JP2010225295A - Manufacturing method of dye-sensitized solar cell, and dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized solar cell and a manufacturing method thereof, in which power generation efficiency degradation due to warpage of a synthetic resin substrate is restrained. <P>SOLUTION: In the manufacturing method of the dye-sensitized solar cell, a counter electrode substrate is formed on a plate, a spacer portion is formed between the counter electrode and a transparent substrate, the transparent substrate is formed into a film body having flexibility and is made to deform along warpage of the counter electrode substrate. Since the transparent substrate is deformed so as to be along the warpage of the counter electrode, there is no risk to have a problem in which the transparent substrate and the counter electrode substrate are in contact with each other. Moreover, since a spacer portion is provided between the counter electrode substrate and the transparent substrate, they are not in contact with each other, the gap is retained constant, fluctuation of a thickness of an electrolyte layer is made small so as to restrain degradation of power generation efficiency. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a dye-sensitized solar cell using a substrate on which an electrode is formed by sputtering vapor deposition of a metal oxide, and the produced dye-sensitized solar cell.

In recent years, various inventions have been disclosed for dye-sensitized solar cells. A substrate used in a dye-sensitized solar cell is a method in which a metal oxide such as indium tin composite oxide (ITO) is sputter-deposited on a glass or synthetic resin substrate to provide an electrode such as a working electrode or a counter electrode. Commonly used. However, when sputter deposition is performed on a plate-shaped substrate, a metal oxide is imparted to the surface of the substrate that has been thermally expanded due to a temperature increase in the deposition process, and a substrate having a smaller thermal expansion coefficient than that of the metal oxide in the process of cooling. In order to shrink more, the electrode side formed by vapor deposition may warp in a convex shape.
The warpage of the substrate causes a change in the distance between the working electrode and the counter electrode, leading to a decrease in power generation efficiency.

  Patent Document 1 discloses an invention that suppresses warping of a substrate. In a dye-sensitized solar cell including a glass substrate, a transparent conductive layer, a porous semiconductor layer that adsorbs a dye, a charge transport layer, and a counter electrode, the size is one side. There is disclosed a dye-sensitized solar cell that is 100 mm or more and that the warp of the glass substrate is 0.001 mm or more and 0.2 mm or less in terms of a measurement distance of 100 mm.

JP 2007-035591 A

  However, although the dye-sensitized solar cell disclosed in Patent Document 1 suppresses the warpage of the substrate by lowering the firing temperature for forming the porous semiconductor layer or the like, it is a technique related to a glass substrate. Yes, it is expected to be difficult to apply to synthetic resin substrates.

  Therefore, the present invention provides a dye-sensitized solar cell and a method for manufacturing the same, in which a decrease in power generation efficiency due to warpage of the substrate is suppressed even in a synthetic resin substrate.

In order to achieve the above object, the present invention is configured as follows.
That is, the method for producing a dye-sensitized solar cell according to the present invention includes a transparent substrate on which a transparent electrode is formed, a counter electrode substrate on which a counter electrode is formed, and a porous semiconductor material formed on the transparent electrode. A semiconductor particle layer formed by supporting a dye; an electrolyte layer made of a liquid or quasi-liquid electrolyte between the semiconductor particle layer and the counter electrode; and the transparent substrate and the counter electrode substrate by sealing the electrolyte layer A method for producing a dye-sensitized solar cell provided with a sealing material for fixing
Forming the counter electrode substrate from a plate;
A spacer portion is provided between the counter electrode substrate and the transparent substrate,
And corresponding to the warpage of the counter electrode substrate that warps convexly to the transparent substrate side by shrinkage after thermal expansion when sputter deposition of metal oxide,
Following the warping of the counter electrode substrate, the transparent substrate is formed from a flexible film body so that the transparent substrate is deformed along the corresponding substrate.

In the dye-sensitized solar cell manufactured by the manufacturing method according to the present invention, since the counter electrode substrate is formed in a plate shape, the shape of the dye-sensitized solar cell does not become unstable and is maintained by the counter electrode substrate. Be drunk.
In addition, since the transparent substrate is formed from a flexible film body, the transparent substrate deforms along the counter electrode substrate so as to follow the warp of the counter electrode substrate, causing a problem that the transparent substrate and the counter electrode substrate are in contact with each other. Absent.
Further, since the spacer portion is provided between the counter electrode substrate and the transparent substrate, the transparent substrate and the counter electrode substrate are not in contact with each other, the gap is kept more constant, the variation in the thickness of the electrolyte layer is reduced, and the power generation efficiency is reduced. Reduction is suppressed.

It is a figure which shows one Embodiment of the dye-sensitized solar cell manufactured with the manufacturing method which concerns on this invention.

Embodiments of the present invention will be specifically described with reference to the drawings.
In the drawings, 1 is a transparent substrate and 2 is a counter substrate.
In the dye-sensitized solar cell according to the present embodiment, an electrolyte layer 4 including an electrolyte is provided between a transparent substrate 1 of a film body and a counter electrode substrate 2 of a plate body arranged so as to face each other. Sealing is performed by filling the gap 5 with the sealing material 5.

The transparent electrode 11 is laminated on the surface of the transparent substrate 1, the counter electrode 21 is laminated on the surface of the counter electrode substrate 2, and these two electrodes are arranged so as to be inside each of the opposing substrates. That is, when the electrolyte layer 4 sealed with the sealing material 5 is in contact with the transparent electrode 11 and the counter electrode 21 laminated on the transparent substrate 1 and the counter electrode 2, the transparent electrode 11 becomes a negative electrode, and the counter electrode A solar battery cell having 21 as a positive electrode is configured. At this time, the electrolyte layer 4 is filled with an electrolyte, and the semiconductor particle layer 3 is formed on the transparent electrode 11 side.
In addition, a spacer portion 6 is provided on the inner side sealed with the sealing material 5 so as to penetrate the electrolyte layer 4, and the spacer portion 6 is formed so as to be in contact with the semiconductor particle layer 3 and the counter electrode 21. is doing.

The material used to form the counter electrode substrate 2 can be formed using an appropriate material when transparency is not required, but glass, tempered glass, and polycarbonate can be formed when transparency is required. Synthetic resins such as resin, acrylic resin, polyarylate resin, polymethacrylate, and polyvinyl chloride can be used, and polyester such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin that has high durability for the electrolyte layer 4 can be used. Polyolefin-based synthetic resins such as synthetic resins, polyethylene, polypropylene, and cyclic polyolefin resins can also be suitably used.
In the present embodiment, a cyclic polyolefin resin formed on a 120 × 150 × 2.5 mm plate is used as the counter electrode substrate 2.

Regarding the formation of the counter electrode 21, a metal oxide such as tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide or the like is formed on the counter substrate 2 by sputtering deposition. Moreover, although only the said metal oxide may be used as a structure of the counter electrode 21, you may use the composite material of these, platinum, carbon, a conductive polymer, etc.
In this embodiment, ITO is sputter-deposited on the counter electrode substrate 2, and platinum is sputter-deposited again on this surface to form the counter electrode 21.

When sputter deposition is performed on the counter electrode substrate 2 of the plate body, the counter electrode substrate 2 is thermally expanded due to a temperature increase in the deposition process.
A metal oxide is applied to the surface of the counter electrode substrate 2 by sputtering deposition to form the counter electrode 21, and then the counter electrode substrate 2 and the counter electrode 21 are cooled.
In this cooling process, the counter electrode substrate 2 formed of a material having a smaller thermal expansion coefficient than the metal oxide forming the counter electrode 21 contracts so as to contract smaller than the counter electrode 21, so that the counter electrode 21 side is convex. The counter electrode substrate 2 is formed so as to warp.

  If the transparent substrate 1 is formed on a plate-like substrate in the same manner as the counter electrode 2 and the transparent electrode 11 is formed by sputter deposition, the transparent electrode 11 side warps in a convex shape. When the two are disposed so as to face each other, the gap between the two substrates is the smallest near the center of the substrate, and the gap becomes larger toward the edge. For this reason, since the thickness of the electrolyte layer 4 provided between both substrates varies so as to be greatly different between the vicinity of the center and the vicinity of the edge of the substrate, the power generation efficiency of the dye-sensitized solar cell configured is reduced. To do.

The transparent substrate 1 of the present embodiment is formed on a flexible film body substrate, and is formed so as to be deformable following the warpage of the counter electrode substrate 2. For this reason, the fluctuation | variation of the thickness of the electrolyte layer 4 as mentioned above is suppressed, and electric power generation efficiency falls.
As a material used for forming the transparent substrate 1, a synthetic resin such as a polycarbonate resin, an acrylic resin, a polyarylate resin, a polymethacrylate, or polyvinyl chloride can be used, and a highly durable polyethylene terephthalate resin for the electrolyte layer 4 Polyester synthetic resins such as polybutylene terephthalate resin and polyethylene naphthalate resin, polyolefin synthetic resins such as polyethylene, polypropylene, and cyclic polyolefin resins can also be suitably used.
In the present embodiment, a cyclic polyolefin resin formed in a 120 × 150 × 0.1 mm film body is used as the transparent substrate 1.
The thickness of the transparent substrate 1 should just be thin to the extent that the transparent substrate 1 has the flexibility which can follow the curvature of the counter electrode substrate 2, and can use it suitably with the thickness of 0.05-0.5 mm.

  For the formation of the transparent electrode 11, a tin-doped indium oxide (ITO), a fluorine-doped tin oxide (FTO), gold, platinum or the like, or a combination thereof, is vacuum deposition, sputter deposition, ion plating, CVD It can be formed on the surface of the transparent substrate 1 by an appropriate method such as electrophoretic electrodeposition.

The sealing material 5 and the spacer portion 6 are configured by containing microspheres 52 inside a base 51 made of synthetic resin.
The microsphere 52 is formed into a spherical body having a uniform particle diameter using a hard material, and in this embodiment, SiO2 is formed into a sphere having a diameter of about 15 μm.
The microspheres 52 are arranged inside the sealing material 5 so as not to overlap each other and are sandwiched between the transparent electrode 11 and the counter electrode 21, so that the gap between the transparent electrode 11 and the counter electrode 21 is reduced. The spherical body 52 can be configured to have a particle size. In addition, by forming the microsphere 52 with a hard material, the gap between the transparent electrode 11 and the counter electrode 21 can be kept so as not to be smaller than the particle size of the microsphere 52.
In the present embodiment, SiO2 is used as the material of the microsphere 52, but the material is not limited to this, and glass, ceramic, synthetic resin, or the like can be suitably used, and the gap between the transparent electrode 11 and the counter electrode 21 can be suitably used. Anything that keeps it.

  The raw material of the base material 51 is not particularly limited as long as it can prevent the electrolyte layer 4 from leaking. For example, epoxy resin, acrylic resin, silicon resin, fluorine resin, melanin resin And phosphazene resins.

In the present embodiment, the sealing material 5 and the spacer portion 6 are composed of the same base material 51 and microspheres 52, but different materials may be used.
In FIG. 1, the spacer portion 6 is described as being formed at one location, but a plurality of locations may be provided, and the shape may be formed in a dot shape, a line shape, or the like.

  For the formation of the electrolyte layer 4, a liquid electrolyte such as a mixed solution of acetonitrile and ethylene carbonate, a solvent such as methoxypropionitrile, an electrolyte such as lithium iodide or metallic iodine, or a polymer gel electrolyte Liquid electrolyte systems such as quasi-solidified electrolytes such as p-type semiconductors, and solid electrolyte systems such as hole transport agents can be used.

The semiconductor particle layer 3 is formed using a semiconductor material such as Fe2O3, Cu2O, In2O3, WO3, Fe2TiO3, PbO, V2O5, FeTiO3, Bi2O3, Nb2O3, SrTiO3, ZnO, BaTiO3, CaTiO3, KTaO3, SnO2, and ZrO2. It can be formed by supporting a sensitizing dye on the surface, and as a semiconductor material, titanium oxide (TiO2) or a transparent thin layer is excellent in terms of cost and workability, and can be electrodeposited. Zinc oxide (ZnO) is preferable, but is not limited thereto, and an appropriate one can be used. The dye supported on the semiconductor particle layer 3 is not particularly limited, and examples thereof include a ruthenium bipyridium complex, a xanthene dye, a porphyrin derivative, and a phthalocyanine derivative complex.
The total thickness of the semiconductor particle layer 3 and the electrolyte layer 4 is formed to be approximately the same as the particle size of the microspheres 52.

  In this embodiment, the transparent substrate 1 is formed in a film body and the counter electrode substrate 2 is formed in a plate body. However, even if the transparent substrate 1 is formed in a plate body and the counter electrode substrate 2 is formed in a film body, Similar effects can be obtained.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 11 Transparent electrode 2 Counter electrode substrate 21 Counter electrode 3 Semiconductor particle layer 3
4 Electrolyte layer 4
5 Sealant 51 Base 52 Microsphere 6 Spacer

Claims (2)

A transparent substrate on which a transparent electrode is formed; a counter electrode substrate on which a counter electrode is formed; a semiconductor particle layer formed on the transparent electrode by carrying a sensitizing dye on a porous semiconductor material; and the semiconductor particles A dye-sensitized solar cell provided with an electrolyte layer made of a liquid or quasi-liquid electrolyte between a layer and a counter electrode, and a sealing material for sealing the electrolyte layer and fixing the transparent substrate and the counter electrode substrate A manufacturing method of
Forming the counter electrode substrate from a plate;
A spacer portion is provided between the counter electrode substrate and the transparent substrate,
And corresponding to the warpage of the counter electrode substrate that warps convexly to the transparent substrate side by shrinkage after thermal expansion when sputter deposition of metal oxide,
Following the warpage of the counter electrode substrate, the transparent substrate is formed from a flexible film body so that the transparent substrate is deformed along the corresponding substrate. Method.   A dye-sensitized solar cell produced by the method for producing a dye-sensitized solar cell according to claim 1.

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