JP2005135798A - Semiconductor film for photocell, lamination body, and paint for manufacturing semiconductor film - Google Patents
Semiconductor film for photocell, lamination body, and paint for manufacturing semiconductor film Download PDFInfo
- Publication number
- JP2005135798A JP2005135798A JP2003371839A JP2003371839A JP2005135798A JP 2005135798 A JP2005135798 A JP 2005135798A JP 2003371839 A JP2003371839 A JP 2003371839A JP 2003371839 A JP2003371839 A JP 2003371839A JP 2005135798 A JP2005135798 A JP 2005135798A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor film
- zinc oxide
- binder
- photovoltaic cell
- dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
Description
本発明は、色素増感太陽電池用半導体膜、積層体、および半導体膜作製用塗料に関する。 The present invention relates to a semiconductor film for a dye-sensitized solar cell, a laminate, and a coating material for producing a semiconductor film.
グレッツェルがＮａｔｕｒｅ：３５３，７３７（１９９１）に、変換効率７．９％の新しい型の光電池（色素増感太陽電池）を発表して以来、これを追試すべく世界的に研究開発が行われてきた。グレッツェルの発表した色素増感太陽電池は、ＴｉＯ２光電極と対向電極とを対峙させ、その間に電解質溶液を配置した構造のものであり、ＴｉＯ２光電極は、フッ素ドープ酸化錫からなる透明導電膜付きガラス板と、その導電膜上に設けられた多孔質ＴｉＯ２膜からなり、さらにそのＴｉＯ２表面に、通常Ｎ３と呼ばれるルテニウム増感色素が吸着されている。対向電極には、導電性ガラス基板に白金をスパッタしたものが用いられ、電解質溶液は、アセトニトリルのような溶媒にＩ-／Ｉ３ -を含む酸化還元溶液で構成されている。この色素増感太陽電池の光電極を作製する従来技術の代表的な方法は、数十ｎｍサイズのＴｉＯ２粉末をポリエチレングリコールやセルロース系結着剤の共存下でペースト状にしてガラス基板上の透明導電膜上に塗布して一旦塗膜層を形成し、その後、５００℃程度の高温で焼成して結着剤を分解し、ＴｉＯ２粉末粒子同士を結合させ、その後、ＴｉＯ２表面に染料を吸着させ、増感することよりなる。 Since Gretzell announced a new type of photovoltaic cell (dye-sensitized solar cell) with a conversion efficiency of 7.9% in Nature: 353, 737 (1991), research and development have been conducted worldwide to try this out. It was. The dye-sensitized solar cell announced by Gretzer has a structure in which a TiO 2 photoelectrode and a counter electrode are opposed to each other and an electrolyte solution is disposed between them. The TiO 2 photoelectrode is a transparent conductive film made of fluorine-doped tin oxide. It consists of a glass plate with a film and a porous TiO 2 film provided on the conductive film, and a ruthenium sensitizing dye usually called N3 is adsorbed on the TiO 2 surface. For the counter electrode, a conductive glass substrate with platinum sputtered is used, and the electrolyte solution is composed of a redox solution containing I − / I 3 − in a solvent such as acetonitrile. The typical method of the prior art for producing the photoelectrode of this dye-sensitized solar cell is that a tens of nanometer-sized TiO 2 powder is made into a paste in the presence of polyethylene glycol or a cellulose-based binder on a glass substrate. It is coated on the transparent conductive film to form a coating layer once, and then fired at a high temperature of about 500 ° C. to decompose the binder, bond the TiO 2 powder particles together, and then dye the TiO 2 surface. Is adsorbed and sensitized.
しかしながら、ＴｉＯ２粉末を使用した従来技術による方法では、高温での焼結工程が存在するので、プラスチックフィルムを基材とする光電極を作製することが困難であった。ところで、将来の光電極は、その用途を拡大していくために基板をプラスチック化して、薄型化、軽量化をはかり、屈曲性をも有する太陽電池を開発することが望まれている。さらに、プラスチックフィルムを基材にして光電極に可撓性を持たせ、連続生産することにより、大幅なコストダウンをはかることも期待されているが、上記従来の技術ではこの必要条件を満たすものではない。 However, in the method according to the prior art using TiO 2 powder, since there is a sintering step at a high temperature, it is difficult to produce a photoelectrode based on a plastic film. By the way, in order to expand the application of future photoelectrodes, it is desired to develop a solar cell having a flexible substrate by reducing the thickness and weight by making the substrate plastic. Furthermore, it is expected that the cost will be greatly reduced by making the photoelectrode flexible by using a plastic film as a base material and continuously producing it. However, the above-mentioned conventional technique satisfies this requirement. is not.
したがって、プラスチックフィルムを基材とした光電極を低温で形成する必要があり、現在下記の方法が提案されている。
（１）ＴｉＯ２微粒子を加圧プレスにより接合する方法（非特許文献１）
（２）ＴｉＯ２微粒子を静電的電着法により成膜する方法（非特許文献２）
（３）ＴｉＯ２微粒子を水熱合成法により成膜する方法（非特許文献３）
しかしながら、上記（１）〜（３）の方法では、ＴｉＯ２微粒子を一旦成膜した後、あらためてこれを染色する工程が必要になるという問題がある。また、（１）の方法では、加圧ロールを使うために原理的には連続生産が可能であるが、幅方向で均一にＴｉＯ２微粒子を加圧接合することは極めて難しい。さらに、（２）および（３）の方法では、特殊なバッチ処理が必須であるために連続生産を行うことができない。
(1) Method of joining TiO 2 fine particles by pressure press (Non-patent Document 1)
(2) Method of forming TiO 2 fine particles by electrostatic electrodeposition (Non-patent Document 2)
(3) Method of forming TiO 2 fine particles by hydrothermal synthesis method (Non-patent Document 3)
However, the above methods (1) to (3) have a problem that a step of once dyeing the TiO 2 fine particles and then dyeing it again is required. In the method (1), since a pressure roll is used, continuous production is possible in principle, but it is extremely difficult to press-bond TiO 2 fine particles uniformly in the width direction. Furthermore, in the methods (2) and (3), since special batch processing is essential, continuous production cannot be performed.
以上にように、色素増感太陽電池のプラスチック化およびその連続生産については、未だ満足できる材料や方法は確立されていないのが現状である。 As described above, regarding the plasticization of the dye-sensitized solar cell and its continuous production, no satisfactory materials and methods have been established yet.
したがって、本発明は、従来の技術における上記の問題をＴｉＯ２とは異なる材料を用いて解決することを目的としてなされたものであって、その目的は、色素増感太陽電池のプラスチック化を行うために低温で成膜可能であり、連続生産も可能な可撓性を有する光電池用半導体膜、積層体および該半導体膜作製用塗料を提供することにある。 Therefore, the present invention has been made for the purpose of solving the above-mentioned problems in the prior art by using a material different from TiO 2, and the purpose is to plasticize the dye-sensitized solar cell. Therefore, an object of the present invention is to provide a flexible semiconductor film for a photovoltaic cell, a laminate, and a coating material for producing the semiconductor film, which can be formed at low temperatures and can be continuously produced.
本発明の光電池用半導体膜は、酸化亜鉛、色素および結着剤を主成分とすることを特徴とする。上記の光電池用半導体膜において、色素は酸化亜鉛に吸着されている。更に上記の光電池用半導体膜の結着剤は、カルボキシメチルセルロ−スを主成分とすることが好ましい。 The semiconductor film for a photovoltaic cell of the present invention is characterized by containing zinc oxide, a dye and a binder as main components. In the above semiconductor film for photovoltaic cells, the dye is adsorbed on zinc oxide. Furthermore, it is preferable that the binder for the above-mentioned semiconductor film for photovoltaic cells is mainly composed of carboxymethyl cellulose.
また、本発明の光電池作製用半導体膜積層体は、剥離性支持体上に、酸化亜鉛、色素および結着剤を主成分とする半導体膜を設けてなることを特徴とする。上記の半導体膜積層体において、色素は酸化亜鉛に吸着されている。また、上記の半導体膜積層体において、結着剤はカルボキシメチルセルロ−スを主成分とすることが好ましい。 Moreover, the semiconductor film laminate for producing a photovoltaic cell of the present invention is characterized in that a semiconductor film containing zinc oxide, a dye and a binder as main components is provided on a peelable support. In the semiconductor film laminate, the dye is adsorbed on zinc oxide. In the above semiconductor film laminate, the binder is preferably composed mainly of carboxymethyl cellulose.
本発明の光電池用半導体膜作製用塗料は、酸化亜鉛、色素、およびビヒクルを主成分とし、結着剤をビヒクル成分として含有することを特徴とする。上記の半導体膜作製用塗料におけるビヒクルは、カルボキシメチルセルロースおよび溶媒からなるのが好ましい。 The coating material for producing a semiconductor film for a photovoltaic cell according to the present invention is characterized by containing zinc oxide, a pigment, and a vehicle as main components and a binder as a vehicle component. It is preferable that the vehicle in the coating material for producing a semiconductor film is composed of carboxymethyl cellulose and a solvent.
本発明の光電池用半導体膜は、以上説明した通り、酸化亜鉛、色素および結着剤という通常の塗工材料を使用して作製できる新規なものである。従来の半導体膜は光電極作製工程で、高温での焼成工程があるのでプラスチック基材は使用できなかったが、本発明では結着剤を使用して低温で乾燥するため、プラスチック化が可能である。また従来技術では、半導体膜を形成後に色素溶液で染色する工程が必要であったが、本発明では塗料中に色素を含ませており、塗料中で又は塗膜形成時に色素が酸化亜鉛に吸着されるため、染色工程を行う必要がない。 As described above, the semiconductor film for a photovoltaic cell of the present invention is a novel film that can be produced using ordinary coating materials such as zinc oxide, a dye, and a binder. The conventional semiconductor film is a photoelectrode manufacturing process, and since there is a baking process at high temperature, a plastic substrate could not be used, but in the present invention, it is dried at a low temperature using a binder, so it can be plasticized. is there. In addition, in the prior art, a process of dyeing with a dye solution after forming a semiconductor film was required. However, in the present invention, a dye is included in the paint, and the dye is adsorbed on zinc oxide in the paint or when forming the coating film. Therefore, it is not necessary to perform a dyeing process.
したがって、本発明の光電池用半導体膜は、酸化亜鉛、色素及び結着剤を含有する塗料を塗工・乾燥するだけで作製できるため、低温で連続的に成膜が可能であり、本発明を利用すれば、太陽電池の作製において、光電極のプラスチック化やロール・ツー・ロールでの連続生産が実現できる。 Therefore, since the semiconductor film for a photovoltaic cell of the present invention can be produced simply by applying and drying a paint containing zinc oxide, a dye and a binder, it can be continuously formed at a low temperature. If used, in the production of solar cells, it is possible to realize plastic production of photoelectrodes and roll-to-roll continuous production.
まず、本発明の光電池用半導体膜について説明する。本発明の光電池用半導体膜に含ませる酸化亜鉛としては、焼成法（フランス法）と湿式法のいずれの方法で作製されたものでも使用可能であり、その平均粒子径は、数ｎｍから数μｍの範囲のものが使用できるが、１０〜２００ｎｍの範囲のものが好ましい。平均粒子径が１０ｎｍ以下では、分散安定性やハンドリング性が悪くなり、一方２００ｎｍ以上では表面積が小さくなって色素の吸着量が低下してしまうためである。ただし、光散乱効果を期待して２００ｎｍ以上の粒径のものを一部使用することは可能である。 First, the semiconductor film for photovoltaic cells of the present invention will be described. As the zinc oxide to be included in the semiconductor film for a photovoltaic cell of the present invention, it is possible to use any one produced by either a baking method (French method) or a wet method, and the average particle size is several nm to several μm. In the range of 10 to 200 nm is preferable. This is because when the average particle size is 10 nm or less, the dispersion stability and handling properties deteriorate, whereas when the average particle size is 200 nm or more, the surface area becomes small and the amount of adsorbed dye decreases. However, it is possible to use a part having a particle diameter of 200 nm or more in anticipation of the light scattering effect.
本発明の光電池用半導体膜に含ませる色素としては、テトラスルフォン酸フタロシアニン金属錯体、テトラブロモフェノールブルー、キサンテン系色素、リボフラビン、ポリピリジンルテニウム錯体（Ｎ３）、クマリン系、ペリレン系、シアニン系、オキソノール系、スクアリリウム等の色素が使用可能であるが、特にキサンテン系色素であるエオシンＹ、エリスロシン、ローズベンガルが好ましい。これらの色素は酸化亜鉛に吸着されて、色素増感として機能する。 Examples of the dye included in the semiconductor film for a photovoltaic cell of the present invention include tetrasulfonic acid phthalocyanine metal complex, tetrabromophenol blue, xanthene dye, riboflavin, polypyridine ruthenium complex (N3), coumarin, perylene, cyanine, and oxonol. Although dyes such as squalylium and squalyllium can be used, eosin Y, erythrosin and rose bengal which are xanthene dyes are particularly preferable. These dyes are adsorbed on zinc oxide and function as dye sensitization.
本発明の光電池用半導体に含ませる結着剤としては、酸化亜鉛の結着剤として作用し成膜可能なものが使用されるが、具体的には、セルロース誘導体、澱粉及びその誘導体、カゼイン、アルギン酸ナトリウム、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリルアミド、ポリビニルメチルエーテル、ポリエチレングリコール、スチレン−無水マレイン酸共重合体、イソブチレン−無水マレイン酸共重合体等があげられる。これらの中でも、特にセルロース誘導体であるカルボキシメチルセルロースは、酸化亜鉛の分散性が良好であり、また電解液に侵されないために好適に使用される。 As the binder to be included in the semiconductor for a photovoltaic cell of the present invention, those capable of forming a film by acting as a binder for zinc oxide are used. Specifically, cellulose derivatives, starch and derivatives thereof, casein, Examples thereof include sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyvinyl methyl ether, polyethylene glycol, styrene-maleic anhydride copolymer, and isobutylene-maleic anhydride copolymer. Among these, carboxymethyl cellulose which is a cellulose derivative is particularly preferably used because it has good dispersibility of zinc oxide and is not affected by the electrolytic solution.
本発明の上記光電池用半導体膜を作製するための塗料は、上記の酸化亜鉛、色素、およびビヒクルを主成分とするものであって、ビヒクルは結着剤とそれを溶解する溶媒とよりなる。結着剤は上記した通りであり、また溶媒としては、水、アルコール、ケトン系、エステル系、アミド系、ニトリル系、カーボネート系、芳香族炭化水素、脂肪族炭化水素等が挙げられ、特に水、アルコールが好適に使用される。これらの溶媒は、単独で使用してもよく、また混合溶媒として使用してもよい。 The coating material for producing the semiconductor film for a photovoltaic cell of the present invention contains the above zinc oxide, pigment, and vehicle as main components, and the vehicle comprises a binder and a solvent for dissolving the binder. The binder is as described above, and examples of the solvent include water, alcohols, ketones, esters, amides, nitriles, carbonates, aromatic hydrocarbons, aliphatic hydrocarbons, etc. Alcohol is preferably used. These solvents may be used alone or as a mixed solvent.
塗料の作製に際し、酸化亜鉛と色素については、塗料中に別々に添加してもよく、予め色素で染色した酸化亜鉛を使用することも可能である。この光電池用半導体膜作製用塗料では、その構成成分である酸化亜鉛を十分に分散することが必要であり、そのためにサンドミルや、ホモジナイザー等の分散装置を使用して調製することが好ましい。 In preparing the paint, the zinc oxide and the dye may be added separately to the paint, or zinc oxide dyed with the dye in advance may be used. In this coating material for producing a semiconductor film for a photovoltaic cell, it is necessary to sufficiently disperse zinc oxide as a constituent component thereof. For this purpose, it is preferably prepared using a dispersing device such as a sand mill or a homogenizer.
塗料中における各成分の配合比率は、その塗料を塗布する方法に適した粘度に合わせて適宜選択される。ただし、酸化亜鉛と結着剤との比率は重量比で１００／１〜１００／２０の範囲が好ましく、１００／１よりも結着剤の比率が少ないと結着力が不足し、逆に１００／２０よりも結着剤比率が多いと、酸化亜鉛微粒子間の接合が不十分となり光電池の変換効率が低下してしまうことになる。 The blending ratio of each component in the paint is appropriately selected according to the viscosity suitable for the method of applying the paint. However, the ratio of zinc oxide to the binder is preferably in the range of 100/1 to 100/20 by weight. If the ratio of the binder is less than 100/1, the binding force is insufficient. If the binder ratio is higher than 20, the bonding between the zinc oxide fine particles is insufficient, and the conversion efficiency of the photovoltaic cell is lowered.
本発明において、光電池用半導体膜は、上記の塗料を剥離性支持体の上に塗布することによって積層体の形態にしてもよい。この場合、例えば、後述のように光電極作製時に剥離性支持体を除去することによって、光電池用半導体膜を形成することができる。剥離性支持体としては、シリコーン樹脂などで表面処理された剥離紙や剥離性フィルムが使用されるが、表面の平滑性からポリエチレンテレフタレート（ＰＥＴ）フィルムが好ましい。剥離性支持体の上に形成される光電池用半導体膜の膜厚は一般には、２〜３０μｍの範囲である。 In the present invention, the semiconductor film for a photovoltaic cell may be in the form of a laminate by applying the above-mentioned paint on a peelable support. In this case, for example, the semiconductor film for a photovoltaic cell can be formed by removing the peelable support during the production of the photoelectrode as described later. As the peelable support, release paper or peelable film that has been surface-treated with a silicone resin or the like is used, and a polyethylene terephthalate (PET) film is preferred because of the smoothness of the surface. The film thickness of the semiconductor film for photovoltaic cells formed on the peelable support is generally in the range of 2 to 30 μm.
本発明の光電池用半導体膜は、光電極の形態で形成されていてもよい。本発明の光電池用半導体膜を用いた光電極は、例えば下記の方法で作製することができる。 The semiconductor film for photovoltaic cells of the present invention may be formed in the form of a photoelectrode. The photoelectrode using the semiconductor film for photovoltaic cells of the present invention can be produced, for example, by the following method.
１）上記本発明の半導体膜作製用塗料を、透明基材上に設けられた透明導電膜上に塗布、乾燥する。乾燥条件としては、ビヒクル中の溶媒を揮発させるだけで十分であり、例えば、１００〜１５０℃で、１〜３０分間程度である。半導体膜の膜厚は、２〜３０μｍの範囲に設定される。ここで得られた透明基体／透明導電膜／半導体膜よりなる積層体は、光電池用の光電極として機能する。 1) The semiconductor film preparation paint of the present invention is applied on a transparent conductive film provided on a transparent substrate and dried. As drying conditions, it is sufficient to volatilize the solvent in the vehicle, for example, at 100 to 150 ° C. for about 1 to 30 minutes. The thickness of the semiconductor film is set in the range of 2 to 30 μm. The laminate comprising the transparent substrate / transparent conductive film / semiconductor film obtained here functions as a photoelectrode for a photovoltaic cell.
２）上記本発明の半導体膜積層体を、透明基材上に設けられた透明導電膜の表面に、半導体膜が隣接するように積層して加圧し、次いで半導体膜積層体の剥離性支持体を剥離して半導体膜を透明導電膜の表面に転写することによって光電極を製造する。 2) The semiconductor film laminate of the present invention is laminated and pressed so that the semiconductor film is adjacent to the surface of the transparent conductive film provided on the transparent substrate, and then the peelable support of the semiconductor film laminate Is peeled off and the semiconductor film is transferred onto the surface of the transparent conductive film to produce a photoelectrode.
なお、これらの方法で光電極を作製するのに必要な透明基材としては、ガラスが一般的であるが、本発明ではプラスチックフィルムも使用可能である。プラスチックフィルムの具体例としては、ポリエチレンテレフタレート、ポリエチレンナフタレート、トリアセチルセルロース、ポリカーボネート、ポリアリレート、ポリイミド、芳香族ポリアミド、ポリスルホン、ポリエーテルスルホン、セロファン、ポリエチレン、ポリプロピレン、ポリビニルアルコール、シクロオレフィン樹脂等が挙げられ、これらの単独または混合、更には積層したものを用いることができる。 In addition, as a transparent base material required in order to produce a photoelectrode by these methods, although glass is common, a plastic film can also be used in this invention. Specific examples of the plastic film include polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, polycarbonate, polyarylate, polyimide, aromatic polyamide, polysulfone, polyethersulfone, cellophane, polyethylene, polypropylene, polyvinyl alcohol, cycloolefin resin, and the like. These may be used singly or as a mixture, or as a laminate.
透明基材上に設けられる透明導電膜は、主にＩＴＯ等の金属酸化物をスパッタリング等の方法で成膜したもので、透明性と導電性が共に高いものが求められる。透明基材の種類により異なるが、透明性としては全光線透過率８５％以上、導電性としては表面抵抗５００Ω／□以下のものが好ましい。 The transparent conductive film provided on the transparent substrate is mainly formed of a metal oxide such as ITO by a method such as sputtering, and is required to have both high transparency and conductivity. Although it differs depending on the type of the transparent substrate, the transparency is preferably a total light transmittance of 85% or more, and the conductivity is preferably a surface resistance of 500Ω / □ or less.
次に、本発明の光電池用半導体膜を使用した光電池について説明する。ガラス又はプラスチックフィルム等の透明基材上に透明導電膜を介して、酸化亜鉛、色素および結着剤を主成分とする半導体膜が積層された光電池用電極を上述の方法で作製する。次にこの電極と対向電極とを適当なスペーサーを使用して向き合った状態で固定する。両電極の間隙に電解液を注入し、最後に電極に配線を取り付けることにより光電池が形成される。電解液には、ヨウ素とヨウ素化合物を溶媒に溶解したものが使用され、ヨウ素化合物としてはヨウ化リチウム、ヨウ化カリウム、テトラプロピルアンモニウムヨウ素、テトラブチルアンモニウムヨウ素、ジメチルプロピルイミダゾリルヨウ素等が使用され、溶媒としてはアセトニトリル、メトキシアセトニトリル、エチレンカーボネート、プロピオンカーボネート、ジメチルカーボネートやこれらの混合溶剤が使用され、またｔ−ブチルピリジンを添加することも有効である。一方、対向電極としては、白金板、白金スパッタ膜を設けたガラス板、カーボン電極等が使用可能である。 Next, a photovoltaic cell using the photovoltaic semiconductor film of the present invention will be described. An electrode for a photovoltaic cell in which a semiconductor film mainly composed of zinc oxide, a dye, and a binder is laminated on a transparent base material such as glass or plastic film through a transparent conductive film is produced by the method described above. Next, this electrode and the counter electrode are fixed in a state of facing each other using an appropriate spacer. A photovoltaic cell is formed by injecting an electrolyte into the gap between both electrodes and finally attaching a wiring to the electrode. For the electrolytic solution, iodine and an iodine compound dissolved in a solvent are used. As the iodine compound, lithium iodide, potassium iodide, tetrapropylammonium iodine, tetrabutylammonium iodine, dimethylpropylimidazolyl iodine, etc. are used. As the solvent, acetonitrile, methoxyacetonitrile, ethylene carbonate, propion carbonate, dimethyl carbonate or a mixed solvent thereof is used, and it is also effective to add t-butylpyridine. On the other hand, as the counter electrode, a platinum plate, a glass plate provided with a platinum sputtered film, a carbon electrode, or the like can be used.
以下、実施例により本発明をより具体的に説明するが、本発明はそれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to those Examples.
エオシンＹの３．５％エタノール溶液１００ｇに、酸化亜鉛（ナノファイン５０、堺化学社製、粒子径２０ｎｍ）２０ｇを分散して、一晩常温で暗所に放置し、その後濾過して得られた染色された酸化亜鉛微粒子を真空乾燥した。この染色済の酸化亜鉛１０ｇと、カルボキシメチルセルロース（ＣＭＣ−ＤＮ−１０Ｌ、ダイセル社製）の２％水溶液２０ｇおよび水１０ｇを混合して撹拌した後、超音波ホモジナイザーにかけて本発明の光電池用半導体膜作製用塗料を調製した。 Obtained by dispersing 20 g of zinc oxide (Nanofine 50, manufactured by Sakai Chemical Co., Ltd., particle size 20 nm) in 100 g of a 3.5% ethanol solution of eosin Y, leaving it in the dark at room temperature overnight, and then filtering. The dyed zinc oxide fine particles were vacuum dried. 10 g of this dyed zinc oxide, 20 g of a 2% aqueous solution of carboxymethylcellulose (CMC-DN-10L, manufactured by Daicel) and 10 g of water are mixed and stirred, and then subjected to an ultrasonic homogenizer to produce a semiconductor film for a photovoltaic cell of the present invention. A paint was prepared.
この塗料をＩＴＯガラス基板（１０×１５×０．７ｔｍｍ、１０Ω／□）上に塗布し、１００℃で１５分間乾燥して本発明の半導体膜が形成された光電極を作製した。半導体膜の乾燥膜厚は１５μｍであった。 This paint was applied on an ITO glass substrate (10 × 15 × 0.7 t mm, 10Ω / □) and dried at 100 ° C. for 15 minutes to produce a photoelectrode on which the semiconductor film of the present invention was formed. The dry film thickness of the semiconductor film was 15 μm.
この半導体膜と白金電極を厚さ０．３ｍｍのポリフルオロエチレンシートからなるスペーサーを用いて対向させ、その間隙に、ヨウ化テトラプロピルアンモニウム０．５ｍｏｌ／ｌとヨウ素０．０５ｍｏｌ／ｌのアセトニトリル溶液からなる電解液を注入して、光電池を組み立てた。 The semiconductor film and the platinum electrode are opposed to each other with a spacer made of a 0.3 mm thick polyfluoroethylene sheet, and an acetonitrile solution of tetrapropylammonium iodide 0.5 mol / l and iodine 0.05 mol / l is placed in the gap. An electrolyte solution was injected to assemble a photovoltaic cell.
この光電池を、ＪＡＳＣＯ社製の太陽電池特性評価システムにかけて、１ｓｕｎ照射下でＩ−Ｖ特性を測定した。なお、この光電池の受光面積は０．２５ｃｍ２であった。
その結果、短絡電流密度（Ｉｓｃ）３．４６ｍＡ／ｃｍ２、開放電圧（Ｖｏｃ）０．５９Ｖ、形状因子（ｆｆ）０．７４、光電変換効率（η）１．５１％の値が得られた。この値は、太陽電池の実用特性として十分なものであった。
This photovoltaic cell was subjected to a solar cell characteristic evaluation system manufactured by JASCO, and the IV characteristics were measured under 1 sun irradiation. The light receiving area of this photovoltaic cell was 0.25 cm 2 .
As a result, a short-circuit current density (I sc ) of 3.46 mA / cm 2 , an open circuit voltage (V oc ) of 0.59 V, a form factor (ff) of 0.74, and a photoelectric conversion efficiency (η) of 1.51% were obtained. It was. This value was sufficient as a practical characteristic of the solar cell.
実施例１で調製した塗料を、剥離性ＰＥＴフィルム（ＰＥＴ３８Ｘ、リンテックス社製、厚さ３８μｍ）上にスクリーン印刷法により５×５ｍｍ□のサイズで印刷して設け、１００℃で１分間乾燥して本発明の半導体膜積層体を作製した。なお、この半導体膜積層体に設けられた半導体膜の厚さは１７μｍであった。この積層体の光電池用半導体膜を、透明導電性ＩＴＯフィルム−３００ＲＥ（東洋紡社製、２５０Ω／□、厚さ１８８μｍ）の導電膜面と重ね合わせ、平板熱プレスで１２０℃、３ｋｇ／ｃｍ２、３分間加圧した。その後、剥離性ＰＥＴフィルムを剥離して、プラスチックフィルムを基材とした光電極を作製した。 The coating material prepared in Example 1 is printed on a peelable PET film (PET38X, manufactured by Lintex, thickness 38 μm) by screen printing at a size of 5 × 5 mm □, and dried at 100 ° C. for 1 minute. Thus, a semiconductor film laminate of the present invention was produced. In addition, the thickness of the semiconductor film provided in this semiconductor film laminated body was 17 micrometers. The laminated semiconductor film for a photovoltaic cell was overlaid on the conductive film surface of a transparent conductive ITO film-300RE (Toyobo Co., Ltd., 250 Ω / □, thickness 188 μm), 120 ° C., 3 kg / cm 2 , Pressurized for 3 minutes. Thereafter, the peelable PET film was peeled off to produce a photoelectrode using a plastic film as a base material.
実施例１と同じ方法で光電池を作製して評価したところ、短絡電流密度（Ｉｓｃ）１．４９ｍＡ／ｃｍ２、開放電圧（Ｖｏｃ）０．５４Ｖ、形状因子（ｆｆ）０．７０、光電変換効率（η）０．６０％であった。 When a photovoltaic cell was produced and evaluated by the same method as in Example 1, the short-circuit current density (I sc ) 1.49 mA / cm 2 , the open-circuit voltage (V oc ) 0.54 V, the form factor (ff) 0.70, photoelectric The conversion efficiency (η) was 0.60%.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003371839A JP4919448B2 (en) | 2003-10-31 | 2003-10-31 | Semiconductor film for photovoltaic cell, laminated body, and coating material for producing semiconductor film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003371839A JP4919448B2 (en) | 2003-10-31 | 2003-10-31 | Semiconductor film for photovoltaic cell, laminated body, and coating material for producing semiconductor film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005135798A true JP2005135798A (en) | 2005-05-26 |
| JP4919448B2 JP4919448B2 (en) | 2012-04-18 |
Family
ID=34648375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003371839A Expired - Fee Related JP4919448B2 (en) | 2003-10-31 | 2003-10-31 | Semiconductor film for photovoltaic cell, laminated body, and coating material for producing semiconductor film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4919448B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007067046A (en) * | 2005-08-30 | 2007-03-15 | Tomoegawa Paper Co Ltd | Semiconductor film forming paint, photoelectric cell electrode, its manufacturing method and photoelectric cell |
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| EP2302650A2 (en) | 2009-09-28 | 2011-03-30 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| EP2306479A2 (en) | 2009-09-28 | 2011-04-06 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| JP2012146505A (en) * | 2011-01-12 | 2012-08-02 | Soken Chem & Eng Co Ltd | Sheet formation material, and method for producing porous semiconductor electrode using the sheet formation material |
| KR101357049B1 (en) | 2011-03-15 | 2014-02-06 | (주) 파루 | Fabrication method of electrode for dye-sensitized solar cell and dye-sensitized solar cell using the same |
| WO2014129575A1 (en) | 2013-02-22 | 2014-08-28 | 富士フイルム株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element and dye-sensitized solar cell |
-
2003
- 2003-10-31 JP JP2003371839A patent/JP4919448B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007067046A (en) * | 2005-08-30 | 2007-03-15 | Tomoegawa Paper Co Ltd | Semiconductor film forming paint, photoelectric cell electrode, its manufacturing method and photoelectric cell |
| WO2010050575A1 (en) | 2008-10-29 | 2010-05-06 | 富士フイルム株式会社 | Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye, and process for producing dye |
| EP2845882A2 (en) | 2008-10-29 | 2015-03-11 | Fujifilm Corporation | Dye, Photoelectric Conversion Element and Photoelectrochemical Cell |
| EP2302650A2 (en) | 2009-09-28 | 2011-03-30 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| EP2306479A2 (en) | 2009-09-28 | 2011-04-06 | Fujifilm Corporation | Method of producing photoelectric conversion element, photoelectric conversion element, and photoelectrochemical cell |
| JP2012146505A (en) * | 2011-01-12 | 2012-08-02 | Soken Chem & Eng Co Ltd | Sheet formation material, and method for producing porous semiconductor electrode using the sheet formation material |
| KR101357049B1 (en) | 2011-03-15 | 2014-02-06 | (주) 파루 | Fabrication method of electrode for dye-sensitized solar cell and dye-sensitized solar cell using the same |
| WO2014129575A1 (en) | 2013-02-22 | 2014-08-28 | 富士フイルム株式会社 | Photoelectric conversion element, method for manufacturing photoelectric conversion element and dye-sensitized solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4919448B2 (en) | 2012-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1562206B1 (en) | Dye-sensitized solar cell having enlarged wavelength range for light absorption and method of fabricating same | |
| JP5191647B2 (en) | Titanium oxide film, titanium oxide film electrode film structure, and dye-sensitized solar cell | |
| JP4863662B2 (en) | Dye-sensitized solar cell module and manufacturing method thereof | |
| JP2008130553A (en) | Dye-sensitized solar battery and manufacturing method of dye-sensitized solar battery | |
| JP2005347245A (en) | Solar cell and its manufacturing method | |
| JP2007287694A (en) | Coloring matter for coloring matter sensitizing solar battery and coloring matter sensitizing solar battery | |
| JP4966602B2 (en) | Dye-sensitized photoelectric conversion element and dye-sensitized photoelectric conversion element module | |
| JP2010118158A (en) | Paste composition for photoelectric conversion element, manufacturing method of porous membrane for photoelectric conversion element, and photoelectric conversion element | |
| JP2006310252A (en) | Transparent electrode, dye-sensitized solar cell having it and dye-sensitized solar cell module | |
| JP4627427B2 (en) | Dye-sensitized solar cell and dye-sensitized solar cell module | |
| EP2272920A1 (en) | Dye for dye-sensitized solar cell and dye-sensitized solar cell including the same | |
| JP4919448B2 (en) | Semiconductor film for photovoltaic cell, laminated body, and coating material for producing semiconductor film | |
| JP2009238571A (en) | Electrolyte for dye-sensitized solar cell | |
| JP2005135799A (en) | Electrode for photocell and manufacturing method of the same, and photocell using the same | |
| JP2005302509A (en) | Dye-sensitized solar cell | |
| KR20120020938A (en) | Photo electrode for dye-sensitized solar cell, manufacturing method of the same and dye-sensitized solar cell including the same | |
| JP4822383B2 (en) | Dye-sensitized photoelectric conversion element | |
| JP5754071B2 (en) | Manufacturing method of oxide semiconductor electrode substrate and dye-sensitized solar cell | |
| JP2012155909A (en) | Dye sensitized solar cell and method for manufacturing the same | |
| KR101166515B1 (en) | Photoelectrode for dye-sensitized solar cell, preparing method of the same, and dye-sensitized solar cell having the same | |
| JP2005011609A (en) | Conductive support and photoelectric transfer element using this | |
| Xie et al. | In situ topological transformation of hierarchical TiO2 hollow nanobricks as efficient scattering layer for dye-sensitized solar cells | |
| JP2007067046A (en) | Semiconductor film forming paint, photoelectric cell electrode, its manufacturing method and photoelectric cell | |
| JP2007280849A (en) | Photoelectric conversion element | |
| JP2003243052A (en) | Photoelectric transducing module |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051216 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090623 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090820 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20091006 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091223 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100202 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20100226 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111013 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120130 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4919448 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150210 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |