two substrates may be the same, and the electrode layers may be the same. Normally, a transparent electrode is provided on the light incident side.

透明電極層の可視光透過率は高い方が好ましく、具体的には５０％以上、特に好ましくは９０％以上であることが望ましい。可視光透過率が低ければ光が透過しにくくなり光電変換効率が低くなることがある。
電極層自体の抵抗値は、各々１００Ω／ｃｍ2以下であることが好ましい。電極層の抵抗値が１００Ω／ｃｍ2を超えて高くなると光電変換効率が低くなることがある。 The visible light transmittance of the transparent electrode layer is preferably higher, specifically 50% or more, particularly preferably 90% or more. If the visible light transmittance is low, light is difficult to transmit and the photoelectric conversion efficiency may be lowered.
The resistance value of the electrode layer itself is preferably 100 Ω / cm 2 or less. When the resistance value of the electrode layer exceeds 100 Ω / cm 2 , the photoelectric conversion efficiency may be lowered.

酸化チタン薄膜
本発明において、必要に応じて電極層(1)ないし(2)上に酸化チタン薄膜を形成していていもよい。酸化チタン薄膜はペルオキシチタン酸水溶液あるいはチタン塩水溶液等を塗布、乾燥するなど従来公知の方法で形成することができ、緻密な膜である。 Titanium oxide thin film In the present invention, a titanium oxide thin film may be formed on the electrode layers (1) or (2) as necessary. The titanium oxide thin film can be formed by a conventionally known method such as coating and drying a peroxytitanic acid aqueous solution or a titanium salt aqueous solution, and is a dense film.

酸化チタン薄膜は、電極層のどちらかの上に形成されていればよく、透明電極層の上でも、透明でない電極層の上に形成されていてもよい。
酸化チタン薄膜が形成されていると暗電流の抑制、電子の再結合の抑制をすることができ光電変換効率を向上させることができる。 The titanium oxide thin film should just be formed on either of the electrode layers, and may be formed on the transparent electrode layer or the non-transparent electrode layer.
When the titanium oxide thin film is formed, the dark current can be suppressed and the recombination of electrons can be suppressed, and the photoelectric conversion efficiency can be improved.

酸化チタン薄膜は膜厚が７０ｎｍ以下、さらには４０ｎｍ以下の範囲にあることが好ましい。酸化チタン薄膜の膜厚が厚すぎると、エネルギー障壁が大きくなりすぎて電子の移動が抑制され、逆に光電変換効率が低下することがある。   The titanium oxide thin film preferably has a thickness in the range of 70 nm or less, more preferably 40 nm or less. If the titanium oxide thin film is too thick, the energy barrier becomes too large and the movement of electrons is suppressed, and conversely, the photoelectric conversion efficiency may decrease.

多孔質金属酸化物半導体膜
前記電極層上に前記した方法で多孔質金属酸化物半導体膜が形成されている。この多孔質金属酸化物半導体膜の膜厚は０．１〜５０μｍの範囲にあることが好ましい。また、多孔質金属酸化物半導体膜の細孔容積は０．１０〜０．８０ｍｌ／ｇ、さらには０．２０〜０．６５ｍｌ／ｇの範囲にあることが好ましい。細孔容積が小さいと、増感色素の吸着が不十分となったり、電解質の拡散性が低下してバックカレントを引き起こすことがあり、変換効率が不充分となることがある。また細孔容積が大きすぎても金属酸化物半導体膜の強度が不充分となることがある。通常、本発明に係る半導体膜は、５〜50nm程度の直径の細孔を有し、かかる細孔に、光増感材を吸着している。 Porous metal oxide semiconductor film A porous metal oxide semiconductor film is formed on the electrode layer by the method described above. The thickness of the porous metal oxide semiconductor film is preferably in the range of 0.1 to 50 μm. The pore volume of the porous metal oxide semiconductor film is preferably in the range of 0.10 to 0.80 ml / g, more preferably 0.20 to 0.65 ml / g. When the pore volume is small, the adsorption of the sensitizing dye may be insufficient, or the diffusibility of the electrolyte may be lowered to cause back current, resulting in insufficient conversion efficiency. Further, even if the pore volume is too large, the strength of the metal oxide semiconductor film may be insufficient. Usually, the semiconductor film according to the present invention has pores having a diameter of about 5 to 50 nm, and a photosensitizer is adsorbed in the pores.

光増感材
光増感材としては、可視光領域、紫外光領域、赤外光領域の光を吸収して励起するものであれば特に制限はなく、たとえば有機色素、金属錯体などを用いることができる。 The photosensitizer is not particularly limited as long as it absorbs and excites light in the visible light region, ultraviolet light region, and infrared light region. For example, an organic dye or a metal complex is used. Can do.

有機色素としては、分子中にカルボキシル基、ヒドロキシアルキル基、ヒドロキシル基、スルホン基、カルボキシアルキル基等の官能基を有する従来公知の有機色素が使用できる。 具体的には、メタルフリーフタロシアニン、シアニン系色素、メタロシアニン系色素、トリフェニルメタン系色素およびウラニン、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等のキサンテン系色素等が挙げられる。これらの有機色素は金属酸化物半導体膜への吸着速度が早いという特性を有している。   As the organic dye, a conventionally known organic dye having a functional group such as a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfone group, or a carboxyalkyl group in the molecule can be used. Specific examples include metal-free phthalocyanines, cyanine dyes, methocyanine dyes, triphenylmethane dyes, and xanthene dyes such as uranin, eosin, rose bengal, rhodamine B, and dibromofluorescein. These organic dyes have a characteristic that the adsorption rate to the metal oxide semiconductor film is fast.

また、金属錯体としては、特開平1-220380号公報、特表平5-504023号公報などに記載された銅フタロシアニン、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、ヘミン、ルテニウム-トリス(2,2'-ビスピリジル-4,4'-ジカルボキシラート)、シス-(ＳＣＮ-)-ビス(2,2'-ビピリジル-4,4'-ジカルボキシレート)ルテニウム、ルテニウム-シス-ジアクア-ビス(2,2'-ビピリジル-4,4'-ジカルボキシラート)などのルテニウム-シス-ジアクア-ビピリジル錯体、亜鉛-テトラ(4-カルボキシフェニル)ポルフィンなどのポルフィリン、鉄-ヘキサシアニド錯体等のルテニウム、オスミウム、鉄、亜鉛などの錯体を挙げることができる。これらの金属錯体は分光増感の効果や耐久性に優れている。たとえば、ダイソル社製のBA(N3)、B2(N719)、DNH2(Z907)、DBL(749)などが好適である。 Examples of the metal complex include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine described in JP-A-1-220380 and JP-A-5-504023, chlorophyll, hemin, ruthenium-tris (2,2 ′ -Bispyridyl-4,4′-dicarboxylate), cis- (SCN − ) -bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium, ruthenium-cis-diaqua-bis (2, Ruthenium-cis-diaqua-bipyridyl complexes such as 2'-bipyridyl-4,4'-dicarboxylate), porphyrins such as zinc-tetra (4-carboxyphenyl) porphine, ruthenium such as iron-hexocyanide complexes, osmium, iron And complexes of zinc and the like. These metal complexes are excellent in the effect of spectral sensitization and durability. For example, BA (N3), B2 (N719), DNH2 (Z907), DBL (749) manufactured by Daisol are suitable.

本発明では、前記した方法によって、半導体膜に特定の有機基が導入されているので、稼働開始当初からほぼ所定の光電変換効率を達成できる。
上記の光増感材としての有機色素または金属錯体は単独で用いてもよく、有機色素または金属錯体の２種以上を混合して用いてもよく、さらに有機色素と金属錯体とを併用してもよい。 In the present invention, since a specific organic group is introduced into the semiconductor film by the above-described method, a substantially predetermined photoelectric conversion efficiency can be achieved from the beginning of operation.
The organic dye or metal complex as the above-mentioned photosensitizer may be used alone, or may be used by mixing two or more kinds of organic dyes or metal complexes. Further, the organic dye and the metal complex are used in combination. Also good.

多孔質金属酸化物半導体膜の光増感材の吸着量は多孔質金属酸化物半導体膜の比表面積１ｃｍ2あたり１００μｇ以上、さらには１５０μｇ以上であることが好ましい。光増感材の吸着量が少ないと光電変換効率が不充分となる。 The adsorption amount of the photosensitizer on the porous metal oxide semiconductor film is preferably 100 μg or more, more preferably 150 μg or more per 1 cm 2 of the specific surface area of the porous metal oxide semiconductor film. If the adsorption amount of the photosensitizer is small, the photoelectric conversion efficiency becomes insufficient.

このような光増感材の吸着方法は、特に制限はなく、光増感材を溶媒に溶解した溶液を、ディッピング法、スピナー法、スプレー法等の方法により多孔質金属酸化物半導体膜に吸収させ、次いで乾燥する等の一般的な方法が採用できる。さらに必要に応じて前記吸収工程を繰り返してもよい。また、光増感材溶液を加熱環流しながら前記基板と接触させて光増感材を多孔質金属酸化物半導体膜に吸着させることもできる。
光増感材を溶解させる溶媒としては、光増感材を溶解するものであればよく、具体的には、水、アルコール類、トルエン、ジメチルホルムアミド、クロロホルム、エチルセルソルブ、Nーメチルピロリドン、テトラヒドロフラン等を用いることができる。
光増感材溶液の光増感材の濃度は多孔質金属酸化物半導体膜の比表面積１ｃｍ2あたり１００μｇ以上、さらには２００μｇ以上となる濃度が好ましい。 The adsorption method of such a photosensitizer is not particularly limited, and a solution obtained by dissolving the photosensitizer in a solvent is absorbed into the porous metal oxide semiconductor film by a method such as a dipping method, a spinner method, or a spray method. General methods such as drying and then drying can be employed. Furthermore, you may repeat the said absorption process as needed. Alternatively, the photosensitizer can be adsorbed to the porous metal oxide semiconductor film by bringing the photosensitizer solution into contact with the substrate while heating and refluxing.
As the solvent for dissolving the photosensitizer, any solvent that dissolves the photosensitizer can be used. Specifically, water, alcohols, toluene, dimethylformamide, chloroform, ethyl cellosolve, N-methylpyrrolidone, Tetrahydrofuran or the like can be used.
The concentration of the photosensitizer in the photosensitizer solution is preferably 100 μg or more, more preferably 200 μg or more per 1 cm 2 of the specific surface area of the porous metal oxide semiconductor film.

電解質層
電解質としては、電気化学的に活性な塩とともに酸化還元系を形成する少なくとも１種の化合物との混合物が使用される。 As the electrolyte layer electrolyte, a mixture of at least one compound that forms an oxidation-reduction system with an electrochemically active salt is used.

電気化学的に活性な塩としては、テトラプロピルアンモニウムアイオダイドなどの４級アンモニウム塩が挙げられる。酸化還元系を形成する化合物としては、キノン、ヒドロキノン、沃素（Ｉ-／Ｉ- 3）、沃化カリウム、臭素（Ｂr-／Ｂr- 3）、臭化カリウム等が挙げられる。場合によってはこれらを混合して使用することもできる。 Examples of the electrochemically active salt include quaternary ammonium salts such as tetrapropylammonium iodide. Examples of the compound forming the redox system, quinone, hydroquinone, iodine (I - / I - 3) , potassium iodide, bromine (Br - / Br - 3) , potassium bromide, and the like. In some cases, these may be used in combination.

このような電解質の使用量は、電解質の種類、後述する溶媒の種類によっても異なるが、概ね０.１〜５モル／リットルの範囲にあることが好ましい。
電解質層には、従来公知の溶媒を用いることができる。具体的には水、アルコール類、オリゴエーテル類、プロピオンカーボネート等のカーボネート類、燐酸エステル類、ジメチルホルムアミド、ジメチルスルホキシド、N-メチルピロリドン、N-ビニルピロリドン、スルホラン６６の硫黄化合物、炭酸エチレン、アセトニトリル、γ−ブチロラクトン等が挙げられる。 The amount of the electrolyte used is preferably approximately in the range of 0.1 to 5 mol / liter, although it varies depending on the type of electrolyte and the type of solvent described later.
A conventionally well-known solvent can be used for an electrolyte layer. Specifically, carbonates such as water, alcohols, oligoethers, propionate carbonate, phosphate esters, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, sulfur compounds of sulfolane 66, ethylene carbonate, acetonitrile , Γ-butyrolactone and the like.

本発明では、前記した表面に電極層(1)を有し、該電極層(1)上に必要に応じて酸化チタン薄膜(1)を有し、かつ電極層(1)上または酸化チタン薄膜(1)上に光増感材を吸着した多孔質金属酸化物半導体膜を有する基板(1)と、表面に電極層(2)を有する基板(2)とを、電極層(1)および電極層(2)が対向するように配置し、側面を樹脂にてシールし、多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質を封入し、さらに電極間をリード線で接続することによって光電気セルを製造することができる。
上記において、多孔質金属酸化物半導体膜は酸化チタン処理されていてもよい。 In the present invention, the electrode layer (1) is provided on the surface, and the electrode layer (1) has a titanium oxide thin film (1) as necessary, and the electrode layer (1) or the titanium oxide thin film. (1) A substrate (1) having a porous metal oxide semiconductor film on which a photosensitizer is adsorbed and a substrate (2) having an electrode layer (2) on the surface, the electrode layer (1) and the electrode Arrange the layers (2) so that they face each other, seal the sides with resin, enclose the electrolyte between the porous metal oxide semiconductor film (1) and the electrode layer (2), and lead between the electrodes Photoelectric cells can be manufactured by connecting with wires.
In the above, the porous metal oxide semiconductor film may be treated with titanium oxide.

[実施例]
以下、本発明を実施例により説明するが、本発明はこれらに実施例により限定されるものではない。 [Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example by these.

[実施例1]
多孔質金属酸化物半導体膜形成用塗料(1)の調製
四塩化チタン溶液(ＴｉＯ2濃度：２７．８質量％)１８３．５ｇを純水でＴｉＯ2濃度が５質量％となるまで希釈し、ｐＨが９．３となるように濃度１５質量％のアンモニア水を加え、よく混合し、酸化チタン水和物ヒドロゲルスラリー(1)を得た。その酸化チタン水和物ヒドロゲルスラリー(1)をろ過洗浄した後、回収したケーキに純水を加えＴｉＯ2濃度５質量％に調整し、これにテトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）の濃度が０．１質量％となるように、濃度２５質量％のＴＭＡＨ水溶液を加え、オートクレーブにて１６５℃にて１５時間熟成し、ついで、常温に冷却した後、硝酸水溶液を用いてｐＨが１．０となるように調整し、限外濾過膜にてＴｉＯ2濃度が２０質量％となるように濃縮を行い、酸化チタン微粒子(1)分散液を調製した。得られた酸化チタン微粒子(1)について、平均粒子径を測定し、Ｘ線回折法により結晶形を同定し、結果を表に示す。 [Example 1]
Preparation of paint for forming porous metal oxide semiconductor film (1) Titanium tetrachloride solution (TiO 2 concentration: 27.8% by mass) 183.5 g was diluted with pure water until the TiO 2 concentration became 5% by mass, Ammonia water having a concentration of 15% by mass was added so as to have a pH of 9.3 and mixed well to obtain a titanium oxide hydrate hydrogel slurry (1). After the titanium oxide hydrate hydrogel slurry (1) was filtered and washed, pure water was added to the recovered cake to adjust the TiO 2 concentration to 5% by mass, and the concentration of tetramethylammonium hydroxide (TMAH) was adjusted to 0. A TMAH aqueous solution having a concentration of 25% by mass is added so as to be 1% by mass, aging is carried out at 165 ° C. for 15 hours in an autoclave, and after cooling to room temperature, the pH becomes 1.0 using an aqueous nitric acid solution. Then, the mixture was concentrated using an ultrafiltration membrane so that the TiO 2 concentration was 20% by mass to prepare a titanium oxide fine particle (1) dispersion. With respect to the obtained titanium oxide fine particles (1), the average particle diameter was measured, the crystal form was identified by the X-ray diffraction method, and the results are shown in the table.

ついで、酸化チタン微粒子(1)分散液１００ｇにエタノール２５０ｇを加えて攪拌した後、遠心分離機にて分離し、沈降した酸化チタン微粒子(1)にエタノールを加えて固形分濃度１２質量％となるように回収して酸化チタン微粒子エタノール分散液(1)を得た。   Next, 250 g of ethanol was added to 100 g of the titanium oxide fine particle (1) dispersion and stirred, and then separated by a centrifugal separator. Ethanol was added to the precipitated titanium oxide fine particle (1) to a solid content concentration of 12% by mass. Thus, a titanium oxide fine particle ethanol dispersion (1) was obtained.

ついで、別途用意した濃度１０質量％となるようにエタノールに溶解したエチルセルロース溶液８０ｇを酸化チタン微粒子エタノール分散液(1)１６６．７ｇに加え、さらに、テルピネオールを８６ｇ加えて充分に攪拌した後、ロータリーエバポレータにてＴｉＯ2濃度が１７．４質量％となるように濃縮して多孔質金属酸化物半導体膜形成用塗料(1)を調製した。 Next, 80 g of an ethyl cellulose solution dissolved in ethanol to a concentration of 10% by mass prepared separately was added to 166.7 g of the titanium oxide fine particle ethanol dispersion (1), and 86 g of terpineol was further added and stirred sufficiently. A porous metal oxide semiconductor film-forming coating material (1) was prepared by concentrating with an evaporator so that the TiO 2 concentration was 17.4% by mass.

有機基導入孔質金属酸化物半導体膜(1)の形成
フッ素ドープＳｎＯ2導電性ガラス(日本板硝子株式会社製：板厚４．０ｍｍ、１０．０×１１．０ｃｍ)をＴｉＯ2濃度が４０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥させて酸化チタン薄膜を形成した後、多孔質金属酸化物半導体膜形成用塗料(1)を１００ｍｅｓｈの版（７５ｍｍ×７５ｍｍ）を使用したスクリーン印刷法により、焼成後の膜厚が１４μｍとなるように、印刷→１２０℃での乾燥→冷却を３回繰返した後、４５０℃にて１時間加熱処理して多孔質金属酸化物半導体膜(1)を形成した。このときの多孔質金属酸化物半導体膜の固形分としての重量は０．１１９９ｇである。 Formation of organic group-introduced porous metal oxide semiconductor film (1) Fluorine-doped SnO 2 conductive glass (manufactured by Nippon Sheet Glass Co., Ltd .: plate thickness 4.0 mm, 10.0 × 11.0 cm) having a TiO 2 concentration of 40 mM After being immersed in an aqueous solution of titanium tetrachloride and kept at 70 ° C. for 30 minutes, it is washed with pure water and ethanol, dried to form a titanium oxide thin film, and then a porous metal oxide semiconductor film-forming coating (1 ) Was repeated three times by printing → drying at 120 ° C. → cooling so that the film thickness after firing was 14 μm by a screen printing method using a 100 mesh plate (75 mm × 75 mm), then at 450 ° C. A porous metal oxide semiconductor film (1) was formed by heat treatment for 1 hour. At this time, the weight of the porous metal oxide semiconductor film as a solid content is 0.1199 g.

ついで、多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール１０ｇをエタノール９０ｇと混合したダイアセトンアルコール／エタノール混合溶液０．３ｇを均一に塗布し、６０℃にて３０分保持した後、４５０℃にて１時間加熱処理した。   Next, 0.3 g of a diacetone alcohol / ethanol mixed solution obtained by mixing 10 g of diacetone alcohol with 90 g of ethanol was uniformly applied to the surface of the substrate with the porous metal oxide semiconductor film (1), and the mixture was heated at 60 ° C. for 30 minutes. After holding, heat treatment was performed at 450 ° C. for 1 hour.

さらにＴｉＯ2濃度が４０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥して酸化チタン処理した後、４５０℃にて１時間焼成して有機基を導入した多孔質金属酸化物半導体膜(1)付基板を形成した。 Further, it is immersed in an aqueous titanium tetrachloride solution having a TiO 2 concentration of 40 mM, held at 70 ° C. for 30 minutes, washed with pure water and ethanol, dried and treated with titanium oxide, and then fired at 450 ° C. for 1 hour. Thus, a substrate with a porous metal oxide semiconductor film (1) into which an organic group was introduced was formed.

一方の有機基導入多孔質金属酸化物半導体膜(1)の一部を採取し、細孔容積および平均細孔径を測定し、結果を表１に示す。また、他の一部を採取し、赤外分光計により有機基を同定するとともに、炭素換算の有機基量を測定し、結果を表１に示す。   A portion of one organic group-introduced porous metal oxide semiconductor film (1) was sampled and measured for pore volume and average pore diameter. Table 1 shows the results. In addition, another part was collected, the organic group was identified by an infrared spectrometer, the amount of organic group in terms of carbon was measured, and the results are shown in Table 1.

なお、有機基の同定について、１３３０〜１３６０ｃｍ-1はＣＨ３基、１５４０〜１５８０ｃｍ-1はＣＯまたはＣＯＯ基の存在を示す。同定した有機基の波数とともに吸収スペクトルの強い場合には◎、明らかに吸収が認められる場合には○、僅かに認められる場合は△、認められない場合は×を付して表１に示す。 Incidentally, the identification of organic groups, 1330～1360Cm -1 is a CH 3 group, 1540～1580Cm -1 indicates the presence of CO or COO group. Table 1 shows ◎ when the absorption spectrum is strong together with the wave number of the identified organic group, ◯ when the absorption is clearly recognized, Δ when the absorption is slightly observed, and × when the absorption is not recognized.

光増感材の吸着
光増感材としてＤＹＥＳＯＬ社製ＤＮＨ２（Ｚ９０７）色素を濃度０．３ｍｍｏｌ／ｌとなるようにアセトニトリルおよびｔｅｒｔ−ブタノール(体積比１：１)の溶液に溶解し光増感材溶液を調製した。この溶液に酸化チタン薄膜および多孔質金属酸化物半導体膜(1)を形成したガラスを５時間漬込み、取り出した後アセトニトリルで洗浄し、色素を吸着させた。 Adsorption of photosensitizer DNH2 (Z907) dye manufactured by DYESOL as a photosensitizer is dissolved in a solution of acetonitrile and tert-butanol (volume ratio 1: 1) to a concentration of 0.3 mmol / l and photosensitized. A material solution was prepared. The glass on which the titanium oxide thin film and the porous metal oxide semiconductor film (1) were formed was immersed in this solution for 5 hours, taken out, washed with acetonitrile, and the dye was adsorbed.

Figure 2014011022
Figure 2014011022

光電気セル(1)の作成
先ず、溶媒として３-メトキシプロピオニトリル中に１-メチルー３-プロピルイミダゾリウムヨーダイド ０．６ｍｏｌ／ｌ、Ｎ−メチルベンゾイミダゾール ０．５ｍｏｌ／ｌ、ヨウ素 ０．１ｍｏｌ／ｌとなるように溶解して電解質を調製した。 Preparation of Photoelectric Cell (1) First, 1-methyl-3-propylimidazolium iodide 0.6 mol / l, N-methylbenzimidazole 0.5 mol / l, iodine in 3-methoxypropionitrile as a solvent. An electrolyte was prepared by dissolving to 1 mol / l.

前記で調製した多孔質金属酸化物半導体膜(1)付基板を５ｍｍ×５ｍｍに裁断し、これを一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、光電気セル(1)を作成した。   The substrate with the porous metal oxide semiconductor film (1) prepared above is cut into 5 mm × 5 mm, this is used as one electrode, and fluorine doped tin oxide is formed as the other electrode, and platinum is formed thereon. A transparent glass substrate into which was introduced was placed oppositely, the side surfaces were sealed with resin, and the above electrolyte solution was sealed between the electrodes to produce a photoelectric cell (1).

光電気セル(1)は、ソーラーシュミレーターで１００Ｗ／ｍ2の強度の光を入射角９０°（セル面と９０°）で照射して、２時間後、５時間後および１０時間後のＶｏｃ（開回路状態の電圧）、Ｊｏｃ（回路を短絡したときに流れる電流の密度）、ＦＦ（曲線因子）およびη（変換効率）を測定し結果を表１に示した。 The photoelectric cell (1) is irradiated with light having an intensity of 100 W / m 2 by a solar simulator at an incident angle of 90 ° (90 ° with the cell surface), and Voc (2 hours, 5 hours, and 10 hours later) The voltage in the open circuit state), Joc (density of current flowing when the circuit is short-circuited), FF (curve factor) and η (conversion efficiency) were measured, and the results are shown in Table 1.

[実施例２]
有機基導入孔質金属酸化物半導体膜(2)の形成
実施例１において、多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール１ｇをエタノール９９ｇと混合したダイアセトンアルコール／エタノール混合溶液０．３ｇを均一に塗布した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(2)を形成した。有機基導入多孔質金属酸化物半導体膜(2)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(2)に色素を吸着させた。
光電気セル(2)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(2)を作成した。 [Example 2]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (2) In Example 1, diacetone alcohol / diacetone alcohol mixed with 99 g of ethanol on the surface of the substrate with the porous metal oxide semiconductor film (1) / A porous metal oxide semiconductor film (2) into which an organic group was introduced was formed in the same manner except that 0.3 g of the ethanol mixed solution was uniformly applied. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (2) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Adsorption of photosensitizer In the same manner as in Example 1, a dye was adsorbed on the organic group-containing porous metal oxide semiconductor film (2).
Preparation of photoelectric cell (2) In the same manner as in Example 1, the electrode prepared above was used as one electrode, the other electrode was formed as fluorine-doped tin oxide, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (2).

光電気セル(2)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (2), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例３]
有機基導入孔質金属酸化物半導体膜(3)の形成
実施例１において、多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール１００ｇに浸漬した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(3)を形成した。有機基導入多孔質金属酸化物半導体膜(3)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(3)に色素を吸着させた。
光電気セル(3)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(3)を作成した。 [Example 3]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (3) In Example 1, an organic group was similarly prepared except that it was immersed in 100 g of diacetone alcohol on the surface of the substrate with the porous metal oxide semiconductor film (1). A porous metal oxide semiconductor film (3) into which was introduced was formed. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (3) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Photosensitizer Adsorption Dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (3) in the same manner as in Example 1.
Preparation of Photoelectric Cell (3) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed as fluorine-doped tin oxide as an electrode, and platinum was introduced thereon. A glass substrate was placed face to face, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (3).

光電気セル(3)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (3), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例４]
有機基導入孔質金属酸化物半導体膜(4)の形成
実施例１において、６０℃にて３０分保持した後、２００℃にて１時間加熱処理した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(4)を形成した。有機基導入多孔質金属酸化物半導体膜(4)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(4)に色素を吸着させた。
光電気セル(4)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(4)を作成した。 [Example 4]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (4) In Example 1, a porous layer in which organic groups were introduced in the same manner except that it was kept at 60 ° C. for 30 minutes and then heat-treated at 200 ° C. for 1 hour. A porous metal oxide semiconductor film (4) was formed. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (4) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Photosensitizer Adsorption Dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (4) in the same manner as in Example 1.
Preparation of photoelectric cell (4) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed using fluorine-doped tin oxide as the electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (4).

光電気セル(4)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (4), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例５]
有機基導入孔質金属酸化物半導体膜(5)の形成
実施例１において、６０℃にて３０分保持した後、６００℃にて１時間加熱処理した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(5)を形成した。有機基導入多孔質金属酸化物半導体膜(5)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(5)に色素を吸着させた。
光電気セル(5)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(5)を作成した。 [Example 5]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (5) In Example 1, a porous layer in which organic groups were introduced in the same manner except that it was kept at 60 ° C. for 30 minutes and then heat-treated at 600 ° C. for 1 hour. A porous metal oxide semiconductor film (5) was formed. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (5) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Photosensitizer Adsorption Dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (5) in the same manner as in Example 1.
Preparation of photoelectric cell (5) In the same manner as in Example 1, the electrode prepared above was used as one electrode, the other electrode was formed as fluorine-doped tin oxide, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (5).

光電気セル(5)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (5), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例６]
有機基導入孔質金属酸化物半導体膜(6)の形成
タノール９０ｇと混合したアセチルアセトン／エタノール混合溶液０．３ｇを均一に塗布した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(6)を形成した。有機基導入多孔質金属酸化物半導体膜(6)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(6)に色素を吸着させた。
光電気セル(6)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(6)を作成した。 [Example 6]
Formation of organic group-introduced porous metal oxide semiconductor film (6) Porous metal oxide semiconductor film into which organic groups were introduced in the same manner except that 0.3 g of acetylacetone / ethanol mixed solution mixed with 90 g of tanol was uniformly applied (6) was formed. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (6) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (6) in the same manner as in Example 1.
Preparation of photoelectric cell (6) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and fluorine doped tin oxide was formed as the other electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (6).

光電気セル(6)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (6), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例７]
有機基導入孔質金属酸化物半導体膜(7)の形成
実施例１において、多孔質金属酸化物半導体膜(1)付基板の表面に、マロン酸ジエチル１０ｇをエタノール９０ｇと混合したマロン酸ジエチル／エタノール混合溶液０．３ｇを均一に塗布した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(7)を形成した。有機基導入多孔質金属酸化物半導体膜(7)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(7)に色素を吸着させた。
光電気セル(7)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(7)を作成した。 [Example 7]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (7) In Example 1, diethyl malonate in which 10 g of diethyl malonate was mixed with 90 g of ethanol on the surface of the substrate with the porous metal oxide semiconductor film (1) / A porous metal oxide semiconductor film (7) into which an organic group was introduced was formed in the same manner except that 0.3 g of the ethanol mixed solution was uniformly applied. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (7) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Adsorption of photosensitizer In the same manner as in Example 1, a dye was adsorbed on the organic group-containing porous metal oxide semiconductor film (7).
Preparation of Photoelectric Cell (7) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and fluorine doped tin oxide was formed as the other electrode as an electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (7).

光電気セル(7)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (7), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例８]
有機基導入孔質金属酸化物半導体膜(8)の形成
実施例１と同様にして多孔質金属酸化物半導体膜(1)を形成した。
ついで、密閉電気炉内に多孔質金属酸化物半導体膜(1)付基板を設置し、温度を４５０℃に維持しながら、ダイアセトンアルコールを０．５Ｖｏｌ％含む窒素ガスを１００ｍｌ／分の速度で１時間供給して有機基を導入した。 [Example 8]
Formation of organic group-introduced porous metal oxide semiconductor film (8) A porous metal oxide semiconductor film (1) was formed in the same manner as in Example 1.
Next, a substrate with a porous metal oxide semiconductor film (1) was placed in a sealed electric furnace, and nitrogen gas containing 0.5 vol% diacetone alcohol was maintained at a rate of 100 ml / min while maintaining the temperature at 450 ° C. The organic group was introduced by supplying for 1 hour.

さらにＴｉＯ2濃度が４０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥して酸化チタン処理した後、４５０℃にて１時間焼成して有機基を導入した多孔質金属酸化物半導体膜(8)を形成した。 Further, it is immersed in an aqueous titanium tetrachloride solution having a TiO 2 concentration of 40 mM, held at 70 ° C. for 30 minutes, washed with pure water and ethanol, dried and treated with titanium oxide, and then fired at 450 ° C. for 1 hour. Thus, a porous metal oxide semiconductor film (8) into which an organic group was introduced was formed.

有機基導入多孔質金属酸化物半導体膜(8)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(8)に色素を吸着させた。
光電気セル(8)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(8)を作成した。 The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (8) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed on the organic group-containing porous metal oxide semiconductor film (8) in the same manner as in Example 1.
Preparation of photoelectric cell (8) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed as fluorine-doped tin oxide as an electrode, and platinum was introduced thereon. A glass substrate was placed face to face, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (8).

光電気セル(8)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (8), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例９]
有機基導入孔質金属酸化物半導体膜(9)の形成
実施例１と同様にして多孔質金属酸化物半導体膜(1)を形成した。さらにＴｉＯ2濃度が４０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥して酸化チタン処理した後、４５０℃にて１時間焼成した。 [Example 9]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (9) A porous metal oxide semiconductor film (1) was formed in the same manner as in Example 1. Further, it is immersed in an aqueous titanium tetrachloride solution having a TiO 2 concentration of 40 mM, held at 70 ° C. for 30 minutes, washed with pure water and ethanol, dried and treated with titanium oxide, and then fired at 450 ° C. for 1 hour. did.

ついで、酸化チタン処理した多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール１０ｇをエタノール９０ｇと混合したダイアセトンアルコール／エタノール混合溶液０．３ｇを均一に塗布して６０℃にて３０分保持した後、４５０℃にて１時間加熱処理して、有機基を導入した多孔質金属酸化物半導体膜(9)を形成した。   Next, 0.3 g of a diacetone alcohol / ethanol mixed solution obtained by mixing 10 g of diacetone alcohol with 90 g of ethanol was uniformly applied to the surface of the substrate with the titanium oxide-treated porous metal oxide semiconductor film (1) at 60 ° C. After being held at 30 ° C. for 30 minutes, heat treatment was performed at 450 ° C. for 1 hour to form a porous metal oxide semiconductor film (9) into which an organic group was introduced.

有機基導入多孔質金属酸化物半導体膜(9)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(9)に色素を吸着させた。
光電気セル(9)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(9)を作成した。 The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (9) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Photosensitizer Adsorption Dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (9) in the same manner as in Example 1.
Preparation of photoelectric cell (9) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed as fluorine-doped tin oxide as an electrode, and platinum was introduced thereon. A glass substrate was placed face to face, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (9).

光電気セル(9)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (9), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例１０]
有機基導入孔質金属酸化物半導体膜(10)の形成
実施例１と同様にして多孔質金属酸化物半導体膜(1)を形成した。
ついで、ＴｉＯ2濃度が４０ｍＭ、ダイアセトンアルコール濃度が４８０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥して酸化チタン処理と同時に有機基を導入した後、４５０℃にて１時間加熱処理して、有機基を導入した多孔質金属酸化物半導体膜(10)を形成した。 [Example 10]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (10) A porous metal oxide semiconductor film (1) was formed in the same manner as in Example 1.
Then, after immersing in a titanium tetrachloride aqueous solution having a TiO 2 concentration of 40 mM and a diacetone alcohol concentration of 480 mM and holding at 70 ° C. for 30 minutes, it is washed with pure water and ethanol, dried and simultaneously with the titanium oxide treatment. After introducing the organic group, heat treatment was performed at 450 ° C. for 1 hour to form a porous metal oxide semiconductor film (10) into which the organic group was introduced.

有機基導入多孔質金属酸化物半導体膜(10)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(10)に色素を吸着させた。
光電気セル(10)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(10)を作成した。 The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (10) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Photosensitizer Adsorption Dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (10) in the same manner as in Example 1.
Preparation of photoelectric cell (10) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed using fluorine-doped tin oxide as an electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (10).

光電気セル(10)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (10), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例１１]
有機基導入孔質金属酸化物半導体膜(11)の形成
実施例１と同様にして多孔質金属酸化物半導体膜(1)を形成した。
ついで、多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール１０ｇをエタノール９０ｇと混合したダイアセトンアルコール／エタノール混合溶液０．３ｇを均一に塗布して６０℃にて３０分保持した後、９５℃にて１時間加熱処理を行った。 [Example 11]
Formation of organic group-introduced porous metal oxide semiconductor film (11) A porous metal oxide semiconductor film (1) was formed in the same manner as in Example 1.
Next, 0.3 g of a diacetone alcohol / ethanol mixed solution obtained by mixing 10 g of diacetone alcohol with 90 g of ethanol was uniformly applied to the surface of the substrate with the porous metal oxide semiconductor film (1), and then at 60 ° C. for 30 minutes. After holding, heat treatment was performed at 95 ° C. for 1 hour.

さらにＴｉＯ2濃度が４０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥して酸化チタン処理した後、４５０℃にて１時間加熱処理して有機基を導入した多孔質金属酸化物半導体膜(11)を形成した。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(11)に色素を吸着させた。
光電気セル(11)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(11)を作成した。 Further, it is immersed in an aqueous titanium tetrachloride solution having a TiO 2 concentration of 40 mM, held at 70 ° C. for 30 minutes, washed with pure water and ethanol, dried and treated with titanium oxide, and then heated at 450 ° C. for 1 hour. A porous metal oxide semiconductor film (11) in which an organic group was introduced by treatment was formed.
Photosensitizer Adsorption Dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (11) in the same manner as in Example 1.
Preparation of photoelectric cell (11) In the same manner as in Example 1, the electrode prepared above was used as one electrode, fluorine-doped tin oxide was formed as the other electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (11).

光電気セル(11)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (11), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[実施例１２]
有機基担持孔質金属酸化物半導体膜(12)の形成
実施例１と同様にして形成した多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール１０ｇをエタノール９０ｇと混合したダイアセトンアルコール／エタノール混合溶液０．３ｇを均一に塗布し、６０℃にて３０分保持した後、４５０℃にて１時間加熱処理して有機基を導入した多孔質金属酸化物半導体膜(12)付基板を形成した。 [Example 12]
Formation of Organic Group-Supported Porous Metal Oxide Semiconductor Film (12) 10 g of diacetone alcohol was mixed with 90 g of ethanol on the surface of the substrate with the porous metal oxide semiconductor film (1) formed in the same manner as in Example 1. A porous metal oxide semiconductor film in which 0.3 g of a diacetone alcohol / ethanol mixed solution was uniformly applied and held at 60 ° C. for 30 minutes and then heat-treated at 450 ° C. for 1 hour to introduce organic groups (12 ) A substrate was formed.

有機基担持多孔質金属酸化物半導体膜(12)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(12)に色素を吸着させた。
光電気セル(12)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を担持した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(12)を作成した。 The pore volume and average pore diameter of the organic group-supported porous metal oxide semiconductor film (12) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (12) in the same manner as in Example 1.
Production of Photoelectric Cell (12) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed with fluorine-doped tin oxide as an electrode, on which platinum was supported. A glass substrate was placed face to face, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (12).

光電気セル(2)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (2), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[比較例１]
多孔質金属酸化物半導体膜(R1)の形成
実施例１と同様にして多孔質金属酸化物半導体膜(1)を形成した。 [Comparative Example 1]
Formation of porous metal oxide semiconductor film (R1) A porous metal oxide semiconductor film (1) was formed in the same manner as in Example 1.

ついで、ＴｉＯ2濃度が４０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥して酸化チタン処理した後、４５０℃にて１時間焼成して多孔質金属酸化物半導体膜(R1)を形成した。 Then, after immersing in a titanium tetrachloride aqueous solution having a TiO 2 concentration of 40 mM, holding at 70 ° C. for 30 minutes, washing with pure water and ethanol, drying and titanium oxide treatment, followed by 450 ° C. for 1 hour Firing was performed to form a porous metal oxide semiconductor film (R1).

多孔質金属酸化物半導体膜(R1)の細孔容積および平均細孔径を測定し、結果を表１に示す。
光増感材の吸着
実施例１と同様にして多孔質金属酸化物半導体膜(R1)に色素を吸着させた。
光電気セル(R1)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(R1)を作成した。 The pore volume and average pore diameter of the porous metal oxide semiconductor film (R1) were measured, and the results are shown in Table 1.
Photosensitizer Adsorption Dye was adsorbed to the porous metal oxide semiconductor film (R1) in the same manner as in Example 1.
Preparation of photoelectric cell (R1) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed using fluorine-doped tin oxide as the electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (R1).

光電気セル(R1)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (R1), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[比較例２]
有機基含有多孔質金属酸化物半導体膜(R2)の形成
実施例１において、多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール０．２ｇをエタノール１９９．８ｇと混合したダイアセトンアルコール／エタノール混合溶液０．３ｇを均一に塗布した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(R2)を形成した。有機基導入多孔質金属酸化物半導体膜(R2)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(R2)に色素を吸着させた。
光電気セル(R2)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(R2)を作成した。 [Comparative Example 2]
Formation of Organic Group-Containing Porous Metal Oxide Semiconductor Film (R2) In Example 1, 0.2 g of diacetone alcohol was mixed with 199.8 g of ethanol on the surface of the substrate with the porous metal oxide semiconductor film (1). A porous metal oxide semiconductor film (R2) into which an organic group was introduced was formed in the same manner except that 0.3 g of a diacetone alcohol / ethanol mixed solution was uniformly applied. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (R2) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (R2) in the same manner as in Example 1.
Preparation of photoelectric cell (R2) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed using fluorine-doped tin oxide as an electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to form a photoelectric cell (R2).

光電気セル(R2)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (R2), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[比較例３]
有機基導入孔質金属酸化物半導体膜(R3)の形成
実施例１において、多孔質金属酸化物半導体膜(1)付基板の表面に、モノステアリン酸グリセリル１０ｇをベンゼン９０ｇと混合したモノステアリン酸グリセリル／ベンゼン混合溶液０．３ｇを均一に塗布した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(R3)を形成した。有機基導入多孔質金属酸化物半導体膜(R3)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(R3)に色素を吸着させた。
光電気セル(R3)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(R3)を作成した。 [Comparative Example 3]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (R3) In Example 1, monostearic acid prepared by mixing 10 g of glyceryl monostearate with 90 g of benzene on the surface of a substrate with a porous metal oxide semiconductor film (1) A porous metal oxide semiconductor film (R3) into which an organic group was introduced was formed in the same manner except that 0.3 g of a glyceryl / benzene mixed solution was uniformly applied. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (R3) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Adsorption of photosensitizer The dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (R3) in the same manner as in Example 1.
Preparation of Photoelectric Cell (R3) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and fluorine doped tin oxide was formed as the other electrode as a transparent electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to form a photoelectric cell (R3).

光電気セル(R3)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (R3), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[比較例４]
有機基導入孔質金属酸化物半導体膜(R4)の形成
実施例１において、多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール／エタノール混合溶液０．３ｇを均一に塗布し、６０℃にて３０分保持した後、７５０℃にて１時間加熱処理した以外は同様にして有機基を導入した多孔質金属酸化物半導体膜(4)を形成した。有機基導入多孔質金属酸化物半導体膜(R4)の細孔容積および平均細孔径を測定し、結果を表１に示す。また、有機基の同定および定量をし、結果を表１に示す。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(R4)に色素を吸着させた。
光電気セル(R4)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(R4)を作成した。 [Comparative Example 4]
Formation of organic group-introduced porous metal oxide semiconductor film (R4) In Example 1, 0.3 g of diacetone alcohol / ethanol mixed solution was uniformly applied to the surface of the substrate with the porous metal oxide semiconductor film (1). Then, after maintaining at 60 ° C. for 30 minutes, a porous metal oxide semiconductor film (4) into which an organic group was introduced was formed in the same manner except that heat treatment was performed at 750 ° C. for 1 hour. The pore volume and average pore diameter of the organic group-introduced porous metal oxide semiconductor film (R4) were measured, and the results are shown in Table 1. The organic group was identified and quantified, and the results are shown in Table 1.
Photosensitizer Adsorption Dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (R4) in the same manner as in Example 1.
Preparation of photoelectric cell (R4) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed using fluorine-doped tin oxide as the electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (R4).

光電気セル(R4)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (R4), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

[比較例５]
有機基導入孔質金属酸化物半導体膜(R5)の形成
実施例１と同様にして多孔質金属酸化物半導体膜(1)を形成した。 [Comparative Example 5]
Formation of Organic Group-Introduced Porous Metal Oxide Semiconductor Film (R5) A porous metal oxide semiconductor film (1) was formed in the same manner as in Example 1.

ついで、多孔質金属酸化物半導体膜(1)付基板の表面に、ダイアセトンアルコール１０ｇをエタノール９０ｇと混合したダイアセトンアルコール／エタノール混合溶０．３ｇを均一に塗布し６０℃にて３０分保持した後、９５℃にて１時間焼成した。   Next, 0.3 g of diacetone alcohol / ethanol mixed solution obtained by mixing 10 g of diacetone alcohol with 90 g of ethanol was uniformly applied to the surface of the substrate with the porous metal oxide semiconductor film (1) and held at 60 ° C. for 30 minutes. And then baked at 95 ° C. for 1 hour.

さらにＴｉＯ2濃度が４０ｍＭの四塩化チタン水溶液に浸漬させ、７０℃にて３０分保持した後、純水洗浄およびエタノール洗浄を行い、乾燥して酸化チタン処理した後、１５０℃にて１時間焼成して有機基を導入した多孔質金属酸化物半導体膜(R5)を形成した。
光増感材の吸着
実施例１と同様にして有機基含有多孔質金属酸化物半導体膜(R5)に色素を吸着させた。
光電気セル(R5)の作成
実施例１と同様にして、前記で調製した電極を一方の電極とし、他方の電極としてフッ素ドープした酸化スズを電極として形成し、その上に白金を導入した透明ガラス基板を対向して配置し、側面を樹脂にてシールし、電極間に上記の電解質溶液を封入し、さらに電極間をリード線で接続して光電気セル(R5)を作成した。 Further, it is immersed in an aqueous titanium tetrachloride solution having a TiO 2 concentration of 40 mM, held at 70 ° C. for 30 minutes, washed with pure water and ethanol, dried and treated with titanium oxide, and then fired at 150 ° C. for 1 hour. Thus, a porous metal oxide semiconductor film (R5) into which an organic group was introduced was formed.
Adsorption of photosensitizer The dye was adsorbed to the organic group-containing porous metal oxide semiconductor film (R5) in the same manner as in Example 1.
Preparation of Photoelectric Cell (R5) In the same manner as in Example 1, the electrode prepared above was used as one electrode, and the other electrode was formed using fluorine-doped tin oxide as an electrode, and platinum was introduced thereon. A glass substrate was placed oppositely, the side surfaces were sealed with resin, the electrolyte solution was sealed between the electrodes, and the electrodes were connected with lead wires to produce a photoelectric cell (R5).

光電気セル(R5)について、実施例１と同様にＶｏｃ、Ｊｏｃ、ＦＦおよびηを測定し結果を表１に示す。   For the photoelectric cell (R5), Voc, Joc, FF and η were measured in the same manner as in Example 1, and the results are shown in Table 1.

Figure 2014011022
Figure 2014011022

Figure 2014011022
Figure 2014011022

１・・・・・電極層(1)
２・・・・・半導体膜(1)
３・・・・・電極層(2)
４・・・・・電解質層(2)
５・・・・・基板(1)
６・・・・・基板(2) 1. Electrode layer (1)
2 ... Semiconductor film (1)
3. Electrode layer (2)
4 ... Electrolyte layer (2)
5 ... Board (1)
6 ... Board (2)

Claims (7)

下記の工程（ｂ）〜（ｄ）からなることを特徴とする光電気セル用多孔質金属酸化物半導体膜の製造方法；
（ｂ）基板上の電極層上に金属酸化物粒子と分散媒とからなる多孔質金属酸化物半導体膜形成用塗料を塗布し、
（ｃ）乾燥および／または加熱処理したのち、
（ｄ）多孔質金属酸化物半導体膜にアシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を導入する。 A method for producing a porous metal oxide semiconductor film for photoelectric cells, comprising the following steps (b) to (d);
(B) Applying a coating for forming a porous metal oxide semiconductor film comprising metal oxide particles and a dispersion medium on the electrode layer on the substrate;
(C) After drying and / or heat treatment,
(D) At least one organic group selected from an acyl group, an aroyl group, and a carboxylate group is introduced into the porous metal oxide semiconductor film. 前記（ｄ）の有機基の導入を、
(d1)多孔質金属酸化物半導体膜にアシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を含む有機化合物を吸収させ、ついで、１００〜７００℃で加熱処理することよって行うか、あるいは、
(d2) 多孔質金属酸化物半導体膜を、１００〜７００℃で加熱しながら、アシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を含む有機化合物に接触させることによって行うことを特徴とする請求項１に記載の光電気セル用多孔質金属酸化物半導体膜の製造方法。 Introduction of the organic group in (d)
(d1) The porous metal oxide semiconductor film is absorbed by an organic compound containing at least one organic group selected from an acyl group, an aroyl group, and a carboxylate group, and then heat-treated at 100 to 700 ° C. Or
(d2) Performing by contacting the porous metal oxide semiconductor film with an organic compound containing at least one organic group selected from an acyl group, an aroyl group, and a carboxylate group while heating at 100 to 700 ° C. The method for producing a porous metal oxide semiconductor film for an photoelectric cell according to claim 1. 前記（ｄ）の有機基の導入を、多孔質金属酸化物半導体膜にチタン化合物およびアシル基、アロイル基、カルボキシレート基から選ばれる少なくとも１種の有機基を含む有機化合物を吸収させ、ついで、１００〜７００℃で加熱処理することを特徴とする請求項１に記載の光電気セル用多孔質金属酸化物半導体膜の製造方法。   The introduction of the organic group in (d) above causes the porous metal oxide semiconductor film to absorb a titanium compound and an organic compound containing at least one organic group selected from an acyl group, an aroyl group, and a carboxylate group, The method for producing a porous metal oxide semiconductor film for an optoelectric cell according to claim 1, wherein the heat treatment is performed at 100 to 700 ° C. 前記（ｃ）乾燥および／または加熱処理の後、または、前記（ｄ）の有機基の導入後に、
多孔質金属酸化物半導体膜にチタン化合物を吸収させ、ついで、２００〜７００℃で加熱処理することを特徴とする請求項１または２に記載の光電気セル用多孔質金属酸化物半導体膜の製造方法。 After (c) drying and / or heat treatment, or after introducing the organic group of (d),
The porous metal oxide semiconductor film according to claim 1 or 2, wherein the porous metal oxide semiconductor film is absorbed with a titanium compound and then heat-treated at 200 to 700 ° C. Method. 前記多孔質金属酸化物半導体膜中の有機基の含有量が炭素換算で５０〜２０００重量ｐｐｍの範囲にあることを特徴とする請求項１に記載の光電気セル用多孔質金属酸化物半導体膜の製造方法。   2. The porous metal oxide semiconductor film for photoelectric cells according to claim 1, wherein the content of the organic group in the porous metal oxide semiconductor film is in the range of 50 to 2000 ppm by weight in terms of carbon. Manufacturing method. （ａ）電極層上に、多孔質金属酸化物半導体膜を形成する前にあらかじめ、酸化チタン薄膜を形成することを特徴とする請求項１〜５のいずれかに記載の多孔質金属酸化物半導体膜の製造方法。   (A) Before forming a porous metal oxide semiconductor film on an electrode layer, a titanium oxide thin film is formed beforehand, The porous metal oxide semiconductor in any one of Claims 1-5 characterized by the above-mentioned. A method for producing a membrane. 表面に電極層(1)を有し、かつ該電極層(1)表面に光増感材を吸着した多孔質金属酸化物半導体膜(1)が形成されてなる基板(1)と、表面に電極層(2)を有する基板(2)とが、
前記電極層(1)および電極層(2)が対向するように配置してなり、
多孔質金属酸化物半導体膜(1)と電極層(2)との間に電解質層を設けてなる光電気セルにおいて、
該多孔質金属酸化物半導体膜(1)が請求項１〜６のいずれかに記載の光電気セル用多孔質金属酸化物半導体膜の製造方法で得られたことを特徴とする光電気セル。 A substrate (1) having an electrode layer (1) on the surface and a porous metal oxide semiconductor film (1) having a photosensitizer adsorbed on the surface of the electrode layer (1); A substrate (2) having an electrode layer (2),
The electrode layer (1) and the electrode layer (2) are arranged so as to face each other,
In the photoelectric cell comprising an electrolyte layer between the porous metal oxide semiconductor film (1) and the electrode layer (2),
A photoelectric cell, wherein the porous metal oxide semiconductor film (1) is obtained by the method for producing a porous metal oxide semiconductor film for an photoelectric cell according to any one of claims 1 to 6.
JP2012146834A 2012-06-29 2012-06-29 Method of forming porous metal oxide semiconductor film for photoelectric cell, and photoelectric cell Pending JP2014011022A (en)

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