JP2011124053A - Method of manufacturing dye-sensitized solar cell of not bad design - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable a dye-sensitized solar cell of not bad design to be freely equipped with a collecting electrode, and to be equipped with fine patterning industrially and inexpensively. <P>SOLUTION: As the method of manufacturing the dye-sensitized solar cell of not bad design, after a transparent electrode layer is formed on a transparent substrate, a cycle of a pattern forming of a porous oxide semiconductor on the transparent electrode layer followed by a pattern forming of a dye-carrying semiconductor by carrying a dye on the porous oxide semiconductor is repeated twice or more, so that an anode member with patterns of specific letters, symbols or figures formed of semiconductors carrying two or more kinds of dyes having mutually different colors is formed, while on the other hand, a cathode member is formed by forming a rear-face electrode layer on a rear-face substrate. A dye-carrying semiconductor side of the anode member and a rear-face electrode layer side of the cathode member are made opposed to each other, so that electrolyte solution is to be filled between the dye-carrying semiconductors and the rear-face electrode layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a dye-sensitized solar cell having a design on a light receiving surface.

  In order to make the solar cell have a design such as a pattern of specific characters, symbols or figures, the surface is provided with characters or designs by printing, etc., or the current collecting electrode is changed to a pattern of specific characters, symbols or figures. Some have been formed (for example, refer to Patent Document 1).

  In addition, by separating the porous semiconductor layer, which is a component of the dye-sensitized solar cell, into a predetermined pattern with a material such as glass frit, it is possible to draw any character, symbol, figure or picture on the light-receiving surface. There exists a solar cell (for example, refer patent document 2).

JP 2002-64214 A JP 2002-75472 A

  However, it is known that if the surface of the solar cell is excessively covered with a printed pattern or a current collecting electrode as in the technique of Patent Document 1, dark current flows in the solar cell, thereby deteriorating the cell characteristics. Yes. In addition, when the current collecting electrode is used as a pattern of each character, symbol, etc., the pattern of each character, symbol, etc. needs to be electrically connected to each other, and the degree of freedom is greatly lost in providing design. There was a problem.

  Further, in the technique of Patent Document 2, since it has complicated steps such as a step of removing the porous semiconductor layer in a predetermined pattern and a step of forming a partition wall in the portion from which the porous semiconductor layer has been removed, it is manufactured industrially at a low cost. I couldn't.

  An object of this invention is to provide the manufacturing method of the dye-sensitized solar cell provided with the design property which does not have said problem.

  In order to achieve the above object, the present invention has the following features.

The method for producing a dye-sensitized solar cell having the design properties of the present invention,
After forming the transparent electrode layer on the transparent substrate, performing pattern formation of the dye-carrying semiconductor by carrying the dye on the porous oxide semiconductor following the pattern formation of the porous oxide semiconductor on the transparent electrode layer more than once While forming an anode member in which a pattern of specific characters, symbols or figures is formed by two or more kinds of dye-carrying semiconductors having different colors,
Forming a back electrode layer on the back substrate to form a cathode member;
The dye-supporting semiconductor side of the anode member and the back electrode layer side of the cathode member are opposed to each other, and an electrolyte solution is filled between the dye-supporting semiconductor and the back electrode layer.

  In the above invention, the pattern formation of the porous oxide semiconductor may be formed by applying a dispersion or colloidal solution of semiconductor fine particles or fibers.

  In the method for producing a dye-sensitized solar cell of the present invention, the pattern formation of the dye-carrying semiconductor is carried out twice or more by carrying the dye on the porous oxide semiconductor following the formation of the pattern of the porous oxide semiconductor on the transparent electrode layer. Thus, a specific character, symbol, or figure pattern is formed by two or more types of dye-carrying semiconductors having different colors. Therefore, it is not necessary to cover the surface of the solar cell with the design layer, and a collecting electrode is also provided freely. Further, it is not necessary to remove the semiconductor layer and to form a partition wall in the removed portion, and it can be manufactured industrially at a low cost. Further, unlike the case where the dye is supported on the porous oxide semiconductor formed on the entire surface, the dye is less likely to bleed and fine patterning is possible.

It is sectional drawing which shows the manufacturing method of the anode member used for the manufacturing method of the dye-sensitized solar cell of this invention. It is sectional drawing which shows the cathode member used for the manufacturing method of the dye-sensitized solar cell of this invention. It is sectional drawing which shows the dye-sensitized solar cell formed by the manufacturing method of the dye-sensitized solar cell of this invention. It is a top view which shows the dye-sensitized solar cell formed by the manufacturing method of the dye-sensitized solar cell of this invention.

  Embodiments of the present invention will be described in detail with reference to the drawings.

Formation of Anode Member First, an anode member 21 in which a pattern of specific characters, symbols, or figures is formed by two or more kinds of dye-carrying semiconductors 11 and 12 having different colors (see FIG. 1D).

  In order to form the anode member 21, after forming the transparent electrode layer 6 on the transparent substrate 7 (see FIG. 1A), porous oxidation following the pattern formation of the porous oxide semiconductor 5 on the transparent electrode layer 6 is performed. The pattern formation of the dye-carrying semiconductors 11 and 12 by carrying the dye on the physical semiconductor 5 is performed twice or more (see FIGS. 1A to 1D).

  Of the solar cell substrate (plate) produced by the method for producing a dye-sensitized solar cell of the present invention, the sunlight receiving side is transparent and does not hinder the reception of sunlight, and the surface thereof is transparent and conductive. Examples of the transparent substrate 7 that can form a film and a photoelectric conversion element include polymethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyethersulfone, polyolefin, polyethylene terephthalate, polyethylene naphthalate, triacetylcellulose, and polyvinyl fluoride. Film, ethylene-tetrafluoroethylene copolymer resin, weather resistant polyethylene terephthalate, weather resistant polypropylene, glass fiber reinforced acrylic resin film, glass fiber reinforced polycarbonate, polyimide, transparent polyimide, fluorine resin, cyclic Polyolefin resin, polyacrylic resin, glass and the like can be used, but are not limited thereto. The transparent substrate 7 may be used as a single base material, but can also be used as a composite substrate in which two or more kinds of base materials are laminated.

  As the transparent conductive film for forming the transparent electrode layer 6, tin oxide, zinc oxide, indium oxide and the like are preferably used, but are not limited thereto. Further, these materials can be doped as necessary. Examples of the method for producing the transparent conductive film include, but are not limited to, a vapor deposition method, a sputtering method, a low pressure CVD (Chemical Vapor Deposition) method, an atmospheric pressure CVD method, a sol-gel method, a pyrolysis spray method, and an electrodeposition method. It is not something.

  Further, by etching the transparent conductive film, it is possible to form irregularities that facilitate light confinement. In this case, since the surface shape of the transparent conductive material can be easily controlled by appropriately changing the type, concentration, etching time, or the like of the etchant, desired irregularities can be easily obtained.

  A method of patterning the dye-carrying semiconductors 11 and 12 on the transparent electrode layer 6 twice or more is as follows.

  First, a pattern of the first porous oxide semiconductor 5 is formed on the transparent electrode layer 6 (see FIG. 1A), and then the dye is supported by the first porous oxide semiconductor 5 supporting the dye. The pattern of the supported semiconductor 11 is formed (see FIG. 1B).

  As the porous oxide semiconductor 5, titanium oxide, niobium oxide, tin oxide, zinc oxide, tungsten oxide, barium titanate, cadmium sulfide, or the like can be used, or a combination thereof can be used.

  Examples of the method for forming a pattern of the porous oxide semiconductor 5 on the transparent electrode layer 6 include a method of applying a semiconductor fine particle or fiber dispersion or colloid solution, drying and firing, and the like. Not. The film thickness of the porous oxide semiconductor 5 is preferably in the range of 1 to 30 μm, and more preferably in the range of 3 to 20 μm.

  The porous oxide semiconductor 5 is desirably fired after the film is formed so that the particles or fibers in the film are in electrical contact with each other and have a preferable crystal structure. The firing temperature is preferably 50 to 600 ° C., and in the case of the second (and subsequent) porous oxide semiconductor 5 described later, a temperature range of 50 ° C. to a temperature at which the dye does not decompose is particularly preferable.

  As the dye to be supported on the porous oxide semiconductor 5, a metal complex dye or an organic dye can be used. As the metal complex dye, a ruthenium-based dye is most preferable, and in particular, a ruthenium bipyridine dye and a ruthenium terpyridine dye which are ruthenium complexes. Examples of organic dyes include, but are not limited to, acridine, azo, indigo, quinone, coumarin, merocyanine, and phenylxanthene dyes. The dye preferably has a suitable linking group for the semiconductor surface, and particularly preferred linking groups include a COOH group, a cyano group, a PO3 H2 group, and a chelating group. Of these, a COOH group and a PO3H2 group are preferable.

  In order to support the dye on the porous oxide semiconductor 5, a method of applying a solution of the dye to the semiconductor fine particle layer can be mentioned, but the method is not limited thereto. Examples of the solvent for dissolving the dye include alcohols, nitriles, nitromethane, halogenated hydrocarbons, ethers, dimethyl sulfoxide, amides, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, Examples thereof include esters, carbonates, ketones, hydrocarbons, and mixed solvents thereof.

  Subsequently, similarly, pattern formation of the second (and subsequent) porous oxide semiconductor 5 is performed on the transparent electrode layer 6 (see FIG. 1C), and the second (and subsequent) porous oxide is formed. A pattern of the dye-carrying semiconductor 12 is formed by carrying the dye on the semiconductor 5 (see FIG. 1D). By doing so, it is possible to form the anode member 21 on which a pattern of specific characters, symbols or figures is formed by two or more kinds of dye-carrying semiconductors 11 and 12 having different colors. Here, the two or more kinds of dye-carrying semiconductors 11 and 12 having different colors may be ones in which dyes of different colors are adsorbed, and even if the dyes of the same color are adsorbed, the amount of adsorption is the same. Different ones may have different shades.

Formation of Cathode Member While the anode member 21 is formed, the back electrode layer 2 is separately formed on the back substrate 1 to form the cathode member 22 (see FIG. 2).

  The back substrate 1 that does not receive sunlight does not need to be transparent and is not particularly limited. For example, in addition to the transparent substrate 7, a SUS thin plate, an Al foil, or the like can also be used. Although the back substrate 1 may be used as a single substrate, it can also be used as a composite substrate in which two or more types of substrates are laminated.

  The conductive film for forming the back electrode layer 2 does not need to be transparent and is not particularly limited. For example, in addition to the transparent conductive film for forming the transparent electrode layer 6, a carbon film or the like can also be used. Moreover, if the back substrate 1 exhibits conductivity, the back electrode layer 2 is not required.

  Further, by etching the transparent conductive film, it is possible to form irregularities that facilitate light confinement. In this case, since the surface shape of the transparent conductive material can be easily controlled by appropriately changing the type, concentration, etching time, or the like of the etchant, desired irregularities can be easily obtained.

  Also, a platinum film 3 or a carbon film can be formed on the surface of the back electrode layer 2 in order to promote the supply of electrons to the electrolyte described later.

Formation of Dye-Sensitized Solar Cell with Design Properties Finally, the dye-carrying semiconductor in a state where the dye-carrying semiconductors 11 and 12 side of the anode member 21 and the back electrode layer 2 side of the cathode member 22 face each other and surrounded by the partition walls 8 By filling the electrolyte solution 4 between 11 and 12 and the back electrode layer 2, the dye-sensitized solar cell 9 having design properties can be manufactured (see FIGS. 3 and 4).

  The electrolyte solution 4 of the dye-sensitized solar cell 9 is not particularly limited as long as it can be generally used in a dye-sensitized solar cell, but is preferably redox, for example, LiI, NaI, KI, CaI2 There are combinations of metal iodides such as metal iodide and iodine, and combinations of metal bromides such as LiBr, NaBr, KBr, and CaBr2 and bromine. Of these, a combination of LiI and iodine is most preferable. This electrolyte is used in a form dissolved in a solvent (for example, a redox electrolyte).

Formation of other members Further, in order to use sunlight more effectively in the present invention, an antireflection layer (not shown) using light interference may be provided either on the substrate layer or between the layers. Is possible. This antireflection layer utilizes the coherence of light, and generally, it is sufficient if it is composed of a layer having a predetermined optical film thickness nd (refractive index n × shape film thickness d) in order to obtain the desired antireflection characteristic. In the present invention, the number of stacked layers is not particularly limited. Although it is possible to provide a single layer of a low refractive index layer such as silicon oxide or an organic fluorine compound as the antireflection film, it is usually preferable to use 1 to 6 layers in terms of cost and antireflection effect. .

  In addition, the antireflection film is a vacuum deposition method such as a vacuum deposition method, a reactive deposition method, an ion beam assisted deposition method, a sputtering method, an ion plating method, a plasma CVD method, a wet coating such as a gravure coating or a screen coating, A film forming process combining a heat drying method, a heat curing method, an ultraviolet ray irradiation curing method, an electron beam irradiation curing method, and the like can be performed, and an optimum method is appropriately selected for the characteristics of each thin film. Any other film forming method may be used.

  In order to increase the weather resistance of the solar cell, a gas barrier layer can be provided either on the substrate layer or between the layers. For example, any one of silicon oxide (SiOx), silicon nitride (SiNx), aluminum oxide (Alx Oy), or a mixture of two or more kinds of vapor-deposited layers, or an inorganic-organic hybrid coat layer Any one type or a composite layer combining two or more types can also be suitably used.

  The above barrier layers such as silicon oxide (SiOx), silicon nitride (SiNx), and aluminum oxide (Alx Oy) can be easily formed on the substrate by vapor deposition, sputtering, CVD, dipping, sol-gel, etc. can do. The thickness of such a barrier layer is preferably in the range of 5 to 500 nm, particularly preferably in the range of 30 to 150 nm.

DESCRIPTION OF SYMBOLS 1 Back substrate 2 Back electrode layer 3 Platinum film 4 Electrolyte solution 5 Porous oxide semiconductor 6 Transparent electrode layer 7 Transparent substrate 8 Partition 9 Dye-sensitized solar cell 11 Dye carrying | support semiconductor 12 Dye carrying | support semiconductor 21 Anode member 22 Cathode member

Claims (2)

After forming the transparent electrode layer on the transparent substrate, performing pattern formation of the dye-carrying semiconductor by carrying the dye on the porous oxide semiconductor following the pattern formation of the porous oxide semiconductor on the transparent electrode layer more than once While forming an anode member in which a pattern of specific characters, symbols or figures is formed by two or more kinds of dye-carrying semiconductors having different colors,
Forming a back electrode layer on the back substrate to form a cathode member;
A dye-sensitized solar cell having a design property, wherein the dye-carrying semiconductor side of the anode member and the back electrode layer side of the cathode member are opposed to each other, and an electrolyte solution is filled between the dye-carrying semiconductor and the back electrode layer Manufacturing method. The method for producing a dye-sensitized solar cell having the design property according to claim 1, wherein the pattern formation of the porous oxide semiconductor is formed by coating a dispersion or colloidal solution of semiconductor fine particles or fibers.

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