JP6703493B2 - Photoelectric conversion element and method for manufacturing photoelectric conversion element - Google Patents

Description

The present invention relates to a photoelectric conversion element and a method for manufacturing a photoelectric conversion element.
The present application claims priority based on Japanese Patent Application No. 2015-008497 filed in Japan on January 20, 2015, and the content thereof is incorporated herein.

Photoelectric conversion elements such as silicon-based solar cells and dye-sensitized solar cells have been attracting attention as clean energy power generators. In recent years, in order to use the rooftops of plants and other large-scale facilities, idle land, and the like, there is a great demand for high-power solar cells, and research into increasing the size of solar cells is underway.
One of the challenges in increasing the size of solar cells is that the resistance value of the conductive film forming the electrodes is relatively high, so even if the area of the module is increased and the amount of power generation is increased, the current collection efficiency will still deteriorate. The output may be difficult to increase. Therefore, conventionally, in order to improve the current collecting efficiency of a large-sized solar cell, a configuration in which a mesh-shaped low-resistance conducting material is arranged on the conductive film has been developed.
In such a dye-sensitized solar cell, when the mesh-shaped metal layer is in direct contact with an electrolytic solution containing an electrolyte such as iodine, the mesh metal layer is corroded by the electrolytic solution and the reverse electron from the mesh metal layer to the electrolytic solution is applied. Since a reaction occurs, there is a problem in terms of durability performance and power generation efficiency.
Therefore, in a conventional dye-sensitized solar cell (Patent Document 1), for example, a transparent electrode layer is formed on a transparent substrate, a mesh-shaped first metal layer is formed on the transparent electrode layer, and a first metal is further formed. A second metal layer having a higher corrosion resistance than the metal used for the first metal layer is provided on the layer as a protective layer.
In the dye-sensitized solar cell of Patent Document 2, a transparent electrode layer is formed on a transparent substrate, a mesh-shaped metal layer is formed on the transparent electrode layer, and a resin protective layer is further formed on the metal layer. It is provided.
Dye-sensitized solar cells having a mesh-like metal layer as described above are, like other dye-sensitized solar cells, conventionally a paste containing oxide fine particles such as titanium oxide or zinc oxide on a transparent conductive film. And then baked to form a semiconductor porous film.

JP, 2011-192631, A JP, 2010-267557, A

However, when the semiconductor porous film is formed on the transparent conductive film having the mesh-shaped metal layer by the printing method and firing, the semiconductor porous film is also formed on the protective layer formed on the mesh metal layer.
That is, in the conventional dye-sensitized solar cell having a mesh-shaped metal layer, the semiconductor porous film is formed on the protective layer, so that the inter-electrode distance (gap ) Becomes large and the power generation efficiency decreases.
Further, when the semiconductor porous film on the protective layer is irradiated with light, the electrons generated in the semiconductor porous film cannot be taken out onto the metal layer or the transparent conductive film, which causes a reverse electron reaction to the electrolytic solution. Therefore, there was a problem that the power generation efficiency was reduced.
In addition, when a fine mesh-shaped metal layer is formed in order to improve current collection efficiency, it is extremely difficult to form the semiconductor porous film only on the electrode while avoiding the metal layer.
Therefore, the present invention provides a photoelectric conversion element and a method for manufacturing the photoelectric conversion element, which are easy to manufacture and have good current collection efficiency and power generation efficiency.

In the photoelectric conversion element of the present invention, a first substrate, a conductive film formed on the first substrate, the conductive film is disposed on the surface of the conductive film so as to be conductive with the conductive film, and the surface is covered with a protective film. A first electrode having a conductive material formed on the conductive film, a semiconductor porous film formed on the conductive film, a second substrate, and a counter conductive film formed on the second substrate. Two electrodes are provided, and the first electrode and the second electrode are arranged such that the conductive film and the counter conductive film face each other.
It is preferable that the semiconductor porous film is not formed on the surface of the protective film.
Here, “the semiconductor porous film is not formed on the surface of the protective film” means that the semiconductor porous film is formed on at least the surface of the protective film facing the counter conductive film. Means not been done.
According to this configuration, since the semiconductor porous film is not formed on the surface of the protective film, the distance between the electrodes between the first electrode and the second base electrode is shortened, the power generation efficiency is good, and the reverse electron reaction does not occur. Hard to be triggered.

The conductive material of the present invention may be arranged in a stripe pattern or a net pattern.
According to this configuration, it is easy to improve the current collection efficiency.

The protective film of the present invention is preferably an insulating member.
The protective film of the present invention may be formed of an elastic member.
According to this structure, when the semiconductor porous film is formed by the aerosol deposition method, it is possible to prevent the semiconductor porous film from being formed on the protective film.

The height of the conductive material whose surface is coated with the protective film of the present invention may be greater than the thickness of the semiconductor porous film.
According to this structure, the protective film can function as a spacer that forms a space between the semiconductor porous film and the counter conductive film.

The photoelectric conversion element manufacturing method of the present invention includes a first step of disposing a conductive material on the surface of the conductive film of the first substrate on which the conductive film is formed, and coating the surface of the conductive material with a protective film. A second step of spraying an aerosol containing semiconductor particles onto the surface of the conductive film by an aerosol deposition method, thereby forming the semiconductor porous film on a region of the surface of the conductive film where the protective film does not exist; , With.
According to this structure, even if the conductive film covered with the protective film is finely arranged to form fine openings for exposing the conductive film, the conductive film is not formed on the surface of the protective film, and the conductive film is not formed. The semiconductor porous film can be efficiently formed only in the exposed region of the surface.

The conductive material of the present invention may be arranged in a striped shape or a net shape.
According to this structure, the conductive material can be finely arranged.

INDUSTRIAL APPLICABILITY The present invention has an effect that it is possible to improve manufacturability, current collection efficiency, and power generation efficiency.

It is sectional drawing which showed typically the photoelectric conversion element of one Embodiment of this invention. It is a top view showing the 1st electrode of the photoelectric conversion element of one embodiment of the present invention. FIG. 3 is an enlarged view of FIG. 2.

Hereinafter, an embodiment of a photoelectric conversion element of the present invention will be described with reference to the drawings, taking a case where the photoelectric conversion element is a dye-sensitized solar cell as an example.
As shown in FIG. 1, a dye-sensitized solar cell (photoelectric conversion element) (hereinafter referred to as “solar cell”) 1 of the present embodiment is formed on a first substrate 2 and a surface 2 a of the first substrate 2. Conductive film 3, a conductive material 5 disposed on the surface 3a of the conductive film 3 and covered with a protective film 4, and a semiconductor porous film formed on the surface of the conductive film 3 (hereinafter referred to as "porous film"). A second film 8 and a second electrode 10 having a second substrate 8 and a counter conductive film 9 formed on the surface 8 a of the second substrate 8. Then, the conductive film 3 and the counter conductive film 9 are opposed to each other, the first electrode 7 and the second electrode 10 are adhered to each other by using the sealing material 11, and the internal space S is filled with an electrolytic solution (not shown). ..

The first substrate 2 and the second substrate 8 are members that are bases of the conductive film 3 and the counter conductive film 9, respectively, and are transparent thermoplastic resins such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET). It may be formed of a material or may be a glass substrate or the like. At least one of the first substrate 2 and the second substrate 8 is formed of a transparent base material. The first substrate 2 and the second substrate 8 may be formed in a film shape.

The conductive film 3 is formed on substantially the entire surface 2a of the first substrate 2.
Examples of the material of the conductive film 3 include tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), antimony-doped tin oxide (ATO), indium oxide/zinc oxide (IZO), Gallium-doped zinc oxide (GZO) or the like is used.

As shown in FIG. 3, the conductive material 5 is a net-like (also referred to as mesh-like) metal material arranged in the vertical, horizontal and/or diagonal directions, and is formed on the surface 3a of the conductive film 3 as shown in FIG. It is attached. As shown in FIGS. 1 and 3, the surface of the conductive material 5 is covered with a protective film 4.
The cross-sectional shape of the conductive material 5 is a quadrangle in FIG. 1, but is not limited to this, and may be a semicircle, a triangle, or the like. Further, the cross-sectional shape of the conductive material 5 covered with the protective film 4 is also a quadrangle in FIG. 1, but is not limited to this, and may be a semicircle, a triangle, or the like.
The conductive material 5 is formed of a linear metal material having a resistance lower than that of the transparent conductive film 3 such as gold, silver, copper, aluminum, magnesium, stainless steel, chromium, titanium, platinum, nickel and chromium.
The conductive material 5 may be formed of only a single metal, or may be formed of an alloy of two or more kinds of metals or a laminated layer of two or more kinds of metals.
From the viewpoint of current collection efficiency and the distance between electrodes, the thickness of the conductive material 5 is set in the range of 0.1 μm to 100 μm, but is preferably set in the range of 1 μm to 50 μm.
From the viewpoints of current collection efficiency and aperture ratio (ratio of the area of the area other than the area occupied by the conductive material in the total area of the conductive film), the line width of the conductive material 5 not covered with the protective film 4 is 0. Although it is set in the range of 01 mm to 5 mm, it is preferably provided in the range of 0.05 mm to 2 mm.

As shown in FIG. 1, the protective film 4 is provided on the entire surface of the conductive material 5 except for the portion where the conductive material 5 and the conductive film 3 are in contact with each other. That is, the conductive material 5 and the conductive film 3 are in direct contact with each other, and the protective film 4 is not covered in the portion where the conductive material 5 is in contact with the conductive film 3. As a result, the conductive material 5 is in a state capable of being electrically connected to the conductive film 3.
For the protective film 4, an epoxy resin, an acrylic resin, an olefin resin, a urethane resin, or another insulating material having elasticity can be used.

The thickness of the protective film 4 is set in the range of 0.1 μm to 1000 μm, preferably in the range of 1 μm to 500 μm, and more preferably in the range of 2 μm to 50 μm.
From the viewpoint of current collection efficiency and aperture ratio, the line width of the protective film 4 (width of the protective film 4) is set in the range of 0.02 mm to 15 mm, but may be provided in the range of 0.1 mm to 6 mm. preferable.
In any of the ranges, the protective film 4 covers the conductive material 5 other than the portion where the conductive material 5 and the conductive film 3 are in contact with each other substantially completely in the height (thickness) and the width direction. There is.
The line width of the protective film 4 is set in the range of 0.1 to 10 times the length of the conductive material in the width direction, but is preferably set in the range of 0.5 to 5 times, and 2 to 3 times. It is more preferable to set the double range.

The protective film 4 is exposed on the surface 6 a side of the porous film 6 without being covered with the porous film 6 in the first electrode 7. In other words, the porous film 6 is not formed on the surface of the protective film 4. Electrons generated in the porous film 6 pass through the transparent conductive film 3 for a short distance and reach the conductive material 5 so that the current collection efficiency is higher. The size of the space can be set in the range of 0.01 mm to 50 mm, and is preferably set in the range of 0.1 mm to 10 mm. Alternatively, the area of the conductive film 3, which is surrounded by conductive material 5 and the protective layer 4 is settable in the range of 0.0001 mm ² to 2500 mm ^2, be set within a range from 0.1 mm ² to 100 mm ² preferable.

Since the porous film 6 is formed between the protective films 4 in the above range, the protective material 4 can serve as a gap material (that is, a material for holding the distance between the electrodes). Further, in the case where the first substrate 2 and the second substrate 8 are formed of a flexible film material, even if the first substrate 2 and the second substrate 8 are bent, a short circuit can be made difficult to occur. .

The porous film 6 has a function of receiving and transporting electrons from a sensitizing dye described later, and is made of a semiconductor made of a metal oxide, and has conductivity other than a portion provided with the conductive material 5 covered with the protective film 4. It is formed on the entire surface 3 a of the film 3. As the metal oxide, for example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ) or the like is used.
The porous film 6 is preferably formed with a thickness equal to or less than the height (thickness) of the conductive material 5 covered with the protective film 4. With such a configuration, the conductive material 5 itself covered with the protective film 4 can also serve as a spacer (that is, ensure a gap).

The porous film 6 carries a sensitizing dye. The sensitizing dye is composed of an organic dye or a metal complex dye. As the organic dye, for example, various organic dyes such as coumarin-based, polyene-based, cyanine-based, hemicyanine-based, and thiophene-based can be used. Examples of the metal complex dye include, for example, cis-di(thiocyanato)-bis(2,2′-bipyridyl-4,4′-dicarboxylic acid)ruthenium(II) and the cis-di(thiocyanato)-bis(2,2). Examples include bis-tetrabutylammonium salt of ruthenium (II) ('-bipyridyl-4,4'-dicarboxylic acid) (hereinafter referred to as N719). A ruthenium complex or the like is preferably used.
The adsorption amount of the sensitizing dye on the porous film 6 is preferably 1×10 ⁻⁹ mol/cm ² or more and 1×10 ⁻⁵ mol/cm ² or less, and 5×10 ⁻⁹ mol/cm ² or more 5 More preferably, it is not more than ×10 ⁻⁶ mol/cm ² . If the amount of the dye compound adsorbed on the porous film 6 is less than 1×10 ⁻⁸ mol/cm ² , the photoelectric conversion efficiency may decrease. On the other hand, if the adsorption amount of the sensitizing dye on the porous film 6 exceeds 1×10 ⁻⁶ mol/cm ² , the open circuit voltage may be lowered.
Thus, the conductive film 3 is formed on one surface 2a of the first substrate 2, and the conductive material 5 and the porous film 6 covered with the protective film 4 are provided on the surface 3a of the conductive film 3 to form the first electrode. 7 are configured.

The counter conductive film 9 is formed on almost the entire surface 8 a of the second substrate 8.
As the material of the counter conductive film 9, for example, a material having a catalytic action for the redox couple in the electrolytic solution and an electrical conductivity, such as platinum, carbon electrode, or conductive polymer electrode, is used. Further, a conductive layer such as a metal layer or a transparent conductive film may be provided between the counter conductive film 9 and the substrate 8 for the purpose of increasing conductivity.

At least one of the first substrate 2 and the second substrate 8 may be formed of a transparent base material and a transparent conductive film, but the conductive film 3 on which the porous film 6 is formed is a transparent base material and a transparent base material. It is preferably formed of a transparent conductive film.

The first electrode 7 and the second electrode 10 are adhered by a sealing material 11.
As the sealing material 11, a hot melt resin, a thermosetting resin, a UV curable resin or the like is used.
The encapsulating material 11 is arranged in a frame shape along the outer circumference of the conductive film 3 and the outer circumference of the counter conductive film 9 facing the conductive film 3, and an electrolytic solution (not shown) is provided between the first electrode 7 and the second electrode 10. The internal space S is sealed in the filled state.
The terminals (not shown) are connected to the conductive material 5.

The electrolytic solution is a solution containing a redox couple that causes a redox reaction for passing electricity in the dye-sensitized solar cell. As such a redox couple, for example, a combination of iodine and an iodide salt such as dimethylpropylimidazolium iodide or lithium iodide (iodide ion (I ⁻ )/triiodide ion (I ₃ ⁻ )) And a combination of bromine and a bromine salt such as dimethylpropylimidazolium bromide and lithium bromide (bromide ion (Br ⁻ )/tribromide ion (Br ₃ ⁻ )).
Examples of the solvent for the electrolytic solution include nonaqueous solvents such as acetonitrile, propionitrile, and γ-butyrolactone, and ionic liquids such as ethylmethylimidazolium tetracyanoborate and ethylmethylimidazolium dicyanamide. Further, the electrolytic solution 20 may be gelled with a gelling agent such as polyacrylonitrile.
Further, the electrolytic solution may contain an additive such as t-butylpyridine in order to prevent the reverse electron transfer reaction.

A spacer or a separator for forming a gap between the porous film 6 and the counter conductive film 9 may be arranged between the first electrode 7 and the second electrode 10.

Next, a method for manufacturing the solar cell 1 will be described.
In the method for manufacturing the solar cell 1 of the present invention, (I) the conductive material 5 is arranged on the surface 3a of the conductive film 3 formed on the surface 2a of the first substrate 2, and the surface of the conductive material 5 is covered with the protective film 4. And the second step (II) of spraying an aerosol containing semiconductor particles onto the surface 2a by the aerosol deposition method, thereby forming the porous film 6 in the region where the protective film 4 does not exist. Have Then, after the second step, the first electrode 7 and the second electrode 10 are pasted together with the sealing material 11, and the internal space S is filled with an electrolytic solution (not shown) to form the solar cell 1.
Hereinafter, each step will be described.

(I) First Step In the first step, as shown in FIG. 1, the conductive material 5 is arranged on the surface 3 a of the conductive film 3 of the first substrate 2, and the surface of the conductive material 5 is covered with the protective film 4.
The conductive material 5 is obtained by dispersing metal particles in a solvent to form a paste or an ink, and printing such as screen printing or gravure printing on the surface 3a of the conductive film 3 of the first substrate 2 as shown in FIGS. It is arranged by a method of forming by a method, a method of forming by a sputtering method, an evaporation method, a method of attaching a metal member previously formed in a mesh shape or the like to the surface of the conductive film 3, or the like.
The protective film 4 is formed by providing a resin on the surface of the conductive material 5 (see FIG. 1) by a printing method or the like and covering the conductive material 5 as shown in FIGS. 2 and 3.

(II) Second Step In the second step, semiconductor particles are sprayed onto the surface 3a of the conductive film 3 on which the conductive material 5 covered with the protective film 4 is arranged by the aerosol deposition method, whereby the protective film 4 is formed. The porous film 6 is formed in a region where no film exists.
The aerosol deposition method is a method in which a fine particle powder, especially a nano-sized powder is transported in a pipe by a gas, and an aerosol formed by dispersing the powder in the gas is sprayed and adhered to a base material to give an impact. It is a method of forming a film under a low temperature condition and a high film forming rate due to a solidification phenomenon.

The average primary particle diameter of the semiconductor fine particles is particularly limited as long as a porous body can be formed on the surface of the base material and the porous film 6 is not formed on the surface of at least the portion of the protective film 4 facing the counter conductive film 9. However, the range of 1 nm to 1000 nm is preferable, and the range of 10 nm to 500 nm is more preferable.
Although the density of the porous particles is not particularly limited but is preferably ^{3.0~5.0g / cm 3, 3.5~4.5g / cm} 3 is more preferable.
When the density is within the above range, the porous film 6 having high porosity can be easily obtained.

The powder of the fine particles may be a mixture of two or more kinds of powders having different average primary particle diameters.
In order to obtain a denser film, the fine particle powder may be subjected to a dispersion treatment in a solvent or a drying step before film formation by the aerosol deposition method.
In addition, the fine particle powder may be subjected to a dispersion treatment in a solvent or a drying step before film formation by the aerosol deposition method for the purpose of strengthening the bond between the particles.

The outside air temperature and the substrate temperature at the time of film formation are not particularly limited, but are preferably not higher than the heat resistant temperature of the substrate. For example, when a base material such as PET or PEN is used as the base material, both the outside air temperature and the base material temperature are preferably room temperature to 100° C. or less.
The speed of spraying particles (aerosol) onto the conductive film 3 is not particularly limited as long as a porous body can be formed on the surface 3a of the conductive film 3 and the porous film 6 is not formed on the protective film 4. Such a speed range can be set to, for example, 1 to 1000 m/sec.
At this time, since the protective film 4 has elasticity, the particles sprayed by the aerosol deposition method do not settle on the protective film 4, so that the porous film 6 is not formed on the protective film 4.

After forming the porous film 6, the porous film 6 is immersed in a sensitizing dye solution in which the sensitizing dye is dissolved in a solvent, and the sensitizing dye is supported on the porous film 6. The method of supporting the sensitizing dye on the porous film 6 is not limited to the above, and a method of continuously introducing, immersing, and lifting the porous film 6 in the sensitizing dye solution while moving it is also adopted. To be done.
As described above, the first electrode 7 shown in FIGS. 2 and 3 is obtained.

As shown in FIG. 1, the second electrode 10 is a catalyst for a redox couple in an electrolytic solution such as platinum, carbon electrode, conductive polymer electrode, etc. on one surface 8a of the second substrate 8 made of polyethylene terephthalate (PET) or the like. A material having an action and electrical conductivity is used. Films of these materials can be formed by a coating method such as a sputtering method, a vacuum evaporation method, or a spin coating method. Further, a conductive layer such as a metal layer or a transparent conductive film may be provided between the counter conductive film 9 and the substrate 8 for the purpose of increasing conductivity.

After that, the first electrode 7 and the second electrode 10 are attached to each other with the sealing material 11, and the internal space S is filled with an electrolytic solution (not shown) to obtain the solar cell (photoelectric conversion element) 1.

With the above-described structure, the photoelectric conversion element 1 has the conductive material 5 having finest mesh and can be formed on the surface 3a of the conductive film 3 without forming the porous film 6 on the protective film 4. The porous film 6 can be formed.
Therefore, the photoelectric conversion element 1 has an effect that the current collection efficiency can be improved as much as possible, and the reduction of the reverse electron reaction and the redox reaction can be prevented to improve the power generation efficiency.

Further, since the method for manufacturing the photoelectric conversion element 1 of the present application adopts a method of forming the porous film 6 by the aerosol deposition method after using an elastic member for the protective film 4, the protective film 4 The formation of the porous film 6 on the top can be very easily avoided. Therefore, according to the method for manufacturing the photoelectric conversion element 1 of the present application, even if the pitch of the conductive material 5 is made as small as possible, in other words, the eyes for forming the porous film 6 are set finely, the surface of the protective film 4 is not removed. It is possible to easily form the porous film 6 on the surface 3 a of the conductive film 3 without forming the porous film 6.

Although the present invention has been described by using the example in which the conductive material 5 coated with the protective film 4 is formed in a lattice shape in the above-described embodiment, the invention is not limited to this. Specifically, the protective film 4 and the conductive material 5 of the photoelectric conversion element 1 are arranged such that the area surrounded by the conductive material 5 and the protective film 4 is formed in a dot shape or a polygonal shape in addition to the stripe shape. May be. In short, any pattern may be provided as long as the conductive material 5 is formed on the conductive film 3 at regular intervals so as to improve the current collecting efficiency.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following description.

(Formation of the first electrode 7)
As the first substrate 2 on which the transparent conductive film 3 was formed, a PEN film having a surface resistance of 15Ω/□ in which ITO was formed on the plate surface of the first substrate 2 was prepared.
As the conductive material 5, a mesh pattern of silver electrodes (film thickness 5 μm, line width 100 μm) was formed on the ITO film by screen printing, and baked at 120° C. for 10 minutes. At this time, the size of one mesh was set to 1100 μm×1100 μm.

(Formation of protective film 4)
A mesh pattern of the protective film 4 (film thickness 10 μm, line width 20 μm) was formed on the first electrode 7 using a screen-printing method using an acrylic UV curing resin, and UV of 3000 mJ/cm 2 was irradiated. At this time, the size of the mesh 1 was set to 1000 μm×1000 μm so that the mesh-shaped silver electrode was covered with the protective film 4.

(Formation of porous film 6)
Using the aerosol deposition method, titanium oxide particles were sprayed onto the ITO film on which the mesh-shaped silver electrode was formed to form the semiconductor porous film 6. At this time, as film forming conditions in the AD method, nitrogen was used as a carrier gas, the gas flow rate was 1 L/min, the temperature was 25° C., and the pressure in the film forming chamber was 100 Pa. At this time, as the titanium oxide particles, a mixed powder was used in which anatase-type TiO ₂ particles having an average particle diameter of about 20 nm and about 200 nm were mixed at a weight ratio of 50:50.

(Formation of the second electrode 10)
The second electrode 10 was formed by sputtering platinum on a titanium foil having a thickness of 50 μm. After that, a hole having a diameter of about 1 mm for injecting an electrolytic solution was formed in the second electrode 10.

(Preparation of electrolyte containing redox couple)
A γ-butyrolactone solution containing 0.05 M iodine as a redox couple and 1.0 M 1,3-dimethyl-2-propylimidazolium iodide was prepared.

The first electrode 7 and the second electrode 10 produced as described above were opposed to each other, the sealing material was arranged leaving an internal space, and the sealing material 11 was cured by heat treatment or the like. Then, the electrolyte solution was injected through the injection hole formed in the counter electrode in advance, and then the injection hole was closed by thermosetting the sealing material 11 to manufacture a dye-sensitized solar cell.

(Evaluation of power generation performance of dye-sensitized solar cell)
The power generation performance of the dye-sensitized solar cell 1 was evaluated by measuring the photoelectric conversion efficiency under irradiation of pseudo sunlight with a light intensity of 100 mW/cm ² using a solar simulator. The results are shown in Table 1.

In forming the first electrode 7, the line width of the silver electrode is changed to 1000 μm, the size of the mesh 1 square is changed to 6000 μm×6000 μm, and in forming the protective film 4, the line width of the protective film 4 is 3000 μm and the size of the mesh 1 square. Was prepared and evaluated in the same manner as in Example 1 except that the thickness was changed to 4000 μm×4000 μm.
[Comparative Example 1]

In the formation of the porous film 6, a titanium oxide paste containing titanium oxide particles having an average particle diameter of 20 nm was printed on the conductive film 3 and then dried at 150° C., and produced and evaluated in the same manner as in Example 1 above. .

(Evaluation results)
As shown in Table 1, the dye-sensitized solar cell 1 of Examples 1 and 2 had a high power generation efficiency of 2% or more, but the dye-sensitized solar cell of Comparative Example 1 had a power generation efficiency of Examples 1 and 2 Stayed low compared to.
From the above, it was found that the power generation efficiency is higher when the porous film 6 is not formed on the protective film 4 than when the porous film 6 is formed on the protective film 4.

1-Solar cell (photoelectric conversion element)
2... First substrate 3... Conductive film 4... Protective film 5... Conductive material 6... Semiconductor porous film 7... First electrode 8... Second substrate 9... -Counter conductive film 10 ... second electrode

Claims (5)

A first substrate, a conductive film formed on the first substrate, a conductive material disposed on the surface of the conductive film so as to be conductive with the conductive film and having a surface covered with a protective film, and the conductive film A first electrode having a semiconductor porous film formed thereon;
A second electrode having a second substrate and a counter conductive film formed on the second substrate;
The protective film is made of an elastic insulating material,
The first electrode and the second electrode are arranged such that the conductive film and the counter conductive film face each other ,
A photoelectric conversion element in which the semiconductor porous film is not formed on the surface of the protective film . The photoelectric conversion element according to claim 1, wherein the conductive material is arranged in a stripe pattern or a mesh pattern. It said height of said conductive material whose surface is coated with a protective film, a photoelectric conversion device according to the greater thickness claim semiconductor porous film 1 or 2. A first step of disposing a conductive material on the surface of the conductive film of the first substrate on which the conductive film is formed, and coating the surface of the conductive material with a protective film made of an insulating material having elasticity ;
By the aerosol deposition method, an aerosol containing semiconductor particles is sprayed onto the surface of the conductive film on which the conductive material coated with the protective film made of the elastic insulating material is arranged , whereby the surface of the conductive film is method of manufacturing a photoelectric conversion device having a second step, the forming a semi-conductive porous membrane in a region where the protective film is not present. The method for manufacturing a photoelectric conversion element according to claim 4 , wherein the conductive material is arranged in a stripe pattern or a mesh pattern.

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