JP2005158726A - Dye-sensitized solar cell, electrode substrate therefor, and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode substrate for a dye-sensitized solar cell which has a high photoelectric conversion efficiency and in which the dye-sensitized solar cell with suppressed aging drop of its performance is obtained easily at a low cost in the electrode substrate for the dye-sensitized solar cell using a transparent resin film as a substrate material. <P>SOLUTION: In manufacturing the electrode substrate 20 for the dye-sensitized solar cell formed on the transparent resin film 1, the transparent electrode 10 includes: the first conductive layer 6 of a metal appearing the shape in combination with many fine wires; a corrosion preventive layer 7 formed of electrolytic plating or electroless plating to cover at least the outer surface of the first conductive layer; and a second conductive layer 8 made of a metal covering the corrosion preventive layer. The corrosion preventive layer is formed of a material which has a corrosion resistance to the electrolyte for the dye-sensitized solar cell. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrode substrate for a dye-sensitized solar cell, a method for producing the same, and a dye-sensitized solar cell.

  The use of solar power generation systems is increasing today because the load on the surrounding environment is small compared to power generation systems using fossil fuels and nuclear fuel, and it is easy to save resources.

  The solar cell used in the photovoltaic power generation system is a photoelectric conversion element that can directly convert light energy into electrical energy. This solar cell includes a silicon solar cell, a compound semiconductor solar cell (gallium arsenide solar cell, Indium phosphide solar cells, CIS (copper indium selenium) solar cells, etc.), dye-sensitized solar cells, and the like. Among these solar cells, silicon solar cells are already widely used as consumer solar cells. In recent years, attention has been focused on dye-sensitized solar cells that can be easily reduced in cost compared to silicon solar cells.

FIG. 6 is a schematic view showing a cross-sectional structure of a typical dye-sensitized solar cell (Gretzel cell). Dye-sensitized solar cell 150 ^shown, _I ^- / I ₃ - is a wet solar cell having a structure which sandwiches an electrolyte solution 105 containing a redox couple at a pair of electrode substrates 120 and 130.

  The electrode substrate 120 includes a transparent glass substrate 111, a transparent conductive film (fluorine-doped tin oxide film) 113 formed on one surface thereof, and a porous semiconductor layer (porous titanium oxide thin film) 115 formed thereon. Have. The porous semiconductor layer 115 is formed by a sol-gel method, and is a sintered body of a large number of anatase-type titanium oxide fine particles. The surface of the porous semiconductor layer 115 is adsorbed with a dye 117 made of one kind of ruthenium (Ru) complex, and the absorption wavelength range of the dye 117 is longer than the absorption wavelength range of titanium oxide. It extends. The energy level of electrons when the dye 117 is photoexcited is higher than the position of the conduction band edge of titanium oxide. In FIG. 6, the dye 117 is drawn as one layer for convenience. On the other hand, the electrode substrate 130 includes a transparent glass substrate 121, a transparent conductive film (fluorine-doped tin oxide film) 123 formed on one surface thereof, and a platinum thin film 125 formed thereon. The transparent conductive film 113 in the electrode substrate 120 and the transparent conductive film 123 in the electrode substrate 130 are connected to the load 140 by lead wires 135a and 135b.

When the dye-sensitized solar cell 150 is irradiated with light within the absorption wavelength range of the dye 117, the dye 117 is excited, and photoexcited electrons (e ⁻ ) are injected into the porous semiconductor layer 115. Electronic (e ^-) dye 117 lost in, ^I in the electrolyte solution 105 - / _{I 3} ^- from redox pairs deprive electrons (I ^- reacts with _{I 3} ^- to occur), return to the original state . On the other hand, the electrons (e ⁻ ) injected into the porous semiconductor layer 115 move to the transparent conductive film 113 and further reach the electrode substrate 130 via the lead wire 135a, the load 140, and the lead wire 135b to reach I ₃ ^−. To give I ⁻ . Therefore, a closed circuit is formed in the dye-sensitized solar cell 150 by the light irradiation. When this closed circuit is formed, the dye-sensitized solar cell 150 generates power constantly. By using the dye 117, it becomes possible to generate power using light having a longer wavelength than the light in the absorption wavelength region of the porous semiconductor layer 115, so that the photoelectric conversion efficiency can be increased. Incidentally, the platinum thin film 125, the serving other to increase the conductivity of the electrode substrate _{^{130, I - / I 3 -}} I 3 of the redox pair ^- is I ^- also serves as a catalyst as it is reduced to.

  Research and development of dye-sensitized solar cells has mainly been focused on improving photoelectric conversion efficiency. By forming a porous semiconductor layer by a sol-gel method, supporting a specific dye on the porous semiconductor layer, and using a specific electrolyte, one having a relatively high photoelectric conversion efficiency is obtained.

  Further, for example, in Patent Document 1, a transparent electrode serving as a base for a semiconductor electrode is formed by a metal film having a large number of holes, and directly or directly on the metal film, such as silicon nitride, aluminum nitride, nickel-chromium metal, etc. There is described a dye-sensitized solar cell that is formed through a transparent conductive layer that is formed through a layer and covers the metal thin film, thereby improving conductivity and thereby improving photoelectric conversion efficiency. Furthermore, Patent Document 1 also describes that a transparent resin film is used instead of the transparent glass substrate.

In general, by using a transparent resin film instead of a transparent glass substrate, a dye-sensitized solar cell rich in flexibility can be obtained. If the flexibility of the dye-sensitized solar cell is high, the degree of freedom in selecting the installation location of the solar cell is increased, so that it is easy to install in various locations over a wide range. As a result, even if the photoelectric conversion efficiency of the dye-sensitized solar cell is relatively low, a desired power generation amount can be ensured as a whole. Further, since the weight is reduced, it is easy to improve the workability at the time of installation even when the solar cell has a large area. Furthermore, when used as a power source for a portable electronic device, it is easy to maintain the portability (lightness) of the portable electronic device.
JP-A-2003-123858 (Claim 21, Stages 0021 to 0045, Stage 0047 and Stage 0067)

  However, when an inexpensive and relatively low heat-resistant transparent resin film such as polyethylene terephthalate (hereinafter abbreviated as “PET”) is used as a material for the electrode substrate, the temperature at which the transparent conductive film is formed is changed to the transparent resin. Since it must be below the heat-resistant temperature of a film, it becomes difficult to form a dense transparent conductive film. The same applies to the case where the above-described layers of silicon nitride, aluminum nitride, nickel-chromium metal and the like described in Patent Document 1 are formed by physical vapor deposition or chemical vapor deposition.

As a result, in a dye-sensitized solar cell manufactured using an electrode substrate using a transparent resin film having a relatively low heat resistance as a base material, the electrolyte penetrates into the transparent conductive film and reaches the underlying layer. easy. From the top to obtain a high dye-sensitized solar cell photoelectric conversion efficiency, the above I ^- / I ₃ ^- is preferably used an electrolyte layer containing a halogen-based redox pair, such as redox pairs, halogen-based Redox pairs are highly chemically active and corrode many metals.

  As the material of the above-mentioned metal thin film in the dye-sensitized solar cell described in Patent Document 1, copper (Cu) is considered most preferable in consideration of conductivity and economy, but copper is a halogen-based redox pair. Corrosion is relatively easy by contact with. For this reason, in the dye-sensitized solar cell described in Patent Document 1, if an attempt is made to obtain a solar cell having high photoelectric conversion efficiency at a low cost, the performance is likely to deteriorate with time, and the performance is deteriorated over time. When trying to obtain a product that is difficult to decrease, a problem arises that it becomes difficult to obtain a product with high photoelectric conversion efficiency.

  The present invention has been made in order to solve the above-mentioned problems, and a first object thereof is a dye-sensitized solar cell electrode substrate using a transparent resin film as a base material, which has a photoelectric conversion efficiency. It is an object of the present invention to provide a dye-sensitized solar cell electrode substrate that is easy to obtain a dye-sensitized solar cell that is high and has reduced performance degradation over time at low cost.

  The second object of the present invention is a dye-sensitized solar cell electrode substrate using a transparent resin film as a base material, which has high photoelectric conversion efficiency and suppresses deterioration in performance over time. An object of the present invention is to provide a method for producing an electrode substrate for a dye-sensitized solar cell, which makes it easy to obtain a sensitized solar cell at low cost.

  A third object of the present invention is a dye-sensitized solar cell using a transparent resin film as a base material for an electrode substrate, which has high photoelectric conversion efficiency and suppresses deterioration in performance over time. Is to provide a dye-sensitized solar cell that can be easily obtained at low cost.

  The electrode substrate for a dye-sensitized solar cell of the present invention that achieves the first object described above uses the transparent resin film, the transparent electrode formed on one side of the transparent resin film, and a large number of semiconductor fine particles. An electrode substrate for a dye-sensitized solar cell, comprising: a porous semiconductor electrode formed on a transparent electrode; and a dye supported on the surface of semiconductor fine particles forming the porous semiconductor electrode, wherein the transparent substrate A first conductive layer made of metal having a shape in which a plurality of thin wires are combined, and a corrosion prevention layer formed by electroplating, electroless plating, or chemical conversion treatment and covering at least the outer surface of the first conductive layer; And a second conductive layer made of a metal oxide covering the corrosion prevention layer, wherein the corrosion prevention layer has corrosion resistance to an electrolyte for a dye-sensitized solar cell (hereinafter, referred to as “the corrosion prevention layer”). This dye-sensitized type The electrode substrate for a solar cell may be referred to as "electrode substrate I".).

  In this electrode substrate I, since the first conductive layer made of metal is formed in addition to the second conductive layer made of metal oxide, the conductivity of the entire electrode substrate I can be relatively easily increased. In addition, since the corrosion prevention layer covering the outer surface of the first conductive layer is formed by electroplating, electroless plating, or chemical conversion treatment, the heat resistance of the transparent resin film as the base material is relatively Even if it is low, it is easy to make the corrosion prevention layer dense. Furthermore, this corrosion prevention layer has corrosion resistance with respect to the electrolyte for dye-sensitized solar cells.

  When the corrosion prevention layer is dense and the corrosion prevention layer has corrosion resistance to the electrolyte for the dye-sensitized solar cell, when the dye-sensitized solar cell is manufactured using the electrode substrate I Further, the penetration of the electrolyte into the first conductive layer is suppressed. Therefore, even if the halogen-based redox couple is contained in the electrolyte of the dye-sensitized solar cell, and even if the material of the first conductive layer is easily corroded by the halogen-based redox couple. The reduction in conductivity of the electrode substrate I due to the corrosion of the first conductive layer by the redox pair can be suppressed. Even when inexpensive and highly conductive copper or the like is used as the material of the first conductive layer, it is possible to suppress a decrease in the conductivity of the electrode substrate I.

  For these reasons, according to the electrode substrate I of the present invention, it is possible to easily obtain a dye-sensitized solar cell with high photoelectric conversion efficiency and suppressed performance degradation over time at low cost. Become.

  In the electrode substrate I of the present invention, (1) the transparent electrode further includes an adhesive layer formed on one side of the transparent resin film, and the first conductive layer is formed on the transparent resin film by the adhesive layer. (Hereinafter, the electrode substrate for the dye-sensitized solar cell may be referred to as “electrode substrate II”), and (2) the corrosion prevention layer is not the outer surface of the first conductive layer. Further, a region of the surface of the base layer of the first conductive layer that is not covered by the first conductive layer is also covered (hereinafter, this dye-sensitized solar cell electrode substrate is referred to as "electrode substrate III"). Or (3) the transparent electrode further includes a surface treatment layer formed by subjecting the corrosion prevention layer to chromate treatment, and the surface treatment layer includes the corrosion prevention layer and the second conductive layer. (Hereinafter referred to as this dye increase) The electrode substrate for type solar cell may be referred to as "electrode substrate IV".) It is preferred.

  According to the electrode substrate II described in (1) above, it is possible to use, for example, a metal foil formed by rolling as the material of the first conductive layer, so that the manufacturing cost can be easily suppressed. According to the electrode substrate III described in (2) above, the corrosion of the first conductive layer caused by the electrolyte permeating into the interface between the first conductive layer and the base layer, or the base layer corrodes or dissolves. Since it becomes possible to suppress the corrosion of the 1st conductive layer resulting from this, it is further easy to suppress the time-dependent fall of the performance of a dye-sensitized solar cell. According to the electrode substrate IV described in (3) above, it is easy to form a corrosion prevention layer having high corrosion resistance against the halogen-based redox couple.

  In any of the electrode substrates I to IV of the present invention, (4) the first conductive layer is formed of a copper thin film, a nickel thin film, or a stainless thin film (hereinafter, this dye-sensitized solar cell electrode substrate is It may be referred to as “electrode substrate V”).

  According to this electrode substrate V, since the conductivity of the first conductive layer is high, it is easy to increase the conductivity of the entire electrode substrate V.

  Another electrode substrate for a dye-sensitized solar cell of the present invention that achieves the first object described above uses a transparent resin film, a transparent electrode formed on one side of the transparent resin film, and a large number of semiconductor fine particles. An electrode substrate for a dye-sensitized solar cell, comprising: a porous semiconductor electrode formed on the transparent electrode; and a dye supported on the surface of the semiconductor fine particles forming the porous semiconductor electrode, The transparent electrode includes a metal first conductive layer having a shape in which a number of thin wires are combined, and a metal oxide second conductive layer covering the first conductive layer, and the first conductive layer is 99. It is characterized by being formed of aluminum having a purity higher than 3% (hereinafter, this dye-sensitized solar cell electrode substrate may be referred to as "electrode substrate VI").

  Aluminum with a purity higher than 99.3% has high corrosion resistance to the redox couple. Therefore, the above-described electrode substrate VI in which the first conductive layer is formed of high-purity aluminum also enables a low-cost dye-sensitized solar cell with high photoelectric conversion efficiency and suppressed performance degradation over time. Can be easily obtained.

  The method for producing a dye-sensitized solar cell electrode substrate of the present invention that achieves the second object described above comprises a transparent resin film, a transparent electrode formed on one side of the transparent resin film, and a large number of semiconductor fine particles. A method for producing an electrode substrate for a dye-sensitized solar cell, comprising: a porous semiconductor electrode formed on the transparent electrode, and a dye supported on the surface of semiconductor fine particles forming the porous semiconductor electrode And a preparation step of preparing a transparent resin film having a metal first conductive layer formed on one side and having a shape formed by combining a number of fine wires, and at least the first conductive layer on the transparent resin film. A corrosion prevention layer forming step in which a corrosion prevention layer is formed by electroplating, electroless plating, or chemical conversion treatment so as to cover the outer surface and having corrosion resistance to the electrolyte for the dye-sensitized solar cell; A second conductive layer forming step of forming a second conductive layer made of a metal oxide covering the corrosion prevention layer; and a porous layer for forming the porous semiconductor electrode on the second conductive layer using a large number of semiconductor fine particles A semiconductor electrode forming step; and a dye supporting step of supporting a dye on the surface of the semiconductor fine particles forming the porous semiconductor electrode.

  According to the method for producing an electrode substrate for a dye-sensitized solar cell of the present invention, the electrode substrate I of the present invention that exhibits the technical effects described above can be produced.

  In the method for producing a dye-sensitized solar cell electrode substrate of the present invention, (A) the preparation step includes a first sub-step of preparing a transparent resin film in which a metal foil is bonded to one side by an adhesive; A second sub-step of patterning a metal foil to obtain the first conductive layer, and (B) in the corrosion prevention layer forming step, in addition to the outer surface of the first conductive layer, Forming a corrosion prevention layer so as to cover a region of the surface of the underlayer that is not covered by the first conductive layer; or (C) a surface treatment step of performing a chromate treatment on the corrosion prevention layer. It is preferable to perform the surface treatment step before the second conductive layer forming step.

  According to the manufacturing method described in the above (A), it is possible to use, for example, a metal foil formed by rolling as the material of the first conductive layer, so that the manufacturing cost can be easily suppressed. According to the manufacturing method described in (B) above, not only the outer surface of the first conductive layer, but also the interface between the first conductive layer and the underlayer, and the surface of the underlayer, the first conductive layer. Since the region not covered with the coating is also covered with the corrosion prevention layer, the corrosion of the first conductive layer caused by the electrolyte permeating into the interface between the first conductive layer and the base layer, or the base layer is corroded or dissolved. Even the corrosion of the first conductive layer due to this is suppressed. As a result, it is possible to obtain an electrode substrate I in which corrosion of the first conductive layer due to the electrolytic solution is less likely to occur. And according to said (C) manufacturing method, it is easy to form the corrosion prevention layer with high corrosion resistance with respect to a halogen-type redox couple.

  In any of the methods for producing a dye-sensitized solar cell electrode substrate of the present invention, (D) the first conductive layer may be formed of a copper thin film, a nickel thin film, or a stainless thin film. .

  According to this manufacturing method, since the conductivity of the first conductive layer is high, the electrode substrate I having high conductivity can be easily obtained.

  The dye-sensitized solar cell of the present invention that achieves the third object described above includes a first electrode substrate having a semiconductor electrode carrying a dye, and a first electrode substrate disposed opposite to the first electrode substrate. A dye-sensitized solar cell comprising two electrode substrates and an electrolyte layer interposed between the first electrode substrate and the second electrode substrate, wherein the first electrode substrate has been described above. It is one of the electrode substrates I to V of the present invention (hereinafter, this dye-sensitized solar cell may be referred to as “dye-sensitized solar cell I”).

  The second electrode substrate is an electrode substrate that does not have a semiconductor electrode, and is used as a counter electrode in a dye-sensitized solar cell. In many cases, a platinum thin film is formed on the inner surface (the inner surface when used in a dye-sensitized solar cell) of the second electrode substrate. Since platinum is not easily corroded even by a halogen-based redox couple, even when a transparent resin film is used as a base material, the second electrode substrate lacks the necessity of forming a corrosion prevention layer in addition to the platinum thin film.

  According to the dye-sensitized solar cell I of the present invention, since any one of the above-described electrode substrates I to V of the present invention is used as the first electrode substrate, the photoelectric conversion efficiency is high, and the performance deteriorates over time. It is easy to obtain what is suppressed at low cost.

  In the dye-sensitized solar cell I of the present invention, the first electrode substrate can be the electrode substrate V of the present invention described above.

  Another dye-sensitized solar cell of the present invention that achieves the third object described above is provided with a first electrode substrate having a semiconductor electrode carrying a dye, and facing the first electrode substrate. A dye-sensitized solar cell comprising a second electrode substrate and an electrolyte layer interposed between the first electrode substrate and the second electrode substrate, wherein the first electrode substrate comprises: It is the electrode substrate VI of the present invention described above (hereinafter, this dye-sensitized solar cell may be referred to as “dye-sensitized solar cell II”).

  As already explained, aluminum having a purity higher than 99.3% has high corrosion resistance against the redox couple. Therefore, according to the dye-sensitized solar cell II of the present invention, since the above-described electrode substrate VI of the present invention is used as the first electrode substrate, the photoelectric conversion efficiency is high and the deterioration of the performance over time is suppressed. It is easy to obtain the product at low cost.

  According to the electrode substrate for a dye-sensitized solar cell of the present invention, it is possible to obtain a dye-sensitized solar cell with high flexibility and photoelectric conversion efficiency and with suppressed deterioration of performance over time at low cost. Therefore, it becomes easy to obtain a practical dye-sensitized solar cell.

  Moreover, according to the manufacturing method of the electrode substrate for dye-sensitized solar cells of this invention, the electrode substrate for dye-sensitized solar cells of this invention mentioned above can be obtained.

  And according to the dye-sensitized solar cell of the present invention, since the electrode substrate for the dye-sensitized solar cell of the present invention described above is used as the first electrode substrate having a semiconductor electrode, flexibility and Those with high photoelectric conversion efficiency can be provided at low cost.

  Hereinafter, the electrode substrate for a dye-sensitized solar cell of the present invention, a method for producing the same, and the form of each of the dye-sensitized solar cells will be sequentially described with reference to the drawings.

<Dye-sensitized solar cell electrode substrate (first embodiment) and production method thereof>
FIG. 1 is a schematic view showing an example of a basic cross-sectional structure of an electrode substrate for a dye-sensitized solar cell of the present invention. In the illustrated dye-sensitized solar cell electrode substrate 20 (hereinafter referred to as “electrode substrate 20”), the first conductive layer 6, the corrosion prevention layer 7, and the second conductive layer 8 are formed on one surface of the transparent resin film 1. The transparent electrode 10 including the porous semiconductor electrode 15 is formed on the transparent electrode 10. The porous semiconductor electrode 15 is formed of a large number of semiconductor fine particles 15a, and a dye 17 is supported on the surface of the semiconductor fine particles 15a. In FIG. 1, the dye 17 is drawn as one layer for convenience. Hereinafter, the electrode substrate 20 and the manufacturing method thereof will be described in detail.

(1) Transparent resin film When the film thickness is 125 μm, the transparent resin film 1 transmits light of a desired wavelength region in a wavelength region ranging from an ultraviolet region to an infrared region in an average value of approximately 85% or more, And what is necessary is just to have desired light resistance and a weather resistance, and it can form by various methods, using arbitrary resin materials and using various additives together as needed. The “desired wavelength range” can be appropriately selected in consideration of the absorption wavelength ranges of the porous semiconductor electrode 15 and the dye 17.

  Examples of the transparent resin film 1 include a biaxially stretched polyethylene terephthalate (PET) film, an ethylene / tetrafluoroethylene copolymer film, a polyethersulfone (PES) film, a polyetheretherketone (PEEK) film, and a polyether. An imide (PEI) film, a polyimide (PI) film, a polyester naphthalate (PEN) film, a polycarbonate (PC) film, a cyclic polyolefin film, or the like can be used. From the viewpoint of reducing the manufacturing cost of the electrode substrate 20, a material formed from a relatively inexpensive resin material is preferable to a material formed from a relatively expensive resin material such as engineering plastic.

  The film thickness of the transparent resin film 1 can be appropriately selected within a range of about 15 to 500 μm depending on the use of the dye-sensitized solar cell produced using the electrode substrate 20. In addition, since it is necessary to heat-process when forming the transparent electrode 10 and the porous semiconductor electrode 15 so that it may mention later, when selecting the material and film thickness of the transparent resin film 1, the heat resistance is also considered. It is preferable to do.

(2) Transparent electrode The transparent electrode 10 receives carriers (electrons) from the porous semiconductor electrode 15 when the dye-sensitized solar cell produced using the electrode substrate 20 is irradiated with light in a desired wavelength region. It is preferable to receive or transmit carriers (holes) to the porous semiconductor electrode 15, and the transparent electrode 10 preferably transmits 80% or more of the light in the “desired wavelength range”. .

  The illustrated transparent electrode 10 includes an adhesive layer 5 formed on one entire surface of the transparent resin film 1, a first conductive layer 6 bonded to the transparent resin film 1 by the adhesive layer 5, and a first conductive layer 6. A corrosion prevention layer 7 covering the outer surface and the exposed surface of the adhesive layer 3 and a second conductive layer 8 covering the corrosion prevention layer 7 are included.

  The adhesive layer 5 is mainly used when the first conductive layer 6 is formed by patterning a metal foil (rolled metal foil, electrolytic metal foil or the like). For example, when the first conductive layer 6 is obtained by patterning a metal vapor deposition film, or when the first conductive layer 6 is directly formed by vapor deposition, the adhesive layer 5 can be omitted.

  The adhesive layer 5 has (i) a light transmittance that allows the light transmittance of the transparent electrode 10 to be a desired value, and (ii) after the metal foil and the transparent resin film are bonded together with an adhesive. When the first conductive layer 6 is formed by patterning the metal foil into a desired shape by etching, it has etching resistance, and (iii) porous in the process of manufacturing the dye-sensitized solar cell. It has solvent resistance to the dye solution used when the dye is supported on the semiconductor electrode, and (iv) resistant to the electrolyte used in the dye-sensitized solar cell (electrolyte resistance) It is preferable to have

  Specific examples of the material of the adhesive layer 5 that satisfies such requirements include acrylic, ester, urethane, fluorine, polyimide, epoxy, polyurethane ester, and acrylic urethane adhesives. . These adhesives may be an ultraviolet curable type or a thermosetting type. The transparent resin film 1 and the above-mentioned metal foil can be joined by a method such as a dry lamination method or a wet lamination method using the above-described adhesive.

  The 1st conductive layer 6 is for improving the electroconductivity of the transparent electrode 10, and is a metal conductive layer which exhibits the shape which combined many thin wires. Here, the “metal conductive layer” in the present invention includes a conductive layer formed of an alloy in addition to a conductive layer formed of a single metal.

  The shape of the first conductive layer 6 in plan view is within a range in which the light transmittance of the transparent electrode 10 takes a desired value, for example, a lattice shape as shown in FIG. It can be selected as appropriate.

  From the viewpoint of obtaining a transparent electrode 10 having high conductivity, the material of the first conductive layer 6 is copper (Cu), iron (Fe), nickel (Ni), chromium (Cr), aluminum (Al), gold ( It is preferable to use a metal or an alloy such as Au), silver (Ag), titanium (Ti), and stainless steel, and among these, it is preferable to use copper, nickel, titanium, stainless steel, and the like, which are highly conductive materials. Further, from the viewpoint of suppressing the manufacturing cost of the electrode substrate 20, it is preferable to use copper, nickel, and stainless steel, which are inexpensive metals. The film thickness of the 1st conductive layer 6 can be suitably selected within the range from which the light transmittance of the transparent electrode 10 and sheet resistance become a desired value according to the material and shape, and is about 5-50 micrometers in general.

  When a copper thin film is used as the material for the first conductive layer 6, a conductive film used as a material for the electromagnetic wave shielding film, that is, a film in which a copper foil is bonded to one side of a transparent resin film by an adhesive, or Since the electromagnetic wave shielding film itself can be diverted, it is advantageous in reducing the manufacturing cost of the electrode substrate 20. When the conductive film or the electromagnetic wave shielding film is diverted, the transparent resin film as the base material can be used as the transparent resin film 1 of the electrode substrate 20 as it is.

  The corrosion prevention layer 7 is for preventing the electrolyte from penetrating into the first conductive layer 6 when a dye-sensitized solar cell is produced using the electrode substrate 20, and electroplating, electroless It is formed by plating or chemical conversion treatment. Moreover, this corrosion prevention layer is formed of a material having corrosion resistance to the electrolyte for the dye-sensitized solar cell.

  The second conductive layer 8 receives carriers (electrons) from the porous semiconductor electrode 15 when the dye-sensitized solar cell is irradiated with light in a predetermined wavelength range, or the porous semiconductor electrode 15 receives carriers. (Hole) is supplied and can be formed using various conductive metal oxides. When the first conductive layer 6 has an opening, the second conductive layer 8 is preferably formed so as to cover the first conductive layer 6 including the opening in plan view.

  The second conductive layer 8 is made of indium tin oxide (ITO), fluorine-doped tin oxide, tin oxide, indium zinc oxide (IZO), zinc oxide (ZnO) or the like in consideration of light transmittance and conductivity. Among these, it is preferable to form by fluorine dope tin oxide or ITO which is a material excellent in both conductivity and light transmittance. The film thickness of the second conductive layer 8 can be appropriately selected within the range of about 0.1 nm to 500 nm, and the sheet resistance is preferably as low as possible, generally about 15Ω / □ or less.

  In manufacturing the electrode substrate 20, first, a preparation process for preparing the transparent resin film 1 having the first conductive layer 6 formed on one side, at least the corrosion prevention layer 7 so as to cover the outer surface of the first conductive layer 6. The transparent electrode 10 is formed on the transparent resin film 1 by sequentially performing a corrosion preventing layer forming step for forming a second conductive layer forming step for forming a second conductive layer 8 made of a metal oxide covering the corrosion preventing layer 7. Form.

  The transparent resin film 1 prepared in the preparation step, that is, the transparent resin film 1 on which the first conductive layer 6 is formed on one side may be manufactured by itself or may be purchased by others.

  When the first conductive layer 6 is formed by itself, the first conductive layer 6 is formed by etching the original metal foil or metal vapor deposition film into a desired pattern shape using, for example, photolithography. be able to. In forming the first conductive layer 6 using photolithography, for example, resist coating, pre-baking, exposure (contact exposure) processing, development processing, and post-baking are sequentially performed to form a resist pattern (etching mask). After this resist pattern (etching mask) is used for etching with an etchant such as iron oxide or ferric chloride solution, the resist pattern (mask) is stripped and rinsed in this order. The metal vapor deposition film can be formed by physical vapor deposition (PVD) such as vacuum vapor deposition, sputtering, or ion plating, or chemical vapor deposition (CVD) such as plasma CVD. it can.

  When forming a metal vapor deposition film, if a mask having an opening having a pattern corresponding to the shape of the first conductive layer 6 to be formed is used, the first conductive layer 6 is directly formed only by forming the metal vapor deposition film. be able to.

  In the corrosion prevention layer forming step performed subsequent to the preparation step described above, the above-described corrosion prevention layer 7 is formed by electroplating, electroless plating, or chemical conversion treatment. According to electroplating, electroless plating, or chemical conversion treatment, even if the heat resistance of the transparent resin fill 1 is low, a relatively dense corrosion prevention layer 7 can be easily formed. The plating conditions and chemical conversion treatment conditions at this time are appropriately selected according to the heat resistance of the transparent resin film 1 and the composition of the corrosion prevention layer 7 to be formed.

  For example, according to electroplating, nickel (Ni), zinc (Zn), gold (Au), platinum (Pt), chromium (Cr), aluminum (Al), cadmium (Cd), tungsten (W), tin (Sn ), Cobalt (Co), iron (Fe), or other metals, or alloys of the above metals, and forming a corrosion prevention layer 7 having corrosion resistance to the electrolyte for dye-sensitized solar cells. it can. Examples of plating baths used for electroplating include ordinary plating baths containing the above-described metal ions (cyanogen bath, borofluoride bath, pyrophosphate bath, zincate bath, hypophosphorous acid or boron hydride salt). A plating bath to which is added) can be used.

  According to electroless plating, nickel (Ni), zinc (Zn), gold (Au), platinum (Pt), chromium (Cr), aluminum (Al), cadmium (Cd), tungsten (W), tin (Sn ), Cobalt (Co), iron (Fe), titanium (Ti), manganese (Mn), zirconium (Zr) and other metals, or an alloy of the above metals, and an electrolyte for dye-sensitized solar cells Therefore, the corrosion prevention layer 7 having corrosion resistance can be formed. As a plating bath at the time of electroless plating, for example, a normal plating bath (alkali bath or the like) containing the above metal ions can be used. According to electroless plating, a corrosion prevention layer can be formed on the entire object by immersing the entire object in the plating solution.

  The formation of the corrosion prevention layer 7 by the chemical conversion treatment method is, for example, a transparent resin in which a chemical conversion treatment agent containing a metal phosphate (hereinafter referred to as “phosphate metal chlorination treatment agent”) is formed up to the first conductive layer 6. It can be carried out by coating the film 1 from the first conductive layer 6 side, or by immersing the transparent resin film 1 formed up to the first conductive layer 6 in a metal phosphate chlorination treatment agent. When applying the metal phosphate chlorination treatment agent, a known method can be used as the application method.

  Specific examples of the metal phosphate include, for example, chromium (III) phosphate, chromium (VI) phosphate, zirconium phosphate, titanium phosphate, lithium phosphate, manganese phosphate, phosphorus Examples include zinc oxide salts, cobalt phosphate salts, tin phosphate salts, nickel phosphate salts, tungsten phosphate salts, and molybdenum phosphate salts. These metal phosphates are used singly or in combination of two or more. The chemical conversion treatment agent may contain one or more water-soluble synthetic resins such as phenol resin, acrylic resin, and urethane resin. When the chemical conversion treatment agent contains a water-soluble synthetic resin, it is preferable to perform a heat treatment at about 80 to 200 ° C. after the chemical conversion treatment to promote a crosslinking reaction such as a covalent bond or a coordinate bond. By this heat treatment, a denser corrosion prevention layer 7 can be formed.

  In addition, when forming the corrosion prevention layer 7, it is preferable to degrease beforehand as a pretreatment. As a method of degreasing treatment, known methods such as an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, and an acid activation method can be used. By performing a degreasing process in advance, a denser corrosion prevention layer 7 can be formed.

  The corrosion prevention layer 7 only needs to cover at least the outer surface (upper surface and each side surface) of the first conductive layer 6, but as illustrated, in addition to the outer surface of the first conductive layer 6, the first conductive layer It is preferable that a region not covered with the first conductive layer 6 in the surface of the base layer 6 (adhesive layer 5 in the illustrated example) is also covered. By forming such a corrosion prevention layer 7, when a dye-sensitized solar cell is manufactured using the electrode substrate 20, the electrolyte penetrates into the interface between the first conductive layer 6 and the underlayer. It is possible to suppress the corrosion of the first conductive layer 6 and the corrosion of the first conductive layer 6 caused by the corrosion or dissolution of the underlayer.

  If necessary, the corrosion prevention layer 7 can be chromated. This chromate treatment is particularly suitable when the main component of the corrosion prevention layer 7 is zinc. By performing the chromate treatment, it is possible to further suppress the penetration of the electrolyte into the first conductive layer 6 when a dye-sensitized solar cell is manufactured using the electrode substrate 20. The conditions for the chromate treatment are appropriately selected according to the heat resistance of the transparent resin film 1 and the composition of the corrosion prevention layer 7. When the corrosion prevention layer 7 is chromated, a surface treatment layer (not shown) formed by the chromate treatment is interposed between the corrosion prevention layer 7 and the second conductive layer 8.

  The surface treatment layer is, for example, a coating made of chromium-containing metal, a chromium alloy made of a copper chromium alloy, or chromium oxide. The chromate treatment is particularly preferably performed on the corrosion prevention layer 7 formed by galvanization or zinc alloy plating. When the chromate treatment target is a zinc plating layer or a zinc alloy plating layer, the adhesion between the surface treatment layer (chromate treatment layer) and the plating layer (corrosion prevention layer 7) can be further enhanced.

  After performing the corrosion prevention layer forming step for forming the corrosion prevention layer as described above, the second conductive layer forming step for forming the metal oxide second conductive layer 8 covering the corrosion prevention layer 7 is performed. The transparent electrode 10 can be obtained.

  The formation of the second conductive layer 8 can be performed by physical vapor deposition such as vacuum deposition, sputtering, or ion plating, and is performed by ion plating or sputtering from the viewpoint of reducing manufacturing costs. It is preferable.

(3) Porous semiconductor electrode The porous semiconductor electrode 15 can receive carriers (electrons) from the photoexcited dye 17, or can transmit carriers (holes) to the photoexcited dye 17. If it is. The porous semiconductor electrode 15 can be a single component layer or a mixture layer. Furthermore, it can also be set as the laminated body of a some porous semiconductor film. The conductivity type of the porous semiconductor electrode 15 is usually N-type.

  Examples of the material of the porous semiconductor electrode 15 include titanium oxide, zinc oxide, tin oxide, indium tin oxide, zirconium oxide, silicon oxide, magnesium oxide, aluminum oxide, cesium oxide, bismuth oxide, manganese oxide, yttrium oxide, and oxide. A metal oxide semiconductor such as tungsten, tantalum oxide, niobium oxide, or lanthanum oxide can be used. These metal oxide semiconductors are suitable for forming a porous semiconductor layer, and are preferable because they can improve the energy conversion efficiency of the dye-sensitized solar cell and reduce the cost. Considering the durability of the dye-sensitized solar cell using the electrode substrate 20 and the safety and economy when manufacturing the electrode substrate 20, titanium oxide is preferable as the material of the porous semiconductor electrode 15, and in particular. Anatase type titanium oxide is preferable. The “semiconductor fine particles” referred to in the present invention include not only fine-particle-shaped semiconductors but also amorphous micro-semiconductors and fine-powder semiconductors.

  The average particle diameter of the metal oxide semiconductor fine particles is preferably within a range of about 10 to 250 nm, and particularly preferably has a size that exhibits a quantum size effect. The film thickness of the porous semiconductor layer 7 can be appropriately selected within a range of approximately 5 to 30 μm.

  In manufacturing the electrode substrate 20, the porous semiconductor electrode forming step of forming the porous semiconductor electrode 15 on the second conductive layer 8 using a large number of semiconductor fine particles is performed following the above-described second conductive layer forming step. . From the viewpoint of increasing the photoelectric conversion efficiency of the dye-sensitized solar cell using the electrode substrate 20, it is preferable to support the dye 9 on the porous semiconductor electrode 15 in a monomolecular film and as much as possible. For this, it is preferable to increase the specific surface area of the porous semiconductor electrode 15 as much as possible. From the same viewpoint, the porous semiconductor electrode 15 is particularly preferably a mesoscopic porous body that exhibits a quantum size effect.

  The porous semiconductor electrode 15 can be formed by, for example, a sol-gel method, but when formed by the sol-gel method, a sintering process at a relatively high temperature is required, and thus the heat resistance of the transparent resin film 1 is low. It is unsuitable for cases. In order to form the porous semiconductor electrode 15 at a relatively low temperature, a coating liquid in which desired metal oxide semiconductor fine particles are dispersed is prepared, and this coating liquid is coated on the second conductive layer 8 and then dried. preferable.

  If necessary, the coating liquid may contain fine particles that function as light scattering centers (not shown) in the porous semiconductor electrode 15. By incorporating these fine particles into the porous semiconductor electrode 15, the amount of light contributing to the photoexcitation of the dye 17 can be increased, and as a result, the photoelectric conversion efficiency of the dye-sensitized solar cell can be improved. Specific examples of the fine particles functioning as the light scattering center include titanium oxide fine particles having a particle diameter of approximately 50 to 200 nm.

  The coating liquid for forming the porous semiconductor electrode 15 is, for example, (i) a method in which semiconductor fine particles are precipitated as crystallized fine particles in a predetermined solvent to form a sol liquid, or (ii) the semiconductor fine particles are ball milled or sand milled. It can be prepared by a method of mixing with an appropriate dispersion medium using a roll mill or the like and dispersing the mixture in a dispersion medium using a known dispersing machine such as a kneader, homogenizer, or planetary mixer. When preparing the coating liquid by the method (ii) above, if the semiconductor fine particles to be used are agglomerated, an appropriate time in the process until obtaining the dispersion liquid, for example, before mixing with the dispersion medium, It is preferable to loosen the agglomerated semiconductor fine particles in the process of mixing with or after mixing with the dispersion medium. The coating solution can also be prepared by mixing the sol solution (i) and the dispersion (ii).

  Examples of the dispersion medium include (a) a chlorine-based dispersion medium such as chloroform, methylene chloride, and dichloroethane, (b) an ether-based dispersion medium such as tetrahydrofuran, and (c) an aromatic hydrocarbon-based dispersion such as toluene and xylene. Medium, (d) ketone dispersion medium such as acetone, methyl ethyl ketone, (e) ester dispersion medium such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, (f) isopropyl alcohol (IPA), ethanol, methanol, butyl alcohol Alcohol-based dispersion medium such as (g) and others (N-methyl-2-pyrrolidone, pure water, etc.) can be used. When a binder described later is contained in the coating solution, a dispersion medium capable of dissolving the binder is used.

  In order to improve the adhesion between the porous semiconductor electrode 15 and the transparent electrode 10 and the mechanical strength of the porous semiconductor electrode 15 itself, a binder made of a polymer material may be dissolved in the coating solution. it can. For example, a cellulose resin, a polyester resin, a polyamide resin, a polyacrylate resin, a polycarbonate resin, a polyurethane resin, a polyolefin resin, a polyvinyl acetal resin, a fluorine resin, a polyimide resin, or a polyethylene glycol Such polyhydric alcohols can be used as a binder. The amount of binder added to the coating solution is preferably as small as possible. Specifically, the ratio of the binder to the total solid content in the coating liquid is preferably 0.5% by mass or less, and more preferably 0.2% by mass or less.

  In addition to the above-described binder, the coating liquid can contain various additives in order to improve the coating suitability. Examples of the additive include a surfactant, a viscosity modifier, a dispersion aid, a pH adjuster, and the like. For example, nitric acid, hydrochloric acid, acetic acid, dimethylformamide, ammonia or the like can be used as a pH adjuster.

  As the coating method of the coating liquid, die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating, bar coating, blade coating, knife coating, air knife coating, slot die coating, slide die coating, dip coating, micro bar coating, Various methods such as microbar reverse coating, screen printing (rotary method), ink jet, spray coating, and the like can be applied. By applying such a coating method one or more times, coating and drying of the coating solution are repeated to form the porous semiconductor electrode 15 having a desired film thickness. The coating film needs to be dried at a temperature lower than the heat resistance temperature of the transparent resin film 1. Specifically, it is preferable to heat and dry within a temperature range of approximately 100 ° C. or higher and lower than the heat resistant temperature of the transparent resin film 1.

(4) Dye Dye 17 is for sensitizing porous semiconductor electrode 15. As this pigment | dye 17, (A) the absorption wavelength range has extended to the long wavelength side rather than the absorption wavelength range of the porous semiconductor electrode 15, (B) The porous semiconductor electrode 15 is an N-type semiconductor. In the case where the energy level of the electrons when photoexcited is higher than the position of the conduction band edge of the porous semiconductor electrode 15, (C) when the porous semiconductor electrode 15 is an N-type semiconductor, The time required to inject carriers into the porous semiconductor electrode 15 is preferably shorter than the time required to recapture carriers from the porous semiconductor electrode 15.

  For example, when the porous semiconductor electrode 15 is formed of anatase-type titanium oxide, it is preferable to use a ruthenium complex represented by the following formula (I) as the dye 17.

  In order to obtain a dye-sensitized solar cell with high photoelectric conversion efficiency using the electrode substrate 20, among the ruthenium complexes represented by the formula (I), X is NCS (thiocyanate) (cis-di ( It is particularly preferred to use thiocyanate) -N, N′-bis (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II).

  Of course, metal complex dyes other than the ruthenium complex described above and organic dyes can also be used. Specific examples of the organic dye include acridine dyes, azo dyes, indigo dyes, quinone dyes, coumarin dyes, merocyanine dyes, and phenylxanthene dyes. Of these organic dyes, coumarin dyes are preferable.

  In manufacturing the electrode substrate 20, a dye supporting step for supporting the dye on the porous semiconductor electrode 15 is performed following the porous semiconductor electrode forming step described above. In this step, the dye 17 is supported on the surface of the semiconductor fine particles 15 a forming the porous semiconductor electrode 15. From the viewpoint of obtaining a dye-sensitized solar cell with high photoelectric conversion efficiency, it is preferable to support the dye 17 on as many semiconductor fine particles 15a as possible, and in particular, each of the semiconductor fine particles 15a forming the porous semiconductor electrode 15. It is preferable to support the dye 17 on the surface.

  For this purpose, it is preferable to support the dye 17 on the porous semiconductor electrode 15 by a method capable of adsorbing the dye 17 to the inner surface of the pores of the porous semiconductor electrode 15. For example, a dye solution (hereinafter referred to as “dye-supporting coating liquid”) is prepared, and the electrode substrate formed up to the porous semiconductor electrode 15 is immersed in the dye-supporting coating liquid, and then dried. According to the method, or a method of applying a dye-supporting coating liquid to the porous semiconductor electrode 15 and allowing it to penetrate and then drying, the dye 9 is adsorbed to the inner surface of the pores of the porous semiconductor electrode 15. It is also possible to carry the dye 17 on the surface of each of the semiconductor fine particles 15a. The dye-supporting coating liquid is prepared by appropriately selecting either an aqueous solvent or an organic solvent according to the type of the dye used.

  From the viewpoint of obtaining a dye-sensitized solar cell with high photoelectric conversion efficiency, it is preferable to support the dye 17 on the porous semiconductor electrode 15 in the state of a monomolecular film. For this purpose, the dye 17 is supported on the porous semiconductor electrode 15. It is preferable that the excess dye is washed and removed with a solvent or the like that can be used for preparing the dye-supporting coating solution.

  By subjecting the porous semiconductor electrode 15 to surface treatment in advance, when the porous semiconductor electrode 15 is an N-type semiconductor, the moving speed of carriers from the dye 17 to the porous semiconductor electrode 15 can be increased. After the dye 17 is supported on the porous semiconductor electrode 15, a predetermined treatment is performed on the porous semiconductor electrode 15 and the dye 17, for example, the porous semiconductor electrode 15 is formed of titanium oxide, and the dye 17 is the ruthenium complex described above. In some cases, the photoelectric conversion efficiency of the dye-sensitized solar cell using the electrode substrate 20 can be improved by performing a treatment with a base such as t-butylpyridine.

(5) Arbitrary member A gas barrier layer, a patterning layer, etc. can be formed in the electrode substrate 20 as needed. Hereinafter, these optional members will be described.

(A) Gas barrier layer The gas barrier layer is formed by allowing oxygen or moisture to enter the dye-sensitized solar cell through the electrode substrate 20 when the dye-sensitized solar cell is manufactured using the electrode substrate 20, and the dye This is to prevent the electrolyte used in the sensitized solar cell from evaporating to the outside through the electrode substrate 20, and between the transparent resin film 1 and the transparent electrode 10 or the back surface of the transparent resin film 1 (transparent It means a surface opposite to the surface on which the electrode 10 is formed.

The oxygen permeability of the gas barrier layer is preferably about 1 cc / m ² / day · atm (about 10 ml / m ² / day / MPa) or less, and the water vapor permeability is about 1 g / m ² / day or less. It is preferable. Such a gas barrier layer is a vapor-deposited film of a desired organic material (meaning a film formed by physical vapor deposition or chemical vapor deposition, the same shall apply hereinafter) or film, or of a desired inorganic material. It can be formed by a deposited film.

  By preventing oxygen from entering the dye-sensitized solar cell, deterioration of the dye 17 and the electrolyte is suppressed, so that a decrease in the performance of the dye-sensitized solar cell over time can be suppressed. In addition, by suppressing the intrusion of moisture, for example, even when the second conductive layer 8 is formed of a material that is relatively easily deteriorated by moisture, such as ITO, the deterioration of its performance over time is suppressed. A decrease in the performance of the solar cell over time can be suppressed.

(B) Patterning layer The “patterning layer” in the present specification means a layer capable of changing the wettability of the surface by light irradiation. Specific examples of this patterning layer include: (i) a photocatalyst-containing layer having a structure in which a photocatalyst (fine particles of photo semiconductor) is dispersed in a hydrophobic binder, and (ii) hydrolysis and polycondensation of chlorosilane, alkoxysilane, or the like. The resulting organopolysiloxane layer, (iii) a reactive silicone-crosslinked organopolysiloxane layer with excellent water repellency and oil repellency, and (iv) a self-assembled film exhibiting water repellency using fluoroalkylsilane, etc. , Etc.

  The photocatalyst-containing layer (i) above changes the wettability of the exposed region by selectively exposing the surface with light in a wavelength region including the absorption wavelength of the photocatalyst contained in the photocatalyst-containing layer. This can be made hydrophilic. Such a photocatalyst-containing layer is prepared by, for example, preparing a coating liquid in which a photocatalyst is dispersed in a hydrophobic binder, applying the coating liquid to a desired location to form a coating film, and then drying the coating film. Can be formed.

  Moreover, each layer of said (ii)-(iv) can change the wettability of the exposed area | region by selectively exposing the surface, for example by ultraviolet light, and can hydrophilize here. In selectively exposing the surface of each layer of (ii) to (iv) above, a photocatalyst-containing layer can be provided on the surface of the photomask (ultraviolet mask) on the exposed object side, if necessary. By providing this photocatalyst-containing layer on the photomask, it is possible to perform a desired hydrophilization treatment with longer wavelength ultraviolet light.

  The patterning layer is provided on the transparent electrode 10 and is used as an underlayer for the porous semiconductor electrode 15. Of the surface of the patterning layer, the region where the porous semiconductor electrode 15 is to be formed is hydrophilized as described above. When the above-mentioned coating liquid that is a material of the porous semiconductor layer 15 is applied on the patterning layer in this state, a coating film, and thus the porous semiconductor electrode 15 is formed substantially only on the hydrophilic region. be able to.

  For example, in order to obtain a dye-sensitized solar cell having a large operating voltage or operating current, a plurality of relatively small cells are electrically connected in parallel or in series to the structure of this dye-sensitized solar cell. A structure is preferred. In this case, one transparent electrode 10 is formed on one electrode substrate 20 and a plurality of porous semiconductor electrodes 15 are formed thereon, or a plurality of transparent electrodes 10 are formed to form individual transparent electrodes 10. One porous semiconductor electrode 15 is formed on each electrode 10. The patterning layer is useful for forming a plurality of porous semiconductor electrodes 15 at desired locations.

  In the electrode substrate 20 composed of the members described above, the first conductive layer 6 made of metal is formed in addition to the second conductive layer 8 made of metal oxide, so that the overall conductivity is relatively easy. Can be increased. Further, since the corrosion prevention layer 7 covering the outer surface of the first conductive layer 6 is formed by electroplating, electroless plating, or chemical conversion treatment, the heat resistance of the transparent resin film 1 is relatively high. Even if it is low, the corrosion prevention layer 7 can be easily densified.

  Furthermore, this corrosion prevention layer 7 has corrosion resistance with respect to the electrolyte for dye-sensitized solar cells. Therefore, even if the halogen-based redox couple is contained in the electrolyte of the dye-sensitized solar cell, and the material of the first conductive layer 6 is easily corroded by the halogen-based redox couple. However, it is possible to suppress a decrease in conductivity of the electrode substrate 20 due to the corrosion of the first conductive layer 6 by the redox pair. Even when inexpensive and highly conductive copper or the like is used as the material of the first conductive layer 6, it is possible to suppress a decrease in the conductivity of the electrode substrate 20.

  For these reasons, according to the electrode substrate 20, it is possible to easily obtain a dye-sensitized solar cell with high photoelectric conversion efficiency and suppressed performance degradation over time at low cost.

<Dye-sensitized solar cell substrate (second embodiment)>
FIG. 3 is a schematic view showing another example of the basic cross-sectional structure of the electrode substrate for a dye-sensitized solar cell of the present invention. The illustrated dye-sensitized solar cell electrode substrate 20A (hereinafter referred to as "electrode substrate 20A") has a first conductive layer 6A formed of aluminum having a purity higher than 99.3%, and FIG. The corrosion prevention layer 7 formed by the electrode substrate 20 of the first form shown in FIG. 5 is different from the electrode substrate 20 of the first form in that it is omitted from the electrode substrate 20A.

  Except this point, the electrode substrate 20A of this embodiment has the same configuration as the electrode substrate 20 of the first embodiment. As illustrated, the second conductive layer 8 covers the outer surface of the first conductive layer 6A and the surface of the adhesive layer 5 exposed without being covered by the first conductive layer 6A. . Among the constituent members shown in FIG. 3, the constituent members other than the first conductive layer 6A are common to the electrode substrate 20 shown in FIG. 1, so that these constituent members have the same reference numerals as those used in FIG. The description is omitted.

  The first conductive layer 6A is made of high-purity aluminum as described above. For example, the first conductive layer 6A is formed by bonding an aluminum foil having a desired film thickness to the transparent resin film 1 with the adhesive layer 5, forming an etching mask having a predetermined shape thereon, and performing etching to form the desired shape. Can be obtained by patterning.

  The purity of aluminum used as the material of the first conductive layer 6A is preferably higher than 99.3% from the viewpoint of obtaining an electrode substrate 20A having high corrosion resistance to an electrolytic solution containing an iodine-based redox couple. More preferably, it is 5% or more.

  As described above, since the electrode substrate 20A has the first conductive layer 6A formed of high-purity aluminum, an electrode for a dye-sensitized solar cell in which an iodine-based redox pair is contained in the electrolytic solution. It is particularly suitable as a substrate. In this electrode substrate 20A5, since the corrosion resistance of the first conductive layer 6A is high, the first conductive layer 6A is corroded even if the corrosion prevention layer 7 used in the electrode substrate 20 of the first form is omitted. It is possible to suppress a decrease in conductivity due to the above. Therefore, according to the electrode substrate 20A, it is possible to easily obtain a dye-sensitized solar cell that has high photoelectric conversion efficiency and suppresses a decrease in performance over time at low cost. If necessary, a corrosion prevention layer covering the outer surface of the first conductive layer 6A may be formed by electroplating, electroless plating, or chemical conversion treatment in the same manner as in the electrode substrate 20 of the first embodiment. it can.

<Dye-sensitized solar cell (first embodiment)>
FIG. 4 is a schematic view showing an example of a basic cross-sectional structure of the dye-sensitized solar cell of the present invention. In the illustrated dye-sensitized solar cell 50, the above-described electrode substrate 20 of the first form is used as a photoelectrode, and the first conductive film 24 and the second conductive film 26 are provided on one side of the transparent resin film 22. A dye-sensitized solar cell electrode substrate 30 (hereinafter referred to as “electrode substrate 30”) stacked in order is used as a counter electrode. Instead of the electrode substrate 30, the transparent electrode 10 shown in FIG. 1 is formed on one side of the transparent resin film, and a conductive film corresponding to the second conductive film 26 shown in FIG. An electrode substrate may be used.

  Since the configuration of the electrode substrate 20 has already been described, the description thereof is omitted here. Moreover, as the transparent resin film 22 and the 1st electrically conductive film 24 in the electrode substrate 30 used as a counter electrode, the thing similar to the transparent resin film 1 or the 2nd conductive layer 8 in the electrode substrate 20 mentioned above is used, respectively. Therefore, description of the transparent resin film 22 and the first conductive film 24 is also omitted here.

  The second conductive film 26 is for improving the conductivity of the electrode substrate 20. The second conductive film 26 may be formed by appropriately selecting a conductive material having corrosion resistance to the electrolyte according to the type of electrolyte used in the dye-sensitized solar cell using the electrode substrate 30. preferable. The material of the second conductive film 26 is most preferably platinum (Pt), but the second conductive film 26 can also be formed of carbon, a conductive polymer, or the like. From the viewpoint of obtaining a dye-sensitized solar cell with high photoelectric conversion efficiency using the electrode substrate 30, one ionic species constituting a redox pair in the electrolyte of the dye-sensitized solar cell reacts with a carrier during light irradiation. The second conductive film 26 is preferably formed of a metal (for example, platinum (Pt)) that can function as a catalyst when generating the other ionic species.

  The second conductive film 26 can be formed by, for example, a vapor deposition method, a sputtering method, a CVD method, or the like, and the film thickness can be appropriately selected within a range of approximately 1 to 500 nm. From the viewpoint of reducing the manufacturing cost of the electrode substrate 30, it is preferable to form the second conductive film 26 by sputtering.

  The electrode substrate 20 that is a photoelectrode and the electrode substrate 30 that is a counter electrode are arranged such that the porous semiconductor electrode 15 in the electrode substrate 20 and the second conductive film 26 in the electrode substrate 30 face each other. The electrolyte layer 35 is interposed between the electrode substrates 20 and 30. The transparent electrode 10 in the electrode substrate 20 is connected to a load 45 by a lead wire 40a, and this load 45 is connected to the first conductive film 24 in the electrode substrate 30 by a lead wire 40b. Although not shown in the drawing, in the dye-sensitized solar cell 50, in order to prevent the electrolyte forming the electrolyte layer 35 from leaking, the periphery of the electrode substrates 20, 30 and the electrolyte layer 35 is disposed. Sealed with a sealant.

  Spacers such as glass spacers, resin spacers, and olefinic porous membranes are disposed between the electrode substrate 20 and the electrode substrate 30 in order to keep the distance between the electrode substrates 20 and 30 accurately at a desired interval and prevent short circuit. May be. The spacer can be formed in advance on one of the electrode substrates 20 and 30, or can be used by being fixed to at least one of the electrode substrates 20 and 30 when assembling the dye-sensitized solar cell. . The spacer can also serve as a sealant.

  The electrolyte layer 35 is located between the electrode substrate 20 and the electrode substrate 30 and is reduced by the photoexcited dye 17, while being oxidized by carriers (electrons) supplied through the electrode substrate 30. A closed circuit including the substrate 20, the lead wire 40a, the load 45, the lead wire 40b, and the electrode substrate 30 can be formed.

  As the material of the electrolyte layer 35, various electrolytes used for dye-sensitized solar cells containing at least a redox pair contributing to carrier transport can be used, and the form thereof is liquid, solid, and It may be any gel. From the viewpoint of improving the durability and stability of the dye-sensitized solar cell 50, it is preferable to use a room temperature molten salt electrolyte or a gel electrolyte.

The redox couple is not particularly limited as long as it is used for an electrolyte, and the combination of raw materials includes a combination of iodine and iodide, or a combination of bromine and bromide. For example, specific examples of combinations of iodine and iodide include metal iodides such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI ₂ ), and iodine. A combination with (I ₂ ) can be mentioned. Specific examples of combinations of bromine and bromide include lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), calcium bromide (CaBr ₂ ), and the like, and bromide (Br). ₂ ) and a combination thereof.

  When a gel electrolyte is used as the material of the electrolyte layer 35, the electrolyte may be a physical gel or a chemical gel. A physical gel is gelled near room temperature due to physical interaction, and a chemical gel is a gel formed by a chemical bond such as a crosslinking reaction. The physical gel can be prepared by using a gelling agent such as polyacrylonitrile or polymethacrylate, and the chemical gel can be an acrylic acid ester or methacrylic acid ester.

  When a solid electrolyte is used as the material of the electrolyte layer 35, it is preferable to use a conductive polymer having a high hole transporting property such as copper iodide (CuI), polypyrrole, or polythiophene as the electrolyte.

  Although the thickness of the electrolyte layer 35 can be selected as appropriate, the sum of the thickness of the electrolyte layer 35 and the thickness of the porous semiconductor electrode 15 is in the range of 2 μm to 100 μm, of which the range is 2 μm to 50 μm. Thus, it is preferable to select the thickness of the electrolyte layer 35. If the thickness of the electrolyte layer 35 is thinner than the above range, the porous semiconductor electrode 15 and the second conductive film 26 are likely to come into contact with each other, causing a short circuit. On the other hand, when the thickness of the electrolyte layer 35 is thicker than the above range, the internal resistance of the dye-sensitized solar cell 50 is increased and the performance is deteriorated.

  The electrolyte layer 35 described above can be formed by various methods depending on the material. For example, a method of forming an electrolyte layer forming coating solution used for forming the electrolyte layer 35 by applying it on the porous semiconductor electrode 15 and drying it (hereinafter sometimes referred to as “coating method”), Alternatively, the electrode substrates 20 and 30 are arranged so that the porous semiconductor electrode 15 and the second conductive layer 26 have a predetermined interval, and an electrolyte layer forming coating solution is placed in the gap between the electrode substrate 20 and the electrode substrate 30. Examples thereof include a method of forming the electrolyte layer 35 by injection (hereinafter sometimes referred to as “injection method”). Hereinafter, these “coating method” and “injection method” will be described.

(I) Coating method The coating method is a method mainly used for forming a solid electrolyte layer. As a coating solution for forming an electrolyte layer used in this coating method, at least a redox pair and this redox pair are used. A material containing a polymer to be retained is used. In addition, it is preferable to add a crosslinking agent, a photopolymerization initiator, and the like.

  The coating solution for forming the electrolyte layer can be applied by die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating, bar coating, blade coating, knife coating, air knife coating, slot die coating, slide die coating, dip coating, and micro bar. It can be performed by various methods such as coating, microbar reverse coating, and screen printing (rotary method).

  When the above-mentioned photopolymerization initiator is contained in the electrolyte layer forming coating solution, the electrolyte layer 35 is formed by applying the electrolyte layer forming coating solution and then exposing the photopolymerization initiator to light. Can do.

(II) Injection Method The injection method is a method used to form a liquid, gel, or solid electrolyte layer. When forming the electrolyte layer 35 by this method, the spacer described above is used. Thus, it is preferable to previously form a cell in which the electrode substrate 20 and the electrode substrate 30 are held at a desired interval. Injection | pouring of the coating liquid for electrolyte layer formation can be performed using a capillary phenomenon, for example. In the case of forming the gel-like or solid electrolyte layer 35, the two-dimensional or three-dimensional crosslinking reaction is performed by, for example, performing temperature adjustment, ultraviolet irradiation, electron beam irradiation, etc. after injecting the electrolyte layer forming coating solution. Give rise to

  Since the dye-sensitized solar cell 50 described above includes the electrode substrate 20 of the first embodiment described above, the photoelectric conversion efficiency is high for the same reason as described in the description of the electrode substrate 20. In addition, it is easy to obtain a product in which a decrease in performance over time is suppressed at low cost.

<Dye-sensitized solar cell (second form)>
FIG. 5 is a schematic view showing another example of the basic cross-sectional structure of the dye-sensitized solar cell of the present invention. The illustrated dye-sensitized solar cell 60 is different from the dye-sensitized solar cell 50 of the first embodiment in that the electrode substrate 20A of the second embodiment shown in FIG. 3 is used as a photoelectrode. Except for this point, the dye-sensitized solar cell 60 of this embodiment has the same configuration as that of the dye-sensitized solar cell 50 of the first embodiment. Therefore, the electrode of the components shown in FIG. Constituent members other than the substrate 20A are denoted by the same reference numerals as those used in FIG. 4 and description thereof is omitted.

  Since the dye-sensitized solar cell 60 having such a configuration includes the electrode substrate 20A of the second embodiment described above, photoelectric conversion is performed for the same reason as described in the description of the electrode substrate 20A. It is easy to obtain a product with high efficiency and suppressed performance degradation over time at low cost.

<Example 1>
(Preparation process)
First, dry lamination using a 100 μm thick polyethylene terephthalate (PET) film (E5100 manufactured by Toyobo Co., Ltd.) and a 9 μm thick copper foil using a urethane adhesive (Tg; 20 ° C., average molecular weight: 30,000). Bonded by processing.

  Next, a resist is applied on the copper foil to form a resist layer, and the resist layer is subjected to an exposure process using a mask having a predetermined shape and a development process in order to form an etching mask having a predetermined shape. After that, the copper foil was etched, and then the resist was removed (peeling of the etching mask). Thereby, the said copper foil was patterned in the grid | lattice form, and the 1st conductive layer was obtained. The size of the opening in the first conductive layer (the part corresponding to the grid eyes) is 300 μm □, and the line width of each part is 10 μm. The aperture ratio of the first conductive layer is 90%. From each opening of the first conductive layer, the adhesive layer used to bond the PET film and the copper foil is exposed.

(Corrosion prevention layer forming process)
First, nickel (Ni) -tin (Sn) is dissolved in water at a rate of 300 g / l of nickel chloride, 15 g / l of tin chloride, 56 g / l of acidic ammonium fluoride, and 30 g / l of boric acid. An alloy plating bath was prepared.

  Next, the above PET film on which the first conductive layer was formed was immersed in the above plating bath and electroplated for 10 minutes. Thereby, the corrosion prevention layer which consists of a Ni-Sn alloy was formed in the outer surface of the 1st conductive layer. The composition of the corrosion prevention layer was identified by X-ray diffraction.

(Second conductive layer forming step)
The PET film formed up to the corrosion prevention layer is placed in the chamber of the ion plating apparatus, and the film forming pressure is 1.5 × 10 ⁻¹ Pa, the argon gas flow rate is 18 sccm, the oxygen gas flow rate is 28 sccm, and the film formation is performed. Indium tin oxide (ITO) as a sublimation material was deposited under the condition of a current value of 60 A to form a second conductive layer made of ITO having a thickness of 150 nm. The second conductive layer covers the corrosion prevention layer and also covers a region of the adhesive layer surface that has been exposed without being covered by the first conductive layer or the corrosion prevention layer.

  By forming up to the second conductive layer, a transparent electrode composed of the adhesive layer, the first conductive layer, and the second conductive layer was formed on one side of the PET film. The surface resistance value of this transparent electrode was 0.052Ω / □.

(Durability check)
In order to confirm the resistance of the PET film formed up to the transparent electrode to the iodine electrolyte, an iodine electrolyte solution using methoxyacetonitrile as a solvent was first prepared. This iodine electrolyte solution was lithium iodide at a rate of 0.1 mol / l, iodine at 0.05 mol / l, dimethylpropylimidazolium iodide at 0.3 mol / l, and tertiary butylpyridine at a rate of 0.5 mol / l. Contains each.

  Next, the above-mentioned PET film formed up to the transparent electrode was immersed in the iodine electrolyte solution all day and night, and then the surface resistance value was measured. As a result, the surface resistance value after being immersed in the iodine electrolyte solution was 0.051Ω / □, and the resistance value before immersion was maintained.

(Porous semiconductor electrode formation process)
First, titanium oxide (TiO ₂ ) fine particles having a primary particle size of 15 nm (F-5 manufactured by Showa Denko KK) and a polyester resin as a binder are used in a mixture of water and polypropylene glycol monomethyl ether. Then, a coating solution (slurry) containing 20.5% by mass of the TiO ₂ fine particles and 0.3% by mass of the binder was prepared.

Next, the slurry is applied onto the transparent electrode by the doctor blade method and then dried at 150 ° C. for 30 minutes to form a porous semiconductor having a film thickness of 12 μm formed by a large number of semiconductor fine particles (TiO ₂ fine particles). An electrode was obtained.

(Dye support process)
A dye-supporting coating solution prepared by dissolving a ruthenium complex (manufactured by Kojima Chemical Co., Ltd.) as a sensitizing dye in ethanol so that its concentration is 3 × 10 ⁻⁴ mol / l is prepared. The PET film formed up to the electrode was immersed in the dye-carrying coating solution and allowed to stand for 1 hour at a liquid temperature of 40 ° C. Next, the PET film was lifted from the dye-carrying coating solution, and the dye-carrying coating solution adhering to the porous semiconductor electrode was air-dried. Thus, the surface of the semiconductor particles forming the porous semiconductor electrode (TiO ₂ fine particles) The above dye is carrying.

  Thereafter, the above-described porous semiconductor electrode is trimmed so as to be a 1 cm × 1 cm square when viewed in plan, and has the same configuration as that of the electrode substrate 20 shown in FIG. A substrate (hereinafter referred to as “electrode substrate A”) was obtained.

<Example 2>
A plating bath was prepared by dissolving nickel chloride in water at a rate of 35 g / l, zinc chloride at 7 g / l, sodium citrate at 118 g / l, and sodium hypophosphite at 64 g / l. A dye-sensitized solar cell electrode substrate (hereinafter referred to as “electrode substrate B”) was obtained in the same manner as in Example 1 except that the corrosion prevention layer was formed by the electroless plating used.

  The corrosion prevention layer formed in this example contains nickel and zinc, and this corrosion prevention layer is not only the outer surface of the first conductive layer but also the adhesive serving as the foundation of the first conductive layer. A region of the layer surface that is not covered by the first conductive layer is also covered.

  After the formation of the corrosion prevention layer, the durability of the transparent electrode was confirmed under the same conditions as in Example 1. As a result, the surface resistance value after immersion in the iodine electrolyte solution was 0.054Ω / □, and the resistance value before confirmation. Was maintained.

<Example 3>
An aqueous solution containing nickel phosphate as a main component (the concentration of nickel phosphate is 10% by mass) and a 5% by mass aqueous solution of an aminophenol-based resin (average molecular weight: 5000, amino content: 50 mol%) A dye-sensitized solar cell electrode substrate (hereinafter referred to as “a”) was prepared in the same manner as in Example 1 except that a metal phosphate chlorination treatment agent was prepared and a corrosion prevention layer was formed by chemical conversion treatment using this chemical conversion treatment agent. Electrode substrate C ") was obtained.

  The chemical conversion treatment was performed by applying a metal phosphate chlorination treatment agent to the first conductive layer and its surroundings with a wire bar and then heating and drying at 120 ° C. for 2 minutes. By this chemical conversion treatment, a chemical conversion treatment film layer (corrosion prevention layer) made of nickel phosphate was formed on the outer surface of the first conductive layer.

  After the formation of the corrosion prevention layer, the durability of the transparent electrode was confirmed under the same conditions as in Example 1. As a result, the surface resistance value after immersion in the iodine electrolyte solution was 0.050Ω / □, and the resistance value before confirmation. Was maintained.

<Example 4>
Adhering to one side of a PET film in the same manner as in Example 1 except that an aluminum foil having a thickness of 12 μm (Toyo Aluminum Co., Ltd., purity: 99.7%) was used as the material for the first conductive layer, and no corrosion prevention layer was formed. A dye-sensitized solar cell electrode substrate (hereinafter referred to as “electrode substrate D”) composed of an agent layer, a first conductive layer, a planarized transparent layer, and a second conductive layer was formed. The surface resistance value of this transparent electrode was 0.009Ω / □.

When the durability of the transparent electrode was confirmed under the same conditions as in Example 1, the surface resistance value after being immersed in the iodine electrolyte solution was 0.010Ω / □, and the resistance value before confirmation was maintained.

<Example 5>
First, under the same conditions as the formation of the second conductive layer in Example 1, an ITO film (thickness 150 nm) as a first conductive film was formed on one side of a 100 μm-thick PET film (E5100 manufactured by Toyobo Co., Ltd.). A platinum thin film (film thickness: 50 nm) as a second conductive film is formed thereon by a sputtering method, and a dye-sensitized solar cell electrode having the same configuration as that of the electrode substrate 30 shown in FIG. A substrate (hereinafter referred to as “electrode substrate X”) was obtained.

  The electrode substrate X and the electrode substrate A prepared in Example 1 were bonded together using a heat-sealing film having a thickness of 20 μm (Surlin (trade name) manufactured by DuPont), and the gap between the electrode substrate X and the electrode substrate A was Then, a coating solution for forming an electrolyte layer was filled to obtain a dye-sensitized solar cell having the same configuration as that of the dye-sensitized solar cell 50 shown in FIG.

  At this time, the above heat-sealing film was used by previously shaping the heat-sealing film into a rectangular frame shape so as to be fused only to the inner edge portions of the electrode substrate X and the electrode substrate A, respectively. As the electrolyte layer forming coating solution, methoxyacetonitrile is used as a solvent, and in this solvent, lithium iodide is 0.1 mol / l, iodine is 0.05 mol / l, and dimethylpropylimidazolium iodide is 0.3 mol / l. 1 and tertiary butylpyridine dissolved in a ratio of 0.5 mol / l were used.

In measuring the performance of the obtained dye-sensitized solar cell, the current-voltage characteristics when using pseudo-sunlight (AM1.5, irradiation intensity 100 mW / cm ² ) as a light source are shown as a source measure unit (Keutley 2400 type). ). As a result, the conversion efficiency as battery characteristics was 5.5%, and the fill factor was 0.62.

<Example 6>
A dye-sensitized solar cell was obtained in the same manner as in Example 5 except that the electrode substrate B produced in Example 2 was used in place of the electrode substrate A. The performance of this dye-sensitized solar cell was determined in the same manner as in Example 5. As a result, the conversion efficiency as battery characteristics was 5.2%, and the fill factor was 0.60.

<Example 7>
A dye-sensitized solar cell was obtained in the same manner as in Example 5 except that the electrode substrate C produced in Example 3 was used instead of the electrode substrate A. When the performance of this dye-sensitized solar cell was determined in the same manner as in Example 5, the conversion efficiency as the cell characteristics was 5.6%, and the fill factor was 0.63.

<Example 8>
A dye-sensitized solar cell was obtained in the same manner as in Example 5 except that the electrode substrate D produced in Example 4 was used instead of the electrode substrate A. The performance of this dye-sensitized solar cell was determined in the same manner as in Example 5. As a result, the conversion efficiency as battery characteristics was 6.2%, and the fill factor was 0.69.

<Comparative Example 1>
A transparent electrode composed of an adhesive layer, a first conductive layer, and a second conductive layer was formed on one side of the PET film in the same manner as in Example 1 except that the corrosion prevention layer was not formed. And the tolerance with respect to the iodine electrolyte of this PET film was confirmed on the same conditions as Example 1. FIG. As a result, the surface resistance value after being immersed in the iodine electrolyte solution all day and night exceeded the measurement limit (10 ⁶ Ω / □).

It is the schematic which shows an example of the basic cross-section of the electrode substrate for dye-sensitized solar cells of this invention. It is a top view which shows roughly an example of the 1st conductive layer which comprises the electrode substrate for dye-sensitized solar cells of this invention. It is the schematic which shows the other example of basic sectional structure of the electrode substrate for dye-sensitized solar cells of this invention. It is the schematic which shows an example of the basic cross-section of the dye-sensitized solar cell of this invention. It is the schematic which shows the other example of the basic cross-section of the dye-sensitized solar cell of this invention. It is the schematic which shows the cross-section of the conventional dye-sensitized solar cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent resin film 5 Adhesive layer 6, 6A 1st conductive layer 7 Corrosion prevention layer 8 2nd conductive layer 10 Transparent electrode 15 Porous semiconductor electrode 15a Semiconductor fine particle 17 Dye 20, 20A Dye-sensitized solar cell electrode substrate 22 Transparent resin film 24 First conductive film 26 Second conductive film 30 Dye-sensitized solar cell electrode substrate 35 Electrolyte layers 50, 60 Dye-sensitized solar cell

Claims (14)

A transparent resin film, a transparent electrode formed on one side of the transparent resin film, a porous semiconductor electrode formed on the transparent electrode using a large number of semiconductor fine particles, and the porous semiconductor electrode are formed. A dye-sensitized solar cell electrode substrate having a dye supported on the surface of semiconductor fine particles,
Corrosion prevention in which the transparent electrode is formed by a metal first conductive layer having a shape in which a number of fine wires are combined, and electroplating, electroless plating, or chemical conversion treatment and covers at least the outer surface of the first conductive layer And a second conductive layer made of a metal oxide covering the corrosion prevention layer, wherein the corrosion prevention layer has corrosion resistance to the electrolyte for the dye-sensitized solar cell. Electrode substrate for dye-sensitized solar cell.   2. The transparent electrode further includes an adhesive layer formed on one side of the transparent resin film, and the first conductive layer is bonded to the transparent resin film by the adhesive layer. The electrode substrate for dye-sensitized solar cells as described in 1 above.   The corrosion prevention layer covers not only the outer surface of the first conductive layer but also a region of the base layer surface of the first conductive layer that is not covered by the first conductive layer. Item 3. The dye-sensitized solar cell electrode substrate according to Item 1 or 2.   The transparent electrode further includes a surface treatment layer formed by subjecting the corrosion prevention layer to chromate treatment, and the surface treatment layer is interposed between the corrosion prevention layer and the second conductive layer. The electrode substrate for a dye-sensitized solar cell according to any one of claims 1 to 3.   The electrode substrate for a dye-sensitized solar cell according to any one of claims 1 to 4, wherein the first conductive layer is formed of a copper thin film, a nickel thin film, or a stainless thin film. A transparent resin film, a transparent electrode formed on one side of the transparent resin film, a porous semiconductor electrode formed on the transparent electrode using a large number of semiconductor fine particles, and the porous semiconductor electrode are formed A dye-sensitized solar cell electrode substrate having a dye supported on the surface of semiconductor fine particles,
The transparent electrode includes a metal first conductive layer having a shape in which a number of thin wires are combined, and a metal oxide second conductive layer covering the first conductive layer, and the first conductive layer is 99. An electrode substrate for a dye-sensitized solar cell, characterized by being made of aluminum having a purity higher than 3%. A transparent resin film, a transparent electrode formed on one side of the transparent resin film, a porous semiconductor electrode formed on the transparent electrode using a large number of semiconductor fine particles, and the porous semiconductor electrode are formed. A method for producing a dye-sensitized solar cell electrode substrate having a dye supported on the surface of semiconductor fine particles,
A preparatory step of preparing a transparent resin film in which a first conductive layer made of metal having a shape combining a number of fine wires is formed on one side;
On the transparent resin film, a corrosion prevention layer having corrosion resistance with respect to the electrolyte for the dye-sensitized solar cell so as to cover at least the outer surface of the first conductive layer is electroplated, electroless plated, or chemically formed. A corrosion prevention layer forming step formed by the treatment;
A second conductive layer forming step of forming a second conductive layer made of a metal oxide covering the corrosion prevention layer;
Forming a porous semiconductor electrode on the second conductive layer using a plurality of semiconductor fine particles; and
A dye carrying step of carrying a dye on the surface of the semiconductor fine particles forming the porous semiconductor electrode;
The manufacturing method of the electrode substrate for dye-sensitized solar cells characterized by including this.   The preparation step includes a first sub-step of preparing a transparent resin film in which a metal foil is bonded to one side by an adhesive, and a second sub-step of patterning the metal foil to obtain the first conductive layer. The manufacturing method of the electrode substrate for dye-sensitized solar cells of Claim 7 characterized by these.   In the corrosion prevention layer forming step, the corrosion prevention is performed by covering not only the outer surface of the first conductive layer but also the region of the base layer surface of the first conductive layer that is not covered by the first conductive layer. The method for producing a dye-sensitized solar cell electrode substrate according to claim 7 or 8, wherein a layer is formed.   10. The method according to claim 7, further comprising a surface treatment step of performing a chromate treatment on the corrosion prevention layer, wherein the surface treatment step is performed before the second conductive layer formation step. A method for producing an electrode substrate for a dye-sensitized solar cell.   The method for producing an electrode substrate for a dye-sensitized solar cell according to any one of claims 7 to 10, wherein the first conductive layer is formed of a copper thin film, a nickel thin film, or a stainless thin film. . A first electrode substrate having a semiconductor electrode carrying a dye; a second electrode substrate disposed opposite to the first electrode substrate; the first electrode substrate; and the second electrode substrate; A dye-sensitized solar cell having an electrolyte layer interposed therebetween,
The dye-sensitized solar cell, wherein the first electrode substrate is the electrode substrate for a dye-sensitized solar cell according to any one of claims 1 to 5.   The dye-sensitized solar cell according to claim 12, wherein the first electrode substrate is the electrode substrate for a dye-sensitized solar cell according to claim 5. A first electrode substrate having a semiconductor electrode carrying a dye; a second electrode substrate disposed opposite to the first electrode substrate; the first electrode substrate; and the second electrode substrate; A dye-sensitized solar cell having an electrolyte layer interposed therebetween,
The dye-sensitized solar cell, wherein the first electrode substrate is the electrode substrate for a dye-sensitized solar cell according to claim 6.

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