JP2000315530A - Photoelectric conversion element and manufacture thereof - Google Patents
Photoelectric conversion element and manufacture thereofInfo
- Publication number
- JP2000315530A JP2000315530A JP11124546A JP12454699A JP2000315530A JP 2000315530 A JP2000315530 A JP 2000315530A JP 11124546 A JP11124546 A JP 11124546A JP 12454699 A JP12454699 A JP 12454699A JP 2000315530 A JP2000315530 A JP 2000315530A
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- absorbed
- oxide semiconductor
- metal oxide
- electrode
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属酸化物半導体
電極とその表面に吸着した色素と酸化還元対を有する電
解質と対向電極とからなる光電変換素子に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoelectric conversion element comprising a metal oxide semiconductor electrode, a dye adsorbed on the surface thereof, an electrolyte having a redox couple, and a counter electrode.
【０００２】[0002]
【従来の技術】太陽電池にはいくつかの種類があるが、
実用化されているものはシリコン半導体の接合を利用し
たダイオード型のものがほとんどである。これらの太陽
電池は現状では製造コストが高く、このことが普及を妨
げる要因となっている。低コスト化の可能性から色素増
感型湿式太陽電池が古くから研究されているが、最近、
Graetzelらがシリコン太陽電池に匹敵する性能を有する
ものを発表した（J. Am.Chem. Soc. 115(1993)6382）こ
とにより、実用化への期待が高まっている。色素増感型
湿式太陽電池の基本構造は、金属酸化物半導体電極とそ
の表面に吸着した色素と酸化還元対を有する電解質と対
向電極とからなる。Graetzelらは酸化チタン（Ｔｉ
Ｏ2）等の金属酸化物半導体電極を多孔質化して表面積
を大きくしたこと及び色素としてルテニウム錯体を単分
子妓着させたことにより光電変換効率を著しく向上させ
た。2. Description of the Related Art There are several types of solar cells.
Most of those practically used are diode-type ones using silicon semiconductor junctions. At present, these solar cells have high manufacturing costs, which is a factor hindering their spread. Dye-sensitized wet-type solar cells have been studied for a long time because of the possibility of cost reduction.
Graetzel et al. (J. Am. Chem. Soc. 115 (1993) 6382) have announced that they have performance comparable to silicon solar cells, raising expectations for their practical use. The basic structure of a dye-sensitized wet solar cell is composed of a metal oxide semiconductor electrode, a dye adsorbed on the surface of the electrode, an electrolyte having a redox pair, and a counter electrode. Graetzel et al.
The photoelectric conversion efficiency was remarkably improved by increasing the surface area of the metal oxide semiconductor electrode such as O 2 ) by making it porous, and by attaching a ruthenium complex as a dye to a single molecule.
【０００３】その後、さらに特性を向上させるべくいく
つかの提案がなされている、例えば、特開平９−２３７
６４１号公報では金属酸化物半導体として酸化ニオブ
（Ｎｂ 2Ｏ5）を用いることにより、開放電圧が大きくな
るとされている。また、特開平８−８１２２２号公報で
はＴｉＯ2電極膜の表面をエッチング処理することによ
り、格子欠陥や不純物が除去され、変換効率が向上する
とされている。[0003] Thereafter, the characteristics are further improved.
Some proposals have been made, for example, in JP-A-9-237.
No. 641 discloses a niobium oxide as a metal oxide semiconductor.
(Nb TwoOFive) Increases open-circuit voltage.
It is said that. Also, in Japanese Patent Application Laid-Open No. 8-81222,
Is TiOTwoBy etching the surface of the electrode film
Removes lattice defects and impurities, improving conversion efficiency
It has been.
【０００４】しかし、色素増感型湿式太陽電池の光電変
換効率を向上させるためには、いかに照射される光を多
く吸収するかが最も重要となる。つまり、従来の色素増
感型湿式太陽電池においては、照射された光はほとんど
セル中を透過してしまい光電変換に利用されていない。
そのため、これまでに吸収波長域の広い増感色素の検討
が数多くなされている。しかしながら、必ずしも照射光
を十分に吸収し、光電変換するまでには至っていない。However, in order to improve the photoelectric conversion efficiency of the dye-sensitized wet-type solar cell, it is most important how to absorb a large amount of irradiated light. That is, in the conventional dye-sensitized wet-type solar cell, the irradiated light hardly passes through the cell and is not used for photoelectric conversion.
Therefore, many studies have been made on sensitizing dyes having a wide absorption wavelength range. However, the irradiation light has not always been sufficiently absorbed and photoelectrically converted.
【０００５】[0005]
【発明が解決しようとする課題】本発明の課題は、この
ような従来技術の問題点を解決し、照射される光エネル
ギーの吸収効率を上げることにより、同じ強度の光照射
下において光電変換効率を向上させることのできる光電
変換素子を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art and to improve the photoelectric conversion efficiency under the same intensity of light irradiation by increasing the absorption efficiency of the irradiated light energy. It is an object of the present invention to provide a photoelectric conversion element capable of improving the density.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記課題を
解決するために鋭意検討を重ねた結果、従来の金属酸化
物半導体電極とその表面に吸着した色素と酸化還元対を
有する電解質と対向電極とからなる光電変換ユニットを
ね合わせる、すなわち光を吸収する働きをする色素が吸
着された金属酸化物半導体層を素子内に複数設けること
で光の吸収量を上げることにより、光電変換効率が向上
することを見出し、本発明を完成するに至った。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a conventional metal oxide semiconductor electrode, a dye adsorbed on the surface thereof, and an electrolyte having a redox couple are used. The photoelectric conversion efficiency is improved by bonding the photoelectric conversion unit including the opposing electrode, that is, by providing a plurality of metal oxide semiconductor layers in which a dye that functions to absorb light is adsorbed in the device to increase the amount of light absorption. Was found to be improved, and the present invention was completed.
【０００７】すなわち、本発明によれば、金属酸化物半
導体電極とその表面に吸着した色素と酸化還元対を有す
る電解液と対向電極とからなる光電変換ユニットを複数
重ね合わせた構造を有することを特徴とする光電変換素
子が提供される。また、本発明によれば、上記構成にお
いて、金属酸化物半導体電極が１枚の透明基板の両面に
形成されており、それぞれの電極面に対して対向電極が
配置されていることを特徴とする光電変換素子が提供さ
れる。また、本発明によれば、上記構成において、一つ
の金属酸化物半導体層の膜厚が２０μｍ以下であること
を特徴とする光電変換素子が提供される。さらに、本発
明によれば、上記構成において、各光電変換ユニットが
電気的に直列に接続されていることを特徴とする光電変
換素子が提供される。That is, according to the present invention, there is provided a structure in which a plurality of photoelectric conversion units each comprising a metal oxide semiconductor electrode, a dye adsorbed on the surface thereof, an electrolytic solution having a redox pair, and a counter electrode are superposed. There is provided a photoelectric conversion element characterized by the following. Further, according to the invention, in the above structure, the metal oxide semiconductor electrodes are formed on both surfaces of one transparent substrate, and opposed electrodes are arranged on each electrode surface. A photoelectric conversion element is provided. Further, according to the present invention, there is provided a photoelectric conversion element having the above structure, in which one metal oxide semiconductor layer has a thickness of 20 μm or less. Further, according to the present invention, there is provided a photoelectric conversion element having the above configuration, wherein the photoelectric conversion units are electrically connected in series.
【０００８】[0008]
【発明の実施の形態】以下、本発明による光電変換素子
の構成を、図を用いて説明するが、本発明の実施の形態
はこれらに限定されるものではない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of a photoelectric conversion device according to the present invention will be described below with reference to the drawings, but the embodiments of the present invention are not limited thereto.
【０００９】まず、図１に従来の色素増感型湿式太陽電
池の代表的な構成例を示す。１はガラス等の透明基板、
２はＩＴＯ、ＳｎＯ2：Ｆ、ＺｎＯ：Ａｌ等からなる透
明導電膜、３は多孔質金属酸化物半導体層、４はルテニ
ウムビピリジル錯体、亜鉛ポルフィリン、銅フタロシア
ニン、クロロフィル、ローズベンガル、エオシン等の色
素、５はＩ-／Ｉ3 -、Ｂｒ-／Ｂｒ3 -等の酸化還元対を有
する電解液、６はＰｔ等からなる対向電極である。光は
図の上方から入射する。First, FIG. 1 shows a typical configuration example of a conventional dye-sensitized wet solar cell. 1 is a transparent substrate such as glass,
2 is a transparent conductive film made of ITO, SnO 2 : F, ZnO: Al, etc., 3 is a porous metal oxide semiconductor layer, 4 is a dye such as ruthenium bipyridyl complex, zinc porphyrin, copper phthalocyanine, chlorophyll, rose bengal, eosin, etc. , 5 I - / I 3 -, Br - / Br 3 - electrolyte having a redox pair, such as, 6 is a counter electrode made of Pt or the like. Light enters from above the figure.
【００１０】次に、本発明の実施形態の一例を図２に基
づいて説明する。図２において１ａ、１ｂ、１ｃはガラ
ス等の透明基板、２ａ、２ｂ、２ｃはＩＴＯ、Ｓｎ
Ｏ2：Ｆ、ＺｎＯ：Ａｌ等からなる透明導電膜、３ａ、
３ｂは多孔質金属酸化物半導体層、４ａ、４ｂはルテニ
ウムビピリジル錯体、亜鉛ポルフィリン、銅フタロシア
ニン、クロロフィル、ローズベンガル、エオシン等の色
素、５ａ、５ｂはＩ-／Ｉ3 -、Ｂｒ-／Ｂｒ3 -等の酸化還
元対を有する電解液、６ｂ、６ｃはＰｔ等からなる対向
電極である。光は図の上方から入射する。Next, an embodiment of the present invention will be described with reference to FIG. In FIG. 2, reference numerals 1a, 1b, and 1c denote transparent substrates such as glass, and reference numerals 2a, 2b, and 2c denote ITO and Sn.
O 2 : F, a transparent conductive film made of ZnO: Al or the like, 3a,
3b is a porous metal oxide semiconductor layer, 4a and 4b are dyes such as ruthenium bipyridyl complex, zinc porphyrin, copper phthalocyanine, chlorophyll, rose bengal, and eosin; 5a and 5b are I − / I 3 − and Br − / Br 3 - electrolyte having a redox pair, such as, 6b, 6c is a counter electrode made of Pt or the like. Light enters from above the figure.
【００１１】本構成例は従来のセル構成を二つ重ね、な
おかつ上下のセルの電気的導通をとり、２ａ、２ｃを電
流を取り出す電極とする１つの積層セルとなっている。
したがって本素子構成において得られる光起電力は従来
の素子構成の約２倍となる。また、入射した光が増感色
素４ａで吸収されず、透過する光についても、下部の増
感色素４ｂにおいて吸収されるため、発生電流も従来に
比べて増大し、光電変換効率も向上する。なお、４ａ及
び４ｂの色素は同じものを使用してもよいし、それぞれ
別の色素を使用することもできる。特に、それぞれの吸
収波長領域が異なる色素を使用する場合、上部の増感色
素４ａで吸収できなかった光を下部の増感色素４ｂで吸
収できるので、入射光を有効に利用することが出来る。
具体的には、ルテニウムビピリジル錯体とフタロシアニ
ンあるいはクロロフィルの組み合わせ等が有効である。This configuration example is a stacked cell in which two conventional cell configurations are stacked, and the upper and lower cells are electrically connected, and 2a and 2c are used as electrodes for extracting current.
Therefore, the photovoltaic power obtained in this element configuration is about twice that of the conventional element configuration. Further, the incident light is not absorbed by the sensitizing dye 4a, and the transmitted light is also absorbed by the lower sensitizing dye 4b, so that the generated current is increased as compared with the conventional case, and the photoelectric conversion efficiency is improved. The same dye may be used as the dyes 4a and 4b, or different dyes may be used. In particular, when dyes having different absorption wavelength regions are used, light that could not be absorbed by the upper sensitizing dye 4a can be absorbed by the lower sensitizing dye 4b, so that incident light can be used effectively.
Specifically, a combination of a ruthenium bipyridyl complex with phthalocyanine or chlorophyll is effective.
【００１２】また、本発明の別の実施形態の一例を図３
に基づいて以下に説明する。１ａ、１ｂ、１ｃはガラス
等の透明基板、２ａ、２ｂ、２ｂ’、２ｃはＩＴＯ、Ｓ
ｎＯ2：Ｆ、ＺｎＯ：Ａｌ等からなる透明導電膜、３
ｂ、３ｂ’は多孔質金属酸化物半導体層、４ｂ、４ｂ’
はルテニウムビピリジル錯体、亜鉛ポルフィリン、銅フ
タロシアニン、クロロフィル、ローズベンガル、エオシ
ン等の色素、５ａ、５ｂはＩ-／Ｉ3 -、Ｂｒ-／Ｂｒ3 -等
の酸化還元対を有する電解液、６ａ、６ｃはＰｔ等から
なる対向電極である。光は図の上方から入射する。An example of another embodiment of the present invention is shown in FIG.
This will be described below based on 1a, 1b, 1c are transparent substrates such as glass, 2a, 2b, 2b ', 2c are ITO, S
a transparent conductive film made of nO 2 : F, ZnO: Al or the like;
b, 3b 'are porous metal oxide semiconductor layers, 4b, 4b'
Are dyes such as ruthenium bipyridyl complex, zinc porphyrin, copper phthalocyanine, chlorophyll, rose bengal, and eosin; 5a and 5b are electrolyte solutions having a redox couple such as I − / I 3 − and Br − / Br 3 − ; 6c is a counter electrode made of Pt or the like. Light enters from above the figure.
【００１３】本構成例は図２に示す構成に対して二つの
透明導電膜２ａ、２ｂ間の構成順序が逆転したものであ
り、なおかつ透明導電膜２ａと２ｂ’の間の電気的導通
をとり、２ｂ、２ｃを電流を取り出す電極とする１つの
素子となっている。したがって本素子構成において得ら
れる光起電力は従来の素子構成の約２倍となる。また、
入射した光が増感色素４ｂで吸収されず、透過する光に
ついても、下部の増感色素４ｂ’において吸収されるた
め、発生電流も従来に比べて増大し、光電変換効率も向
上する。In this configuration example, the configuration order between the two transparent conductive films 2a and 2b is reversed with respect to the configuration shown in FIG. 2, and electrical conduction between the transparent conductive films 2a and 2b 'is established. , 2b, and 2c are one element that serves as an electrode for extracting a current. Therefore, the photovoltaic power obtained in this element configuration is about twice that of the conventional element configuration. Also,
The incident light is not absorbed by the sensitizing dye 4b, and the transmitted light is also absorbed by the lower sensitizing dye 4b ', so that the generated current is increased as compared with the related art, and the photoelectric conversion efficiency is also improved.
【００１４】また、本素子構成においては図２に示す構
成に比べて、その製造過程において上部基板１ａと下部
基板１ｃ、及びその上に形成する透明導電膜２ａ、２
ｃ、対極６ａ、６ｃは同一プロセスで製造可能であり、
また中央基板１ｂに形成する金属酸化物半導体層、及び
色素の吸着も表裏同一であるため、特に浸漬法などを利
用すれば容易に作製可能であるため、低コストで製造可
能な素子構成となる。Further, in this element configuration, as compared with the configuration shown in FIG. 2, the upper substrate 1a and the lower substrate 1c and the transparent conductive films 2a, 2
c, counter electrodes 6a and 6c can be manufactured by the same process,
The metal oxide semiconductor layer formed on the central substrate 1b and the adsorption of the dye are also the same on the front and back, so that the element can be easily manufactured particularly by using an immersion method or the like. .
【００１５】次に、上記太陽電池の製造方法の一例を図
３の構成について説明する。まず、ガラス基板１ａ、１
ｂ、１ｃ上にスパッタリング法、ＣＶＤ法、ゾルゲル法
等により例えばＳｎＯ2：Ｆ膜２を片面に形成したもの
を２枚、両面に形成したものを１枚用意する。Ｓｎ
Ｏ2：Ｆ膜は集電体として機能するためシート抵抗が５
０Ω／□以下、好ましくは１０Ω／□以下とするのが望
ましい。基体には、加熱焼成温度に耐えうるセラミック
ス、ガラス、耐熱性のプラスチックなどが適用できる。
特に半導体電極を作製する際には金属あるいはＩＴＯや
ＳｎＯ2等の透明電極が適用できる。これらの内、透明
導電膜を両面に形成したものについては前述の多孔質金
属酸化物半導体薄膜３ｂ、３ｂ’を形成した後、増感色
素、例えばルテニウムビピリジル錯体を吸着させる。金
属酸化物半導体層の膜厚は１〜２０μｍ程度が好まし
い。これは金属酸化物半導体層の膜厚を必要以上に厚く
しても得られる電流に限りがある一方で、光の透過率が
減少し、第２の金属酸化物半導体層に到達する光が減少
するからである。Next, an example of a method for manufacturing the above-mentioned solar cell will be described with reference to FIG. First, the glass substrates 1a, 1
For example, two pieces of SnO 2 : F film 2 formed on one side by sputtering method, CVD method, sol-gel method, etc. are prepared on b and 1c, and one piece formed on both sides is prepared. Sn
O 2 : F film has a sheet resistance of 5 because it functions as a current collector.
It is desirably 0 Ω / □ or less, preferably 10 Ω / □ or less. As the substrate, ceramics, glass, heat-resistant plastic, or the like that can withstand the heating and firing temperature can be used.
In particular, when manufacturing a semiconductor electrode, a metal or a transparent electrode such as ITO or SnO 2 can be applied. Among these, those having a transparent conductive film formed on both surfaces are formed by forming the above-described porous metal oxide semiconductor thin films 3b and 3b ', and then adsorbing a sensitizing dye such as a ruthenium bipyridyl complex. The thickness of the metal oxide semiconductor layer is preferably about 1 to 20 μm. This is because even if the thickness of the metal oxide semiconductor layer is unnecessarily large, the current that can be obtained is limited, but the light transmittance is reduced, and the light reaching the second metal oxide semiconductor layer is reduced. Because you do.
【００１６】基体に金属酸化物半導体層を形成する塗布
液を塗布するためには、例えば、ディッピング、スピン
コート、スプレー塗布等の公知の方法が利用できる。塗
布液には基体に対する成膜性を上げるために界面活性剤
を加えることができる。また、エチレングリコール等の
グリコール類や水溶性高分子などを添加して塗布液の粘
性を制御することもできる。In order to apply the coating solution for forming the metal oxide semiconductor layer to the substrate, a known method such as dipping, spin coating, spray coating and the like can be used. A surfactant can be added to the coating liquid in order to improve the film forming property on the substrate. The viscosity of the coating solution can be controlled by adding a glycol such as ethylene glycol or a water-soluble polymer.
【００１７】金属酸化物半導体層に色素を吸着させるに
は金属酸化物半導体電極を、水、アルコール、トルエン
等の溶媒に該色素を溶かした溶液中に浸漬すればよい。
色素の分子中にカルボキシル基、ヒドロキシル基、スル
ホン基等の官能基を有すると、金属酸化物表面に該色素
が化学的に固定されるため好ましい。代表的なものとし
て［ルテニウム（４，４’−ジカルボキシ−２，２’−
ビピリジン）2（イソチオシアナト）2］で表されるルテ
ニウム錯体がある。前記の片面にＳｎＯ2：Ｆ膜を形成
した基板上にはスパッタリング法、蒸着法、電気化学的
方法等により例えばＰｔ（微粒子）層６ａ、６ｃを形成
する。その膜厚は１〜５０ｎｍ程度が好ましい。The dye may be adsorbed on the metal oxide semiconductor layer by immersing the metal oxide semiconductor electrode in a solution in which the dye is dissolved in a solvent such as water, alcohol or toluene.
It is preferable to have a functional group such as a carboxyl group, a hydroxyl group or a sulfone group in the molecule of the dye because the dye is chemically fixed on the surface of the metal oxide. As a typical example, [ruthenium (4,4'-dicarboxy-2,2'-
Bipyridine) 2 (isothiocyanato) 2 ]. For example, Pt (fine particle) layers 6a and 6c are formed on the substrate having the SnO 2 : F film formed on one surface by a sputtering method, a vapor deposition method, an electrochemical method, or the like. The thickness is preferably about 1 to 50 nm.
【００１８】上記のように形成された３枚の基板をスペ
ーサーを介して重ね合わせた後、例えばＩ-／Ｉ3 -酸化
還元対を有する電解質溶液５を注入し、シール剤で封止
する。電解質溶液としてはエチレンカーボネートとアセ
トニトリルの混合溶媒にヨウ素とテトラプロピルアンモ
ニウムアイオダイドを加えたもの等が好適に使用でき
る。最後に透明導電膜２ａと２ｂ’の間の電気的導通を
とる。このようにして形成された素子には紫外線を吸収
する部材として、例えばＣｅＯ2等を含む鉛ガラス（市
販のＬ−４０、Ｌ−４２等のシャープカットフィルター
を用いてもよい）を光の入射側に貼り合わせてもよい。[0018] After the three substrates formed as described above superposed through a spacer, for example, I - / I 3 - is injected an electrolytic solution 5 having an oxidation-reduction pair is sealed by a sealing agent. As the electrolyte solution, a solution obtained by adding iodine and tetrapropylammonium iodide to a mixed solvent of ethylene carbonate and acetonitrile can be suitably used. Finally, electrical continuity is established between the transparent conductive films 2a and 2b '. For the element thus formed, a lead glass containing CeO 2 or the like (a commercially available sharp cut filter such as L-40 or L-42 may be used) is used as a member for absorbing ultraviolet light. It may be attached to the side.
【００１９】実施例１（図２の素子構成） ガラス基板３枚のうち、２枚については片面、１枚につ
いては両面にゾルゲル法によりＳｎＯ2：Ｆ膜２をシー
ト抵抗が１０Ω／□となるように形成した。両面に形成
した基板については表裏の導通をとった。このうち基板
１ｂ、１ｃについては真空蒸着法によりＰｔ膜を膜厚２
０ｎｍに堆積した。また、アナターゼ型酸化チタン粉末
（石原テクノ社製）３ｇに上記過酸化チタンゾル１０ｍ
ｌとアセチルアセトン０．２ｍｌを加え、乳鉢で酸化チ
タン粉末の凝集を解くようにして混合し、塗布液を調製
した。この塗布液を上記ガラス基板１ａ、１ｂ上に塗布
し、３０分間自然乾燥の後、４５０℃で３０分間加熱焼
成し膜厚約１０μｍの多孔質酸化チタン半導体電極を得
た。この多孔質酸化チタン半導体電極を［ルテニウム
（４，４’−ジカルボキシ−２，２’−ビピリジン）2
（イソチオシアナト）2］で表されるルテニウム錯体の
エタノール溶液中に浸漬し、１０分間還流してＴｉＯ2
電極表面にルテニウム錯体を吸着させた。これらの両基
板をビーズ又はロッド状の絶縁性スペーサーを介して、
約１０μｍの間隙を保って重ね合わせ、エチレンカーボ
ネートとアセトニトリルの混合溶媒にヨウ素とテトラプ
ロピルアンモニウムアイオダイドを加えた酸化還元電解
質溶液を注入した後、エポキシ系接着剤でシールし、光
電変換素子を作製した。この光電変換素子の疑似太陽光
照射下（ＡＭ１．５、１００ｍＷ／ｃｍ2）における光
電変換効率は７．５％であった。Example 1 (Element Configuration in FIG. 2) Of the three glass substrates, two of the substrates had a SnO 2 : F film 2 on one side and one had a sheet resistance of 10 Ω / □ on both sides by a sol-gel method. Formed as follows. With respect to the substrates formed on both sides, conduction between the front and back was taken. Of these, the substrates 1b and 1c were made to have a Pt film having a thickness of 2 by a vacuum evaporation method.
Deposited at 0 nm. In addition, 3 g of anatase type titanium oxide powder (manufactured by Ishihara Techno Co., Ltd.) was added to the above titanium peroxide sol 10 m.
and 0.2 ml of acetylacetone were added and mixed in a mortar to dissolve the aggregation of the titanium oxide powder to prepare a coating solution. This coating solution was applied onto the glass substrates 1a and 1b, air-dried for 30 minutes, and fired at 450 ° C. for 30 minutes to obtain a porous titanium oxide semiconductor electrode having a thickness of about 10 μm. This porous titanium oxide semiconductor electrode was treated with [ruthenium (4,4′-dicarboxy-2,2′-bipyridine) 2
Immersed in an ethanol solution of a ruthenium complex represented by (isothiocyanato) 2], TiO 2 was refluxed for 10 minutes
The ruthenium complex was adsorbed on the electrode surface. Via both of these substrates via beads or rod-shaped insulating spacers,
After superimposing with a gap of about 10 μm, a redox electrolyte solution obtained by adding iodine and tetrapropylammonium iodide to a mixed solvent of ethylene carbonate and acetonitrile was injected, and then sealed with an epoxy-based adhesive to produce a photoelectric conversion element. did. The photoelectric conversion efficiency of this photoelectric conversion element under simulated sunlight irradiation (AM 1.5, 100 mW / cm 2 ) was 7.5%.
【００２０】実施例２（図３の素子構成） ガラス基板３枚のうち、２枚については片面、１枚につ
いては両面にゾルゲル法によりＳｎＯ2：Ｆ膜２をシー
ト抵抗が１０Ω／□となるように形成した。このうち基
板１ａ、１ｃについては真空蒸着法によりＰｔ膜を膜厚
２０ｎｍに堆積した。また、アナターゼ型酸化チタン粉
末（石原テクノ社製）３ｇに上記過酸化チタンゾル１０
ｍｌとアセチルアセトン０・２ｍｌを加え、乳鉢で酸化
チタン粉末の凝集を解くようにして混合し、塗布液を調
製した。この塗布液を上記ガラス基板１ｂの両面に塗布
し、３０分間自然乾燥の後、４５０℃で３０分間加熱焼
成し、膜厚約１０μｍの多孔質酸化チタン半導体電極を
得た。この多孔質酸化チタン半導体電極を［ルテニウム
（４，４’−ジカルボキシ２，２’−ビピリジン）
2（イソチオシアナト）2］で表されるルテニウム錯体の
エタノール溶液中に浸漬し、１０分間還流してＴｉＯ2
電極表面にルテニウム錯体を吸着させた。これらの両基
板をビーズ又はロッド状の絶縁性スペーサーを介して、
約１０μｍの間隙を保って重ね合わせ、エチレンカーボ
ネートとアセトニトリルの混合溶媒にヨウ素とテトラプ
ロピルアンモニウムアイオダイドを加えた酸化還元電解
質溶液を注入した後、エポキシ系接着剤でシールし、光
電変換素子を作製した。この光電変換素子の疑似太陽光
照射下（ＡＭ１．５、１００ｍＷ／ｃｍ2）における光
電変換効率は７．８％であった。Example 2 (Element Configuration of FIG. 3) Of the three glass substrates, two of the substrates had a SnO 2 : F film 2 on one side and one had a sheet resistance of 10 Ω / □ on both sides by a sol-gel method. Formed as follows. Among these, a Pt film was deposited to a thickness of 20 nm on the substrates 1a and 1c by a vacuum evaporation method. In addition, 3 g of anatase type titanium oxide powder (manufactured by Ishihara Techno Co.) was added to the above titanium peroxide sol 10
Then, 0.2 ml of acetylacetone and 0.2 ml of acetylacetone were added and mixed in a mortar so as to disaggregate the titanium oxide powder to prepare a coating solution. This coating solution was applied to both surfaces of the glass substrate 1b, air-dried for 30 minutes, and baked at 450 ° C. for 30 minutes to obtain a porous titanium oxide semiconductor electrode having a thickness of about 10 μm. This porous titanium oxide semiconductor electrode was treated with [ruthenium (4,4'-dicarboxy2,2'-bipyridine)
2 was dipped in an ethanol solution of a ruthenium complex represented by (isothiocyanato) 2], TiO 2 was refluxed for 10 minutes
The ruthenium complex was adsorbed on the electrode surface. Via both of these substrates via beads or rod-shaped insulating spacers,
After superimposing with a gap of about 10 μm, a redox electrolyte solution obtained by adding iodine and tetrapropylammonium iodide to a mixed solvent of ethylene carbonate and acetonitrile was injected, and then sealed with an epoxy-based adhesive to produce a photoelectric conversion element. did. The photoelectric conversion efficiency of this photoelectric conversion element under simulated sunlight irradiation (AM 1.5, 100 mW / cm 2 ) was 7.8%.
【００２１】比較例１（図１の素子構成） ガラス基板２枚のそれぞれの片面にゾルゲル法によりＳ
ｎＯ2：Ｆ膜２をシート抵抗が１０Ω／□となるように
形成した。このうち１枚については真空蒸着法によりＰ
ｔ膜を膜厚２０ｎｍに堆積した。また、アナターゼ型酸
化チタン粉末（石原テクノ社製）３ｇに上記過酸化チタ
ンゾル１０ｍｌとアセチルアセトン０．２ｍｌを加え、
乳鉢で酸化チタン粉末の凝集を解くようにして混合し、
塗布液を調製した。この塗布液をもう一方の上記ガラス
基板上に塗布し３０分間自然乾燥の後、４５０℃で３０
分間加熱焼成し、膜厚約１０μｍの酸化チタン半導体電
極を得た。この多孔質酸化チタン半導体電極を［ルテニ
ウム（４，４’−ジカルボキシ−２，２’−ビピリジ
ン）2（イソチオシアナト）2］で表されるルテニウム錯
体のエタノール溶液中に浸漬し、１０分間還流してＴｉ
Ｏ2電極表面にルテニウム錯体を吸着させた。これらの
両基板をビーズ又はロッド状の絶縁性スペーサーを介し
て、約１０μｍの間隙を保って重ね合わせ、エチレンカ
ーボネートとアセトニトリルの混合溶媒にヨウ素とテト
ラプロピルアンモニウムアイオダイドを加えた酸化還元
電解質溶液を注入した後、エポキシ系接着剤でシール
し、光電変換素子を作製した。この光電変換素子の疑似
太陽光照射下（ＡＭ１．５、１００ｍＷ／ｃｍ2）にお
ける光電変換効率は６．９％であった。Comparative Example 1 (Element Configuration of FIG. 1) S
The nO 2 : F film 2 was formed such that the sheet resistance became 10Ω / □. One of them is P
A t film was deposited to a thickness of 20 nm. Further, to 3 g of anatase type titanium oxide powder (manufactured by Ishihara Techno Co., Ltd.), 10 ml of the above titanium peroxide sol and 0.2 ml of acetylacetone were added,
Mix in a mortar to dissolve the aggregation of titanium oxide powder,
A coating solution was prepared. This coating solution was applied on the other glass substrate and air-dried for 30 minutes.
The resultant was baked for about 10 minutes to obtain a titanium oxide semiconductor electrode having a thickness of about 10 μm. This porous titanium oxide semiconductor electrode is immersed in an ethanol solution of a ruthenium complex represented by [ruthenium (4,4'-dicarboxy-2,2'-bipyridine) 2 (isothiocyanato) 2 ] and refluxed for 10 minutes. Ti
The ruthenium complex was adsorbed on the O 2 electrode surface. These two substrates are overlapped via a bead or rod-shaped insulating spacer with a gap of about 10 μm, and a redox electrolyte solution obtained by adding iodine and tetrapropylammonium iodide to a mixed solvent of ethylene carbonate and acetonitrile is used. After the injection, the resultant was sealed with an epoxy adhesive to produce a photoelectric conversion element. The photoelectric conversion efficiency of this photoelectric conversion element under simulated sunlight irradiation (AM 1.5, 100 mW / cm 2 ) was 6.9%.
【００２２】[0022]
【発明の効果】請求項１の発明によれば、金属酸化物半
導体電極とその表面に吸着した色素と酸化還元対を有す
る電解液と対向電極とからなる光電変換素子ユニットを
複数重ねることにより素子を構成したので、光の吸収量
が増え、光電変換効率が向上する。請求項２の発明によ
れば、透明基板の両面に透明導電膜および表面に色素を
吸着した金属酸化物半導体層を形成する構成にすること
により、単に二つの光電変換素子ユニットを重ね合わせ
る場合に比べ、基板枚数を一枚減らすことができるの
で、薄型、軽量化できる。請求項３の発明によれば、一
つの金属酸化物半導体層の膜厚を２０μｍ以下にするこ
とにより、複数の色素吸着した金属酸化半導体電極層の
光吸収のバランスが良くなるので、光電変換効率がより
一層向上する。請求項４の発明によれば、複数ユニット
の金属酸化物半導体電極と対極が電気的にそれぞれ直列
に接続されているため、低コストで製造可能な素子構成
となる。According to the first aspect of the present invention, an element is formed by stacking a plurality of photoelectric conversion element units each including a metal oxide semiconductor electrode, a dye adsorbed on the surface thereof, an electrolyte having a redox pair, and a counter electrode. , The amount of light absorption increases, and the photoelectric conversion efficiency improves. According to the second aspect of the present invention, a transparent conductive film is formed on both surfaces of a transparent substrate and a metal oxide semiconductor layer having a dye adsorbed on the surface thereof is formed. In comparison, the number of substrates can be reduced by one, so that the thickness and weight can be reduced. According to the third aspect of the invention, by setting the thickness of one metal oxide semiconductor layer to 20 μm or less, the light absorption balance of the plurality of dye-adsorbed metal oxide semiconductor electrode layers is improved, so that the photoelectric conversion efficiency is improved. Is further improved. According to the invention of claim 4, since the metal oxide semiconductor electrode and the counter electrode of the plurality of units are electrically connected in series, respectively, the element configuration can be manufactured at low cost.
【図１】従来の光電変換素子の一例を模式的に示す断面
図である。FIG. 1 is a cross-sectional view schematically illustrating an example of a conventional photoelectric conversion element.
【図２】本発明による光電変換素子の一例を模式的に示
す断面図である。FIG. 2 is a cross-sectional view schematically showing one example of a photoelectric conversion element according to the present invention.
【図３】本発明による光電変換素子の別の一例を模式的
に示す断面図である。FIG. 3 is a cross-sectional view schematically showing another example of the photoelectric conversion element according to the present invention.
１ａ、１ｂ、１ｃ 透明基板 ２ａ、２ｂ、２ｂ’、２ｃ 透明導電膜 ３ａ、３ｂ、３ｂ’ 金属酸化物半導体層 ４ａ、４ｂ、４ｂ’ 増感色素 ５ 酸化還元対を有する電解液 ６ａ、６ｂ、６ｃ 対向電極 1a, 1b, 1c Transparent substrate 2a, 2b, 2b ', 2c Transparent conductive film 3a, 3b, 3b' Metal oxide semiconductor layer 4a, 4b, 4b 'Sensitizing dye 5 Electrolyte solution having redox couple 6a, 6b, 6c Counter electrode
Claims (4)
した色素と酸化還元対を有する電解液と対向電極とから
なる光電変換ユニットを複数重ね合わせた構造を有する
ことを特徴とする光電変換素子。1. A photoelectric conversion element having a structure in which a plurality of photoelectric conversion units each comprising a metal oxide semiconductor electrode, a dye adsorbed on the surface thereof, an electrolyte having a redox pair, and a counter electrode are superposed. .
の両面に形成されており、それぞれの電極面に対して対
向電極が配置されていることを特徴とする請求項１に記
載の光電変換素子。2. The photoelectric device according to claim 1, wherein metal oxide semiconductor electrodes are formed on both surfaces of one transparent substrate, and opposing electrodes are arranged on respective electrode surfaces. Conversion element.
μｍ以下であることを特徴とする請求項１又は２に記載
の光電変換素子。3. The film thickness of one metal oxide semiconductor layer is 20.
The photoelectric conversion device according to claim 1, wherein the size is not more than μm.
続されていることを特徴とする請求項１〜３のいずれか
に記載の光電変換素子。4. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion units are electrically connected in series.
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| JP12454699A JP4155431B2 (en) | 1999-04-30 | 1999-04-30 | Photoelectric conversion element |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12454699A JP4155431B2 (en) | 1999-04-30 | 1999-04-30 | Photoelectric conversion element |
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| Publication Number | Publication Date |
|---|---|
| JP2000315530A true JP2000315530A (en) | 2000-11-14 |
| JP4155431B2 JP4155431B2 (en) | 2008-09-24 |
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ID=14888162
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002075479A (en) * | 2000-09-05 | 2002-03-15 | Hiroshi Komiyama | Pigment sensitized solar cell |
| JP2005191137A (en) * | 2003-12-24 | 2005-07-14 | Kyocera Corp | Stacked photoelectric converter |
| JP2006244954A (en) * | 2005-03-07 | 2006-09-14 | Fujimori Kogyo Co Ltd | Wiring connection structure of dye-sensitized solar battery cell and dye-sensitized solar cell module |
| JP2007172917A (en) * | 2005-12-20 | 2007-07-05 | Fujikura Ltd | Photoelectric transducer |
| WO2009105743A2 (en) * | 2008-02-21 | 2009-08-27 | Sunlight Photonics Inc. | Method and appartus for manufacturing multi-layered electro-optic devices |
| US8187906B2 (en) | 2008-02-28 | 2012-05-29 | Sunlight Photonics Inc. | Method for fabricating composite substances for thin film electro-optical devices |
| RU2545352C1 (en) * | 2013-12-17 | 2015-03-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" | Photoconverter element |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11273753A (en) * | 1998-03-25 | 1999-10-08 | Sekisui Chem Co Ltd | Coloring matter sensitizing type photocell |
| JP2000090989A (en) * | 1998-09-16 | 2000-03-31 | Toshiba Corp | Coloring matter sensitized photochemical cell |
| JP2000200627A (en) * | 1999-01-06 | 2000-07-18 | Nikon Corp | Pigment sensitized solar battery and its manufacture |
-
1999
- 1999-04-30 JP JP12454699A patent/JP4155431B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11273753A (en) * | 1998-03-25 | 1999-10-08 | Sekisui Chem Co Ltd | Coloring matter sensitizing type photocell |
| JP2000090989A (en) * | 1998-09-16 | 2000-03-31 | Toshiba Corp | Coloring matter sensitized photochemical cell |
| JP2000200627A (en) * | 1999-01-06 | 2000-07-18 | Nikon Corp | Pigment sensitized solar battery and its manufacture |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002075479A (en) * | 2000-09-05 | 2002-03-15 | Hiroshi Komiyama | Pigment sensitized solar cell |
| JP2005191137A (en) * | 2003-12-24 | 2005-07-14 | Kyocera Corp | Stacked photoelectric converter |
| JP2006244954A (en) * | 2005-03-07 | 2006-09-14 | Fujimori Kogyo Co Ltd | Wiring connection structure of dye-sensitized solar battery cell and dye-sensitized solar cell module |
| JP2007172917A (en) * | 2005-12-20 | 2007-07-05 | Fujikura Ltd | Photoelectric transducer |
| WO2009105743A2 (en) * | 2008-02-21 | 2009-08-27 | Sunlight Photonics Inc. | Method and appartus for manufacturing multi-layered electro-optic devices |
| WO2009105743A3 (en) * | 2008-02-21 | 2009-12-03 | Sunlight Photonics Inc. | Method and appartus for manufacturing multi-layered electro-optic devices |
| US8343794B2 (en) | 2008-02-21 | 2013-01-01 | Sunlight Photonics Inc. | Method and apparatus for manufacturing multi-layered electro-optic devices |
| US8187906B2 (en) | 2008-02-28 | 2012-05-29 | Sunlight Photonics Inc. | Method for fabricating composite substances for thin film electro-optical devices |
| RU2545352C1 (en) * | 2013-12-17 | 2015-03-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" | Photoconverter element |
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|---|---|
| JP4155431B2 (en) | 2008-09-24 |
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