JP2008257895A - Manufacturing method of dye-sensitized solar cell, and dye-sensitized solar cell - Google Patents

Manufacturing method of dye-sensitized solar cell, and dye-sensitized solar cell Download PDF

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JP2008257895A
JP2008257895A JP2007095809A JP2007095809A JP2008257895A JP 2008257895 A JP2008257895 A JP 2008257895A JP 2007095809 A JP2007095809 A JP 2007095809A JP 2007095809 A JP2007095809 A JP 2007095809A JP 2008257895 A JP2008257895 A JP 2008257895A
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dye
sensitized
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solar cell
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Eiji Suzuki
栄二 鈴木
Shogo Mori
正吾 森
Hisanao Usami
久尚 宇佐美
Nobuhiro Yada
修丈 矢田
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Shinshu University NUC
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/542—Dye sensitized solar cells
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a dye-sensitized solar cell capable of reducing cost and improving characteristics. <P>SOLUTION: The dye-sensitized solar cell 1 is a tandem type dye-sensitized solar cell having a first electrode pair with a dye-sensitized semiconductor layer 12 and an electrolyte layer 13 between, and a second electrode pair with a dye-sensitized semiconductor layer 24 and an electrolyte layer 23 between. In the dye-sensitized solar cell 1, a translucent electrode layer 11, the dye-sensitized semiconductor layer 12, the electrolyte layer 13, a current collecting layer 19, a translucent electrode layer 25, the dye-sensitized semiconductor layer 24, the second electrolyte layer 23, and a counter electrode layer 21 are arranged in this order. The translucent electrode layer 25 constitutes the first electrode pair with the translucent electrode layer 11 and the second electrode pair with the counter electrode layer 21. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、色素増感を利用した色素増感太陽電池に関するものである。   The present invention relates to a dye-sensitized solar cell using dye sensitization.

色素増感太陽電池は、図５(ａ)に示すように、透光性電極層２５、色素増感半導体層２４、電解質層２３、および対極層２１がこの順に配置された構造を備えており、透光性電極層２５としては、例えば、ガラス基板などからなるアノード基板１１０の表面に成膜されたＩＴＯ(Indium Tin Oxide)やＳｎＯ2：Ｆ(ＦＴＯ層／フッ素ドープ酸化錫)などが用いられる。また、対極層２１としては、例えば、カソード基板２１０の表面に透光性導電膜２１１と金属膜２１２とを積層したものなどを用いることができる(例えば、特許文献１参照)。 As shown in FIG. 5A, the dye-sensitized solar cell has a structure in which a translucent electrode layer 25, a dye-sensitized semiconductor layer 24, an electrolyte layer 23, and a counter electrode layer 21 are arranged in this order. As the translucent electrode layer 25, for example, ITO (Indium Tin Oxide) or SnO 2 : F (FTO layer / fluorine-doped tin oxide) formed on the surface of the anode substrate 110 made of a glass substrate or the like is used. It is done. Further, as the counter electrode layer 21, for example, a layer in which a light-transmitting conductive film 211 and a metal film 212 are stacked on the surface of the cathode substrate 210 can be used (for example, see Patent Document 1).

また、色素増感太陽電池としては、透光性電極層２５、色素増感半導体層２４、電解質層２３、および対極層２１がこの順に配置された２つのセル５０を積層したタンデム型のものが提案されており、かかるタンデム型の色素増感太陽電池では、色素増感半導体層２４および電解質層２３を間に備えた第１電極対と、色素増感半導体層２４および電解質層２３を間に備えた第２電極対とを積層した構造を有している。従って、タンデム型の色素増感太陽電池では、２つのセルの各色素増感半導体層２４において異なる波長領域に感応する色素を用いれば、２つのセルの双方での光電効果を利用できるので、高い開放電圧を得ることができるという利点がある。
特開２００３−３０８８９２号公報 Moreover, as a dye-sensitized solar cell, the tandem type | mold which laminated | stacked the two cells 50 by which the translucent electrode layer 25, the dye-sensitized semiconductor layer 24, the electrolyte layer 23, and the counter electrode layer 21 were arrange | positioned in this order. In such a tandem type dye-sensitized solar cell, a first electrode pair having the dye-sensitized semiconductor layer 24 and the electrolyte layer 23 therebetween, and the dye-sensitized semiconductor layer 24 and the electrolyte layer 23 interposed therebetween are proposed. It has the structure which laminated | stacked the provided 2nd electrode pair. Therefore, in the tandem dye-sensitized solar cell, if the dyes sensitive to different wavelength regions are used in the dye-sensitized semiconductor layers 24 of the two cells, the photoelectric effect in both the two cells can be used, which is high. There is an advantage that an open circuit voltage can be obtained.
JP 2003-308892 A

しかしながら、色素増感太陽電池は、従来、セルが１つのもの、２つのもののいずれにおいても、図５(ｂ)を参照して説明する工程により製造するため、生産性が低く、コストが高いという問題点がある。すなわち、従来の色素増感太陽電池を製造する場合には、図５(ｂ)に示すように、カソード基板２１０の表面に透光性導電膜２１１および薄い金属膜２１２を積層してカソード電極体５２を形成する一方、アノード基板１１０の表面に透光性導電膜２５、色素増感半導体層２４および電解質層２３を積層してアノード電極体５１を形成し、しかる後に、カソード電極体５２とアノード電極体５１とを接合する必要があるため、製造工程数が多いという問題点がある。また、タンデム型の色素増感太陽電池を製造する場合には、２つのカソード電極体５２と、２つのアノード電極体５１を交互に接合する必要があるため、製造工程数が多いという問題点がある。   However, since the dye-sensitized solar cell is conventionally manufactured by the process described with reference to FIG. 5 (b) for both one and two cells, the productivity is low and the cost is high. There is a problem. That is, when a conventional dye-sensitized solar cell is manufactured, as shown in FIG. 5B, a light-transmitting conductive film 211 and a thin metal film 212 are laminated on the surface of the cathode substrate 210 to form a cathode electrode body. 52 is formed, and the anode electrode body 51 is formed by laminating the translucent conductive film 25, the dye-sensitized semiconductor layer 24, and the electrolyte layer 23 on the surface of the anode substrate 110. After that, the cathode electrode body 52 and the anode are formed. Since it is necessary to join the electrode body 51, there exists a problem that there are many manufacturing processes. Further, when manufacturing a tandem type dye-sensitized solar cell, since it is necessary to join two cathode electrode bodies 52 and two anode electrode bodies 51 alternately, there is a problem that the number of manufacturing processes is large. is there.

また、従来の製造方法によってタンデム型の色素増感太陽電池を製造すると、低コスト化および薄型化が困難であるとともに、十分な特性を得ることができないという問題点がある。すなわち、図５(ａ)、(ｂ)から分かるように、タンデム型の色素増感太陽電池では、２枚のアノード基板および２枚のカソード基板の計４枚の基板を積層するため、厚さ寸法が、例えば１．０ｍｍ以上と厚く、かつ、基板代が嵩むという問題点がある。また、４枚の基板の各々に透光性電極層を形成する必要があるため、その点でも製造コストが嵩むという問題点がある。さらに、従来のタンデム型の色素増感太陽電池では、２つの色素増感半導体層のうち、光の入射側とは反対側に位置する色素増感半導体層に光が届くには、計３枚の基板および計３層分の透光性電極層を光が透過する必要があり、その間の光損失が大きい。また、従来のタンデム型の色素増感太陽電池において、セル内での電子の移動経路を辿ると、透光性電極層の中央側から外周側に電子が移動した後、別の透光性電極層では外周側から中央に電子が移動する必要があり、電子の移動経路が例えば５〜１０ｃｍと長い分、内部抵抗が大きいという問題点がある。   In addition, when a tandem dye-sensitized solar cell is manufactured by a conventional manufacturing method, there are problems in that it is difficult to reduce the cost and thickness, and sufficient characteristics cannot be obtained. That is, as can be seen from FIGS. 5 (a) and 5 (b), in the tandem dye-sensitized solar cell, a total of four substrates, two anode substrates and two cathode substrates, are laminated. For example, the size is as thick as 1.0 mm or more, and the substrate cost increases. Moreover, since it is necessary to form a translucent electrode layer on each of the four substrates, there is also a problem that the manufacturing cost increases. Further, in the conventional tandem type dye-sensitized solar cell, in order for light to reach the dye-sensitized semiconductor layer located on the opposite side to the light incident side of the two dye-sensitized semiconductor layers, a total of three sheets It is necessary to transmit light through the substrate and a total of three light-transmitting electrode layers, and the light loss therebetween is large. Further, in the conventional tandem dye-sensitized solar cell, when the electron movement path in the cell is traced, the electron moves from the center side to the outer peripheral side of the translucent electrode layer, and then another translucent electrode. In the layer, electrons need to move from the outer peripheral side to the center, and there is a problem that the internal resistance is large because the electron movement path is as long as 5 to 10 cm, for example.

以上の問題点に鑑みて、本発明の課題は、コストの低減を図ることができる色素増感太陽電池の製造方法、および色素増感太陽電池を提供することにある。   In view of the above problems, an object of the present invention is to provide a method for producing a dye-sensitized solar cell and a dye-sensitized solar cell capable of reducing cost.

次に、本発明の課題は、コストの低減を図ることができるとともに、特性の向上を図ることのできる色素増感太陽電池の製造方法、および色素増感太陽電池を提供することにある。   Next, the subject of this invention is providing the manufacturing method of a dye-sensitized solar cell which can aim at reduction of cost, and can aim at the improvement of a characteristic, and a dye-sensitized solar cell.

上記課題を解決するために、本発明では、透光性電極層、色素増感半導体層、電解質層、および対極層がこの順に配置された色素増感太陽電池の製造方法において、少なくとも、前記透光性電極層、前記色素増感半導体層を形成するための半導体層、前記電解質層を形成するための層、および前記対極層をこの順序あるいは逆の順序で積層していくことを特徴とする。   In order to solve the above problems, in the present invention, in the method for producing a dye-sensitized solar cell in which a translucent electrode layer, a dye-sensitized semiconductor layer, an electrolyte layer, and a counter electrode layer are arranged in this order, A photoelectrode layer, a semiconductor layer for forming the dye-sensitized semiconductor layer, a layer for forming the electrolyte layer, and the counter electrode layer are laminated in this order or reverse order. .

本発明においては、例えば、少なくとも、前記対極層の上層側に前記電解質層を形成するための層を形成する電解質層形成工程と、当該電解質層を形成するための層の上層側に前記色素増感半導体層を形成するための半導体層を形成する半導体層形成工程と、前記半導体層の上層側に前記透光性電極層を積層する透光性電極層形成工程と、をこの順序で行う。   In the present invention, for example, at least an electrolyte layer forming step of forming a layer for forming the electrolyte layer on the upper side of the counter electrode layer, and the dye enhancement on the upper side of the layer for forming the electrolyte layer. A semiconductor layer forming step for forming a semiconductor layer for forming a sensitive semiconductor layer and a translucent electrode layer forming step for laminating the translucent electrode layer on the upper side of the semiconductor layer are performed in this order.

本発明では、色素増感太陽電池に用いるセル構造体を形成する際、少なくとも、前記透光性電極層、前記色素増感半導体層を形成するための半導体層、前記電解質層を形成するための層、および前記対極層をこの順序あるいは逆の順序で積層するため、カソード電極体とアノード電極体とを別々に形成した後に接合するという工程を行う必要がない。従って、製造工程を連続的に行うことができるので、生産性を向上することができ、コストの低減を図ることができる。   In the present invention, when forming a cell structure used for a dye-sensitized solar cell, at least the translucent electrode layer, the semiconductor layer for forming the dye-sensitized semiconductor layer, and the electrolyte layer are formed. Since the layers and the counter electrode layer are laminated in this order or in the reverse order, there is no need to perform a step of joining after forming the cathode electrode body and the anode electrode body separately. Therefore, since the manufacturing process can be performed continuously, productivity can be improved and cost can be reduced.

本発明においては、少なくとも、前記電解質層形成工程、前記半導体層形成工程、および前記透光性電極層形成工程を行った後、前記半導体層に対して色素を保持させることが好ましい。このように構成すると、半導体層に対して色素を保持させた後、透光性電極層形成工程を行う場合と比較して、透光性電極層を形成する際、半導体層から色素が脱離するなどの問題を回避することができる。   In this invention, it is preferable to hold | maintain a pigment | dye with respect to the said semiconductor layer after performing the said electrolyte layer formation process, the said semiconductor layer formation process, and the said translucent electrode layer formation process at least. With this configuration, the dye is detached from the semiconductor layer when the light-transmitting electrode layer is formed as compared with the case where the light-transmitting electrode layer forming step is performed after the dye is held on the semiconductor layer. It is possible to avoid problems such as

本発明において、前記電解質層形成工程では、例えば、電解液を保持する多孔性絶縁層を形成し、少なくとも、前記電解質層形成工程、前記半導体層形成工程、および前記透光性電極層形成工程を行った後、前記多孔性絶縁層に前記電解液を保持させる構成を採用することができる。このように構成すると、前記半導体層形成工程および前記透光性電極層形成工程を安定して行うことができる。   In the present invention, in the electrolyte layer forming step, for example, a porous insulating layer that holds an electrolytic solution is formed, and at least the electrolyte layer forming step, the semiconductor layer forming step, and the translucent electrode layer forming step are performed. After performing, the structure which hold | maintains the said electrolyte solution in the said porous insulating layer is employable. If comprised in this way, the said semiconductor layer formation process and the said translucent electrode layer formation process can be performed stably.

本発明において、色素増感太陽電池をタンデム構造とする場合、前記透光性電極層、前記色素増感半導体層、前記電解質層、および前記対極層がこの順に配置された第１セル構造体(ボトムセル)に対して、透光性電極層に色素増感半導体層および電解質層が積層された第２セル構造体(トップセル)を、前記第１セル構造体の前記透光性電極層側に接合することを特徴とする。このように構成すると、必要最小限の接合工程でタンデム型の色素増感太陽電池を製造できるので、生産性を向上することができ、コストの低減を図ることができる。   In the present invention, when the dye-sensitized solar cell has a tandem structure, the first cell structure in which the translucent electrode layer, the dye-sensitized semiconductor layer, the electrolyte layer, and the counter electrode layer are arranged in this order ( The second cell structure (top cell) in which the dye-sensitized semiconductor layer and the electrolyte layer are laminated on the light-transmitting electrode layer is disposed on the light-transmitting electrode layer side of the first cell structure. It is characterized by joining. With such a configuration, a tandem dye-sensitized solar cell can be manufactured with a minimum necessary joining step, so that productivity can be improved and cost can be reduced.

本発明に係る方法で製造した場合、透光性電極層、色素増感半導体層、電解質層、対極層がこの順に配置された色素増感太陽電池において、前記透光性電極層、前記色素増感半導体層を形成するための半導体層、前記電解質層を形成するための層、および前記対極層は、この順序あるいは逆の順序で積層されてなる構造を有している。   When produced by the method according to the present invention, in the dye-sensitized solar cell in which the translucent electrode layer, the dye-sensitized semiconductor layer, the electrolyte layer, and the counter electrode layer are arranged in this order, the translucent electrode layer and the dye-sensitized solar cell are arranged. The semiconductor layer for forming the sensitive semiconductor layer, the layer for forming the electrolyte layer, and the counter electrode layer have a structure in which they are stacked in this order or in the reverse order.

また、本発明では、第１色素増感半導体層および第１電解質層を間に備えた第１電極対と、第２色素増感半導体層および第２電解質層を間に備えた第２電極対とを有するタンデム型の色素増感太陽電池において、少なくとも、第１透光性電極層、前記第１色素増感半導体層、前記第１電解質層、第２透光性電極層、前記第２色素増感半導体層、前記第２電解質層、および対極層がこの順に配置され、前記第２透光性電極層は、前記第１透光性電極と前記第１電極対を構成しているとともに、前記対極層と前記第２電極対を構成していることを特徴とする。   In the present invention, the first electrode pair having the first dye-sensitized semiconductor layer and the first electrolyte layer in between, and the second electrode pair having the second dye-sensitized semiconductor layer and the second electrolyte layer in between. A tandem dye-sensitized solar cell having at least a first light-transmissive electrode layer, the first dye-sensitized semiconductor layer, the first electrolyte layer, a second light-transmissive electrode layer, and the second dye. A sensitized semiconductor layer, the second electrolyte layer, and a counter electrode layer are arranged in this order, and the second light transmissive electrode layer constitutes the first light transmissive electrode and the first electrode pair, The counter electrode layer and the second electrode pair are configured.

本発明に係るタンデム型の色素増感太陽電池において、前記第２透光性電極層は、前記第１透光性電極と前記第１電極対を構成しているとともに、前記対極層と前記第２電極対を構成しており、２つのセル(トップセルおよびボトムセル)の間で共通化されている。このため、２つのセルの間に基板がないので、少ない枚数の基板でタンデム型の色素増感太陽電池を構成することができる。また、透光性電極の形成回数が少なくてよい。それ故、コストを低減することができるとともに、タンデム型の色素増感太陽電池の薄型化を図ることができる。また、光の入射側とは反対側に位置する第２色素増感半導体層に光が届くまでに透過する基板の枚数や透光性電極層の層数が少ないので、その間の光損失が少ない。また、セル内での電子の移動経路は、カソードからアノードに向けて直進するものと見なすことができるので、電子の移動経路が短い分、内部抵抗が小さいという利点がある。   In the tandem dye-sensitized solar cell according to the present invention, the second translucent electrode layer constitutes the first translucent electrode and the first electrode pair, and the counter electrode layer and the first electrode A two-electrode pair is formed and shared between two cells (top cell and bottom cell). For this reason, since there is no substrate between two cells, a tandem dye-sensitized solar cell can be configured with a small number of substrates. Moreover, the number of times of forming the translucent electrode may be small. Therefore, the cost can be reduced and the tandem dye-sensitized solar cell can be thinned. In addition, since the number of substrates to be transmitted and the number of light-transmitting electrode layers are small before the light reaches the second dye-sensitized semiconductor layer located on the side opposite to the light incident side, light loss between them is small. . Further, since the electron movement path in the cell can be regarded as going straight from the cathode toward the anode, there is an advantage that the internal resistance is small because the electron movement path is short.

本発明の色素増感太陽電池の製造方法では、セル構造体を形成する際、少なくとも、前記透光性電極層、前記色素増感半導体層を形成するための半導体層、前記電解質層を形成するための層、および前記対極層をこの順序あるいは逆の順序で積層し、カソード電極体とアノード電極体とを別々に形成した後に接合するという方法を行わない、従って、製造工程を連続的に行うことができるので、生産性を向上することができ、コストの低減を図ることができる。   In the method for producing a dye-sensitized solar cell of the present invention, when forming a cell structure, at least the translucent electrode layer, the semiconductor layer for forming the dye-sensitized semiconductor layer, and the electrolyte layer are formed. And the counter electrode layer are laminated in this order or in the reverse order, and the cathode electrode body and the anode electrode body are separately formed and then joined, so that the manufacturing process is continuously performed. Therefore, productivity can be improved and cost can be reduced.

また、本発明のタンデム型の色素増感太陽電池では、第２透光性電極層が２つのセル(トップセルおよびボトムセル)の間で共通化されているため、２つのセルの間に基板がない。従って、少ない枚数の基板でタンデム型の色素増感太陽電池を構成することができるとともに、透光性電極の形成回数が少なくてよい。それ故、コストを低減することができるとともに、タンデム型の色素増感太陽電池の薄型化を図ることができる。また、光の入射側とは反対側に位置する第２色素増感半導体層に光が届くまでに透過する基板の枚数や透光性電極層の層数が少ないので、その間の光損失が少ない。また、セル内での電子の移動経路は、カソードからアノードに向けて直進するものと見なすことができるので、電子の移動経路が短い分、内部抵抗が小さいという利点がある。   In the tandem dye-sensitized solar cell of the present invention, the second light-transmitting electrode layer is shared between the two cells (the top cell and the bottom cell), so that the substrate is interposed between the two cells. Absent. Therefore, a tandem dye-sensitized solar cell can be formed with a small number of substrates, and the number of times of forming the translucent electrode may be small. Therefore, the cost can be reduced and the tandem dye-sensitized solar cell can be thinned. In addition, since the number of substrates to be transmitted and the number of light-transmitting electrode layers are small before the light reaches the second dye-sensitized semiconductor layer located on the side opposite to the light incident side, light loss between them is small. . Further, since the electron movement path in the cell can be regarded as going straight from the cathode toward the anode, there is an advantage that the internal resistance is small because the electron movement path is short.

図面を参照して、本発明の実施の形態を説明する。なお、以下に参照する図面においては、各層や各部材を図面上で認識可能な程度の大きさとするため、各層や各部材毎に縮尺を異ならしめてある。   Embodiments of the present invention will be described with reference to the drawings. In the drawings to be referred to below, the scales of the layers and members are different for each layer and each member so that each layer and each member can be recognized on the drawings.

［実施の形態１］
図１は、本発明の実施の形態１に係る色素増感太陽電池の基本構成を示す説明図である。図１において、本形態の色素増感太陽電池１は、透光性電極層２５、色素増感半導体層２４、電解質層２３、および対極層２１がこの順に配置されており、透光性電極層２５は、ＩＴＯやＦＴＯ層などにより構成されている。対極層２１は、ガラス基板や金属基板などのカソード基板２１０の表面に成膜されたＩＴＯやＦＴＯ層などの透光性導電膜２１１の表面に白金などの薄い金属膜２１２(集電層)が積層されたものが用いられている。電解質層２３は、例えば、シリコン酸化物粒子層などからなる多孔性絶縁層２３０(電解質層２３を形成するための層)に対して、Ｉ-／Ｉ3 -、Ｂｒ-／Ｂｒ3 -、Ｃｏ2+／Ｃｏ3+などの酸化還元対を備えた電解液が保持された構成などを有している。色素増感半導体層２４は、多孔性酸化物半導体層２４０(色素増感半導体層２４を形成するための層)に、ルテニウム有機錯体などの有機金属錯体系色素、メロシアニン系色素、フタロシアニン系色素、ポルフィリン系色素、シアニン系色素などの色素が保持された構成、例えば、多孔性の酸化チタン層や酸化亜鉛層にルテニウム有機錯体やメロシアニン系色素が保持された構成を備えており、本形態では、色素増感ｎ型半導体層が用いられている。 [Embodiment 1]
FIG. 1 is an explanatory diagram showing a basic configuration of a dye-sensitized solar cell according to Embodiment 1 of the present invention. In FIG. 1, the dye-sensitized solar cell 1 according to the present embodiment includes a light-transmitting electrode layer 25, a dye-sensitized semiconductor layer 24, an electrolyte layer 23, and a counter electrode layer 21 arranged in this order. Reference numeral 25 denotes an ITO or FTO layer. The counter electrode layer 21 has a thin metal film 212 (collecting layer) such as platinum on the surface of a light-transmitting conductive film 211 such as an ITO or FTO layer formed on the surface of a cathode substrate 210 such as a glass substrate or a metal substrate. Stacked ones are used. For example, the electrolyte layer 23 is made of I − / I 3 − , Br − / Br 3 − , Co to the porous insulating layer 230 (layer for forming the electrolyte layer 23) made of, for example, a silicon oxide particle layer. It has a configuration in which an electrolytic solution including a redox pair such as 2 + / Co 3+ is held. The dye-sensitized semiconductor layer 24 includes a porous oxide semiconductor layer 240 (layer for forming the dye-sensitized semiconductor layer 24), an organometallic complex dye such as a ruthenium organic complex, a merocyanine dye, a phthalocyanine dye, It has a structure in which a dye such as a porphyrin dye or a cyanine dye is held, for example, a structure in which a ruthenium organic complex or a merocyanine dye is held in a porous titanium oxide layer or a zinc oxide layer. A dye-sensitized n-type semiconductor layer is used.

このように構成した色素増感太陽電池１において、透光性電極層２５、色素増感半導体層２４を形成するための多孔性酸化物半導体層２４０(半導体層)、電解質層２３を形成するための多孔性絶縁層２３０、および対極層２１は、この順序あるいは逆の順序で積層してなる層である。   In the dye-sensitized solar cell 1 configured as described above, the transparent electrode layer 25, the porous oxide semiconductor layer 240 (semiconductor layer) for forming the dye-sensitized semiconductor layer 24, and the electrolyte layer 23 are formed. The porous insulating layer 230 and the counter electrode layer 21 are layers laminated in this order or in the reverse order.

すなわち、本形態では、色素増感太陽電池１を製造する際、カソード基板２１０に対して、塗布法、ゾル−ゲル法、スパッタ法、ＣＶＤ法、蒸着法などにより、透光性導電膜２１１、および白金などの薄い金属膜２１２を積層して対極層２１を形成した後、まず、電解質層形成工程において、対極層２１の上に多孔性絶縁層２３０を分散液やコロイド液を用いた塗布法、ゾル−ゲル法、スパッタ法、ＣＶＤ法などにより積層する。   That is, in this embodiment, when the dye-sensitized solar cell 1 is manufactured, the translucent conductive film 211 is applied to the cathode substrate 210 by a coating method, a sol-gel method, a sputtering method, a CVD method, a vapor deposition method, or the like. After forming the counter electrode layer 21 by laminating a thin metal film 212 such as platinum and the like, first, in the electrolyte layer forming step, the porous insulating layer 230 is coated on the counter electrode layer 21 using a dispersion liquid or a colloid liquid. Lamination is performed by a sol-gel method, a sputtering method, a CVD method, or the like.

次に、半導体層形成工程において、多孔性絶縁層２３０(電解質層２３)の上層側に、色素増感半導体層２４を形成するための多孔性酸化物半導体層２４０を分散液やコロイド液を用いた塗布法、ゾル−ゲル法、スパッタ法、ＣＶＤ法などにより形成する。   Next, in the semiconductor layer forming step, the porous oxide semiconductor layer 240 for forming the dye-sensitized semiconductor layer 24 is formed on the upper side of the porous insulating layer 230 (electrolyte layer 23) using a dispersion liquid or a colloid liquid. It is formed by the conventional coating method, sol-gel method, sputtering method, CVD method or the like.

次に、透光性電極層形成工程において、多孔性酸化物半導体層２４０の上層側に透光性電極層２５を分散液やコロイド液を用いた塗布法、ゾル−ゲル法、スパッタ法、ＣＶＤ法などにより積層する。   Next, in the translucent electrode layer forming step, the translucent electrode layer 25 is applied to the upper layer side of the porous oxide semiconductor layer 240 by a coating method using a dispersion or a colloidal solution, a sol-gel method, a sputtering method, a CVD method. Laminate by the method.

しかる後には、多孔性酸化物半導体層２４０に色素を保持させて色素増感半導体層２４を形成するとともに、多孔性絶縁層２３０に電解液を含浸して電解質層２３を形成する。   Thereafter, the dye is sensitized on the porous oxide semiconductor layer 240 to form the dye-sensitized semiconductor layer 24, and the electrolyte layer 23 is formed by impregnating the porous insulating layer 230 with the electrolytic solution.

このように、本形態では、色素増感太陽電池１を製造する際、少なくとも、対極層２１、電解質層２３を形成するための多孔性絶縁層２３０、色素増感半導体層２４を形成するための多孔性酸化物半導体層２４０、および透光性電極層２５をこの順序で積層するため、カソード電極体とアノード電極体とを別々に形成した後に接合するという工程を行う必要がない。従って、本形態によれば、製造工程を連続的に行うことができるので、色素増感太陽電池１の生産性を向上することができ、コストの低減を図ることができる。   As described above, in this embodiment, when the dye-sensitized solar cell 1 is manufactured, at least the counter electrode layer 21, the porous insulating layer 230 for forming the electrolyte layer 23, and the dye-sensitized semiconductor layer 24 are formed. Since the porous oxide semiconductor layer 240 and the translucent electrode layer 25 are laminated in this order, it is not necessary to perform a step of joining after forming the cathode electrode body and the anode electrode body separately. Therefore, according to this embodiment, since the manufacturing process can be performed continuously, the productivity of the dye-sensitized solar cell 1 can be improved and the cost can be reduced.

［実施の形態１の具体的構成例１］
図２(ａ)は、本発明の実施の形態１の具体的構成例１に係る色素増感太陽電池１の概略構成を示す説明図である。 [Specific Configuration Example 1 of Embodiment 1]
FIG. 2A is an explanatory diagram showing a schematic configuration of the dye-sensitized solar cell 1 according to the specific configuration example 1 of the first embodiment of the present invention.

図２(ａ)において、本形態の色素増感太陽電池１は、実施の形態１と同様、透光性電極層２５、色素増感半導体層２４、電解質層２３、および対極層２１がこの順に配置されており、透光性電極層２５は、ＦＴＯ層などにより構成されている。対極層２１は、銅、アルミニウム、銀、ニッケル、コバルト、鉄、チタン、ステンレス等の金属基板自身によって構成されている。電解質層２３は、多孔性絶縁層２３０に対して、ヨウ素イオンなどを含む電解液が保持された構成などを有している。色素増感半導体層２４は、多孔性の酸化チタン層や酸化亜鉛層などの多孔性酸化物半導体層２４０にルテニウム有機錯体やメロシアニン系色素などの色素が保持された構成を備えており、本形態では、色素増感ｎ型半導体層が用いられている。   In FIG. 2A, the dye-sensitized solar cell 1 of the present embodiment has a light-transmitting electrode layer 25, a dye-sensitized semiconductor layer 24, an electrolyte layer 23, and a counter electrode layer 21 in this order, as in the first embodiment. The translucent electrode layer 25 is composed of an FTO layer or the like. The counter electrode layer 21 is composed of a metal substrate itself such as copper, aluminum, silver, nickel, cobalt, iron, titanium, and stainless steel. The electrolyte layer 23 has a configuration in which an electrolytic solution containing iodine ions or the like is held with respect to the porous insulating layer 230. The dye-sensitized semiconductor layer 24 has a configuration in which a dye such as a ruthenium organic complex or a merocyanine dye is held in a porous oxide semiconductor layer 240 such as a porous titanium oxide layer or a zinc oxide layer. Then, a dye-sensitized n-type semiconductor layer is used.

このように構成した色素増感太陽電池１において、本形態では、まず、電解質層形成工程において、金属基板自身からなる対極層２１の上層側に多孔性絶縁層２３０を積層する。次に、半導体層形成工程において、多孔性絶縁層２３０(電解質層２３)の上層に色素増感半導体層２４を形成するための多孔性酸化物半導体層２４０を塗布法、ゾル−ゲル法、スパッタ法、ＣＶＤ法などにより積層する。次に、透光性電極層形成工程において、多孔性酸化物半導体層２４０の上層側に透光性電極層２５を塗布法、ゾル−ゲル法、スパッタ法、ＣＶＤ法などにより積層する。次に、多孔性酸化物半導体層２４０に色素を保持させて色素増感半導体層２４を形成するとともに、多孔性絶縁層２３０に電解液を含浸して電解質層２３を形成する。しかる後に、色素増感半導体層２４および電解質層２３の周りを囲むように保護用の樹脂層４１を形成する。   In the dye-sensitized solar cell 1 configured as described above, in this embodiment, first, in the electrolyte layer forming step, the porous insulating layer 230 is laminated on the upper layer side of the counter electrode layer 21 made of the metal substrate itself. Next, in the semiconductor layer forming step, a porous oxide semiconductor layer 240 for forming the dye-sensitized semiconductor layer 24 is formed on the porous insulating layer 230 (electrolyte layer 23) by a coating method, a sol-gel method, a sputtering method. Lamination is performed by a method, a CVD method or the like. Next, in the translucent electrode layer forming step, the translucent electrode layer 25 is laminated on the upper side of the porous oxide semiconductor layer 240 by a coating method, a sol-gel method, a sputtering method, a CVD method, or the like. Next, the dye is held in the porous oxide semiconductor layer 240 to form the dye-sensitized semiconductor layer 24, and the electrolyte layer 23 is formed by impregnating the porous insulating layer 230 with an electrolytic solution. Thereafter, a protective resin layer 41 is formed so as to surround the dye-sensitized semiconductor layer 24 and the electrolyte layer 23.

このように構成した色素増感太陽電池１では、透光性電極層２５、および金属基板からなる対極層２１によってアノードおよびカソードが各々、形成される。   In the dye-sensitized solar cell 1 configured as described above, an anode and a cathode are formed by the translucent electrode layer 25 and the counter electrode layer 21 made of a metal substrate, respectively.

［実施の形態１の具体的構成例２］
図２(ｂ)は、本発明の実施の形態１の具体的構成例２に係る色素増感太陽電池１の概略構成を示す説明図である。 [Specific Configuration Example 2 of Embodiment 1]
FIG.2 (b) is explanatory drawing which shows schematic structure of the dye-sensitized solar cell 1 which concerns on the specific structural example 2 of Embodiment 1 of this invention.

図２(ｂ)において、本形態の色素増感太陽電池１は、実施の形態１と同様、透光性電極層２５、色素増感半導体層２４、電解質層２３、および対極層２１がこの順に配置されており、透光性電極層２５は、ＦＴＯ層などにより構成されている。対極層２１は、ガラス基板などからなるカソード基板２１０の表面を覆う絶縁膜２９上に形成された白金などの薄い金属膜などからなる。また、カソード基板２１０の表面には、対極層２１と同時形成されたアノード端子部２６が形成されており、アノード端子部２６と対極層２１とは絶縁層３１で分離されている。電解質層２３は、多孔性絶縁層２３０に対して、ヨウ素イオンなどを含む電解液が保持された構成などを有している。色素増感半導体層２４は、多孔性酸化物半導体層２４０に色素が保持された構成を備えており、本形態では、色素増感ｎ型半導体層が用いられている。   In FIG. 2 (b), the dye-sensitized solar cell 1 of the present embodiment is similar to the first embodiment in that the translucent electrode layer 25, the dye-sensitized semiconductor layer 24, the electrolyte layer 23, and the counter electrode layer 21 are in this order. The translucent electrode layer 25 is composed of an FTO layer or the like. The counter electrode layer 21 is made of a thin metal film such as platinum formed on the insulating film 29 covering the surface of the cathode substrate 210 made of a glass substrate or the like. An anode terminal portion 26 formed simultaneously with the counter electrode layer 21 is formed on the surface of the cathode substrate 210, and the anode terminal portion 26 and the counter electrode layer 21 are separated by an insulating layer 31. The electrolyte layer 23 has a configuration in which an electrolytic solution containing iodine ions or the like is held with respect to the porous insulating layer 230. The dye-sensitized semiconductor layer 24 has a configuration in which a dye is held in the porous oxide semiconductor layer 240. In this embodiment, a dye-sensitized n-type semiconductor layer is used.

このように構成した色素増感太陽電池１を製造するにあたっては、カソード基板２１０に対して、絶縁膜２９および白金などの薄い金属膜を形成した後、フォトリソグラフィ技術を用いて金属膜をパターニングし、対極層２１およびアノード端子部２６を形成する。また、対極層２１およびアノード端子部２６との間を絶縁層３１で埋める。次に、電解質層形成工程において、対極層２１の上層に多孔性絶縁層２３０を積層する。次に、半導体層形成工程において、多孔性絶縁層２３０(電解質層２３)の上層側に、色素増感半導体層２４を形成するための多孔性酸化物半導体層２４０を形成する。次に、多孔性酸化物半導体層２４０の上層に透光性電極層２５を積層する。その際、透光性電極層２５を多孔性酸化物半導体層２４０および多孔性絶縁層２３０の側面部の一部も覆うように形成し、透光性電極層２５をアノード端子部２６に電気的に接続する。次に、多孔性酸化物半導体層２４０に色素を保持させて色素増感半導体層２４を形成するとともに、多孔性絶縁層２３０に電解液を含浸して電解質層２３を形成する。しかる後に、色素増感半導体層２４および電解質層２３の側面のうち、露出している部分を保護用の樹脂層４１により覆う。   In manufacturing the dye-sensitized solar cell 1 configured as described above, an insulating film 29 and a thin metal film such as platinum are formed on the cathode substrate 210, and then the metal film is patterned using a photolithography technique. The counter electrode layer 21 and the anode terminal portion 26 are formed. Further, the insulating layer 31 is filled between the counter electrode layer 21 and the anode terminal portion 26. Next, in the electrolyte layer forming step, the porous insulating layer 230 is laminated on the counter electrode layer 21. Next, in the semiconductor layer forming step, a porous oxide semiconductor layer 240 for forming the dye-sensitized semiconductor layer 24 is formed on the upper layer side of the porous insulating layer 230 (electrolyte layer 23). Next, the translucent electrode layer 25 is stacked on the porous oxide semiconductor layer 240. At that time, the translucent electrode layer 25 is formed so as to cover part of the side surfaces of the porous oxide semiconductor layer 240 and the porous insulating layer 230, and the translucent electrode layer 25 is electrically connected to the anode terminal portion 26. Connect to. Next, the dye is held in the porous oxide semiconductor layer 240 to form the dye-sensitized semiconductor layer 24, and the electrolyte layer 23 is formed by impregnating the porous insulating layer 230 with an electrolytic solution. Thereafter, the exposed portions of the side surfaces of the dye-sensitized semiconductor layer 24 and the electrolyte layer 23 are covered with a protective resin layer 41.

このように構成した色素増感太陽電池１では、カソード基板２１０上に形成された対極層２１およびアノード端子部２６を各々、カソードおよびアノードとして用いる。   In the dye-sensitized solar cell 1 configured as described above, the counter electrode layer 21 and the anode terminal portion 26 formed on the cathode substrate 210 are used as a cathode and an anode, respectively.

［実施の形態２］
図３(ａ)、(ｂ)は各々、本発明の実施の形態２に係るタンデム型の色素増感太陽電池の基本構成を示す説明図、およびその製造方法を示す説明図である。 [Embodiment 2]
3 (a) and 3 (b) are respectively an explanatory view showing a basic configuration of a tandem dye-sensitized solar cell according to Embodiment 2 of the present invention and an explanatory view showing a manufacturing method thereof.

図３(ａ)において、本形態の色素増感太陽電池１は、色素増感半導体層１２(第１色素増感半導体層)および電解質層１３(第１電解質層)を間に備えた第１電極対と、色素増感半導体層２４(第２色素増感半導体層)および電解質層２３(第２電解質層)を間に備えた第２電極対とを有するタンデム型の色素増感太陽電池である。本形態においては、透光性電極層１１(第１透光性電極層)、色素増感半導体層１２(第１色素増感半導体層)、電解質層１３(第１電解質層)、集電層１９、透光性電極層２５(第２透光性電極層)、色素増感半導体層２４(第２色素増感半導体層)、第２電解質層２３(第２電解質層)、および対極層２１がこの順に配置されており、透光性電極層２５は、透光性電極層１１と第１電極対を構成しているとともに、対極層２１と第２電極対を構成している。   In FIG. 3A, the dye-sensitized solar cell 1 of the present embodiment includes a first dye-sensitized semiconductor layer 12 (first dye-sensitized semiconductor layer) and an electrolyte layer 13 (first electrolyte layer) provided therebetween. A tandem dye-sensitized solar cell having an electrode pair and a second electrode pair having a dye-sensitized semiconductor layer 24 (second dye-sensitized semiconductor layer) and an electrolyte layer 23 (second electrolyte layer) in between. is there. In this embodiment, the translucent electrode layer 11 (first translucent electrode layer), the dye-sensitized semiconductor layer 12 (first dye-sensitized semiconductor layer), the electrolyte layer 13 (first electrolyte layer), and the current collecting layer 19, translucent electrode layer 25 (second translucent electrode layer), dye-sensitized semiconductor layer 24 (second dye-sensitized semiconductor layer), second electrolyte layer 23 (second electrolyte layer), and counter electrode layer 21 Are arranged in this order, and the translucent electrode layer 25 constitutes the translucent electrode layer 11 and the first electrode pair, and constitutes the counter electrode layer 21 and the second electrode pair.

透光性電極層１１は、ガラス基板などからなるアノード基板１１０の表面に成膜されたＦＴＯ層などにより構成されている。対極層２１は、ガラス基板や金属基板などのカソード基板２１０の表面に成膜されたＦＴＯ層などの透光性導電膜２１１と、その表面に積層された白金などの薄い金属膜２１２とからなる。電解質層１３、２３はいずれも、多孔性絶縁層１３０、２３０に対して、ヨウ素イオンなどを含む電解液が保持された構成などを有している。色素増感半導体層１２、２４はいずれも、多孔性酸化物半導体層１２０、２４０に色素が保持された構成、例えば、多孔性の酸化チタン層や酸化亜鉛層に、ルテニウム有機錯体やメロシアニン系色素などの色素が保持された構成を備えており、本形態では、色素増感ｎ型半導体層が用いられている。ここで、色素増感半導体層１２、２４に用いた色素は各々、異なる波長帯域の光に感応する。例えば、色素増感半導体層１２に用いた色素は短波長領域に感応し、色素増感半導体層２４に用いた色素は近赤外領域に感応する。   The translucent electrode layer 11 is composed of an FTO layer formed on the surface of an anode substrate 110 made of a glass substrate or the like. The counter electrode layer 21 includes a translucent conductive film 211 such as an FTO layer formed on the surface of a cathode substrate 210 such as a glass substrate or a metal substrate, and a thin metal film 212 such as platinum laminated on the surface. . Each of the electrolyte layers 13 and 23 has a configuration in which an electrolytic solution containing iodine ions or the like is held with respect to the porous insulating layers 130 and 230. Each of the dye-sensitized semiconductor layers 12 and 24 has a structure in which a dye is held in the porous oxide semiconductor layers 120 and 240, for example, a ruthenium organic complex or a merocyanine dye in a porous titanium oxide layer or a zinc oxide layer. In this embodiment, a dye-sensitized n-type semiconductor layer is used. Here, the dyes used in the dye-sensitized semiconductor layers 12 and 24 are sensitive to light of different wavelength bands. For example, the dye used for the dye-sensitized semiconductor layer 12 is sensitive to the short wavelength region, and the dye used for the dye-sensitized semiconductor layer 24 is sensitive to the near infrared region.

このように構成した色素増感太陽電池１において、透光性電極層２５、色素増感半導体層２４を形成するための多孔性酸化物半導体層２４０(半導体層)、電解質層２３を形成するための多孔性絶縁層２３０、および対極層２１は、この順序あるいは逆の順序で積層してなる層である。   In the dye-sensitized solar cell 1 configured as described above, the transparent electrode layer 25, the porous oxide semiconductor layer 240 (semiconductor layer) for forming the dye-sensitized semiconductor layer 24, and the electrolyte layer 23 are formed. The porous insulating layer 230 and the counter electrode layer 21 are layers laminated in this order or in the reverse order.

すなわち、本形態では、色素増感太陽電池１を製造する際、図３(ｂ)に示すように、カソード基板２１０に対して、透光性導電膜２１１、白金などの薄い金属膜２１２を形成して対極層２１を形成した後、まず、電解質層形成工程において、多孔性絶縁層２３０を形成する。次に、半導体層形成工程において、多孔性絶縁層２３０(電解質層２３)の上層側に、色素増感半導体層２４を形成するための多孔性酸化物半導体層２４０を形成する、次に、透光性電極層形成工程において、多孔性酸化物半導体層２４０の上層側に透光性電極層２５を積層する。次に、透光性電極層２５の上層に、白金などの薄い金属膜を集電層１９として積層し、セル構造体２０(第１セル構造体)を形成する。そして、多孔性酸化物半導体層２４０に色素を保持させて第２色素増感半導体層２４を形成するとともに、多孔性絶縁層２３０に電解液を含浸して第２電解質層２３を形成し、セル構造体２０を形成する。   That is, in this embodiment, when the dye-sensitized solar cell 1 is manufactured, a light-transmitting conductive film 211 and a thin metal film 212 such as platinum are formed on the cathode substrate 210 as shown in FIG. After forming the counter electrode layer 21, first, the porous insulating layer 230 is formed in the electrolyte layer forming step. Next, in the semiconductor layer forming step, a porous oxide semiconductor layer 240 for forming the dye-sensitized semiconductor layer 24 is formed on the upper layer side of the porous insulating layer 230 (electrolyte layer 23). In the photoelectrode layer forming step, the translucent electrode layer 25 is laminated on the upper layer side of the porous oxide semiconductor layer 240. Next, a thin metal film such as platinum is stacked as the current collecting layer 19 on the translucent electrode layer 25 to form a cell structure 20 (first cell structure). Then, the dye is held in the porous oxide semiconductor layer 240 to form the second dye-sensitized semiconductor layer 24, and the porous insulating layer 230 is impregnated with the electrolytic solution to form the second electrolyte layer 23. A structure 20 is formed.

一方、アノード基板１１０側では、ＦＴＯ層などからなる透光性電極層１１を形成した後、色素増感半導体層１２を形成するための多孔性酸化物半導体層１２０(半導体層)、電解質層１３を形成するための多孔性絶縁層１３０をこの順序で形成し、第２セル構造体２０を形成する。また、セル構造体１０(第２セル構造体)でも、多孔性酸化物半導体層１２０に色素を保持させて色素増感半導体層１２を形成するとともに、多孔性絶縁層１３０に電解液を含浸して電解質層１３を形成しておく。   On the other hand, on the anode substrate 110 side, after forming the translucent electrode layer 11 made of an FTO layer or the like, a porous oxide semiconductor layer 120 (semiconductor layer) for forming the dye-sensitized semiconductor layer 12 and the electrolyte layer 13 are formed. The porous insulating layer 130 for forming the second cell structure 20 is formed in this order. In the cell structure 10 (second cell structure) as well, the dye is sensitized on the porous oxide semiconductor layer 120 to form the dye-sensitized semiconductor layer 12, and the porous insulating layer 130 is impregnated with an electrolytic solution. Thus, the electrolyte layer 13 is formed.

しかる後に、セル構造体１０、２０を接合し、タンデム型の色素増感太陽電池１を得る。なお、電解質層１３を形成するにあたっては、多孔性絶縁層１３０に電解液を含浸した構造に代えて、枠状のスペーサを配置し、その内側に電解液が充填、保持されている構造を採用してもよい。   Thereafter, the cell structures 10 and 20 are joined to obtain the tandem dye-sensitized solar cell 1. In forming the electrolyte layer 13, a structure in which a frame-like spacer is arranged and the electrolyte is filled and held instead of the structure in which the porous insulating layer 130 is impregnated with the electrolyte is adopted. May be.

このように構成した色素増感太陽電池１において、透光性電極層２５は、透光性電極層１１と第１電極対を構成しているとともに、対極層２１と第２電極対を構成しており、２つのセル(トップセルおよびボトムセル)の間で共通化されている。このため、２つのセルの間に基板がないので、少ない枚数の基板でタンデム型の色素増感太陽電池１を構成することができる。また、透光性電極の形成回数が少なくてよい。それ故、コストを低減することができるとともに、タンデム型の色素増感太陽電池１を例えば０．２ｍｍ以下にまで薄型化することができる。また、光の入射側とは反対側に位置する色素増感半導体層２４に光が届くまでに透過する必要のある基板の枚数や透光性電極層２５の層数が少ないので、その間の光損失が少ない。また、セル内での電子の移動経路は、カソードからアノードに向けて、例えば０．３μｍ程度の距離を直進するものと見なすことができるので、電子の移動経路が短い分、内部抵抗が小さいという利点がある。   In the dye-sensitized solar cell 1 configured as described above, the translucent electrode layer 25 constitutes the translucent electrode layer 11 and the first electrode pair, and constitutes the counter electrode layer 21 and the second electrode pair. And common to two cells (top cell and bottom cell). For this reason, since there is no substrate between the two cells, the tandem dye-sensitized solar cell 1 can be configured with a small number of substrates. Moreover, the number of times of forming the translucent electrode may be small. Therefore, the cost can be reduced and the tandem dye-sensitized solar cell 1 can be thinned to, for example, 0.2 mm or less. In addition, since the number of substrates that need to be transmitted before the light reaches the dye-sensitized semiconductor layer 24 located on the side opposite to the light incident side and the number of light-transmitting electrode layers 25 are small, There is little loss. Also, the electron movement path in the cell can be regarded as going straight, for example, a distance of about 0.3 μm from the cathode to the anode, so the internal resistance is small because the electron movement path is short. There are advantages.

［実施の形態２の具体的構成例１］
図４(ａ)は、本発明の実施の形態２の具体的構成例１に係るタンデム型の色素増感太陽電池１の概略構成を示す説明図である。本形態は基本的な構成が、図３を参照して説明した構成と同様であるため、共通する部分には同一の符号を付してそれらの詳細な説明を省略する。 [Specific Configuration Example 1 of Embodiment 2]
FIG. 4A is an explanatory diagram showing a schematic configuration of a tandem dye-sensitized solar cell 1 according to a specific configuration example 1 of the second embodiment of the present invention. Since the basic configuration of this embodiment is the same as the configuration described with reference to FIG. 3, common portions are denoted by the same reference numerals, and detailed description thereof is omitted.

図４(ａ)において、本形態のタンデム型の色素増感太陽電池１は、実施の形態２と同様、色素増感半導体層１２(第１色素増感半導体層)および電解質層１３(第１電解質層)を間に備えた第１電極対と、色素増感半導体層２４(第２色素増感半導体層)および電解質層２３(第２電解質層)を間に備えた第２電極対とを有するタンデム型の色素増感太陽電池である。本形態においては、透光性電極層１１(第１透光性電極層)、色素増感半導体層１２(第１色素増感半導体層)、電解質層１３(第１電解質層)、集電層１９、透光性電極層２５(第２透光性電極層)、色素増感半導体層２４(第２色素増感半導体層)、第２電解質層２３(第２電解質層)、および対極層２１がこの順に配置されており、透光性電極層２５は、透光性電極層１１と第１電極対を構成しているとともに、対極層２１と第２電極対を構成している。   In FIG. 4A, the tandem dye-sensitized solar cell 1 of the present embodiment is similar to the second embodiment in the dye-sensitized semiconductor layer 12 (first dye-sensitized semiconductor layer) and the electrolyte layer 13 (first first). A first electrode pair provided with an electrolyte layer) and a second electrode pair provided with a dye-sensitized semiconductor layer 24 (second dye-sensitized semiconductor layer) and an electrolyte layer 23 (second electrolyte layer). A tandem dye-sensitized solar cell. In this embodiment, the translucent electrode layer 11 (first translucent electrode layer), the dye-sensitized semiconductor layer 12 (first dye-sensitized semiconductor layer), the electrolyte layer 13 (first electrolyte layer), and the current collecting layer 19, translucent electrode layer 25 (second translucent electrode layer), dye-sensitized semiconductor layer 24 (second dye-sensitized semiconductor layer), second electrolyte layer 23 (second electrolyte layer), and counter electrode layer 21 Are arranged in this order, and the translucent electrode layer 25 constitutes the translucent electrode layer 11 and the first electrode pair, and constitutes the counter electrode layer 21 and the second electrode pair.

本形態において、対極層２１は、ステンレスなどの金属基板２１ａの表面に白金などの薄い金属膜２１２が形成された構成になっている。また、本形態において、色素増感半導体層１２はその周りが電解質層１３により覆われている。また、色素増感半導体層２４および電解質層２３の周りは保護用の樹脂層４３により覆われ、色素増感半導体層１２および電解質層１３の周りは保護用の樹脂層４４により覆われている。   In this embodiment, the counter electrode layer 21 has a configuration in which a thin metal film 212 such as platinum is formed on the surface of a metal substrate 21a such as stainless steel. In this embodiment, the periphery of the dye-sensitized semiconductor layer 12 is covered with the electrolyte layer 13. Further, the periphery of the dye-sensitized semiconductor layer 24 and the electrolyte layer 23 is covered with a protective resin layer 43, and the periphery of the dye-sensitized semiconductor layer 12 and the electrolyte layer 13 is covered with a protective resin layer 44.

このように構成した色素増感太陽電池１においても、透光性電極層２５は、透光性電極層１１と第１電極対を構成しているとともに、対極層２１と第２電極対を構成しており、２つのセル(トップセルおよびボトムセル)の間で共通化されているため、コストを低減することができるとともに、タンデム型の色素増感太陽電池１の薄型化を図ることができるなど、実施の形態２と同様な効果を奏する。   Also in the dye-sensitized solar cell 1 configured as described above, the translucent electrode layer 25 configures the translucent electrode layer 11 and the first electrode pair, and configures the counter electrode layer 21 and the second electrode pair. In addition, since it is shared between the two cells (top cell and bottom cell), the cost can be reduced and the tandem dye-sensitized solar cell 1 can be thinned. The same effects as those of the second embodiment are obtained.

［実施の形態２の具体的構成例２］
図４(ｂ)は、本発明の実施の形態２の具体的構成例２に係るタンデム型の色素増感太陽電池１の概略構成を示す説明図である。 [Specific Configuration Example 2 of Embodiment 2]
FIG. 4B is an explanatory diagram showing a schematic configuration of the tandem dye-sensitized solar cell 1 according to the specific configuration example 2 of the second embodiment of the present invention.

図４(ｂ)において、本形態のタンデム型の色素増感太陽電池１は、実施の形態２と同様、色素増感半導体層１２(第１色素増感半導体層)および電解質層１３(第１電解質層)を間に備えた第１電極対と、色素増感半導体層２４(第２色素増感半導体層)および電解質層２３(第２電解質層)を間に備えた第２電極対とを有するタンデム型の色素増感太陽電池である。本形態においては、透光性電極層１１(第１透光性電極層)、色素増感半導体層１２(第１色素増感半導体層)、電解質層１３(第１電解質層)、集電層１９、透光性電極層２５(第２透光性電極層)、色素増感半導体層２４(第２色素増感半導体層)、第２電解質層２３(第２電解質層)、および対極層２１がこの順に配置されており、透光性電極層２５は、透光性電極層１１と第１電極対を構成しているとともに、対極層２１と第２電極対を構成している。   In FIG. 4B, the tandem dye-sensitized solar cell 1 of the present embodiment is similar to the second embodiment in the dye-sensitized semiconductor layer 12 (first dye-sensitized semiconductor layer) and the electrolyte layer 13 (first first). A first electrode pair provided with an electrolyte layer) and a second electrode pair provided with a dye-sensitized semiconductor layer 24 (second dye-sensitized semiconductor layer) and an electrolyte layer 23 (second electrolyte layer). A tandem dye-sensitized solar cell. In this embodiment, the translucent electrode layer 11 (first translucent electrode layer), the dye-sensitized semiconductor layer 12 (first dye-sensitized semiconductor layer), the electrolyte layer 13 (first electrolyte layer), and the current collecting layer 19, translucent electrode layer 25 (second translucent electrode layer), dye-sensitized semiconductor layer 24 (second dye-sensitized semiconductor layer), second electrolyte layer 23 (second electrolyte layer), and counter electrode layer 21 Are arranged in this order, and the translucent electrode layer 25 constitutes the translucent electrode layer 11 and the first electrode pair, and constitutes the counter electrode layer 21 and the second electrode pair.

本形態において、対極層２１は、ステンレスなどの金属基板２１ａの表面に白金などの薄い金属膜２１２が形成された構成になっている。また、本形態において、色素増感半導体層１２、電解質層２３、集電層１９、透光性電極層２５、色素増感半導体層２４、および電解質層２３は、周りが共通の樹脂層４５により覆われている。   In this embodiment, the counter electrode layer 21 has a configuration in which a thin metal film 212 such as platinum is formed on the surface of a metal substrate 21a such as stainless steel. Further, in this embodiment, the dye-sensitized semiconductor layer 12, the electrolyte layer 23, the current collecting layer 19, the translucent electrode layer 25, the dye-sensitized semiconductor layer 24, and the electrolyte layer 23 are formed by a resin layer 45 having a common periphery. Covered.

このように構成した色素増感太陽電池１においても、透光性電極層２５は、透光性電極層１１と第１電極対を構成しているとともに、対極層２１と第２電極対を構成しており、２つのセル(トップセルおよびボトムセル)の間で共通化されているため、コストを低減することができるとともに、タンデム型の色素増感太陽電池１の薄型化を図ることができるなど、実施の形態２と同様な効果を奏する。   Also in the dye-sensitized solar cell 1 configured as described above, the translucent electrode layer 25 configures the translucent electrode layer 11 and the first electrode pair, and configures the counter electrode layer 21 and the second electrode pair. In addition, since it is shared between the two cells (top cell and bottom cell), the cost can be reduced and the tandem dye-sensitized solar cell 1 can be thinned. The same effects as those of the second embodiment are obtained.

［その他の実施の形態］
本発明の技術範囲は上記各実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。例えば、図１に示す色素増感太陽電池１を製造する際、対極層２１、多孔性絶縁層２３０、多孔性酸化物半導体層２４０、および透光性電極層２５の順序で形成したが、透光性電極層２５をアノード基板上に形成した後、透光性電極層２５の上層に多孔性酸化物半導体層２４０、多孔性絶縁層２３０、および対極層２１をこの順序で形成してもよい。また、図３に示すタンデム型の色素増感太陽電池１を製造する際、透光性電極層１１(第１透光性電極層)、色素増感半導体層１２(第１色素増感半導体層)、電解質層１３(第１電解質層)、集電層１９、透光性電極層２５(第２透光性電極層)、色素増感半導体層２４(第２色素増感半導体層)、第２電解質層２３(第２電解質層)、および対極層２１をこの順序あるいは逆の順序で連続的に形成してもよい。なお、電極材料の種類などによっては、集電層１９などを省略してもよい。 [Other embodiments]
The technical scope of the present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention. For example, when the dye-sensitized solar cell 1 shown in FIG. 1 is manufactured, the counter electrode layer 21, the porous insulating layer 230, the porous oxide semiconductor layer 240, and the translucent electrode layer 25 are formed in this order. After forming the photoelectrode layer 25 on the anode substrate, the porous oxide semiconductor layer 240, the porous insulating layer 230, and the counter electrode layer 21 may be formed in this order on the translucent electrode layer 25. . Further, when the tandem dye-sensitized solar cell 1 shown in FIG. 3 is manufactured, the translucent electrode layer 11 (first translucent electrode layer) and the dye-sensitized semiconductor layer 12 (first dye-sensitized semiconductor layer). ), Electrolyte layer 13 (first electrolyte layer), current collecting layer 19, translucent electrode layer 25 (second translucent electrode layer), dye-sensitized semiconductor layer 24 (second dye-sensitized semiconductor layer), first The two electrolyte layers 23 (second electrolyte layer) and the counter electrode layer 21 may be continuously formed in this order or in the reverse order. Depending on the type of electrode material, the current collecting layer 19 and the like may be omitted.

本発明の実施の形態１に係る色素増感太陽電池の基本構成を示す説明図である。It is explanatory drawing which shows the basic composition of the dye-sensitized solar cell which concerns on Embodiment 1 of this invention. (ａ)、(ｂ)は各々、本発明の実施の形態１の具体的構成例を示す説明図である。(a), (b) is each explanatory drawing which shows the specific structural example of Embodiment 1 of this invention. (ａ)、(ｂ)は各々、本発明の実施の形態２に係る色素増感太陽電池の基本構成を示す説明図、およびその製造方法を示す説明である。(a), (b) is explanatory drawing which shows the basic composition of the dye-sensitized solar cell which concerns on Embodiment 2 of this invention, respectively, and description which shows the manufacturing method. (ａ)、(ｂ)は各々、本発明の実施の形態２の具体的構成例を示す説明図である。(a), (b) is explanatory drawing which shows the specific structural example of Embodiment 2 of this invention, respectively. (ａ)、(ｂ)は各々、従来の色素増感太陽電池の基本構成を示す説明図、およびその製造方法を示す説明である。(a), (b) is explanatory drawing which shows the basic composition of the conventional dye-sensitized solar cell, respectively, and description which shows the manufacturing method.

符号の説明Explanation of symbols

１ 色素増感太陽電池
１１ 透光性電極層
１２、２４ 色素増感半導体層
１３、２３ 電解質層
２１ 対極層 1 Dye-sensitized solar cell 11 Translucent electrode layers 12 and 24 Dye-sensitized semiconductor layers 13 and 23 Electrolyte layer 21 Counter electrode layer

Claims (7)

透光性電極層、色素増感半導体層、電解質層、および対極層がこの順に配置された色素増感太陽電池の製造方法において、
少なくとも、前記透光性電極層、前記色素増感半導体層を形成するための半導体層、前記電解質層を形成するための層、および前記対極層をこの順序あるいは逆の順序で積層することを特徴とする色素増感太陽電池の製造方法。 In the method for producing a dye-sensitized solar cell in which the translucent electrode layer, the dye-sensitized semiconductor layer, the electrolyte layer, and the counter electrode layer are arranged in this order,
At least the light-transmitting electrode layer, the semiconductor layer for forming the dye-sensitized semiconductor layer, the layer for forming the electrolyte layer, and the counter electrode layer are laminated in this order or reverse order. A method for producing a dye-sensitized solar cell. 少なくとも、
前記対極層の上層側に前記電解質層を形成するための層を形成する電解質層形成工程と、
当該電解質層を形成するための層の上層側に前記色素増感半導体層を形成するための半導体層を形成する半導体層形成工程と、
前記半導体層の上層側に前記透光性電極層を積層する透光性電極層形成工程と、
をこの順序で行うことを特徴とする請求項１に記載の色素増感太陽電池の製造方法。 at least,
An electrolyte layer forming step of forming a layer for forming the electrolyte layer on the upper layer side of the counter electrode layer;
A semiconductor layer forming step of forming a semiconductor layer for forming the dye-sensitized semiconductor layer on the upper layer side of the layer for forming the electrolyte layer;
A translucent electrode layer forming step of laminating the translucent electrode layer on the upper side of the semiconductor layer;
Are performed in this order, The manufacturing method of the dye-sensitized solar cell of Claim 1 characterized by the above-mentioned. 少なくとも、前記電解質層形成工程、前記半導体層形成工程、および前記透光性電極層形成工程を行った後、
前記半導体層に対して色素を保持させることを特徴とする請求項２に記載の色素増感太陽電池の製造方法。 After performing at least the electrolyte layer forming step, the semiconductor layer forming step, and the translucent electrode layer forming step,
The method for producing a dye-sensitized solar cell according to claim 2, wherein a dye is held in the semiconductor layer. 前記電解質層形成工程では、電解液を保持するための多孔性絶縁層を形成し、
少なくとも、前記電解質層形成工程、前記半導体層形成工程、および前記透光性電極層形成工程を行った後、前記多孔性絶縁層に前記電解液を保持させることを特徴とする請求項２または３に記載の色素増感太陽電池の製造方法。 In the electrolyte layer forming step, a porous insulating layer for holding the electrolytic solution is formed,
4. The electrolytic solution is retained in the porous insulating layer after performing at least the electrolyte layer forming step, the semiconductor layer forming step, and the translucent electrode layer forming step. The manufacturing method of the dye-sensitized solar cell as described in 1 above. 前記透光性電極層、前記色素増感半導体層、前記電解質層、および前記対極層がこの順に配置された第１セル構造体に対して、
透光性電極層に色素増感半導体層および電解質層が積層された第２セル構造体を、前記第１セル構造体の前記透光性電極層側に接合してタンデム構造とすることを特徴とする請求項１乃至４の何れか一項に記載の色素増感太陽電池の製造方法。 For the first cell structure in which the translucent electrode layer, the dye-sensitized semiconductor layer, the electrolyte layer, and the counter electrode layer are arranged in this order,
A second cell structure in which a dye-sensitized semiconductor layer and an electrolyte layer are laminated on a translucent electrode layer is joined to the translucent electrode layer side of the first cell structure to form a tandem structure. The manufacturing method of the dye-sensitized solar cell as described in any one of Claims 1 thru | or 4. 透光性電極層、色素増感半導体層、電解質層、および対極層がこの順に配置された色素増感太陽電池において、
前記透光性電極層、前記色素増感半導体層を形成するための半導体層、前記電解質層を形成するための層、および前記対極層は、この順序あるいは逆の順序で積層されてなることを特徴とする色素増感太陽電池。 In the dye-sensitized solar cell in which the translucent electrode layer, the dye-sensitized semiconductor layer, the electrolyte layer, and the counter electrode layer are arranged in this order,
The translucent electrode layer, the semiconductor layer for forming the dye-sensitized semiconductor layer, the layer for forming the electrolyte layer, and the counter electrode layer are laminated in this order or reverse order. Dye-sensitized solar cell characterized. 第１色素増感半導体層および第１電解質層を間に備えた第１電極対と、第２色素増感半導体層および第２電解質層を間に備えた第２電極対とを有するタンデム型の色素増感太陽電池において、
少なくとも、第１透光性電極層、前記第１色素増感半導体層、前記第１電解質層、第２透光性電極層、前記第２色素増感半導体層、前記第２電解質層、および対極層がこの順に配置され、
前記第２透光性電極層は、前記第１透光性電極と前記第１電極対を構成しているとともに、前記対極層と前記第２電極対を構成していることを特徴とする色素増感太陽電池。 A tandem type having a first electrode pair having a first dye-sensitized semiconductor layer and a first electrolyte layer in between, and a second electrode pair having a second dye-sensitized semiconductor layer and a second electrolyte layer in between In dye-sensitized solar cells,
At least a first light-transmissive electrode layer, the first dye-sensitized semiconductor layer, the first electrolyte layer, a second light-transmissive electrode layer, the second dye-sensitized semiconductor layer, the second electrolyte layer, and a counter electrode The layers are arranged in this order,
The second translucent electrode layer constitutes the first translucent electrode and the first electrode pair, and constitutes the counter electrode layer and the second electrode pair. Sensitized solar cell.
JP2007095809A 2007-03-31 2007-03-31 Manufacturing method of dye-sensitized solar cell, and dye-sensitized solar cell Pending JP2008257895A (en)

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