JP2000243466A - Photoelectric transducer - Google Patents

Photoelectric transducer

Info

Publication number
JP2000243466A
JP2000243466A JP11045475A JP4547599A JP2000243466A JP 2000243466 A JP2000243466 A JP 2000243466A JP 11045475 A JP11045475 A JP 11045475A JP 4547599 A JP4547599 A JP 4547599A JP 2000243466 A JP2000243466 A JP 2000243466A
Authority
JP
Japan
Prior art keywords
photoelectric conversion
dye
semiconductor layer
semiconductor
conversion element
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.)
Pending
Application number
JP11045475A
Other languages
Japanese (ja)
Inventor
Tatsuo Toyoda
竜生 豊田
Yumiko Takeishi
裕美子 武石
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aisin Corp
Original Assignee
Aisin Seiki Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Aisin Seiki Co Ltd filed Critical Aisin Seiki Co Ltd
Priority to JP11045475A priority Critical patent/JP2000243466A/en
Publication of JP2000243466A publication Critical patent/JP2000243466A/en
Pending legal-status Critical Current

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

Abstract

PROBLEM TO BE SOLVED: To improve conversion characteristics from light energy to electric energy by expanding an absorption wavelength zone of a light spectrum. SOLUTION: In this photoelectric transducer, a plurality of semiconductor layers 32 to 34 are provided and layered on conductive substrates 30, 31, a catalyst is borne on conductive substrates 36, 37 forming an opposite pole 39 to the conductive substrates 30, 31, an electrolyte layer 35 is provided between the two groups of conductive substrates 30, 31, and 36, 37, pigments different in absorption wavelength from each other are borne by the semiconductor layers 32 to 34, respectively, and the absorption wavelength of the pigment in the semiconductor layer positioned on the side of incoming light is adapted to be shorter than the absorption wavelength of the pigment in the semiconductor layer positioned behind the semiconductor layer.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は光電変換素子に関す
る。[0001] The present invention relates to a photoelectric conversion element.

【０００２】[0002]

【従来の技術】近年の産業の発達によりエネルギーおよ
び電力の使用量が急増している。そのため二酸化炭素な
どの地球温暖化物質の排出も増え、地球環境を守るため
無視できない量になっている。太陽エネルギーを電気に
変換する太陽電池は、直接には二酸化炭素を排出せずに
電力を製造できるので、その普及が期待されている。し
かし、従来のシリコンを使用した太陽電池は、製造コス
トが高い問題があり、大規模電力用としては期待される
ような普及に至っていない。2. Description of the Related Art The use of energy and electric power has increased rapidly due to recent industrial development. For this reason, emissions of global warming substances such as carbon dioxide also increase, and the amount is not negligible to protect the global environment. 2. Description of the Related Art Solar cells that convert solar energy into electricity can produce electric power without directly emitting carbon dioxide, and are expected to spread. However, the conventional solar cell using silicon has a problem of high manufacturing cost, and has not yet spread as expected for large-scale electric power.

【０００３】このシリコンを使用した太陽電池に替わる
製造コストが低い太陽電池として、半導体電極に可視光
を吸収する色素を担持した湿式太陽電池が注目されてい
る。半導体自身が本来持つ光吸収領域より低いエネルギ
ー領域で、言い換えれば長波長側で光電変換させる原理
は光増感と呼ばれ古くから知られていた。それを光電変
換素子に応用し太陽電池とした場合、変換効率は低かっ
た。As a solar cell having a low manufacturing cost in place of a solar cell using silicon, a wet solar cell in which a semiconductor electrode carries a dye that absorbs visible light has attracted attention. The principle of photoelectric conversion in the energy region lower than the light absorption region of the semiconductor itself, in other words, on the longer wavelength side, is called photosensitization and has been known for a long time. When it was applied to a photoelectric conversion element to form a solar cell, the conversion efficiency was low.

【０００４】Ｍ．Ｇｒａｅｔｚｅｌらは、Ｎａｔｕｒ
ｅ、ｖｏｌ．３５７、７３７ページ、（１９９１年）
に、ｎ型半導体である酸化チタンを微粒子化しフィルム
状に形成し、それに色素としてルテニウム錯体（ＲｕＬ
２（ＮＣＳ）２、Ｌ＝４，４−ジカルボキシル−２，
２’ビピリジン）を表面に吸着させた光電変換素子を発
表している。酸化チタンの微粒子を用いることにより表
面粗さ係数であるラフネスファクタ（電極内実表面積／
投影面積）が大きくなる。これにより光の受光面積が大
きくなるので、変換効率が大幅に向上した。[0004] M. Graetzel et al., Natur
e, vol. 357, 737, (1991)
First, titanium oxide, which is an n-type semiconductor, is made into fine particles to form a film, and a ruthenium complex (RuL
2 (NCS) 2 , L = 4,4-dicarboxyl-2,
A photoelectric conversion element having 2 'bipyridine) adsorbed on its surface has been announced. Roughness factor (actual surface area in electrode /
Projection area). As a result, the light receiving area is increased, and the conversion efficiency is greatly improved.

【０００５】しかし、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ，Ｖ
ｏｌ．１１５，Ｎｏ１４，６３８２ページ（１９９３
年）のＭ．Ｇｒａｅｔｚｅｌらの論文にあるように、こ
の色素は波長５３０−５５０ｎｍをピークとし４００〜
８００ｎｍの波長しか利用していない。太陽光は紫外光
から赤外光に至るまでエネルギーのスペクトル分布が広
い。したがって、この方法では太陽光のエネルギーの一
部しか利用できない問題がある。変換効率を上げるため
には太陽エネルギーを十分吸収することが重要である。However, J. J. Am. Chem. Soc, V
ol. 115, No. 14, 6382 pages (1993
Year) M. As described by Graetzel et al., This dye peaks at a wavelength of 530-550 nm and has a wavelength of 400-400 nm.
Only a wavelength of 800 nm is used. Sunlight has a wide energy spectrum distribution from ultraviolet light to infrared light. Therefore, this method has a problem that only a part of the energy of sunlight can be used. It is important to absorb solar energy enough to increase conversion efficiency.

【０００６】従来技術１として、特開平０９−１９９７
４４公報には、色素の吸収波長域を拡大させる新規増感
色素とそれを用いた湿式太陽電池が開示されている。こ
れは、新規色素をナノ構造を持つ酸化物半導体に担持さ
せたものである。As prior art 1, Japanese Patent Application Laid-Open No. 09-1997
No. 44 discloses a novel sensitizing dye for expanding the absorption wavelength range of the dye and a wet solar cell using the same. In this method, a novel dye is supported on an oxide semiconductor having a nanostructure.

【０００７】従来技術２として、Ｊｐｎ．Ｊ．Ａｐｐ
ｌ．Ｐｈｙｓ．Ｖｏｌ．３７，Ｌ１３２−１３５ペー
ジ，Ｐａｒｔ２，Ｎｏ２Ａ（１９９８年）には、複数の
色素を酸化チタンに担持させた技術が開示されている。
すなわち、２つの色素テトラスルホニドガリウムフタロ
シアニン（ＧａＴｓＰｃ）とテトラスルホニド亜鉛ポル
フェリン（ＺｎＴｓＰＰ）をＤＭＳＯ溶液に溶解し酸化
チタンに担持させたものである。As prior art 2, Jpn. J. App
l. Phys. Vol. 37, L132-135, Part 2, No. 2A (1998) discloses a technique in which a plurality of dyes are supported on titanium oxide.
That is, two dyes tetrasulfonide gallium phthalocyanine (GaTsPc) and tetrasulfonide zinc porpherin (ZnTsPP) are dissolved in a DMSO solution and supported on titanium oxide.

【０００８】[0008]

【発明が解決しようとする課題】しかしながら、従来技
術１は、単独の色素を使用しているので、新規色素とい
えども吸収スペクトルの範囲が限定されてしまうため
太陽光を利用する場合、太陽光のごく一部のスペクトル
しか吸収できず、その結果全体の光電変換効率は低いも
のとなる。However, in the prior art 1, since a single dye is used, the range of the absorption spectrum is limited even for a new dye.
When using sunlight, only a part of the spectrum of sunlight can be absorbed, and as a result, the overall photoelectric conversion efficiency is low.

【０００９】また従来技術２は、光子−電子変換量子効
率（ＩＰＣＥ）が短波長側４００−５００ｎｍの波長で
単独の色素ＺｎＴｓＰＰに比べ激減し、長波長側６００
−７５０ｎｍで若干向上し吸収波長域は拡大が認められ
るものの、光電流としては大きな値が得られないため全
体の光電変換効率は小さい。この原因として、色素の会
合やそれによる色素同士の相互作用で光励起された色素
から半導体電極に全ての電荷が注入されないことが考え
られる。In the prior art 2, the photon-electron conversion quantum efficiency (IPCE) is drastically reduced as compared with the single dye ZnTsPP at a wavelength of 400 to 500 nm on the short wavelength side, and 600 nm on the long wavelength side.
Although the absorption wavelength range is slightly improved at -750 nm and the absorption wavelength range is expanded, a large value is not obtained as the photocurrent, so that the overall photoelectric conversion efficiency is small. As a cause of this, it is considered that not all charges are injected into the semiconductor electrode from the dye photoexcited due to the association of the dyes and the interaction between the dyes.

【００１０】本発明は上記課題を解決したもので、光ス
ペクトルの吸収波長領域を拡大し、光エネルギーから電
気エネルギーへの変換特性を向上させる手段を提供する
ものである。[0010] The present invention has been made to solve the above-mentioned problems, and provides a means for expanding an absorption wavelength region of an optical spectrum and improving a conversion characteristic from light energy to electric energy.

【００１１】[0011]

【課題を解決するための手段】上記技術的課題を解決す
るために、本発明の請求項１において講じた技術的手段
（以下、第１の技術的手段と称する。）は、導電性基板
上に複数の半導体層が積層して設けられ、該導電性基板
の対極をなす導電性基板上に触媒が担持され、前記の両
導電性基板の間に電解質層が設けられ、前記半導体層に
異なる吸収波長を有する色素が担持され、入射光側に位
置する半導体層の色素の吸収波長が、該半導体層の後方
の半導体層の色素の吸収波長より短波長になっているこ
とを特徴とする光電変換素子である。Means for Solving the Problems In order to solve the above-mentioned technical problems, the technical means (hereinafter referred to as first technical means) taken in claim 1 of the present invention is provided on a conductive substrate. A plurality of semiconductor layers are stacked and provided, a catalyst is supported on a conductive substrate that is a counter electrode of the conductive substrate, an electrolyte layer is provided between the two conductive substrates, and the semiconductor layer is different. A dye having an absorption wavelength is carried, and the absorption wavelength of the dye of the semiconductor layer located on the incident light side is shorter than the absorption wavelength of the dye of the semiconductor layer behind the semiconductor layer. It is a conversion element.

【００１２】上記第１の技術的手段による効果は、以下
のようである。The effects of the first technical means are as follows.

【００１３】すなわち、複数の半導体層に、それぞれ異
なる吸収波長を有する色素が担持され、入射光側の半導
体層色素の方がより短波長の光を吸収し、長波長の光を
透過し、この長波長の光を次の半導体層の色素が吸収
し、かつ色素が別々の半導体層に担持されていて色素の
会合や色素同士の相互作用がないので、入射光の広い波
長を利用することができるため、光電効率を向上させる
ことができる。That is, dyes having different absorption wavelengths are carried on the plurality of semiconductor layers, respectively. The semiconductor layer dye on the incident light side absorbs shorter wavelength light and transmits longer wavelength light. The long wavelength light is absorbed by the dye in the next semiconductor layer, and the dye is supported on separate semiconductor layers, so there is no dye association or interaction between dyes. Therefore, photoelectric efficiency can be improved.

【００１４】上記技術的課題を解決するために、本発明
の請求項２において講じた技術的手段（以下、第２の技
術的手段と称する。）は、導電性基板、色素を担持した
半導体層、電解質層および触媒を担持した導電性基板を
有する光電変換セルを複数積層し、入射光側に位置する
半導体層の色素の吸収波長が、該半導体層の後方の半導
体層の色素の吸収波長より短波長になっていることを特
徴とする光電変換素子である。[0014] In order to solve the above technical problems, the technical means (hereinafter referred to as second technical means) taken in claim 2 of the present invention comprises a conductive substrate, a semiconductor layer carrying a dye. A plurality of photoelectric conversion cells having a conductive substrate supporting an electrolyte layer and a catalyst are stacked, and the absorption wavelength of the dye of the semiconductor layer located on the incident light side is greater than the absorption wavelength of the dye of the semiconductor layer behind the semiconductor layer. It is a photoelectric conversion element characterized by having a short wavelength.

【００１５】上記第２の技術的手段による効果は、以下
のようである。The effects of the second technical means are as follows.

【００１６】すなわち、複数の光電変換セルの半導体層
に、それぞれ異なる吸収波長を有する色素が担持され、
入射光側の光電変換セル半導体層の色素の方がより短波
長の光を吸収し、長波長の光を透過し、この長波長の光
を次の光電変換セル半導体層の色素が吸収し、かつ半導
体層が分離されていて色素の会合や色素同士の相互作用
がないので、入射光の広い波長を利用することができる
ため、光電効率を向上させることができる。That is, dyes having different absorption wavelengths are carried on the semiconductor layers of the plurality of photoelectric conversion cells, respectively.
The dye of the photoelectric conversion cell semiconductor layer on the incident light side absorbs light of a shorter wavelength and transmits light of a longer wavelength, and the dye of the next photoelectric conversion cell semiconductor layer absorbs this longer wavelength light, In addition, since the semiconductor layer is separated and there is no association of dyes or interaction between dyes, a wide wavelength of incident light can be used, so that photoelectric efficiency can be improved.

【００１７】上記技術的課題を解決するために、本発明
の請求項３において講じた技術的手段（以下、第３の技
術的手段と称する。）は、前記半導体が、酸化物・リン
化物・炭化物・硫化物・セレン化物の少なくとも一つで
あることを特徴とする請求項１、２のいずれかに記載の
光電変換素子である。In order to solve the above technical problem, the technical means (hereinafter referred to as third technical means) taken in claim 3 of the present invention is that the semiconductor is composed of oxide, phosphide, The photoelectric conversion device according to claim 1, wherein the photoelectric conversion device is at least one of carbide, sulfide, and selenide.

【００１８】上記第３の技術的手段による効果は、以下
のようである。The effects of the third technical means are as follows.

【００１９】すなわち、これらの物質は色素から効率的
に電子を受け取ることができるので、光電効率を向上さ
せることができる。That is, since these substances can efficiently receive electrons from the dye, the photoelectric efficiency can be improved.

【００２０】上記技術的課題を解決するために、本発明
の請求項４において講じた技術的手段（以下、第４の技
術的手段と称する。）は、色素がオリゴフェニレン、オ
キサゾール、オキサジアゾール、スチルベン、キノロ
ン、クロロフィル、クマリン、キサンテン系、メロシア
ニン、スクアリリウム、シアニン、フタロシアニン、ピ
リリウム塩、オキサジン系、チアジン系、ペリレン、ス
チルベン系、クロコニウムであることを特徴とする請求
項１、２のいずれかに記載の光電変換素子である。In order to solve the above-mentioned technical problems, the technical means (hereinafter referred to as the fourth technical means) of the present invention is that the pigment is oligophenylene, oxazole, oxadiazole. Stilbene, quinolone, chlorophyll, coumarin, xanthene type, merocyanine, squarylium, cyanine, phthalocyanine, pyrylium salt, oxazine type, thiazine type, perylene, stilbene type, croconium. 3. The photoelectric conversion element according to item 1.

【００２１】上記第４の技術的手段による効果は、以下
のようである。The effects of the fourth technical means are as follows.

【００２２】すなわち、これらの色素は、光を吸収して
半導体に伝達する色素増感作用を有しているので、吸収
波長の異なる色素を組み合わせることにより光電変換効
率を向上させることができる。That is, since these dyes have a dye sensitizing effect of absorbing light and transmitting the light to the semiconductor, the photoelectric conversion efficiency can be improved by combining dyes having different absorption wavelengths.

【００２３】上記技術的課題を解決するために、本発明
の請求項５において講じた技術的手段（以下、第５の技
術的手段と称する。）は、前記電解質層が、ハロゲン化
物、硫黄化物、ハイドロキノン、シアン化鉄の少なくと
も一つのの酸化還元種を含んでいることを特徴とする請
求項１、２のいずれかに記載の光電変換素子である。In order to solve the above technical problems, the technical means (hereinafter referred to as the fifth technical means) in claim 5 of the present invention is as follows. 3. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion element contains at least one of redox species, hydroquinone, and iron cyanide.

【００２４】上記第５の技術的手段による効果は、以下
のようである。The effects of the fifth technical means are as follows.

【００２５】すなわち、これらの材料は、酸化還元反応
を能率的に行うので、光電変換効率を向上させることが
できる。That is, since these materials efficiently perform the oxidation-reduction reaction, the photoelectric conversion efficiency can be improved.

【００２６】上記技術的課題を解決するために、本発明
の請求項６において講じた技術的手段（以下、第６の技
術的手段と称する。）は、前記触媒層の触媒が、白金、
カーボンの少なくとも一つであることを特徴とする請求
項１、２のいずれかに記載の光電変換素子である。In order to solve the above technical problem, the technical means (hereinafter referred to as sixth technical means) taken in claim 6 of the present invention is as follows.
The photoelectric conversion element according to claim 1, wherein the photoelectric conversion element is at least one of carbon.

【００２７】上記第６の技術的手段による効果は、以下
のようである。The effects of the sixth technical means are as follows.

【００２８】すなわち、白金やカーボンは、酸化状態の
酸化還元種に対極の電子を効率的に渡す電気化学触媒と
しての機能に優れているので、光電変換効率を向上させ
ることができる。That is, platinum and carbon have an excellent function as an electrochemical catalyst that efficiently transfers a counter electrode to an oxidation-reduction species in an oxidized state, so that the photoelectric conversion efficiency can be improved.

【００２９】[0029]

【発明の実施の形態】図３は、一般的な色素増感型光電
変換素子の構成を説明する概略断面図である。ガラスな
どで代表される透光性基板１１の増感色素担持半導体１
３と接する側に透明導電膜１２を備えた光電極１と、そ
れに対向する位置に、透光性基板１６の前記光電極１と
対向する側に触媒担持した透明導電膜１５を備えた対極
２が設けられている。FIG. 3 is a schematic cross-sectional view illustrating the structure of a general dye-sensitized photoelectric conversion element. Sensitizing dye-carrying semiconductor 1 on translucent substrate 11 represented by glass or the like
3, a photoelectrode 1 provided with a transparent conductive film 12 on the side thereof, and a counter electrode 2 provided with a transparent conductive film 15 carrying a catalyst on a side of the translucent substrate 16 facing the photoelectrode 1 at a position facing the photoelectrode 1. Is provided.

【００３０】光電極１と対極２の間の空隙に、電子を放
出して酸化され対極２から電子を獲得し還元される例え
ばＩ−／Ｉ３ −などのような酸化還元種を含み、それら
が移動しやすい電解液を注入した電解質層１４が設けら
れている。図３の場合は、半導体光電極１、対極２がと
もに透光性でるので光を図３の左右どちらから入射させ
てもよいが、光の入射側と反対側の電極の基板や導電膜
は透明でなくてもよい。The gap between the photoelectrode 1 and the counter electrode 2 contains a redox species such as I − / I 3 − which emits electrons to be oxidized and obtains and reduces electrons from the counter electrode 2. Is provided with an electrolyte layer 14 into which an electrolyte solution that easily moves. In the case of FIG. 3, since both the semiconductor photoelectrode 1 and the counter electrode 2 are translucent, light may be incident from either the left or right in FIG. 3, but the substrate or conductive film of the electrode on the side opposite to the light incident side is It does not have to be transparent.

【００３１】図４は、一般的な色素増感型光電変換素子
の作動原理を説明するエネルギーダイアグラム図であ
る。２１ａ、２１ｂ、２２〜２４はエネルギー準位であ
り、２８は光電極、２９は対極である。光電極２８と対
極２９は、外部回路２７を介して連結されている。FIG. 4 is an energy diagram for explaining the operation principle of a general dye-sensitized photoelectric conversion element. 21a, 21b, 22 to 24 are energy levels, 28 is a photoelectrode, and 29 is a counter electrode. The photoelectrode 28 and the counter electrode 29 are connected via an external circuit 27.

【００３２】前記のエネルギー準位で、２１ａは半導体
の伝導帯準位、２１ｂは半導体のフェルミレベル、２２
は増感色素の励起状態準位、２３は増感色素の基底状態
準位、２４は酸化還元種の酸化還元準位である。半導体
はｎ型半導体であり、フェルミレベル２１ｂと伝導帯準
位２１ａは近い。In the above energy levels, 21a is the conduction band level of the semiconductor, 21b is the Fermi level of the semiconductor,
Is the excited state level of the sensitizing dye, 23 is the ground state level of the sensitizing dye, and 24 is the redox level of the redox species. The semiconductor is an n-type semiconductor, and the Fermi level 21b and the conduction band level 21a are close.

【００３３】ｈν（ｈ：プランク定数、ν：光の振動
数）のエネルギーを持った光子が増感色素に吸収される
と、色素は基底状態準位２３から励起状態準位２２へ励
起され、励起された増感色素の電子は半導体の伝導帯準
位２１ａへ注入され、増感色素は酸化状態となる。半導
体の伝導帯準位２１ａへ注入された電子は半導体のフェ
ルミレベル２１ｂに落ちる。そこから電子は外部回路２
７を介して対極２９に移動する。When a photon having an energy of hν (h: Planck constant, ν: frequency of light) is absorbed by the sensitizing dye, the dye is excited from the ground state level 23 to the excited state level 22, The excited electrons of the sensitizing dye are injected into the conduction band level 21a of the semiconductor, and the sensitizing dye is oxidized. The electrons injected into the conduction band level 21a of the semiconductor fall to the Fermi level 21b of the semiconductor. From there, the electrons go to the external circuit 2.
7 to the counter electrode 29.

【００３４】酸化状態の色素は、酸化還元種の還元状態
Ｉ−から電子を受け取り基底状態準位２３に戻る。一
方、電子を色素に渡し酸化された電解質中の酸化還元種
の酸化状態Ｉ３ −は、外部回路２７を介して対極２９に
移動した電子を受け取り還元状態Ｉ−に戻ることで電子
の流れが１サイクル完結する。The dye of oxidation state, redox species of reduced state I - return the electrons to receive ground state level 23 from. On the other hand, the oxidation state I 3 − of the redox species in the oxidized electrolyte by passing the electrons to the dye receives the electrons moved to the counter electrode 29 via the external circuit 27 and returns to the reduced state I − , whereby the flow of electrons is reduced. One cycle is completed.

【００３５】この光電変換素子の最大発生電位は、半導
体フェルミレベル２１ｂと電解質中の酸化還元種の酸化
還元準位２４の差で規定される。色素の励起状態準位２
２は半導体の伝導帯準位２１ａよりもエネルギー的に高
くないと効果的な電子注入が行われない。The maximum generated potential of this photoelectric conversion element is defined by the difference between the semiconductor Fermi level 21b and the redox level 24 of the redox species in the electrolyte. Excited state level of dye 2
No. 2 does not perform effective electron injection unless the energy is higher than the conduction band level 21a of the semiconductor.

【００３６】従来、透光性基板１１にガラスを用い、透
明導電膜１２にフッ素ドープの酸化スズ膜、増感色素担
持半導体１３の半導体にナノサイズ結晶の酸化チタン、
増感色素にルテニウム錯体を用いている。また電解質層
１４はエチレンカーボネート８０ｖｏｌ％、アセトニト
リル２０ｖｏｌ％の混合溶媒中にヨウ素、テトラプロピ
ルアンモニウムアイオダイト｛（Ｃ３Ｈ７）４ＮＩ｝を
加えたもので、３Ｉ−／Ｉ３ −を酸化還元対として利用
している。また対極２の透明導電膜１５は触媒として白
金Ｐｔを担持したフッ素ドープの酸化スズ膜が用いら
れ、透光性基板１６としてガラスが用いられている。Conventionally, glass is used for the light-transmitting substrate 11, a fluorine-doped tin oxide film is used for the transparent conductive film 12, nano-sized crystal titanium oxide is used for the semiconductor of the sensitizing dye-carrying semiconductor 13,
A ruthenium complex is used as a sensitizing dye. The electrolyte layer 14 is obtained by adding iodine and tetrapropylammonium iodide {(C 3 H 7 ) 4 NI} to a mixed solvent of 80 vol% of ethylene carbonate and 20 vol% of acetonitrile, and redoxes 3I − / I 3 −. We use as a pair. Further, as the transparent conductive film 15 of the counter electrode 2, a fluorine-doped tin oxide film supporting platinum Pt is used as a catalyst, and glass is used as the translucent substrate 16.

【００３７】このように提案された光電変換素子は例え
ば太陽光エネルギーを直接電気エネルギーに変換できる
が、入射光の波長５３０−５５０ｎｍをピークとし４０
０〜８００ｎｍの波長の一部を増感色素で吸収できるも
のの、その波長を含む入射光の大部分が半導体層１３を
透過してしまい入射光を有効に利用できず光電変換効率
を低いものとしていた。The photoelectric conversion element proposed in this way can directly convert, for example, sunlight energy into electric energy.
Although a part of the wavelength of 0 to 800 nm can be absorbed by the sensitizing dye, most of the incident light including that wavelength is transmitted through the semiconductor layer 13 so that the incident light cannot be used effectively and the photoelectric conversion efficiency is low. Was.

【００３８】本発明者は鋭意研究し、吸収波長の異なる
複数の色素を効率的に使用する光電変換素子を考案し
た。単に一つの半導体層に複数の増感色素を担持させる
だけでは、色素の会合および色素同士の相互作用によ
り、光励起された色素から半導体にすべての電荷が注入
されないので、結果的に光電変換効率が下がってしま
う。The present inventors have conducted intensive studies and have devised a photoelectric conversion element that efficiently uses a plurality of dyes having different absorption wavelengths. Simply carrying a plurality of sensitizing dyes on one semiconductor layer does not allow all charges to be injected from the photoexcited dye into the semiconductor due to association of the dyes and interaction between the dyes, resulting in an increase in photoelectric conversion efficiency. Will go down.

【００３９】本発明では、複数の半導体層を積層し、そ
れぞれの半導体層ごとに吸収波長の異なる色素を担持さ
せて光電極とし、この光電極と対極を組み合わせ、両極
の間に酸化還元が速やかに行われる酸化還元種を含む電
解質を挟んだ光電変換素子とした。この半導体層は、担
持されている色素の吸収波長が入射光側から順に短波長
から長波長になるように入射光に対して順次垂直に積層
されている。According to the present invention, a plurality of semiconductor layers are laminated, and a dye having a different absorption wavelength is carried on each semiconductor layer to form a photoelectrode. The photoelectric conversion element sandwiching the electrolyte containing the oxidation-reduction species performed in the above was used. The semiconductor layers are sequentially stacked perpendicularly to the incident light so that the absorption wavelength of the dye carried from the incident light side becomes shorter to longer.

【００４０】また半導体層に色素を１種吸着させ、その
光電極と対極を組み合わせ、両極の間に酸化還元が速や
かに行われる酸化還元種を含む電解質を挟んで光電変換
セルを構成した。この光電変換セルを複数積層して光電
変換素子を形成した。この光電変換セルは、各半導体層
に担持されている色素の吸収波長が入射光側から順に短
波長から長波長になるように入射光に対して順次垂直に
積層されている。なお、積層される光電変換セルの光電
極導電性基板、対極導電性基板は透光性であり、隣接す
る光電極導電性基板、対極導電性基板は同電位とするよ
う構成されている。One type of dye was adsorbed on the semiconductor layer, the photoelectrode and the counter electrode were combined, and a photoelectric conversion cell was constructed by sandwiching an electrolyte containing a redox species which rapidly performs redox between the two electrodes. A plurality of the photoelectric conversion cells were stacked to form a photoelectric conversion element. The photoelectric conversion cells are sequentially stacked perpendicularly to the incident light such that the absorption wavelength of the dye carried on each semiconductor layer becomes shorter to longer at the incident light side. The photoelectrode conductive substrate and the counter electrode conductive substrate of the stacked photoelectric conversion cells are translucent, and the adjacent photoelectrode conductive substrate and counter electrode conductive substrate are configured to have the same potential.

【００４１】図１は、本発明の請求項１にかかわる光電
変換素子の構成を説明する概略断面図である。本光電変
換素子は、透光性基板３０、透明導電膜３１、半導体層
３２〜３４、電解質層３５、触媒担持導電膜３６および
対極基板３７から構成されている。FIG. 1 is a schematic sectional view for explaining the structure of a photoelectric conversion element according to the first aspect of the present invention. The photoelectric conversion element includes a light-transmitting substrate 30, a transparent conductive film 31, semiconductor layers 32 to 34, an electrolyte layer 35, a catalyst-carrying conductive film 36, and a counter electrode substrate 37.

【００４２】前記透光性基板３０としてガラスもしくは
ガスバリア処理を施したポリエチレンテレフタレート
（ＰＥＴ）やポリカーボネート（ＰＣ）などを利用でき
る。この上にフッ素ドープの酸化スズやＩＴＯなどの透
明導電膜３１が薄膜処理されている。As the translucent substrate 30, glass or polyethylene terephthalate (PET) or polycarbonate (PC) subjected to a gas barrier treatment can be used. On top of this, a transparent conductive film 31 such as fluorine-doped tin oxide or ITO is thin-film treated.

【００４３】半導体層３２〜３４は、前記透明導電膜３
１の上に、あらかじめ色素を担持させた半導体粒子をペ
ースト化しスクリーン印刷もしくはバーコーターやナイ
フコーターなど各種コーターで順次形成する。前記透光
性基板３０、透明導電膜３１、半導体層３２〜３４で光
電極３８が形成されている。The semiconductor layers 32 to 34 are formed of the transparent conductive film 3
The semiconductor particles previously supporting a dye are formed into a paste on 1 and are sequentially formed by screen printing or various coaters such as a bar coater and a knife coater. A photoelectrode 38 is formed by the translucent substrate 30, the transparent conductive film 31, and the semiconductor layers 32-34.

【００４４】前記半導体粒子としては、ＴｉＯ２、Ｚｎ
Ｏ、ＳｎＯ２などの酸化物、ＧａＰ、ＩｎＰなどのリン
化物、ＳｉＣなどの炭化物、ＣｄＳなどの硫化物、Ｇａ
Ａｓ、ＣｄＴｅなどの化合物半導体などでｎ型半導体に
なるものを用いることができるが、平均粒径０．５μｍ
以下、望ましくは５〜５００ｎｍの酸化チタンがよい。The semiconductor particles include TiO 2 , Zn
Oxides such as O and SnO 2 , phosphides such as GaP and InP, carbides such as SiC, sulfides such as CdS, Ga
An n-type semiconductor such as a compound semiconductor such as As or CdTe can be used.
Hereinafter, titanium oxide of 5 to 500 nm is desirable.

【００４５】前記半導体粒子に担持させる色素として
は、オリゴフェニレン、オキサゾール、オキサジアゾー
ル、スチルベン、キノロン、クロロフィル、クマリン、
キサンテン系、メロシアニン、スクアリリウム、シアニ
ン、フタロシアニン、ピリリウム塩、オキサジン系、チ
アジン系、ペリレン、スチルベン系、クロコニウムなど
の色素がある。The dyes supported on the semiconductor particles include oligophenylene, oxazole, oxadiazole, stilbene, quinolone, chlorophyll, coumarin,
There are dyes such as xanthene type, merocyanine, squarylium, cyanine, phthalocyanine, pyrylium salt, oxazine type, thiazine type, perylene, stilbene type and croconium.

【００４６】前記キサンテン系の色素としてはフルオレ
セインローズベンガル、ローダミンなどがある。前記オ
キサジン系の色素としてはナイルブルーなどがある。前
記チアジン系の色素としてはチオニン、メチレンブルー
などがある。前記チアジン系の色素としてはスチリルア
ントラセンなどがある。The xanthene dyes include fluorescein rose bengal and rhodamine. Examples of the oxazine-based dye include Nile Blue. Examples of the thiazine dyes include thionine and methylene blue. Examples of the thiazine dye include styryl anthracene.

【００４７】前記半導体粒子に担持するための色素溶液
の溶媒は、増感色素を溶解するものなら任意のものが使
用可能である。このようなものとして例えばＤＭＥ・Ｄ
ＭＳＯ・アルコール・アセトニトリルなどが挙げられ、
その溶媒に所定濃度で色素を溶解させた溶液に半導体粒
子を所定時間浸漬する。半導体粒子と色素溶液をろ過し
液体成分を除いたのち乾燥し、これを有機溶媒に溶解し
たバインダと混合し所定粘度のペーストとする。As the solvent of the dye solution to be supported on the semiconductor particles, any solvent can be used as long as it can dissolve the sensitizing dye. For example, DME · D
MSO, alcohol, acetonitrile, etc.
The semiconductor particles are immersed for a predetermined time in a solution in which a dye is dissolved at a predetermined concentration in the solvent. The semiconductor particles and the dye solution are filtered to remove liquid components and then dried, and then mixed with a binder dissolved in an organic solvent to obtain a paste having a predetermined viscosity.

【００４８】溶媒中の固形分である半導体粒子の濃度は
１〜７０重量％であり、好ましくは１０〜６０重量％で
ある。必要に応じ界面活性剤や粘度調整剤を加える。吸
収波長の異なる色素をそれぞれ同様な方法でペースト化
する。The concentration of the semiconductor particles as a solid content in the solvent is 1 to 70% by weight, preferably 10 to 60% by weight. If necessary, a surfactant or a viscosity modifier is added. Dyes having different absorption wavelengths are pasted in the same manner.

【００４９】太陽光入射側から波長の短い吸収波長をも
つ増感色素を担持したペーストをスクリーン印刷し塗布
膜を乾燥し、この印刷と乾燥を繰り返すことで積層する
と、光電極３８が構成できる。図３は図面左側から入射
した場合の断面図であり、半導体層３２、３３、３４の
順序で吸収波長が長くなる色素を担持した半導体層であ
る。入射光が右側からの場合は半導体層３４，３３，３
２の順で吸収波長が長くなる色素を担持した半導体層を
設ける。必要に応じプレスなどで光電極膜厚の制御や光
電極密度を制御する。The photoelectrode 38 can be formed by screen-printing a paste carrying a sensitizing dye having a short absorption wavelength from the sunlight incident side, drying the coating film, and repeating this printing and drying. FIG. 3 is a cross-sectional view when light enters from the left side of the drawing, and is a semiconductor layer carrying a dye whose absorption wavelength becomes longer in the order of the semiconductor layers 32, 33, and. When the incident light is from the right side, the semiconductor layers 34, 33, 3
A semiconductor layer carrying a dye whose absorption wavelength becomes longer in the order of 2 is provided. If necessary, the thickness of the photoelectrode and the density of the photoelectrode are controlled by a press or the like.

【００５０】本発明において半導体層３２〜３４は多孔
質膜とし、その全体の膜厚は１〜５００μｍとする。あ
らかじめ色素を個別に担持した半導体層を順次積層する
利点は、複数の色素溶液に浸漬する場合や同一の半導体
粒子に色素溶液を順次変え吸着させる方法に比べて、色
素間の相互作用がなく、励起状態から半導体フェルミレ
ベルに電子が効率的に注入されることである。色素混合
溶液や色素溶液の順次吸着では色素間で電子注入やバッ
クエレクトロンが発生し、その結果光電流が小さくなっ
てしまう。In the present invention, the semiconductor layers 32 to 34 are porous films, and the entire film thickness is 1 to 500 μm. The advantage of sequentially laminating semiconductor layers individually supporting dyes in advance is that there is no interaction between the dyes when compared to a method of immersing in a plurality of dye solutions or sequentially changing the dye solution to the same semiconductor particles and adsorbing them. This means that electrons are efficiently injected from the excited state to the semiconductor Fermi level. In the sequential adsorption of the dye mixture solution or the dye solution, electron injection or back electron is generated between the dyes, and as a result, the photocurrent is reduced.

【００５１】対極３９は、対極基板３７に触媒を担持し
た触媒担持導電膜３６を形成してつくられている。採光
の必要がある場合は、触媒担持導電膜３６としてフッ素
ドープの酸化スズやＩＴＯを、対極基板３７としてガラ
スもしくはガスバリア処理を施したポリエチレンテレフ
タレート（ＰＥＴ）やポリカーボネート（ＰＣ）などを
用いて透明な対極３９を形成する。採光の必要性がなけ
れば白金触媒を担持した導電体が対極３９として用いら
れる。The counter electrode 39 is formed by forming a catalyst supporting conductive film 36 in which a catalyst is supported on a counter electrode substrate 37. When daylighting is required, the catalyst-supporting conductive film 36 is made of fluorine-doped tin oxide or ITO, and the counter electrode substrate 37 is made of glass or gas-barrier-treated polyethylene terephthalate (PET) or polycarbonate (PC). The counter electrode 39 is formed. If there is no need for daylighting, a conductor carrying a platinum catalyst is used as the counter electrode 39.

【００５２】電解質としてＩ−／Ｉ３ −、Ｂｒ−／Ｂｒ
３ −などのハロゲン化物、Ｓ−／Ｓ２ −などの硫黄化
物、ハイドロキノン、ＦｅＣＮ４ −／ＦｅＣＮ３ −など
のシアン化鉄系などの酸化還元種を有するものが挙げら
れる。これらを単独あるいは混合し、有機溶媒のプロピ
レンカーボネート、エチレンカーボネート、アセトニト
リルなどの単独あるいは混合溶媒に溶解し電解液とす
る。As electrolytes, I − / I 3 − , Br − / Br
3 - halides such as, S - / S 2 - sulfur compound such as hydroquinone, FeCN 4 - / FeCN 3 - include those having a redox species such as cyanide iron, such as. These are used alone or as a mixture, and dissolved in an organic solvent such as propylene carbonate, ethylene carbonate, acetonitrile, etc., alone or in a mixed solvent to prepare an electrolyte.

【００５３】なお、図１では、３層の半導体層の場合を
示したが、光電変換の光エネルギースペクトルに応じ、
吸収波長の異なる色素を担持した半導体層の数は２層以
上であればいくつでもよい。Although FIG. 1 shows the case of three semiconductor layers, according to the light energy spectrum of the photoelectric conversion,
The number of semiconductor layers supporting dyes having different absorption wavelengths may be any number as long as it is two or more.

【００５４】図２は、本発明の請求項２にかかわる光電
変換素子の構成を説明する概略断面図である。本光電変
換素子は、透光性基板４０ａ、中間透光性基板４６ａ、
４６ｂ、透明導電膜４１ａ〜４１ｃ、導電膜４１ｄ、半
導体層４２、４４、４５、電解質層４３ａ〜４３ｃおよ
び対極基板４０ｂから構成されている。FIG. 2 is a schematic sectional view for explaining the structure of a photoelectric conversion element according to a second aspect of the present invention. This photoelectric conversion element includes a light-transmitting substrate 40a, an intermediate light-transmitting substrate 46a,
46b, the transparent conductive films 41a to 41c, the conductive film 41d, the semiconductor layers 42, 44, 45, the electrolyte layers 43a to 43c, and the counter electrode substrate 40b.

【００５５】前記透光性基板４０ａに透明導電膜４１ａ
および半導体層４２を形成すると、光電極４９ができ
る。前記対極基板４０ｂに透明導電膜４１ｃを形成する
と対極５０ができる。A transparent conductive film 41a is formed on the transparent substrate 40a.
When the semiconductor layer 42 is formed, a photoelectrode 49 is formed. When the transparent conductive film 41c is formed on the counter electrode substrate 40b, the counter electrode 50 is formed.

【００５６】前記透明導電膜４１ｂは中間透光性基板４
６ａの全表面を被覆しており、この片側に触媒が担持さ
れ、もう片側に半導体層４４を形成すると中間電極４７
ができる。前記透明導電膜４１ｃは中間透光性基板４６
ｂの全表面を被覆しており、この片側に触媒が担持さ
れ、もう片側に半導体層４５を形成すると中間電極４８
ができる。The transparent conductive film 41b is formed on the intermediate light-transmitting substrate 4
6a, the catalyst is supported on one side and the semiconductor layer 44 is formed on the other side.
Can be. The transparent conductive film 41c is formed of an intermediate light-transmitting substrate 46.
b, the catalyst is supported on one side and the semiconductor layer 45 is formed on the other side.
Can be.

【００５７】前記の光電極４９、電解質層４３ａ、中間
電極４７は、この順に積層され光電変換セル５１を形成
している。前記の中間電極４７、電解質層４３ｂ、中間
電極４８は、この順に積層され光電変換セル５２を形成
している。前記の中間電極４８、電解質層４３ｃ、対極
５０は、この順に積層され光電変換セル５３を形成して
いる。前記光電変換セル５１、５２、５３は、この順に
積層され、本光電変換素子を形成している。The photoelectrode 49, the electrolyte layer 43a, and the intermediate electrode 47 are stacked in this order to form a photoelectric conversion cell 51. The intermediate electrode 47, the electrolyte layer 43b, and the intermediate electrode 48 are stacked in this order to form a photoelectric conversion cell 52. The intermediate electrode 48, the electrolyte layer 43c, and the counter electrode 50 are stacked in this order to form a photoelectric conversion cell 53. The photoelectric conversion cells 51, 52, and 53 are stacked in this order to form the present photoelectric conversion element.

【００５８】透光性基板４０ａ、対極基板４０ｂ、中間
透光性基板４６ａ、４６ｂとしてガラスもしくはガスバ
リア処理を施したポリエチレンテレフタレート（ＰＥ
Ｔ）やポリカーボネート（ＰＣ）などを利用できる。透
明導電膜４１ａ〜４１ｃ、導電膜４１ｄとしてフッ素ド
ープの酸化スズやＩＴＯを薄膜処理した膜を利用でき
る。The light-transmitting substrate 40a, the counter electrode substrate 40b, and the intermediate light-transmitting substrates 46a and 46b are made of glass or polyethylene terephthalate (PE) subjected to a gas barrier treatment.
T) and polycarbonate (PC) can be used. As the transparent conductive films 41a to 41c and the conductive film 41d, a film obtained by performing a thin film treatment on fluorine-doped tin oxide or ITO can be used.

【００５９】半導体層４２、４４、４５は、あらかじめ
色素を担持させた半導体粒子をペースト化しスクリーン
印刷もしくはバーコーターやナイフコーターなど各種コ
ーターで膜を形成する方法もしくは半導体粒子をペース
ト化し、その後増感色素溶液を含浸吸着させる方法のい
ずれかで形成される。The semiconductor layers 42, 44, and 45 are formed by pasting semiconductor particles previously supporting a dye into a paste, forming the film by screen printing or using a coater such as a bar coater or a knife coater, or forming the semiconductor particles into a paste, and then sensitizing. It is formed by any of the methods of impregnating and adsorbing a dye solution.

【００６０】半導体層４２、４４、４５に用いる色素
は、太陽光入射側から波長の短い吸収領域をもつ色素で
ある。すなわち、図２は図面左側から入射した場合の断
面図であるので、半導体層４２、４４、４５の順序で吸
収波長が長くなる色素を担持した半導体層で形成されて
いる。逆に、入射光が右側からの場合は半導体層４４，
４３，４２の順で吸収波長が長くなる色素を担持した半
導体層を形成する。The dye used for the semiconductor layers 42, 44 and 45 is a dye having an absorption region having a short wavelength from the sunlight incident side. That is, since FIG. 2 is a cross-sectional view when light enters from the left side of the drawing, the semiconductor layers 42, 44, and 45 are formed of a semiconductor layer carrying a dye whose absorption wavelength becomes longer in the order of the semiconductor layers 42, 44, and 45. Conversely, when the incident light is from the right side, the semiconductor layer 44,
A semiconductor layer supporting a dye whose absorption wavelength becomes longer in the order of 43 and 42 is formed.

【００６１】電解質層４３ａ〜４３ｃは、図１の電解質
層３５と同じく酸化還元種を含む電解液である。本発明
において、半導体層４２、４４、４５は多孔質膜とし、
その全体の膜厚は１〜１００μｍとする。The electrolyte layers 43a to 43c are electrolyte solutions containing redox species as in the case of the electrolyte layer 35 of FIG. In the present invention, the semiconductor layers 42, 44, 45 are porous films,
The overall film thickness is 1 to 100 μm.

【００６２】それぞれ吸収波長の異なる素子を順次積層
する利点は、図１で説明した色素間相互作用を皆無にす
るためである。色素間での電子注入やバックエレクトロ
ンの発生がなくなるためである。The advantage of sequentially laminating elements having different absorption wavelengths is that the interaction between dyes described with reference to FIG. 1 is completely eliminated. This is because electron injection between the dyes and generation of back electrons are eliminated.

【００６３】透明導電膜４１ｂ、４１ｃに微細孔を導入
し、酸化還元種を含む電解質層４３ａ、４３ｂ、４３ｃ
の電位を同じにすれば光電流が大きくなり、１セルずつ
電解質層４３ａ、４３ｂ、４３ｃを完全隔離すれば電圧
が大きくとれる。Micropores are introduced into the transparent conductive films 41b, 41c, and the electrolyte layers 43a, 43b, 43c containing redox species are provided.
, The photocurrent increases, and the voltage can be increased by completely isolating the electrolyte layers 43a, 43b, 43c one cell at a time.

【００６４】ここで用いられる半導体粒子、色素、色素
溶液の溶媒、電解液などは図１の説明で説明したものと
同じものを同じ方法で使用できる。The semiconductor particles, the dye, the solvent of the dye solution, the electrolytic solution, and the like used here can be the same as those described with reference to FIG. 1 and used in the same manner.

【００６５】以下、本発明の実施例について説明する。
実施例は、太陽スペクトルを光電変換する色素増感型の
湿式太陽電池で説明しているが 本発明は太陽電池に限
定するものではなく、広く紫外光〜赤外光を受光するセ
ンサなど、紫外光〜赤外光の光エネルギーを電気エネル
ギーに変換する光電変換素子として広く利用できる。Hereinafter, embodiments of the present invention will be described.
Although the embodiments have been described with reference to a dye-sensitized wet solar cell that photoelectrically converts the solar spectrum, the present invention is not limited to a solar cell, and a sensor that widely receives ultraviolet light to infrared light, such as an ultraviolet light sensor. It can be widely used as a photoelectric conversion element for converting light energy of light to infrared light into electric energy.

【００６６】実施例においては、いずれも半導体として
平均粒子径２０ｎｍ、比表面積９０ｍ２／ｇの酸化チタ
ン微粒子を用いた。また基板はソーダガラス、透明導電
膜はフッ素をドープした酸化スズ薄膜でそのシート抵抗
は１０〜１３Ω／□（シート抵抗）であるものを用い
た。In each of the examples, titanium oxide fine particles having an average particle diameter of 20 nm and a specific surface area of 90 m 2 / g were used as semiconductors. The substrate used was soda glass, and the transparent conductive film used was a tin oxide thin film doped with fluorine and having a sheet resistance of 10 to 13 Ω / □ (sheet resistance).

【００６７】また対極として、特に断りのない限り、上
記ガラス基板上に透明導電膜処理を施したものに塩化白
金酸溶液をスピンコートし、４５０℃の熱処理でおおよ
そ２０ｎｍの白金を析出担持させたものを用いた。As a counter electrode, unless otherwise specified, a transparent conductive film treatment was performed on the above-mentioned glass substrate, a chloroplatinic acid solution was spin-coated, and a platinum film of about 20 nm was deposited and supported by a heat treatment at 450 ° C. Was used.

【００６８】光電変換特性の評価は、光電変換素子の光
入射面積が１Ｘ１ｃｍ２であり、光源にフィルタ付きの
キセノンランプを用い、１００ｍＷ／ｃｍ２の照射強度
で行った。この光源のスペクトルは、ほぼ太陽光のスペ
クトルと同じである。作製した光電変換素子について、
光照射時の短絡電流及び開放端の電圧の測定して光電変
換特性を評価した。The evaluation of the photoelectric conversion characteristics was performed using a xenon lamp with a filter as a light source, with a light incident area of the photoelectric conversion element of 1 × 1 cm 2, and an irradiation intensity of 100 mW / cm 2 . The spectrum of this light source is almost the same as the spectrum of sunlight. About the produced photoelectric conversion element,
The short-circuit current and the voltage at the open end during light irradiation were measured to evaluate the photoelectric conversion characteristics.

【００６９】以下、実施例、比較例について説明する。
実施例１ａ〜１ｃ、比較例１ａ、１ｂは図１用いて説明
し、実施例２、比較例２は図２を用いて説明する。Hereinafter, examples and comparative examples will be described.
Examples 1a to 1c and Comparative Examples 1a and 1b will be described with reference to FIG. 1, and Example 2 and Comparative Example 2 will be described with reference to FIG.

【００７０】（実施例１ａ）色素は短波長（紫外光〜可
視光）で光増感するオリゴフェニレン色素のポリフェニ
ル１を溶媒ＤＭＳＯに１Ｘ１０−３Ｍ溶解する。それを
酸化チタン微粒子に吸着させ乾燥させたものをアルコー
ルに溶解したバインダと混合しペースト化し透明導電膜
３１が形成している透光性基板３０上にスクリーン印刷
で成膜し乾燥した。乾燥後の半導体層３２の膜厚は３〜
６μｍであった。(Example 1a) As a dye, 1 × 10 −3 M of an oligophenylene dye polyphenyl 1 which is photosensitized at a short wavelength (from ultraviolet light to visible light) is dissolved in a solvent DMSO. The resultant was adsorbed on titanium oxide fine particles, dried, and mixed with a binder dissolved in alcohol to form a paste. The film was formed on the translucent substrate 30 on which the transparent conductive film 31 was formed by screen printing and dried. The thickness of the semiconductor layer 32 after drying is 3 to
It was 6 μm.

【００７１】同様に中波長（可視光）で光増感するキサ
ンテン系であるローダミンＢをＤＭＳＯに１Ｘ１０−３
Ｍ溶解する。それを酸化チタン微粒子に吸着させ乾燥さ
せたものをアルコールに溶解したバインダと混合しペー
スト化し、乾燥した半導体層３２の上からスクリーン印
刷で形成し再度乾燥した。半導体層３３の乾燥後の膜厚
は３〜６μｍであった。Similarly, rhodamine B, which is a xanthene type photosensitized at a medium wavelength (visible light), is added to DMSO at 1 × 10 −3.
Dissolve M. It was adsorbed on titanium oxide fine particles, dried and mixed with a binder dissolved in alcohol to form a paste, formed on the dried semiconductor layer 32 by screen printing, and dried again. The thickness of the semiconductor layer 33 after drying was 3 to 6 μm.

【００７２】また長波長（可視光〜赤外）で光増感する
シアニンのＩＲ１４０をＤＭＳＯに１Ｘ１０−３Ｍ溶解
する。それを酸化チタン微粒子に吸着させ乾燥させたも
のをアルコールに溶解したバインダと混合しペースト化
し半導体層３３上にスクリーン印刷で膜を形成し乾燥し
た。乾燥後の半導体層３４の膜厚は３−６μｍであっ
た。Further, 1 × 10 −3 M of cyanine IR140 which is photosensitized at a long wavelength (visible light to infrared) is dissolved in DMSO. The resultant was adsorbed on titanium oxide fine particles, dried and mixed with a binder dissolved in alcohol to form a paste, and a film was formed on the semiconductor layer 33 by screen printing and dried. The thickness of the semiconductor layer 34 after drying was 3 to 6 μm.

【００７３】こうして得られた光電極３８と対極３９を
組み合わせ電解液注入口を残しシールする。ヨウ素０．
６Ｍテトラプロピルアイオダイト０．４Ｍを混合溶媒
（エチレンカーボネート８０ｖｏｌ％アセトニトリル２
０ｖｏｌ％）に溶解し電解液とする。電解液を注入後、
注入口を封止して光電変換素子を作製した。The photoelectrode 38 thus obtained and the counter electrode 39 are combined and sealed while leaving the electrolyte injection port. Iodine 0.
6M tetrapropyl iodide 0.4M mixed solvent (ethylene carbonate 80 vol% acetonitrile 2
0 vol%) to obtain an electrolytic solution. After injecting the electrolyte,
The injection port was sealed to produce a photoelectric conversion element.

【００７４】（実施例１ｂ）実施例１ａで半導体層３２
〜３４に担持した色素の替わりに、それぞれスチルベン
１、クマリン、ペリレンを使用した以外、実施例１ａと
同じ方法で光電変換素子を作製した。(Example 1b) The semiconductor layer 32 of Example 1a
A photoelectric conversion element was produced in the same manner as in Example 1a, except that stilbene 1, coumarin, and perylene were used instead of the dyes carried on Nos. To 34, respectively.

【００７５】（実施例１ｃ）実施例１ａで半導体層３２
〜３４に担持した色素の替わりに、それぞれキノロン、
オキサジン、シアニンであるＤＴＴＣ−Ｉｏｄｉｄｅ
（３−３’ジエチルシアトリカルボシアニンイオダイ
ト）を使用した以外、実施例１ａと同じ方法で光電変換
素子を作製した。(Example 1c) The semiconductor layer 32 of Example 1a
~ 34, instead of the dye carried on each, quinolone,
Oxazine, DTTC-iodide which is cyanine
A photoelectric conversion element was produced in the same manner as in Example 1a, except that (3-3′diethyl cyanotricarbocyanine iodide) was used.

【００７６】（比較例１ａ）実施例１ａで半導体層３２
〜３４に担持した色素の替わりに、すべて同じキサンテ
ンサン系のローダミンＢを使用した以外、実施例１ａと
同じ方法で光電変換素子を作製した。(Comparative Example 1a) The semiconductor layer 32 of Example 1a
A photoelectric conversion element was produced in the same manner as in Example 1a, except that the same xanthenesan-based rhodamine B was used in place of the dyes supported on Nos. To 34.

【００７７】（比較例１ｂ）実施例１ａで半導体層３２
〜３４に担持した色素の替わりに、すべて同じオリゴフ
ェニレン色素のポリフェニル１とキサンテン系であるロ
ーダミンＢとシアニンであるＩＲ１４０を等量混合して
使用した以外、実施例１ａと同じ方法で光電変換素子を
作製した。(Comparative Example 1b) The semiconductor layer 32 of Example 1a
The photoelectric conversion was carried out in the same manner as in Example 1a, except that the same oligophenylene dye, polyphenyl 1, xanthene-based rhodamine B, and cyanine IR140 were mixed and used in place of the dyes supported on Nos. ~ 34. An element was manufactured.

【００７８】色素の混合は、短波長（紫外光〜可視光）
で光増感するポリフェニル１と可視光で光増感するロー
ダミンＢと可視光〜赤外光で光増感するＩＲ１４０を各
々３Ｘ１０−４Ｍの濃度でＤＭＳＯに溶解して行い、実
施例１ａと同じ方法で半導体粒子に担持した。The mixture of the dyes has a short wavelength (from ultraviolet light to visible light).
Example 1a was conducted by dissolving each of polyphenyl 1 photosensitized with the above, rhodamine B photosensitized with the visible light, and IR140 photosensitized with the visible light to the infrared light at a concentration of 3 × 10 −4 M in DMSO. Supported on semiconductor particles in the same manner as described above.

【００７９】（評価結果１）表１に、実施例１ａ〜１
ｃ、比較例１ａ、１ｂの光電変換特性の評価結果を示
す。実施例１は、光電変換特性を表す短絡電流・開放端
電圧が比較例に比べ格段によいことがわかる。このこと
は、実施例１の場合、色素分離吸着による３層構造のた
め吸収波長領域の拡大が起こり広い波長の入射光を透過
することなく有効利用できたため、光電変換効率が高い
と考えられる。(Evaluation Result 1) Table 1 shows Examples 1a to 1
c shows the evaluation results of the photoelectric conversion characteristics of Comparative Examples 1a and 1b. It can be seen that in Example 1, the short-circuit current and the open-circuit voltage representing the photoelectric conversion characteristics are much better than the comparative example. This is considered to be due to the high photoelectric conversion efficiency in Example 1 because the absorption wavelength region was expanded due to the three-layer structure due to the dye separation and adsorption and the incident light of a wide wavelength could be effectively used without transmitting.

【００８０】[0080]

【表１】 [Table 1]

【００８１】一方、比較例１ａの場合、特定波長の吸収
だけであるため入射光が有効に利用できず特性の向上が
できなかったものと考えられる。また、比較例１ｂの場
合、酸化チタン上に吸着した隣接する色素間で相互作用
が起こり酸化チタン半導体の伝導帯準位への電荷注入が
阻害されたため、光電変換効率が低いと考えられる。On the other hand, in the case of Comparative Example 1a, it is considered that the incident light could not be used effectively because the absorption was only at a specific wavelength, and the characteristics could not be improved. In the case of Comparative Example 1b, the photoelectric conversion efficiency is considered to be low because an interaction occurs between the adjacent dyes adsorbed on the titanium oxide and the charge injection into the conduction band level of the titanium oxide semiconductor is inhibited.

【００８２】（実施例２）酸化チタン微粒子をアルコー
ルに溶解したバインダと混合しペースト化し透明導電膜
４１ａが形成されている透光性基板４０ａ上にスクリー
ン印刷で成膜、乾燥した。乾燥後の膜厚は３〜６μｍで
あった。これを大気雰囲気下４７５℃、３０分焼成し多
孔質な半導体層４２を得た。焼成後の膜厚変化はなかっ
た。色素は短波長（紫外光〜可視光）で光増感するオリ
ゴフェニレン色素のポリフェニル１を用い溶媒ＤＭＳＯ
に１Ｘ１０−３Ｍ溶解した。これに前記半導体層４２を
浸漬し色素を担持し、光電極５０を作製した。(Example 2) Titanium oxide fine particles were mixed with a binder dissolved in alcohol, made into a paste, and formed into a film by screen printing on a light transmitting substrate 40a on which a transparent conductive film 41a was formed, and dried. The film thickness after drying was 3 to 6 μm. This was fired at 475 ° C. for 30 minutes in an air atmosphere to obtain a porous semiconductor layer 42. There was no change in film thickness after firing. The dye used is polyphenyl 1, an oligophenylene dye that photosensitizes at a short wavelength (ultraviolet light to visible light).
Was dissolved in 1 × 10 −3 M. The semiconductor layer 42 was immersed in this to carry a dye, thereby producing a photoelectrode 50.

【００８３】一方、全表面に透明導電膜４１ｂが形成さ
れ表裏同電位になっている中間透光性基板４６ａの片側
に塩化白金酸を塗布し、反対側に酸化チタン微粒子をア
ルコールに溶解したバインダと混合しペースト化したも
のをスクリーン印刷で成膜し乾燥した。On the other hand, chloroplatinic acid is applied to one side of an intermediate translucent substrate 46a having a transparent conductive film 41b formed on the entire surface and having the same potential on the front and back, and a binder obtained by dissolving titanium oxide fine particles in alcohol on the other side. Was formed into a paste by screen printing and dried.

【００８４】その後、大気雰囲気下４７５℃、３０分焼
成した。これにより、片側に白金微粒子が担持され、も
う一方に多孔質な半導体層４４が形成された中間電極４
７を得た。中波長（可視光）で光増感するキサンテン系
であるローダミンＢを用いＤＭＳＯに１Ｘ１０−３Ｍ溶
解した。これに前記中間電極４７を浸漬し色素を吸着し
た。Thereafter, firing was performed at 475 ° C. for 30 minutes in an air atmosphere. Thus, the intermediate electrode 4 on which platinum fine particles are supported on one side and the porous semiconductor layer 44 is formed on the other side.
7 was obtained. 1 × 10 −3 M was dissolved in DMSO using rhodamine B, which is a xanthene-based photosensitizer at medium wavelength (visible light). The intermediate electrode 47 was immersed in this to adsorb the dye.

【００８５】同様に、全表面に透明導電膜４１ｃが形成
され表裏同電位になっている中間透光性基板４６ｂの片
側に白金微粒子を担持し、もう一方側に多孔質な酸化チ
タン膜の半導体層４５を形成した中間電極４８を、長波
長（可視光〜赤外）で光増感するシアニンのＩＲ１４０
の色素をＤＭＳＯに１Ｘ１０−３Ｍ溶解した溶液に浸漬
し色素を吸着した。対極５０は、実施例１の対極３９と
同じ方法で作製した。Similarly, a transparent conductive film 41c is formed on the entire surface, and one side of an intermediate translucent substrate 46b having the same potential on both sides carries platinum fine particles, and the other side has a porous titanium oxide film semiconductor. The intermediate electrode 48 on which the layer 45 has been formed is irradiated with a cyanine IR140 that is photosensitized at a long wavelength (visible light to infrared).
Was immersed in a solution of 1 × 10 −3 M of the dye in DMSO to adsorb the dye. The counter electrode 50 was manufactured by the same method as the counter electrode 39 of the first embodiment.

【００８６】前記光電極４９、中間電極４７、４８、対
極５０を、この順で組み合わせ電解液注入口を残しシー
ルする。こうして得られた積層体は、光電変換セル５１
〜５３が３個、直列に積層した光電変換素子を形成して
いる。The photoelectrode 49, the intermediate electrodes 47 and 48, and the counter electrode 50 are combined in this order, and sealing is performed except for the electrolyte injection port. The laminate obtained in this manner is a photoelectric conversion cell 51
To 53 form a photoelectric conversion element in which three photoelectric conversion elements are stacked in series.

【００８７】それぞれの光電変換素子にヨウ素０．６Ｍ
テトラプロピルアイオダイト０．４Ｍを混合溶媒（エチ
レンカーボネート８０ｖｏｌ％アセトニトリル２０ｖｏ
ｌ％）に溶解し電解液とする。電解液を注入後、注入口
を封止すると光電変換素子が完成する。この光電変換素
子の評価を前述の方法で行った。For each photoelectric conversion element, iodine 0.6M
0.4M of tetrapropyl iodide is mixed with a mixed solvent (ethylene carbonate 80vol% acetonitrile 20vo)
1%) to obtain an electrolyte. After injecting the electrolyte, the inlet is sealed to complete the photoelectric conversion element. The evaluation of this photoelectric conversion element was performed by the method described above.

【００８８】（比較例２）実施例１ａで半導体層４２、
４４、４５に担持した色素の替わりに、すべて同じキサ
ンテンサン系のローダミンＢを使用した以外、実施例１
ａと同じ方法で光電変換素子を作製した。(Comparative Example 2) In Example 1a, the semiconductor layer 42
Example 1 except that the same xanthenesan rhodamine B was used instead of the dyes supported on 44 and 45.
A photoelectric conversion element was produced in the same manner as in a.

【００８９】（評価結果２）実施例２、比較例２の光電
変換特性の評価結果も表１に示した。実施例２の短絡電
流・開放端電圧が比較例２に比べ格段に良いことがわか
る。このことは、実施例２の場合、各光電変換セルの色
素の吸収波長が異なっているため、吸収波長領域の拡大
が起こり広い波長の入射光を透過することなく有効利用
できたためと考えられる。一方、比較例２の場合、色素
が同一のため吸収波長領域が制限され、特定波長の入射
光は有効に利用できるものの、それ以外の波長は透過し
てしまい、全体としては入射光は有効に利用できなかっ
たものと思われる。(Evaluation Result 2) The evaluation results of the photoelectric conversion characteristics of Example 2 and Comparative Example 2 are also shown in Table 1. It can be seen that the short-circuit current and open-end voltage of Example 2 are much better than Comparative Example 2. This is presumably because in the case of Example 2, since the absorption wavelengths of the dyes of the respective photoelectric conversion cells were different, the absorption wavelength region was expanded and incident light of a wide wavelength could be effectively used without transmitting. On the other hand, in the case of Comparative Example 2, the absorption wavelength region is limited because the dye is the same, and although incident light of a specific wavelength can be used effectively, other wavelengths are transmitted, and as a whole, the incident light is effectively used. Probably not available.

【００９０】以上の結果、本発明の吸収波長特性の異な
る増感色素を担持した複数の半導体層を有する光電変換
素子は、従来技術と異なりその性能は高められることが
証明できた。本発明の光電変換素子は、シリコン系や化
合物半導体の物理的光電変換素子と異なり安価な原料と
安価な製造設備で生産可能なため、安価に生産供給が可
能である。また本発明により、色素増感光型電変換素子
の積層が容易に作製できることになり、その結果、光電
変換特性の大幅向上を成立させることができた。As a result, it has been proved that the performance of the photoelectric conversion device of the present invention having a plurality of semiconductor layers carrying sensitizing dyes having different absorption wavelength characteristics can be improved unlike the prior art. Since the photoelectric conversion element of the present invention can be produced with inexpensive raw materials and inexpensive manufacturing equipment, unlike a silicon-based or compound semiconductor physical photoelectric conversion element, it can be produced and supplied at low cost. In addition, according to the present invention, a dye-sensitized photoelectric conversion element can be easily laminated, and as a result, the photoelectric conversion characteristics can be significantly improved.

【００９１】また、物理的光電変換素子では、ヘテロジ
ャンクションの格子不整合による問題があり、多大な研
究が行われてきたが解決に至っていない。本発明の光電
変換素子では、格子不整合の問題はなく、この種の問題
が回避できる。Further, in the physical photoelectric conversion element, there is a problem due to lattice mismatch of heterojunction, and a great deal of research has been conducted, but it has not been solved. In the photoelectric conversion element of the present invention, there is no problem of lattice mismatch, and this kind of problem can be avoided.

【００９２】[0092]

【発明の効果】以上のように、本発明は、導電性基板上
に複数の半導体層が積層して設けられ、該導電性基板の
対極をなす導電性基板上に触媒が担持され、前記の両導
電性基板の間に電解質層が設けられ、前記半導体層ごと
に異なる吸収波長を有する色素が担持され、入射光側に
位置する半導体層の色素の吸収波長が、該半導体層の後
方の半導体層の色素の吸収波長より短波長になっている
ことを特徴とする光電変換素子および導電性基板、色素
を担持した半導体層、電解質層および触媒を担持した導
電性基板を有する光電変換セルを複数積層し、入射光側
に位置する半導体層の色素の吸収波長が、該半導体層の
後方の半導体層の色素の吸収波長より短波長になってい
ることを特徴とする光電変換素子であるので、光スペク
トルの吸収波長領域を拡大し、光エネルギーから電気エ
ネルギーへの変換特性を向上させることができる。As described above, according to the present invention, a plurality of semiconductor layers are laminated on a conductive substrate, and a catalyst is supported on a conductive substrate which is a counter electrode of the conductive substrate. An electrolyte layer is provided between the two conductive substrates, and a dye having a different absorption wavelength is carried for each of the semiconductor layers. A plurality of photoelectric conversion elements having a wavelength shorter than the absorption wavelength of the dye in the layer, and a plurality of photoelectric conversion cells having a conductive substrate, a semiconductor layer carrying the dye, an electrolyte layer and a conductive substrate carrying a catalyst. Since the photoelectric conversion element is stacked, the absorption wavelength of the dye of the semiconductor layer positioned on the incident light side is shorter than the absorption wavelength of the dye of the semiconductor layer behind the semiconductor layer. Absorption wavelength region of optical spectrum Expanding, it is possible to improve the characteristics of the light energy into electrical energy.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の請求項１にかかわる光電変換素子の構
成を説明する概略断面図FIG. 1 is a schematic sectional view illustrating the configuration of a photoelectric conversion element according to claim 1 of the present invention.

【図２】本発明の請求項２にかかわる光電変換素子の構
成を説明する概略断面図FIG. 2 is a schematic sectional view illustrating the configuration of a photoelectric conversion element according to claim 2 of the present invention.

【図３】一般的な色素増感型光電変換素子の構成を説明
する概略断面図FIG. 3 is a schematic cross-sectional view illustrating a configuration of a general dye-sensitized photoelectric conversion element.

【図４】一般的な色素増感型光電変換素子の作動原理を
説明するエネルギーダイアグラム図FIG. 4 is an energy diagram illustrating the operation principle of a general dye-sensitized photoelectric conversion element.

【符号の説明】[Explanation of symbols]

３０、４０ａ、４６ａ、４６ｂ…透明性基板 ３１、４１ａ〜４１ｃ…透明導電膜 ３２〜３４、４２、４４、４５…半導体層 ３５、４３ａ〜４３ｃ…電解質層 ３６…触媒担持導電膜 ３７…対極基板 ３８、４９…光電極 ３９、５０…対極 ４１ｄ…導電膜 ４７、４８…中間電極 ５１〜５３…光電変換セル 30, 40a, 46a, 46b ... Transparent substrate 31, 41a-41c ... Transparent conductive film 32-34, 42, 44, 45 ... Semiconductor layer 35, 43a-43c ... Electrolyte layer 36 ... Catalyst carrying conductive film 37 ... Counter electrode substrate 38, 49 ... Photoelectrode 39, 50 ... Counter electrode 41d ... Conductive film 47, 48 ... Intermediate electrode 51-53 ... Photoelectric conversion cell

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 導電性基板上に複数の半導体層が積層し
て設けられ、該導電性基板の対極をなす導電性基板上に
触媒が担持され、前記の両導電性基板の間に電解質層が
設けられ、前記半導体層ごとに異なる吸収波長を有する
色素が担持され、入射光側に位置する半導体層の色素の
吸収波長が、該半導体層の後方の半導体層の色素の吸収
波長より短波長になっていることを特徴とする光電変換
素子。1. A semiconductor device comprising: a plurality of semiconductor layers laminated on a conductive substrate; a catalyst supported on a conductive substrate serving as a counter electrode of the conductive substrate; and an electrolyte layer interposed between the conductive substrates. Is provided, a dye having a different absorption wavelength is carried for each semiconductor layer, the absorption wavelength of the dye of the semiconductor layer located on the incident light side is shorter than the absorption wavelength of the dye of the semiconductor layer behind the semiconductor layer. A photoelectric conversion element, characterized in that: 【請求項２】 導電性基板、色素を担持した半導体層、
電解質層および触媒を担持した導電性基板を有する光電
変換セルを複数積層し、入射光側に位置する半導体層の
色素の吸収波長が、該半導体層の後方の半導体層の色素
の吸収波長より短波長になっていることを特徴とする光
電変換素子。2. A conductive substrate, a semiconductor layer supporting a dye,
A plurality of photoelectric conversion cells each having an electrolyte layer and a conductive substrate carrying a catalyst are stacked, and the absorption wavelength of the dye of the semiconductor layer located on the incident light side is shorter than the absorption wavelength of the dye of the semiconductor layer behind the semiconductor layer. A photoelectric conversion element having a wavelength. 【請求項３】 前記半導体が、酸化物・リン化物・炭化
物・硫化物・セレン化物の少なくとも一つであることを
特徴とする請求項１、２のいずれかに記載の光電変換素
子。3. The photoelectric conversion device according to claim 1, wherein the semiconductor is at least one of oxide, phosphide, carbide, sulfide, and selenide. 【請求項４】 色素がオリゴフェニレン、オキサゾー
ル、オキサジアゾール、スチルベン、キノロン、クロロ
フィル、クマリン、キサンテン系、メロシアニン、スク
アリリウム、シアニン、フタロシアニン、ピリリウム
塩、オキサジン系、チアジン系、ペリレン、スチルベン
系、クロコニウムであることを特徴とする請求項１、２
のいずれかに記載の光電変換素子。4. The pigment is oligophenylene, oxazole, oxadiazole, stilbene, quinolone, chlorophyll, coumarin, xanthene, merocyanine, squarylium, cyanine, phthalocyanine, pyrylium salt, oxazine, thiazine, perylene, stilbene, croconium 3. The method according to claim 1, wherein
The photoelectric conversion element according to any one of the above. 【請求項５】 前記電解質層が、ハロゲン化物、硫黄化
物、ハイドロキノン、シアン化鉄の少なくとも一つのの
酸化還元種を含んでいることを特徴とする請求項１、２
のいずれかに記載の光電変換素子。5. The electrolyte layer according to claim 1, wherein the electrolyte layer contains at least one redox species of halide, sulfuride, hydroquinone, and iron cyanide.
The photoelectric conversion element according to any one of the above. 【請求項６】 前記触媒層の触媒が、白金、カーボンの
少なくとも一つであることを特徴とする請求項１、２の
いずれかに記載の光電変換素子。6. The photoelectric conversion element according to claim 1, wherein the catalyst of the catalyst layer is at least one of platinum and carbon.
JP11045475A 1999-02-23 1999-02-23 Photoelectric transducer Pending JP2000243466A (en)

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