JP2014056779A - Photocatalyst film formation method of dye-sensitized solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocatalyst film formation method of a dye-sensitized solar cell, which enables formation of a photocatalyst film in a short time in which an oxide semiconductor film is color-coded by a plurality of colors.SOLUTION: A photocatalyst film formation method of a dye-sensitized solar cell including a transparent electrode 1, a counter electrode, an electrolyte layer arranged between both electrodes and a photocatalyst film 4 which is arranged between both electrodes and on the transparent electrode 1 side and which is formed by adsorption of a photosensitized dye to an oxide semiconductor film 41 comprises: forming a dye inhibition film 5 which composes the dye-sensitized solar cell in an intended range in the oxide semiconductor film 41 arranged on the transparent electrode 1 side; and subsequently, inhibiting adsorption of the photosensitized dye from being adsorbed in the range where the dye inhibition film 5 is formed by bringing the oxide semiconductor film 41 into contact with a dye solution and causing the photosensitized dye to be adsorbed by a portion of the oxide semiconductor film 41 other than the range where the dye inhibition film 5 is formed.

Description

  The present invention relates to a method for forming a photocatalytic film in a dye-sensitized solar cell.

In general, a dye-sensitized solar cell includes, as its elements, a transparent electrode in which a transparent conductive film is formed on a transparent substrate such as a glass plate, a counter electrode, and an iodine-based electrolyte disposed between these electrodes. And a photocatalyst film disposed between the electrodes and on the surface of the transparent electrode. As the photocatalyst film, a film obtained by forming an oxide semiconductor film such as titanium oxide (TiO ₂ ) and adsorbing a photosensitizing dye such as ruthenium to the oxide semiconductor film is known (for example, Patent Document 1). reference).

  Such a dye-sensitized solar cell has an advantage that the design can be improved by combining the color and the pattern because the photocatalyst film is colored with the photosensitizing dye.

  And the following three are mentioned as an example of the dye-sensitized solar cell which improved the designability, and its manufacturing method. The first is a dye-sensitized solar cell in which lightness and saturation are changed by reflected light from the reflection means by providing a reflection means having irregularities on the counter electrode side (see, for example, Patent Document 2). ). The second is a dye-sensitized solar cell in which the thickness of the oxide semiconductor film, the particle diameter of the titanium oxide fine particles, and the like are made different so as to produce shades of color (for example, see Patent Document 3). Third, a partition device divided into a plurality of spaces is installed in the oxide semiconductor film, and a different dye solution is injected into each of the divided spaces to separately paint the colors of the oxide semiconductor film ( For example, see Patent Document 4).

JP 2001-35549 A Japanese Patent No. 4936648 JP 2010-3468 A JP 2010-9769 A

  However, according to the dye-sensitized solar cell described in Patent Document 2, although the brightness and saturation change with reflected light, the colors of the oxide semiconductor film cannot be applied separately. Further, according to the dye-sensitized solar cell described in Patent Document 3, although the color density can be obtained, this color is limited to only one color. Further, according to the method described in Patent Document 4, colors can be applied separately, but the oxide semiconductor film may be damaged, and the partition device needs to be manufactured separately.

  Further, in the dye-sensitized solar cells described in Patent Documents 1 to 4, even if a dye contact prevention mask is used to paint different colors, this mask is removed without constituting the dye-sensitized solar cell. Therefore, the dye penetrates into a slight gap between the mask and the oxide semiconductor film. For this reason, after the removal of the mask, a cleaning process for removing the infiltrated dye is necessary, and there is a problem that it takes time to form the photocatalyst film.

  Therefore, an object of the present invention is to provide a method for forming a photocatalyst film in a dye-sensitized solar cell, in which a photocatalyst film in which an oxide semiconductor film is coated in a plurality of colors can be formed in a short time.

In order to solve the above problems, a method for forming a photocatalyst film in a dye-sensitized solar cell of the present invention according to claim 1 includes a transparent electrode, a counter electrode, an electrolyte disposed between these electrodes, and a gap between both electrodes. And a method for forming a photocatalyst film in a dye-sensitized solar cell, which is disposed on the transparent electrode side and comprises a photocatalyst film formed by adsorbing a dye to an oxide semiconductor film,
In a desired range in the oxide semiconductor film disposed on the transparent electrode side, a dye-inhibiting film constituting a dye-sensitized solar cell is formed,
Thereafter, the dye solution is brought into contact with the oxide semiconductor film to inhibit the dye from adsorbing in the range where the dye inhibition film is formed, and the dye inhibition film in the oxide semiconductor film is formed. A dye is adsorbed outside the range.

A method for forming a photocatalyst film in a dye-sensitized solar cell of the present invention according to claim 2 is the method for forming a photocatalyst film in a dye-sensitized solar cell according to claim 1, wherein a dye solution is applied to the oxide semiconductor film. Before contact
A dye-inhibiting film constituting the dye-sensitized solar cell is formed in a range where the oxide semiconductor film in the transparent electrode is not disposed.

  Furthermore, the method for forming a photocatalyst film in the dye-sensitized solar cell of the present invention according to claim 3 is characterized in that the dye-inhibiting film in the method for forming a photocatalyst film in the dye-sensitized solar cell according to claim 1 is a dye solution. And does not elute into the electrolyte.

Moreover, the formation method of the photocatalyst film | membrane in the dye-sensitized solar cell of this invention which concerns on Claim 4 is a pigment | dye in the formation method of the photocatalyst film | membrane in the dye-sensitized solar cell as described in any one of Claims 1 thru | or 3. As a method of forming an inhibitory film,
A mask in which a desired range is hollowed is placed on the oxide semiconductor film,
Thereafter, a dye-inhibiting film precursor or solution is applied to the oxide semiconductor film by a spray method, a spin coating method, a squeegee method, or a screen printing method,
The applied precursor or solution is dried.

  Further, in the method for forming a photocatalyst film in the dye-sensitized solar cell of the present invention according to claim 5, the mask in the method for forming a photocatalyst film in the dye-sensitized solar cell according to claim 4 includes a predetermined portion and another mask. The portion that passes through the dye-inhibiting membrane precursor or solution is different in the portion.

  Moreover, the formation method of the photocatalyst film | membrane in the dye-sensitized solar cell of this invention which concerns on Claim 6 is formed in the formation method of the photocatalyst film | membrane in the dye-sensitized solar cell as described in any one of Claims 1 thru | or 5. The inhibition rate at which the dye inhibition film inhibits the adsorption of the dye is different between the predetermined portion and the other portion.

Moreover, the formation method of the photocatalyst film in the dye-sensitized solar cell of this invention which concerns on Claim 7 is the dye inhibition in the formation method of the photocatalyst film in the dye-sensitized solar cell as described in any one of Claims 1 thru | or 3. The film is a metal film,
Sputtering is used as a method for forming the dye-inhibiting film.

  According to the method for forming a photocatalyst film in the dye-sensitized solar cell, it is possible to form a photocatalyst film in which an oxide semiconductor film is coated in a plurality of colors in a short time.

It is sectional drawing which shows schematic structure of the dye-sensitized solar cell which concerns on embodiment of this invention. It is a schematic perspective view for demonstrating a mode that a mask is arrange | positioned to the oxide semiconductor film in the dye-sensitized solar cell, and a pigment | dye inhibition film solution is apply | coated. It is sectional drawing for demonstrating the formation method of the photocatalyst film | membrane in the same dye-sensitized solar cell, (a) is a figure which apply | coats a pigment | dye inhibition film solution, (b) is a figure which removes a mask, (c) is pigment inhibition. It is a figure which adsorb | sucks a photosensitizing dye outside the range in which the film | membrane was formed. It is the top view which looked at the transparent electrode in which the photocatalyst film in the same dye-sensitized solar cell was formed from the counter electrode side.

Hereinafter, a method for forming a photocatalyst film in a dye-sensitized solar cell according to an embodiment of the present invention will be described.
First, a schematic configuration of the dye-sensitized solar cell according to the embodiment will be described with reference to FIG.

  As shown in FIG. 1, the dye-sensitized solar cell includes a transparent electrode 1 as a negative electrode, a counter electrode 2 as a positive electrode, an electrolyte layer 3 disposed between the electrodes 1 and 2, and both electrodes 1. , 2 and on the transparent electrode 1 side, a photocatalyst film (also referred to as a photocatalyst layer or a power generation layer) 4 and a sealing portion 6 that seals the outer edge between the electrodes 1 and 2 are provided. ing. The photocatalyst film 4 is formed by adsorbing a photosensitizing dye (not shown) to the oxide semiconductor film 41. Further, the dye-inhibiting film 5 remains in the dye-sensitized solar cell in the process of forming the photocatalytic film 4 (that is, constitutes a dye-sensitized solar cell), and the photosensitizing dye is added to the oxide semiconductor film 41. It is formed to inhibit adsorption. For this reason, in the oxide semiconductor film 41, the photosensitizing dye is adsorbed in the area where the dye inhibiting film 5 is not formed to become the photocatalytic film 4, and the photosensitizing dye is formed in the area where the dye inhibiting film 5 is formed. The oxide semiconductor film 41 remains as it is not adsorbed (or a slight amount of photosensitizing dye is adsorbed). That is, the oxide semiconductor film 41 is coated in a plurality of colors. Therefore, when the dye-sensitized solar cell is from the counter electrode 2 side, the color and pattern of the photocatalyst film 4 (color of the photosensitizing dye) and the dye-inhibiting film 5 (transparent or colored) can be seen. In the dye-sensitized solar cell, the color and pattern of the photocatalyst film 4 (photosensitizing dye color) and the oxide semiconductor film 41 (usually white) can be seen from the transparent electrode 1 side.

  The transparent electrode 1 includes a transparent substrate 11 and a transparent conductive film 12 formed (arranged) on the surface of the transparent substrate 11. The counter electrode 2 includes a transparent substrate 21 and a transparent conductive film 22 formed (arranged) on the surface of the transparent substrate 21.

  The transparent substrates 11 and 21 are not particularly limited, but although a synthetic resin plate, a glass plate, or the like is used as appropriate, it is light in weight, low in price, and safe (not easily damaged). A film made of a thermoplastic resin is preferred. Examples of the thermoplastic resin include polyester resins such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), polycarbonate resins, and resins such as polyolefins.

Further, the transparent conductive films 12 and 22 are not particularly limited, but include tin-added indium oxide (ITO), fluorine-added tin oxide (FTO), tin oxide (SnO ₂ ), and indium zinc oxide (IZO). A thin film containing a conductive metal oxide such as zinc oxide (ZnO) is used. The transparent conductive film 22 of the counter electrode 2 is formed by forming a catalytic material.

  By the way, the counter electrode 2 is not limited to the transparent substrate 21 and the transparent conductive film 22 formed with a material having catalytic properties, as described above. As the counter electrode 2, a material such as platinum or carbon having catalytic properties may be formed on a metal sheet such as aluminum, copper or tin or a mesh electrode. Examples of the method for forming the material having catalytic properties include sputtering and immersing the counter electrode 2 in a platinum nanocolloid solution. The counter electrode 2 has a conductive adhesive layer formed on the surface of the transparent substrate 21 on the electrolyte layer 3 side, and a vertically aligned carbon nanotube group generated separately is transferred to the conductive adhesive layer. It may be.

  For example, an iodine electrolyte solution is used as the electrolyte layer 3. This is an electrolyte component such as iodine, iodide ion, or tertiary butyl pyridine dissolved in an organic solvent such as ethylene carbonate or methoxyacetonitrile. The electrolyte layer 3 is not limited to the electrolytic solution, and may be a solid electrolyte.

As the solid electrolyte, for example, is illustrated DMPImI (dimethylpropyl imidazolium iodide), but this addition, LiI, NaI, KI, CsI, metal iodide such as CaI _2, tetraalkylammonium iodide and quaternary ammonium compounds Bromide such as a combination of iodide such as iodine salt and I ₂ , metal bromide such as LiBr, NaBr, KBr, CsBr and CaBr ₂ , and bromide salt of quaternary ammonium compound such as tetraalkylammonium bromide and Br ₂ And the like can be used as appropriate.

The photocatalytic film 4 is formed of an oxide semiconductor film 41 to which a photosensitizing dye is adsorbed. Examples of the oxide semiconductor include fine particles of metal oxide such as titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), tungsten oxide (WO ₃ ), zinc oxide (ZnO), and niobium oxide (Nb ₂ O ₅ ). Photocatalyst fine particles) are used. The particle size of these fine particles is not particularly limited, but is preferably about 5 to 100 μm. Examples of photosensitizing dyes include ruthenium complexes and iron complexes having ligands containing a bipyridine structure or a terpyridine structure, porphyrin-based or phthalocyanine-based metal complexes, or organic dyes such as eosin, rhodamine, merocyanine, and coumarin. used. In particular, it is preferable to use a ruthenium complex from the viewpoint of versatility, and it is preferable to use an organic dye from the viewpoint of solubility in an organic solvent. As a solvent for dissolving the photosensitizing dye, alcohol such as ethanol, acetonitrile, or the like is used. When titanium oxide (TiO ₂ ) was used as the oxide semiconductor, it was obtained by dissolving titanium (IV) isopropoxide (TTIP) in propanol for the purpose of strengthening the bond of titanium oxide. A solution (which is a photocatalyst precursor solution) may be mixed with the dye solution.

Hereinafter, a method for forming (manufacturing) the photocatalytic film 4 which is the gist of the present invention will be described.
First, a mask M in which a desired range (a range in which the dye-sensitized solar cell and the photocatalyst film 4 are not desired to be colored) is cut out is prepared in advance. FIG. 2 shows, as an example, a mask M for manufacturing a dye-sensitized solar cell designed as an emergency exit lamp. As shown in FIG. 4, the dye-sensitized solar cell manufactured using this mask M is formed on the oxide semiconductor film 41 of an evacuated figure and its surrounding portion (reference numeral 4 in FIG. 4) in an emergency exit lamp. The photosensitizing dye is adsorbed to prevent the photosensitizing dye from adsorbing to the oxide semiconductor film 41 in the portion between the human shadow and the enclosure (reference numerals 5 and 41 shown in FIG. 4). That is, as shown in FIG. 2, the mask M has an area between the human figure and the enclosure in the emergency exit lamp design. Although not shown, it is preferable to form a collector electrode on the oxide semiconductor film 41 before forming the dye inhibiting film 5 using the mask M.

  Next, this mask M is disposed on the oxide semiconductor film 41 formed on the transparent electrode 1. At this time, the outer peripheral edge of the mask M and the outer peripheral edge of the oxide semiconductor film 41 are matched. As a result, the mask M is not covered with a range outside the outer peripheral edge of the mask M (that is, a range where the oxide semiconductor film 41 is not formed in the transparent electrode 1) and the above-described desired portion cut out in the mask M. With a range. Thereafter, as shown in FIG. 3 (a), the dye is applied to the range not covered with the mask M by a spraying method in which the dye inhibiting film solution is sprayed from above the mask M with the spray S (consisting of the main body S1 and the nozzle S2). The inhibitor film 5 solution is applied. This coating method is not limited to the spray method described above, and an electrostatic spray method, a spin coating method, a squeegee method, a screen printing method, or the like may be used.

  Here, the thickness of the dye-inhibiting film 5 may be different between a predetermined part and another part by adjusting the number of times of application of the dye-inhibiting film solution, the application pressure, the application speed, and the like. In addition, the dye inhibiting film 5 may have different particle diameters and polymer types between a predetermined portion and another portion. A simple way to do this is to spray the dye-inhibiting membrane solutions of different materials (solutes) with the spray S multiple times. Thus, if the thickness, the particle size, and the type of polymer of the dye inhibiting film 5 are different between the predetermined part and the other part, the dye inhibiting film 5 that the photosensitizing dye is adsorbed to the oxide semiconductor film 41 is obtained. Since the inhibition rate (hereinafter referred to as pigment inhibition rate) is different, coloring can be shaded.

  The dye inhibiting film solution is obtained by dissolving the material of the dye inhibiting film 5 in a solvent. As the material of the dye inhibiting film 5, a material that is resistant to the solvent and electrolyte of the dye solution, that is, a material that does not elute into the dye solution and the electrolyte is used. This is a polymer (eg, polyvinyl alcohol), a metal or organic (eg, ITO) material, a resin, or a glass coating agent that does not elute into the dye solution and the electrolyte. Quartz-based, silane-based, silicon-based, or resin-based materials are used as the glass coating agent. Moreover, when the material of the pigment | dye inhibition film | membrane 5 is a metal, a metal organic compound or a metal inorganic compound etc. are used as a precursor. Examples of the metal organic compound include metal alkoxide, metal acetylacetonate, metal carboxylate and the like. Metal inorganic compounds include nitrates, oxysalt compounds, chlorides and the like. A solution in which such a precursor is dissolved in a solvent for preparing a homogeneous solution may be used. In addition, since the dye inhibition film 5 constitutes a dye-sensitized solar cell (remains in the dye-sensitized solar cell), if the dye inhibition film 5 has conductivity, the parallel direction of the oxide semiconductor film 41 Improve the conductivity. In this case, in order to prevent a short circuit between the metal film as the dye inhibiting film 5 and the counter electrode 2, it is necessary to arrange a spacer between the both electrodes 1 and 2.

  Then, as shown in FIG. 3B, after removing the mask M from the oxide semiconductor film 41, the dye inhibiting film solution on the oxide semiconductor film 41 and the transparent electrode 1 is dried. Then, the dye inhibiting film 5 is formed in a range that is not covered with the mask M on the oxide semiconductor film 41 and the transparent electrode 1. In addition, if the material of the pigment | dye inhibition film | membrane 5 is a metal, sputtering may be used instead of said application | coating and drying.

  Thereafter, the transparent electrode 1 is immersed in a dye solution in a substantially horizontal posture, and a photosensitizing dye is brought into contact with the oxide semiconductor film 41. This dye solution is obtained by dissolving a photosensitizing dye in a solvent such as alcohol or acetonitrile. The temperature of the dye solution is normal temperature to 80 ° C., and the immersion time is about 10 to 120 minutes. Then, as illustrated in FIG. 3C, the dye is adsorbed in the oxide semiconductor film 41 in a range where the dye inhibiting film 5 is not formed. Further, even in the range where the dye inhibiting film 5 is formed, the dye is adsorbed very slightly depending on the film thickness. Here, the posture of the transparent electrode 1 immersed in the dye solution is not limited to being substantially horizontal, and may be substantially vertical or inclined. Of course, as long as the photosensitizing dye is brought into contact with and adsorbed on the oxide semiconductor film 41, the method is not limited to the method of immersing the dye solution in the transparent electrode 1, but the method of dropping the dye solution onto the oxide semiconductor film 41. There may be. In this way, the photocatalyst film 4 is formed in which the desired range is not colored and the others are colored.

Next, the manufacturing method of the dye-sensitized solar cell manufactured using the transparent electrode 1 in which this photocatalyst film | membrane 4 was formed is demonstrated.
When an electrolytic solution is used as the electrolyte, a hole for injecting the electrolytic solution is previously formed in the transparent electrode 1 or the counter electrode 2 on which the photocatalytic film 4 is formed. Then, the transparent electrode 1 and the counter electrode 2 are opposed to each other so that the photocatalytic film 4 is disposed between the electrodes 1 and 2. Next, the periphery between the electrodes 1 and 2 is sealed with a heat-sealing film or a sealant, and the electrolyte layer 3 is disposed by injecting an electrolyte solution between the electrodes 1 and 2 through the holes.

  On the other hand, when a highly viscous electrolyte is used as the electrolyte, the transparent electrode 1 and the counter electrode 2 are opposed to each other so that the photocatalyst film 4 is disposed between both the electrodes 1 and 2, and A solid electrolyte is disposed between the electrodes 1 and 2 (more precisely, between the photocatalyst film 4 and the counter electrode 2). Next, the periphery of both electrodes 1 and 2 is sealed with a sealant and heat bonded. For this heat bonding, both the electrodes 1 and 2 are pressed with a mold and the encapsulant is heated and cured, the encapsulant is irradiated with an energy beam to cure the encapsulant, and the applied ultraviolet light There is a method of curing a cured resin by ultraviolet irradiation. Examples of the energy beam include plasma, visible light having a wavelength of 600 nm or more, infrared rays, and microwaves. By the way, when the dye-sensitized solar cell has a large area of about 100 mm square or more, a spacer may be disposed in the electrolyte solution in order to prevent short-circuiting of both electrodes 1 and 2.

  As described above, according to the method for forming the photocatalytic film 4, the dye-inhibiting film 5 constituting the dye-sensitized solar cell is formed in the desired range of the oxide semiconductor film 41. Since the dye solution does not enter the range, and cleaning for removing the dye solution that has entered the oxide semiconductor film 41 is not necessary, the formation time of the photocatalyst film 4 can be shortened.

  In addition, since the dye inhibiting film 5 constituting the dye-sensitized solar cell is formed in the transparent electrode 1 in the area where the oxide semiconductor film 41 is not disposed, the dye solution is also used in the area where the dye inhibiting film 5 is used. Therefore, it is not necessary to perform cleaning for removing the dye solution that has entered the transparent electrode 1, so that the formation time of the photocatalytic film 4 can be further shortened.

  Furthermore, since the dye inhibition film 5 constituting the dye-sensitized solar cell does not elute into the dye solution, the shape of the dye inhibition film 5 is maintained, and the oxide semiconductor film 41 can be neatly applied. Moreover, since the pigment | dye inhibition film | membrane 5 does not elute to electrolyte, the fall of the battery performance of the dye-sensitized solar cell manufactured can be prevented.

  Moreover, when the pigment | dye inhibition film | membrane 5 is a metal film, since the electroconductivity of the parallel direction of the oxide semiconductor film 41 improves, the battery performance of the dye-sensitized solar cell manufactured can be improved.

Hereinafter, a method of forming the photocatalyst film 4 in the dye-sensitized solar cell according to the example showing the above embodiment more specifically will be described.
The oxide semiconductor film 41 formed on the transparent electrode 1 was a titanium oxide film. To form this titanium oxide film, titanium oxide fine particles (photocatalyst fine particles) having a particle diameter of 20 nm, t-butanol, and water are mixed and stirred to produce a titanium oxide paste, and this titanium oxide paste is transparent. The electrode 1 was applied and baked. The thickness of the titanium oxide film was 4 to 10 μm. Although not shown, a collector electrode having a thickness of about 10 μm was formed on the titanium oxide film.

  Next, the mask M shown in FIG. 2 was placed on the titanium oxide film formed on the transparent electrode 1. At this time, the outer peripheral edge of the mask M and the outer peripheral edge of the titanium oxide film were matched. Thereafter, as shown in FIG. 3A, the dye-inhibiting film solution was applied to the area not covered with the mask M by spraying from above the mask M. As this dye inhibiting film solution, a solution in which polyvinyl alcohol was dissolved in water was used.

  Then, as shown in FIG. 3B, after removing the mask M from the titanium oxide film, the dye-inhibiting film solution on the titanium oxide film and on the transparent electrode 1 was dried at about 150 ° C. Then, the pigment | dye inhibition film | membrane 5 was formed in the range which was not covered with the mask M on a titanium oxide film and the transparent electrode 1. FIG. In addition, the thickness of this pigment | dye inhibition film | membrane 5 was 10 micrometers (it should be several micrometers-several tens of micrometers).

  Thereafter, the transparent electrode 1 was immersed in a dye solution in a substantially horizontal posture, and a photosensitizing dye was brought into contact with the titanium oxide film. In this dye solution, the squarylium dye SQ2 and the organic dye are dissolved in ethanol (which is an example of an alcohol), and the dye concentration is 0.1 mmol / L (may be 0.04 to 0.5 mmol / L). It is a thing. In this dye solution, the weight mixing ratio of the squarylium dye SQ2 and the organic dye is 1: 9, but the present invention is not limited to this. The temperature of the dye solution was arbitrarily selected from room temperature to 80 ° C., and the immersion time was arbitrarily determined from 10 to 120 minutes. Thus, the photocatalyst film 4 in which the desired range was not colored and the others were colored was formed.

Next, a 100 mm square dye-sensitized solar cell was manufactured using the transparent electrode 1 on which the photocatalytic film 4 was formed. The dye-sensitized solar cell was irradiated with a standard light source of AM 1.5, 100 mW / cm ² to measure the power conversion efficiency. As a result, the current density was 3.43 mA / cm ² , the open-circuit voltage was 0.70 V, the fill factor was 0.51, and the conversion efficiency was 1.22%.

Thus, according to the method for forming the photocatalyst film 4 according to the present example, the same effect as the method for forming the photocatalyst film 4 according to the above embodiment was obtained.
In addition, the dye-sensitized solar cell according to this example was able to prevent the battery performance from being deteriorated regardless of the element.

  By the way, in the said embodiment and Example, although the element of the dye-sensitized solar cell was demonstrated, the module of a dye-sensitized solar cell may be sufficient. Specifically, each element is connected in parallel or in series to manufacture a module. When connected in parallel, in the adjacent elements, the transparent conductive film 12, the electrolyte layer 3, the photocatalyst film 4, and the transparent conductive film 22 are partitioned by a sealing material, and the transparent conductive film 12 and the transparent conductive film 22 are separated by a conductor. Connected. When connected in series, only the electrolyte layer 3 and the photocatalyst film 4 are separated by a sealing material in adjacent elements, and the transparent substrate 11, the transparent conductive film 12, the transparent conductive film 22, and the transparent substrate 21 are shared. To do.

  In the above-described embodiment and examples, the material of the mask M has not been described in detail. For example, a partially meshed mask M may be used. Specifically, only a predetermined part of the mask M may be meshed so that the dye-inhibiting membrane solution is slightly passed through the part. As a result, the dye inhibiting film 5 having a very small thickness is formed on the predetermined portion. This slight thickness of the dye-inhibiting film 5 has a low dye inhibition rate and adsorbs a slight amount of photosensitizing dye to the oxide semiconductor film 41. For this reason, the oxide semiconductor film 41 is lightly colored in the portion where the dye inhibiting film 5 having the slight thickness is formed. Therefore, by using the mask M, the pigment inhibition rate of the pigment inhibition film 5 to be formed is different between the predetermined portion and other portions, so that the coloring can be shaded.

  Furthermore, in the said embodiment and Example, although the mask M designed as an emergency exit lamp was used, this design is only an example and, of course, another design may be sufficient.

M mask 1 transparent electrode 2 counter electrode 4 photocatalytic film 5 dye inhibiting film 11 transparent substrate 12 transparent conductive film 41 oxide semiconductor film

Claims (7)

A dye comprising: a transparent electrode; a counter electrode; an electrolyte disposed between the two electrodes; and a photocatalyst film disposed between the electrodes and on the transparent electrode side and having the oxide semiconductor film adsorbed with the dye. A method of forming a photocatalytic film in a sensitized solar cell,
In a desired range in the oxide semiconductor film disposed on the transparent electrode side, a dye-inhibiting film constituting a dye-sensitized solar cell is formed,
Thereafter, the dye solution is brought into contact with the oxide semiconductor film to inhibit the dye from adsorbing in the range where the dye inhibition film is formed, and the dye inhibition film in the oxide semiconductor film is formed. A method for forming a photocatalyst film in a dye-sensitized solar cell, wherein a dye is adsorbed outside the range. Before bringing the dye solution into contact with the oxide semiconductor film,
The formation of a photocatalytic film in a dye-sensitized solar cell according to claim 1, wherein a dye-inhibiting film constituting the dye-sensitized solar cell is formed in a range where the oxide semiconductor film in the transparent electrode is not disposed. Method.   The method for forming a photocatalyst film in a dye-sensitized solar cell according to claim 1 or 2, wherein the dye-inhibiting film does not elute into the dye solution and the electrolyte. As a method of forming a dye-inhibiting film,
A mask in which a desired range is hollowed is placed on the oxide semiconductor film,
Thereafter, a dye-inhibiting film precursor or solution is applied to the oxide semiconductor film by a spray method, a spin coating method, a squeegee method, or a screen printing method,
The method for forming a photocatalytic film in a dye-sensitized solar cell according to any one of claims 1 to 3, wherein the applied precursor or solution is dried.   5. The photocatalytic film in a dye-sensitized solar cell according to claim 4, wherein the mask has different pass rates for allowing the precursor or the solution of the dye-inhibiting film to pass between the predetermined part and the other part. Forming method.   6. The formed dye-inhibiting film has different inhibition rates for inhibiting the adsorption of the dye between the predetermined part and the other part, according to any one of claims 1 to 5. Of forming a photocatalytic film in a dye-sensitized solar cell. The dye inhibiting film is a metal film,
The method for forming a photocatalytic film in a dye-sensitized solar cell according to any one of claims 1 to 3, wherein sputtering is used as a method of forming the dye-inhibiting film.

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