WO2013031939A1 - Electrode for photoelectric conversion element, method for manufacturing electrode for photoelectric conversion element, and photoelectric conversion element - Google Patents

Abstract

This electrode for a photoelectric conversion element is provided with: a conductive substrate having a substrate and a conductive film, which is provided on the substrate and contains tin; and a wiring section, which is provided on the conductive film of the conductive substrate, and has current-collecting wiring containing silver particles. The current-collecting wiring has a contact section in contact with the conductive film, the contact section has a silver-tin alloy section composed of an alloy of silver and tin, and a gap is formed between the current-collecting wiring and the conductive film by being adjacent to the contact section. Consequently, excellent durability is imparted to the photoelectric conversion element.

Description

Electrode for photoelectric conversion element, method for producing the same, and photoelectric conversion element

The present invention relates to an electrode for a photoelectric conversion element, a manufacturing method thereof, and a photoelectric conversion element.

As a photoelectric conversion element, a dye-sensitized solar cell is attracting attention because it is inexpensive and high photoelectric conversion efficiency can be obtained, and various developments have been made on the dye-sensitized solar cell.

A dye-sensitized solar cell generally includes a working electrode having a porous oxide semiconductor layer, a counter electrode, an electrolyte disposed therebetween, and a working electrode and a counter electrode, and a sealing provided around the electrolyte. Department.

As such a dye-sensitized solar cell, a dye-sensitized solar cell described in Patent Document 1 below is known. Patent Document 1 below has a working electrode and a counter electrode, and the working electrode includes a transparent conductive layer provided on a substrate, a metal wiring layer formed on the transparent conductive layer, and a surface of the metal wiring layer. A dye-sensitized solar cell having an insulating layer to cover is disclosed. In Patent Document 1 below, a metal wiring layer is coated on a transparent conductive layer so as to form a predetermined pattern with a paste formed by blending a metal powder that becomes conductive particles and a binder such as glass fine particles. It is disclosed that it can be obtained by heating and firing.

JP 2010-140909 A

However, the dye-sensitized solar cell described in Patent Document 1 described above cannot be said to have a sufficiently small decrease in photoelectric conversion efficiency over time, and has room for improvement in terms of durability.

This invention is made | formed in view of the said situation, It aims at providing the electrode for photoelectric conversion elements which can provide the outstanding durability to a photoelectric conversion element, its manufacturing method, and a photoelectric conversion element. To do.

The inventors of the present invention have examined the cause of the decrease in photoelectric conversion efficiency that is not sufficiently small in the dye-sensitized solar cell described in Patent Document 1. As a result, in the dye-sensitized solar cell described in Patent Document 1, when the transparent conductive layer in the working electrode is thermally contracted or expanded, excessive stress is applied to the interface between the metal wiring layer and the transparent conductive layer. It was thought that this stress might cause the metal wiring layer to peel off from the transparent conductive layer. In addition, the present inventors considered that the adhesion of the metal wiring layer to the transparent conductive layer is still insufficient, which may be one of the factors that cause the metal wiring layer to peel from the transparent conductive layer. Then, the present inventors considered that the contact resistance is increased by peeling the metal wiring layer from the transparent conductive layer, and as a result, it cannot be said that the decrease in photoelectric conversion efficiency is sufficiently small. Therefore, as a result of further earnest studies, the present inventors have found that the above-described problems can be solved by the following invention.

That is, the present invention provides a substrate, a conductive substrate provided on the substrate and having a conductive film containing tin, and a current collector wiring provided on the conductive film of the conductive substrate and containing silver particles. The current collector wiring has a contact portion that contacts the conductive film, and the contact portion has a silver-tin alloy portion made of an alloy of silver and tin, and the current collector wiring A gap is formed between the conductive film and the conductive film, and a gap is formed adjacent to the contact portion.

According to this electrode, when the conductive film is thermally contracted or expanded, the current collecting wiring in the wiring portion is subjected to excessive stress near the interface with the conductive film due to thermal contraction or thermal expansion. At this time, even if stress is applied to the contact portion between the current collector wiring and the conductive film, a gap is formed adjacent to the contact portion between the current collector wiring and the conductive film. Is sufficiently relaxed. The contact part has a silver-tin alloy part made of a silver-tin alloy. Here, the silver tin alloy part contains tin common to the conductive film containing tin, and contains silver common to the current collector wiring containing silver particles. For this reason, a silver tin alloy part has high adhesiveness with respect to both a current collection wiring and a electrically conductive film. For this reason, peeling of the current collector wiring from the conductive film is sufficiently suppressed, and an increase in contact resistance between the current collector wiring and the conductive film is sufficiently suppressed. Therefore, according to the photoelectric conversion element electrode of the present invention, it is possible to sufficiently suppress a decrease in photoelectric conversion efficiency, and to impart excellent durability to the photoelectric conversion element using the photoelectric conversion element electrode as an electrode. it can.

Moreover, it is preferable that the contact portion further includes an inorganic binder.

In this case, since the contact portion between the current collector wiring and the conductive film further has an inorganic binder, the adhesion between the current collector wiring and the conductive film can be further enhanced by the inorganic binder.

It is preferable that the current collecting wiring further includes a gap.

In this case, even when the current collecting wiring is thermally expanded or contracted, the stress applied to the current collecting wiring is sufficiently relaxed, and the generation of cracks is sufficiently suppressed.

The current collector wiring may further include a main body provided on the side opposite to the conductive film with respect to the contact portion, and the main body may further include an inorganic binder.

It is preferable that the wiring portion further includes a wiring protective layer that covers and protects the current collecting wiring.

When the electrode having the wiring portion is used as an electrode of a photoelectric conversion element having an electrolyte, the wiring protective layer sufficiently suppresses corrosion of the current collecting wiring due to the electrolyte.

In the photoelectric conversion element electrode having a wiring protective layer among the photoelectric conversion element electrodes, the current collector wiring further includes a main body provided on a side opposite to the conductive film with respect to the contact portion, and the main body A first current collecting wiring portion provided on the contact portion and including an inorganic binder and silver particles; a second current collecting wiring portion provided on the first current collecting wiring portion and including silver particles; The first current collecting wiring part and the second current collecting wiring part have a gap, and the porosity of the second current collecting wiring part is smaller than the porosity of the first current collecting wiring part. preferable.

According to this photoelectric conversion element electrode, the first current collecting wiring part and the second current collecting wiring part have a gap, and the porosity of the second current collecting wiring part is higher than the porosity of the first current collecting wiring part. small. For this reason, even when the sealing part forming material is bonded to the photoelectric conversion element electrode by heating, for example, even if the air contained in the gap of the first current collector wiring part expands, the expanded air is protected against the wiring. Penetration through the layer is sufficiently suppressed. For this reason, generation | occurrence | production of the path | route which an electrolyte can penetrate | invade in a wiring protective layer is fully suppressed. As a result, when the obtained electrode for a photoelectric conversion element is applied as an electrode for a photoelectric conversion element of a dye-sensitized solar cell having an electrolyte, corrosion of the current collecting wiring by the electrolyte is sufficiently suppressed. Therefore, according to the electrode for a photoelectric conversion element of the present invention, it is possible to impart excellent durability to the photoelectric conversion element.

In the photoelectric conversion element electrode, it is preferable that the content of the inorganic binder in the second current collector wiring portion is smaller than the content of the inorganic binder in the first current collector wiring portion.

In this case, the resistance of the entire current collecting wiring can be reduced more sufficiently.

In the photoelectric conversion element electrode, the content of the inorganic binder in the second current collector wiring portion is smaller than the content of the inorganic binder in the first current collector wiring portion, and the first current collector wiring portion. The difference between the content of the inorganic binder in the content and the content of the inorganic binder in the second current collector wiring portion is preferably 0.1 to 3% by mass.

In this case, the adhesion between the first current collector wiring and the second current collector wiring is more easily maintained.

In the photoelectric conversion element electrode, it is preferable that the maximum diameter of the void in the second current collector wiring portion is 1 to 10 μm.

In this case, the stress inside the current collector wiring at high and low temperatures can be more fully relieved by the air gap.

Moreover, this invention is a photoelectric conversion element containing the electrode for photoelectric conversion elements mentioned above.

Furthermore, the present invention includes a wiring portion forming step of forming a wiring portion on a conductive substrate in which a conductive film is provided on the substrate, and the wiring portion forming step forms a current collector wiring on the conductive substrate. The current collector wiring forming step, wherein the current collector wiring has a contact portion in contact with the conductive film, and the contact portion is made of an alloy of silver and tin. It is a manufacturing method of the electrode for photoelectric conversion elements formed so that it may have an alloy part, and a space | gap is formed adjacent to the said contact part between the said current collection wiring and the said electrically conductive film.

According to the said manufacturing method, the fall for photoelectric conversion efficiency can fully be suppressed, and the photoelectric conversion element electrode which can provide the outstanding durability with respect to the photoelectric conversion element which uses the electrode for photoelectric conversion elements as an electrode is manufactured. it can.

In the manufacturing method, the wiring portion forming step includes forming a wiring protective layer by covering the current collecting wiring with a wiring protective layer forming material and heat-treating the wiring protective layer forming material. A first collecting current wiring portion including an inorganic binder and silver particles, wherein the collecting wiring is provided on the conductive substrate in the collecting wiring forming step; A second current collecting wiring part including silver particles provided on the wiring part, wherein the first current collecting wiring part and the second current collecting wiring part have a gap, and the second current collecting wiring part includes: It is a manufacturing method of the electrode for photoelectric conversion elements formed so that a porosity may become smaller than the porosity of the said 1st current collection wiring part.

According to the above manufacturing method, in the obtained electrode for a photoelectric conversion element, the first current collector wiring part and the second current collector wiring part have voids, and the porosity of the second current collector wiring part is the first current collector wiring. It becomes smaller than the porosity of the part. For this reason, when the wiring protective layer is formed by heat-treating the wiring protective layer forming material, even if the air contained in the gap of the first current collecting wiring part expands, the second current collecting wiring part The expanded air is sufficiently suppressed from penetrating the wiring protective layer. As a result, in the wiring protective layer, generation of a path through which the electrolyte can enter is sufficiently suppressed. Further, for example, when the sealing part is bonded to the obtained photoelectric conversion element electrode by heating, even if the air contained in the gap of the first current collecting wiring part expands, the second current collecting wiring part causes the expansion. The air that has passed through the wiring protective layer is sufficiently suppressed. For this reason, generation | occurrence | production of the path | route which an electrolyte can penetrate | invade in a wiring protective layer is fully suppressed. As a result, when the obtained electrode for a photoelectric conversion element is applied as the electrode for a photoelectric conversion element of a photoelectric conversion element having an electrolyte, corrosion of the current collector wiring due to the electrolyte is sufficiently suppressed. Therefore, according to the manufacturing method of the electrode for photoelectric conversion elements of this invention, the electrode for photoelectric conversion elements which can provide the outstanding durability with respect to a photoelectric conversion element can be manufactured.

In the above manufacturing method, it is preferable that the content of the inorganic binder in the second current collector wiring portion is smaller than the content of the inorganic binder in the first current collector wiring portion.

In this case, it is possible to easily realize the porosity of the second current collector wiring portion to be smaller than the porosity of the first current collector wiring portion.

In the manufacturing method, the difference between the content of the inorganic binder in the first current collector wiring portion and the content of the inorganic binder in the second current collector wiring portion is 0.1 to 3% by mass. Is preferred.

In this case, compared with the case where the difference between the content of the inorganic binder in the first current collector wiring portion and the content of the inorganic binder in the second current collector wiring portion is out of the above range, the first current collector wiring portion The porosity generated in the second current collector wiring portion can be made smaller than the generated porosity.

In the above manufacturing method, it is preferable that the maximum diameter of the void in the second current collecting wiring portion is 1 to 10 μm.

In this case, when the wiring protective layer is formed by heat-treating the wiring protective layer forming material, even if the air contained in the voids of the first current collector wiring portion expands, the expanded air forms the wiring protective layer. Penetration is effectively suppressed.

In the present invention, the “void ratio” of the first current collector wiring portion and the second current collector wiring portion refers to the cross-sectional area of the wiring portion in each cross section of the first current collector wiring portion and the second current collector wiring portion. The percentage of voids in The wiring section cross-sectional area is the area of the surface surrounded by the outer layer of the first current collecting wiring portion and the conductive substrate for the first current collecting wiring portion. Here, the outer layer of the first current collector wiring part means that the entire surface of the first current collector wiring part excluding the surface in contact with the conductive substrate is covered with the second current collector wiring part. This means the second current collector wiring part. Of the first current collector wiring part, a part of the surface excluding the surface in contact with the conductive substrate is covered with the second current collector wiring part, and the remaining part is covered with the wiring protective layer. In this case, it means the second current collecting wiring part and the wiring protective layer. Also, the wiring section cross-sectional area refers to the second current collecting wiring portion, the entire surface of the first current collecting wiring portion excluding the surface in contact with the conductive substrate is covered with the second current collecting wiring portion. In this case, the area of the surface surrounded by the outer layer of the second current collector wiring portion, the first current collector wiring portion, and the conductive substrate, excluding the surface of the first current collector wiring portion that is in contact with the conductive substrate. When a part of the surface is covered with the second current collecting wiring part and the remaining part is covered with the wiring protective layer, the area of the surface surrounded by the outer layer of the second current collecting wiring part and the first current collecting wiring part It is. The outer layer of the second current collector wiring portion means a wiring protective layer.

Each of the above-described void ratios is a value calculated by dividing the occupied area of the void having a diameter of 1 μm or more in an image observed with a scanning electron microscope (SEM) by the cross-sectional area of each current collector wiring portion. Here, the “diameter” is the following formula when the area of the void in the image observed with the SEM is S1:
R1 = 2 × (S1 / π) ^1/2
The value of R1 calculated based on

In the present invention, the “inorganic binder content” is calculated by a plasma mass spectrometer (ICP).

Furthermore, in the present invention, “the maximum diameter of the void in the second current collector wiring portion” refers to the largest diameter among the diameters of the voids observed in at least three wiring section cross sections when measuring the porosity described above. Shall. Here, the “diameter” refers to a diameter calculated in the same manner as the above-described gap diameter.

According to the present invention, there are provided an electrode for a photoelectric conversion element capable of imparting excellent durability to the photoelectric conversion element, a manufacturing method thereof, and a photoelectric conversion element.

It is sectional drawing which shows 1st Embodiment of the photoelectric conversion element which concerns on this invention. It is a fragmentary sectional view which shows the wiring part of FIG. It is a fragmentary sectional view which shows the wiring part in 2nd Embodiment of the photoelectric conversion element which concerns on this invention. It is a fragmentary sectional view which shows 3rd Embodiment of the photoelectric conversion element of this invention. It is a fragmentary sectional view which shows the electrode for photoelectric conversion elements of FIG. It is sectional drawing which shows an example of the current collection wiring of FIG. It is a figure which shows 1 process of the manufacturing method of the electrode for photoelectric conversion elements of FIG. It is a figure which shows 1 process of the manufacturing method of the electrode for photoelectric conversion elements of FIG. It is a figure which shows 1 process of the manufacturing method of the electrode for photoelectric conversion elements of FIG. It is a figure which shows 1 process of the manufacturing method of the electrode for photoelectric conversion elements of FIG. It is a fragmentary sectional view which shows the modification of the current collection wiring of FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In all the drawings, the same or equivalent components are denoted by the same reference numerals, and redundant description is omitted.

<First Embodiment>
First, a first embodiment of a photoelectric conversion element according to the present invention will be described with reference to FIG. 1 and FIG. FIG. 1 is a cross-sectional view showing a first embodiment of a photoelectric conversion element according to the present invention, and FIG. 2 is a partial cross-sectional view showing a wiring portion of FIG.

As shown in FIG. 1, the dye-sensitized solar cell 100 includes a working electrode 10 and a counter electrode 20 disposed so as to face the working electrode 10. An electrolyte 30 is disposed between the working electrode 10 and the counter electrode 20, and a sealing portion 40 that connects the working electrode 10 and the counter electrode 20 is provided around the electrolyte 30. Note that the dye-sensitized solar cell 100 includes not only an element that converts sunlight into electricity but also an element that converts light from an indoor light source (for example, a fluorescent lamp) into electricity.

The working electrode 10 includes a conductive substrate 11, a porous oxide semiconductor layer 12 provided on the conductive substrate 11, and a wiring provided on the conductive substrate 11 so as to surround the porous oxide semiconductor layer 12. Part 13. The conductive substrate 11 includes a transparent substrate 14 and a transparent conductive film 15 provided on the counter electrode 20 side of the transparent substrate 14 and containing tin. A photosensitizing dye is supported on the porous oxide semiconductor layer 12 of the working electrode 10.

The counter electrode 20 includes a counter electrode substrate 21 and a conductive catalyst layer 22 provided on the working electrode 10 side of the counter electrode substrate 21 to promote a reduction reaction on the surface of the counter electrode 20.

As shown in FIG. 2, the wiring portion 13 includes a current collecting wiring 16 provided on the transparent conductive film 15 and a wiring protective layer 17 that covers the current collecting wiring 16 and protects it from the electrolyte 30.

The current collector wiring 16 is composed of a sintered body containing silver particles 51. The current collector wiring 16 has a contact portion B that comes into contact with the transparent conductive film 15 and a main body portion C provided on the contact portion B. The contact portion B has a silver-tin alloy portion 52 made of an alloy of silver and tin and an inorganic binder 53, and is adjacent to the contact portion B between the current collector wiring 16 and the transparent conductive film 15. A gap A is formed. In addition, the current collector wiring 16 has a gap A1 and an inorganic binder 53 in the main body C that is separated from the transparent conductive film 15. Further, the contact portion B may also have a gap A1.

According to this dye-sensitized solar cell 100, when the transparent conductive film 15 is thermally contracted or expanded, the current collecting wiring 16 of the wiring portion 13 is excessively large due to thermal contraction or thermal expansion in the vicinity of the interface with the transparent conductive film 15. Under stress. At this time, even if stress is applied to the contact portion B between the current collector wiring 16 and the transparent conductive film 15, a gap A is formed adjacent to the contact portion B between the current collector wiring 16 and the transparent conductive film 15. Therefore, the stress applied to the contact portion B by the gap A is sufficiently relaxed. Moreover, the contact part B has the silver tin alloy part 52 which consists of a silver tin alloy. Here, the silver tin alloy part 52 contains tin common to the transparent conductive film 15 containing tin, and contains silver common to the current collector wiring 16 containing the silver particles 51. For this reason, the silver-tin alloy part 52 has high adhesion to both the current collector wiring 16 and the transparent conductive film 15. For this reason, peeling of the current collector wiring 16 from the transparent conductive film 15 is sufficiently suppressed, and an increase in contact resistance between the transparent conductive film 15 and the current collector wiring 16 is sufficiently suppressed. Therefore, according to the dye-sensitized solar cell 100, the fall of a photoelectric conversion characteristic can fully be suppressed and it becomes possible to have the outstanding durability.

In the dye-sensitized solar cell 100, the contact portion B between the current collecting wiring 16 and the transparent conductive film 15 has a silver tin alloy portion 52 and an inorganic binder 53. For this reason, the adhesiveness of the current collection wiring 16 and the transparent conductive film 15 can be improved more by the inorganic binder 53, and peeling of the current collection wiring 16 from the transparent conductive film 15 can be suppressed more fully.

Furthermore, in the dye-sensitized solar cell 100, the wiring portion 13 further includes a wiring protective layer 17 that covers and protects the current collecting wiring 16. For this reason, the wiring protective layer 17 sufficiently suppresses the corrosion of the current collecting wiring 16 by the electrolyte 30.

Furthermore, in the dye-sensitized solar cell 100, the main body C of the current collecting wiring 16 includes the gap A1. For this reason, even when the current collecting wiring 16 is thermally expanded or contracted, the stress applied to the main body C of the current collecting wiring 16 is sufficiently relaxed, and the occurrence of cracks is sufficiently suppressed.

Next, the working electrode 10, the photosensitizing dye, the counter electrode 20, the electrolyte 30, and the sealing portion 40 will be described in detail.

(Working electrode)
The material which comprises the transparent substrate 14 should just be a transparent material, for example, As such a transparent material, glass, such as borosilicate glass, soda-lime glass, white board glass, quartz glass, polyethylene terephthalate (PET), for example , Polyethylene naphthalate (PEN), polycarbonate (PC) and polyethersulfone (PES). The thickness of the transparent substrate 14 is appropriately determined according to the size of the dye-sensitized solar cell 100 and is not particularly limited, but may be in the range of 50 to 10,000 μm, for example.

The transparent conductive film 15 may be made of a transparent material containing tin. Examples of the transparent material containing tin include indium-tin-oxide (ITO) and tin oxide (ITO). Examples thereof include conductive metal oxides such as SnO ₂ ) and fluorine-doped tin oxide (FTO). The transparent conductive film 15 may be a single layer or a laminate of a plurality of layers made of different conductive metal oxides. When the transparent conductive film 15 is composed of a single layer, the transparent conductive film 15 is preferably composed of FTO because it has high heat resistance and chemical resistance. In addition, it is preferable to use a laminate composed of a plurality of layers as the transparent conductive film 15 because the characteristics of each layer can be reflected. Among these, it is preferable to use a laminate of a layer made of ITO and a layer made of FTO. In this case, the transparent conductive film 15 having high conductivity, heat resistance and chemical resistance can be realized. The thickness of the transparent conductive film 15 may be in the range of 0.01 to 2 μm, for example.

The porous oxide semiconductor layer 12 is porous and composed of oxide semiconductor particles. The average particle size of the oxide semiconductor particles is 1 to 1000 nm, which increases the surface area of the oxide semiconductor covered with the photosensitizing dye, that is, widens the field for photoelectric conversion and generates more electrons. It is preferable because it can be performed. Here, it is preferable that the porous oxide semiconductor layer 12 is composed of a laminated body in which oxide semiconductor particles having different particle size distributions are laminated. In this case, it becomes possible to cause reflection of light repeatedly in the laminated body, and light can be efficiently converted into electrons without escaping incident light to the outside of the laminated body. The thickness of the porous oxide semiconductor layer 12 may be, for example, 0.5 to 50 μm. In addition, the porous oxide semiconductor layer 12 can also be comprised with the laminated body of the several semiconductor layer which consists of a different material.

Examples of the oxide semiconductor particles include titanium oxide (TiO ₂ ), silica (SiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₅ ), niobium oxide (Nb ₂ O ₅ ), and strontium titanate (SrTiO _5). ), Tin oxide (SnO ₂ ), indium oxide (In ₃ O ₃ ), zirconium oxide (ZrO ₂ ), thallium oxide (Ta ₂ O ₅ ), lanthanum oxide (La ₂ O ₃ ), yttrium oxide (Y ₂ O ₃₎ ), Holmium oxide (Ho ₂ O ₃ ), bismuth oxide (Bi ₂ O ₃ ), cerium oxide (CeO ₂ ), aluminum oxide (Al ₂ O ₃ ), and the like. These can be used alone or in combination of two or more.

The current collector wiring 16 contains silver particles 51. The average particle diameter of the silver particles 51 is preferably 0.3 to 10 μm, and more preferably 0.5 to 2.0 μm. When the average particle diameter of the silver particles 51 is in the range of 0.3 to 10 μm, the volume resistance can be more sufficiently reduced than when the average particle diameter is out of the range. In addition, the average particle diameter of silver particle means the average value of the particle diameter of 100 silver particles when the cross section of current collection wiring is observed by SEM. Here, the “particle size” is the following formula when the area of the silver particles in the image observed with the SEM is S2.
R2 = 2 × (S2 / π) ^1/2
The value of R2 calculated based on

Further, the porosity, which is the ratio occupied by the gap A1 in the current collector wiring 16, is preferably 30% or less, and more preferably 20% or less. Here, “the porosity, which is the ratio of the gap A1 in the current collector wiring 16” refers to the ratio of the area of the void in the current collector wiring 16 when the cross section of the current collector wiring is observed with the SEM. To do.

In this case, the volume resistance can be made smaller than when the porosity exceeds 30%.

However, the porosity of the current collecting wiring 16 is preferably 1% or more because the contact resistance between the transparent conductive film 15 and the current collecting wiring 16 can be reduced.

Examples of the inorganic binder 53 include glass frit and solder. These can be used alone or in combination.

The wiring protective layer 17 protects the current collecting wiring 16 from the electrolyte 30 and is made of, for example, a resin material or an inorganic material.

Examples of the resin material include modified polyolefin resins, polyimide resins, silicones including thermoplastic resins such as ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, and ethylene-vinyl alcohol copolymers. Examples thereof include heat-resistant resins such as resins and fluororesins, ultraviolet curable resins, and vinyl alcohol polymers.

Examples of the inorganic material include inorganic insulating materials such as non-lead transparent low melting point glass frit. As the low melting point glass frit, one having a softening point of 150 to 550 ° C. can be used.

(Photosensitizing dye)
Examples of the photosensitizing dye include a ruthenium complex (for example, black dye) having a ligand containing a bipyridine structure, a terpyridine structure, etc., an osmium complex, an iron complex, a copper complex, a platinum complex, a porphyrin metal complex, a phthalocyanine metal complex, etc. And organic dyes such as porphyrin, eosin, rhodamine, merocyanine, cyanine, merocyanine, mercurochrome, xanthene dye, azo dye, and coumarin dye.

(Counter electrode)
As the counter electrode substrate 21, for example, a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, or tungsten, or a material obtained by laminating a conductive oxide such as ITO or FTO on the transparent substrate 14 described above is used. be able to.

The catalyst layer 22 is composed of platinum, a carbon-based material, a conductive polymer, or the like.

The thickness of the counter electrode 20 is appropriately determined according to the size of the dye-sensitized solar cell 100 and is not particularly limited. The thickness of the counter electrode 20 may be in the range of 0.005 to 0.5 mm, for example.

(Electrolytes)
The electrolyte 30 is usually composed of an electrolytic solution, and this electrolytic solution contains an oxidation-reduction pair such as I ⁻ / I ₃ ⁻ and an organic solvent. Examples of organic solvents include acetonitrile, methoxyacetonitrile, methoxypropionitrile, propionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, valeronitrile, pivalonitrile, glutaronitrile, methacrylonitrile, isobutyronitrile, Phenylacetonitrile, acrylonitrile, succinonitrile, oxalonitrile, pentanitrile, adiponitrile and the like can be used. Examples of the redox pair include I ⁻ / I ₃ ^— and a redox pair such as bromine / bromide ion, zinc complex, iron complex, and cobalt complex.

The electrolyte 30 may be an ionic liquid instead of the organic solvent.

As the ionic liquid, for example, a known iodine salt such as a pyridinium salt, an imidazolium salt, or a triazolium salt, and a room temperature molten salt that is in a molten state near room temperature is used. Examples of such room temperature molten salts include 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylimidazolium iodide, 1-ethyl-3-propylimidazolium iodide. Id, dimethylimidazolium iodide, ethylmethylimidazolium iodide, dimethylpropylimidazolium iodide, butylmethylimidazolium iodide, or methylpropylimidazolium iodide is preferably used.

The electrolyte 30 may be a mixture of the ionic liquid and the organic solvent instead of the organic solvent.

An additive can be added to the electrolyte 40. Examples of the additive include LiI, I ₂ , 4-t-butylpyridine, guanidinium thiocyanate, 1-methylbenzimidazole, 1-butylbenzimidazole and the like.

Further, as the electrolyte 30, a nanocomposite gel electrolyte which is a pseudo solid electrolyte formed by kneading nanoparticles such as SiO ₂ , TiO ₂ , and carbon nanotubes with the above electrolyte may be used, or polyvinylidene fluoride. Alternatively, an electrolyte gelled with an organic gelling agent such as a polyethylene oxide derivative or an amino acid derivative may be used.

(Sealing part)
The sealing portion 40 is made of, for example, a resin material. Examples of such resin materials include modified polyolefin resins including thermoplastic resins such as ionomers, ethylene-vinyl acetic anhydride copolymers, ethylene-methacrylic acid copolymers, ethylene-vinyl alcohol copolymers, and ultraviolet curing. Examples thereof include resins and vinyl alcohol polymers.

Next, a method for manufacturing the dye-sensitized solar cell 100 will be described.

[Preparation process]
First, the working electrode 10 and the counter electrode 20 are prepared.

(Working electrode)
The working electrode 10 can be obtained as follows.

First, a transparent conductive film 15 is formed on a transparent substrate 14 to form a laminate. As a method for forming the transparent conductive film 15, a sputtering method, a vapor deposition method, a spray pyrolysis method (SPD), a CVD method, or the like is used.

Next, a porous oxide semiconductor layer forming paste is printed on the transparent conductive film 15 obtained as described above. The paste for forming a porous oxide semiconductor layer contains a resin such as polyethylene glycol and a solvent such as terpineol in addition to the oxide semiconductor particles. As a printing method of the paste for forming the porous oxide semiconductor layer, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

Next, the porous oxide semiconductor layer forming paste is baked to form the porous oxide semiconductor layer 12 on the transparent conductive film 15. The firing temperature varies depending on the oxide semiconductor particles, but is usually 100 to 600 ° C., preferably 350 to 600 ° C. The firing time also varies depending on the oxide semiconductor particles, but is usually 1 to 5 hours.

Next, the current collecting wiring 16 is formed on the transparent conductive film 15 of the conductive substrate 11. At this time, the current collecting wiring 16 is formed so as to surround the porous oxide semiconductor layer 12.

The current collector wiring 16 is prepared, for example, by preparing a conductive paste containing silver particles, an organic binder resin, an inorganic binder made of glass frit, and a solvent, and using the conductive paste by a screen printing method or the like. 15 can be obtained by coating on 15, heating and baking. At this time, the content of the inorganic binder is preferably 0.5 to 5.0% by mass, and more preferably 1.5 to 3.5% by mass. When the content of the inorganic binder is within the above range, peeling of the current collector wiring 16 from the transparent conductive film 15 can be more sufficiently suppressed than when the content is outside the above range.

Examples of the organic binder resin include dihydroterpineol. Examples of the solvent include ethyl cellulose.

In order to obtain the silver-tin alloy part 52 in the contact part B, the conductive paste may be heated to a temperature at which both the silver particles in the conductive paste and the transparent conductive film 15 are melted. Specifically, the conductive paste may be heated to 400 to 600 ° C.

In order to form the gap A between the current collecting wiring 16 and the transparent conductive film 15, the amount of the solvent in the conductive paste and the amount of the inorganic binder may be adjusted.

Further, in order to form the gap A1 in the current collecting wiring 16, an inorganic binder having a melting point lower than that of silver particles is used. In this case, since the inorganic binder is melted before the silver particles 51, the inorganic binder can be directed to the transparent conductive film 15 by the action of gravity. As a result, a gap A1 is formed in the current collecting wiring 16.

Next, the current collecting wiring 16 is covered with a wiring protective layer 17. At this time, the wiring protective layer 17 completely covers the current collecting wiring 16 and contacts the conductive substrate 11.

Thus, the current collector wiring 16 and the wiring protective layer 17 are sequentially formed on the conductive substrate 11 to form the wiring portion 13.

The working electrode 10 is obtained as described above.

[Photosensitizing dye supporting step]
Next, a photosensitizing dye is supported on the porous oxide semiconductor layer 12 of the working electrode 10. For this purpose, the working electrode 10 is immersed in a solution containing a photosensitizing dye, and the photosensitizing dye is adsorbed on the porous oxide semiconductor layer 12, and then an extra solvent component is added to the solution. The photosensitizing dye may be adsorbed to the porous oxide semiconductor layer 12 by washing away the photosensitizing dye and drying it. However, the photosensitizing dye can also be adsorbed on the porous oxide semiconductor layer 12 by applying a solution containing the photosensitizing dye to the porous oxide semiconductor layer 12 and then drying it. Can be supported on the porous oxide semiconductor layer 12.

(Counter electrode)
On the other hand, the counter electrode 20 can be obtained as follows.

That is, first, the counter substrate 21 is prepared. Then, the catalyst layer 22 is formed on the counter electrode substrate 21. As a method for forming the catalyst layer 22, a sputtering method, a vapor deposition method, or the like is used. Of these, sputtering is preferred from the viewpoint of film uniformity.

[Sealing part fixing process]
Next, the sealing portion forming material is fixed to a portion of the working electrode 10 on the surface of the transparent conductive film 15 and surrounding the porous oxide semiconductor layer 12. For example, when the sealing portion 40 is made of an inorganic insulating material such as a lead-free transparent low-melting-point inorganic binder, the sealing portion forming material is coated with a paste containing the inorganic insulating material on the annular portion. It can be obtained by firing. The sealing part forming material may be fixed not only to the annular part surrounding the porous oxide semiconductor layer 12 among the parts on the surface of the working electrode 10 but also to the annular part on the surface of the counter electrode 20. .

[Electrolyte placement process]
Next, the electrolyte 30 is disposed on the working electrode 10 and inside the sealing portion forming material. The electrolyte 30 can be obtained by being injected on the inside of the sealing portion forming material on the working electrode 10 or printing by a printing method such as screen printing.

Here, when the electrolyte 30 is in a liquid state, the electrolyte 30 can be injected until it overflows beyond the sealing portion forming material to the outside of the sealing portion forming material. In this case, the electrolyte 30 can be sufficiently injected inside the sealing portion forming material. When the sealing portion forming material fixed to the surface of the working electrode 10 and the sealing portion forming material fixed to the surface of the counter electrode 20 are bonded to form the sealing portion 40, the working electrode 10 and the counter electrode are formed. Air can be sufficiently removed from the cell space surrounded by the sealing portion 40 and the sealing portion 40, and the photoelectric conversion characteristics can be sufficiently improved.

[Lamination process]
(Polymerization process)
Next, the working electrode 10 and the counter electrode 20 are opposed to each other, and the sealing portion forming material fixed to the working electrode 10 and the counter electrode 20 are overlapped. In other words, the counter electrode 20 is overlapped so as to close the opening of the sealing portion forming material fixed to the working electrode 10. When the sealing part forming material is fixed to the annular portion on the surface of the counter electrode 20, the sealing part forming material fixed to the working electrode 10 and the sealing part forming material fixed to the counter electrode 20 are overlapped. .

(Sealing part forming step)
Next, the sealing portion forming material is heated and melted while being pressurized. At this time, the pressure of the sealing portion forming material is usually 1 to 50 MPa, preferably 2 to 30 MPa, more preferably 3 to 20 MPa. Thus, the working electrode 10 and the counter electrode 20 are bonded together, and the sealing portion 40 is formed between the working electrode 10 and the counter electrode 20. At this time, the bonding between the working electrode 10 and the counter electrode 20 may be performed under atmospheric pressure or under reduced pressure, but is preferably performed under reduced pressure. When the working electrode 10 and the counter electrode 20 are bonded together under reduced pressure, the working electrode 10 and the counter electrode 20 are bonded by, for example, disposing the working electrode 10 and the counter electrode 20 in a reduced pressure space. This can be done by reducing the pressure.

In this case, the pressure in the decompression space is usually in the range of 50 Pa or more and less than 1013 hPa, preferably 50 to 800 Pa, more preferably 300 to 800 Pa.

For example, when a thermoplastic resin is used as the resin constituting the sealing portion forming material, the temperature at which the sealing portion forming material is melted is equal to or higher than the melting point of the sealing portion forming material.

However, the temperature at which the sealing part forming material is melted is preferably (melting point of the resin contained in the sealing part forming material + 200 ° C.) or less. When the temperature exceeds (the melting point of the resin contained in the sealing portion forming material + 200 ° C.), the resin contained in the sealing portion forming material may be decomposed by heat.

Thus, the dye-sensitized solar cell 100 is obtained, and the manufacture of the dye-sensitized solar cell 100 is completed.

<Second Embodiment>
Next, a second embodiment of the photoelectric conversion element according to the present invention will be described with reference to FIG. FIG. 3 is a partial cross-sectional view showing a wiring portion of the photoelectric conversion element according to this embodiment.

As shown in FIG. 3, the dye-sensitized solar cell of this embodiment is different from the dye-sensitized solar cell 100 of the first embodiment in that a wiring portion 213 is used instead of the wiring portion 13. Here, in the wiring part 213, the main body part C of the current collecting wiring 216 does not have the inorganic binder 53, and the contact part B between the current collecting wiring 216 and the transparent conductive film 15 does not have the inorganic binder 53. This is different from the wiring unit 13 in that respect.

According to the dye-sensitized solar cell of this embodiment, since the current collection wiring 216 does not have the inorganic binder 53, the volume resistance of the current collection wiring 216 can be reduced. Further, in the current collector wiring 216, the contact portion B does not have the inorganic binder 53. That is, the contact part B is composed of only the silver-tin alloy part 52. For this reason, contact resistance can be reduced compared with the case where the inorganic binder 53 is provided.

In addition, in order to obtain the current collection wiring 216 of this embodiment, it is only necessary not to include an inorganic binder in the silver paste for forming the current collection wiring 216. At this time, the content of silver particles in the silver paste is preferably 50 to 80% by mass, and more preferably 60 to 75% by mass. The content of the solvent in the silver paste is preferably 1 to 5% by mass, and more preferably 2 to 4% by mass. The content of the binder resin in the silver paste is preferably 20 to 30% by mass, more preferably 22 to 26% by mass.

<Third Embodiment>
Next, a third embodiment of the photoelectric conversion element according to the present invention will be described with reference to FIGS. 4 is a partial cross-sectional view showing a third embodiment of the photoelectric conversion element according to the present invention, FIG. 5 is a partial cross-sectional view showing the working electrode of FIG. 4, and FIG. 6 is an example of the current collector wiring of FIG. It is sectional drawing shown.

As shown in FIG. 4, a dye-sensitized solar cell 300 as a photoelectric conversion element includes a working electrode 310, a counter electrode 20 that faces the working electrode 310, and an annular sealing unit 40 that connects the working electrode 310 and the counter electrode 20. And an electrolyte 30 disposed in a cell space formed by the working electrode 310, the counter electrode 20, and the sealing portion 40.

The counter electrode 20 includes a counter electrode substrate 21 formed of a conductive substrate, and a catalyst layer 22 provided on the working electrode 310 side of the counter electrode substrate 21 to promote a catalytic reaction.

As shown in FIG. 5, the working electrode 310 includes a conductive substrate 11, a porous oxide semiconductor layer 12 provided on the conductive substrate 11, and a porous oxide semiconductor layer 12 on the conductive substrate 11. And a wiring portion 313 provided around. The porous oxide semiconductor layer 12 carries a photosensitizing dye. The conductive substrate 11 includes a transparent substrate 14 and a transparent conductive film 15 provided on the transparent substrate 14. The wiring portion 313 includes a current collecting wiring 316 provided on the transparent conductive film 15 and a wiring protective layer 17 that covers the current collecting wiring 316 and protects it from the electrolyte 30.

As shown in FIG. 6, the current collector wiring 316 includes a contact portion B that contacts the transparent conductive film 15 and a main body portion C provided on the contact portion B. The contact portion B includes a silver-tin alloy portion 52 made of an alloy of silver and tin and an inorganic binder 53, and is adjacent to the contact portion B between the current collector wiring 316 and the transparent conductive film 15. A gap A is formed. The main body portion C is provided on the contact portion B, is provided on the first current collector wiring portion 18 including the inorganic binder 53 and the silver particles 15, and is provided on the first current collector wiring portion 18 and includes the silver particles 61. 2nd current collection wiring part 19 is included. Here, the 1st current collection wiring part 18 and the 2nd current collection wiring part 19 have gap A3, respectively, and the porosity of the 2nd current collection wiring part 19 is smaller than the porosity of the 1st current collection wiring part 18 It has become. Note that the contact portion B may have a gap A3.

Next, a method for manufacturing the dye-sensitized solar cell 300 will be described with reference to FIGS.

<Method for producing working electrode>
First, a method for manufacturing the working electrode 310 will be described.

First, a conductive substrate 11 formed by forming a transparent conductive film 15 on a transparent substrate 14 is prepared.

Next, a porous oxide semiconductor layer 12 is formed on the conductive substrate 11 in the same manner as in the method for manufacturing the dye-sensitized solar cell 100 of the first embodiment.

(Wiring section forming process)
Next, the wiring part 313 is formed on the conductive substrate 11.

First, the current collector wiring 316 is formed on the transparent conductive film 15 of the conductive substrate 11 (current collector wiring forming step). Subsequently, the current collector wiring 316 is covered with a wiring protective layer forming material, and the wiring protective layer forming material is heated to form the wiring protective layer 17 (wiring protective layer forming step).

Here, as shown in FIG. 6, the current collector wiring 316 includes a contact portion B provided on the transparent conductive film 15 of the conductive substrate 11 and a main body portion C provided on the contact portion B. Yes. The main body portion C is provided on the first current collector wiring portion 18 including the inorganic binder 53 and the silver particles 51, and the second current collector wiring portion 19 including the silver particles 61 provided on the first current collector wiring portion 18. Including. In the present embodiment, the second current collector wiring portion 19 covers the entire surface of the first current collector wiring portion 18 except the surface in contact with the conductive substrate 11 and is bonded to the conductive substrate 11. In the current collecting wiring 316, the first current collecting wiring portion 18 and the second current collecting wiring portion 19 each have a gap A 3, and the porosity of the second current collecting wiring portion 19 is that of the first current collecting wiring portion 18. It is formed to be smaller than the porosity.

Thus, the wiring part 313 is formed on the transparent conductive film 15 of the conductive substrate 11.

At this time, in the current collecting wiring 316, the first current collecting wiring portion 18 and the second current collecting wiring portion 19 each have a gap A3, and the porosity of the second current collecting wiring portion 19 is the first current collecting wiring portion 18. It is formed so as to be smaller than the void ratio. Therefore, when the current collector wiring 316 is covered with the wiring protective layer forming material and the wiring protective layer forming material is heat-treated to form the wiring protective layer 17, the current collecting wiring 316 is included in the gap A3 of the first current collecting wiring portion 18. Even if the generated air expands due to heating, the second current collector wiring portion 19 sufficiently suppresses the air from penetrating the wiring protective layer 17. For this reason, in the wiring protective layer 17, the production | generation of the path | route which the electrolyte 30 can penetrate | invades is fully suppressed.

The 1st current collection wiring part 18 contains silver particles 51 and inorganic binder 53 as mentioned above.

The content of the inorganic binder 53 in the first current collecting wiring portion 18 is usually 1 to 5% by mass, but preferably 0.1 to 3% by mass.

In this case, it is possible to exhibit better adhesion to the conductive substrate 11 than in the case where the content of the inorganic binder 53 in the first current collector wiring portion 18 is less than 0.1 mass%. Compared with the case where the amount exceeds 3 mass%, the resistance of the first current collector wiring portion 18 can be more sufficiently reduced.

The thickness of the first current collector wiring portion 18 may be 2 to 60 μm, for example.

The second current collector wiring part 19 includes silver particles 61.

The 2nd current collection wiring part 19 may further contain the inorganic binder 63, as shown in FIG. Examples of the inorganic binder 63 include glass frit such as low-melting glass and solder as in the first current collector wiring portion 18.

The thickness of the second current collector wiring portion 19 may be, for example, 2 to 60 μm.

The content of the inorganic binder 63 in the second current collector wiring portion 19 is preferably smaller than the content of the inorganic binder 53 in the first current collector wiring portion 18.

In this case, it is possible to easily realize the porosity of the second current collector wiring portion 19 to be smaller than the porosity of the first current collector wiring portion 18.

Further, when the content of the inorganic binder 63 in the second current collector wiring portion 19 is smaller than the content of the inorganic binder 53 in the first current collector wiring portion 18, the inorganic binder in the first current collector wiring portion 18. The difference between the content of 53 and the content of the inorganic binder 63 in the second current collector wiring portion 19 is preferably 0.1 to 3% by mass.

In this case, compared with the case where the difference between the content of the inorganic binder 53 in the first current collector wiring portion 18 and the content of the inorganic binder 63 in the second current collector wiring portion 19 is out of the above range, The porosity generated in the second current collector wiring portion 19 can be made smaller than the porosity generated in the electrical wiring portion 18.

The maximum diameter of the gap A3 in the second current collecting wiring portion 19 is usually 1 to 30 μm, preferably 1 to 10 μm, and more preferably 1 to 5 μm.

In this case, when the wiring protective layer 17 is formed by heat-treating the wiring protective layer forming material, even if the air contained in the gap A3 of the first current collector wiring portion 18 expands due to heating, the expanded air Can effectively be prevented from penetrating the wiring protective layer 17.

The current collector wiring 316 having the above-described configuration can be formed as follows, for example.

First, as shown in FIG. 7, the first current collector wiring is formed by applying a silver paste for forming a first current collector wiring portion containing silver particles, an inorganic binder, and a solvent to the transparent conductive film 15 of the conductive substrate 11 and drying it. A first precursor portion 18A to be a precursor of the portion 18 is formed. At this time, the average particle diameter of the silver particles is preferably 2000 nm or less, and more preferably 1000 nm or less. When the average particle diameter of the silver particles is in the range of 2000 nm or less, the denser first current collector wiring portion 18 can be obtained as compared with the case of exceeding 2000 nm or less.

Next, as shown in FIG. 8, a second current collector wiring part forming silver paste containing silver particles and a solvent is applied to the first precursor part 18 </ b> A and dried to dry the precursor of the second current collector wiring part 19. A second precursor portion 19A to be a body is formed. At this time, the average particle diameter of the silver particles is preferably 1500 nm or less, and more preferably 900 nm or less. When the average particle diameter of the silver particles is in the range of 1500 nm or less, a denser second current collector wiring portion 19 can be obtained as compared with the case where the average particle diameter exceeds 1500 nm. The average particle diameter of the silver particles contained in the second current collector wiring portion forming silver paste may be the same as or different from the silver particles contained in the first current collector wiring portion forming silver paste. Also good.

Finally, the first precursor part 18A and the second precursor part 19A are fired. At this time, the silver particles in the first precursor portion 18A and the second precursor portion 19A are sintered and the solvent is removed. Thus, the contact portion B having the silver-tin alloy portion 52 is formed, and the first current collecting wiring portion 18 and the second current collecting wiring portion 19 having the gap A3 are formed (see FIGS. 6 and 9). Further, a gap A is formed adjacent to the contact portion B between the current collector wiring 316 and the transparent conductive film 15 (see FIG. 6).

At this time, in order to obtain the silver-tin alloy part 52 in the contact part B, the first precursor part 18A is heated to a temperature at which both the silver particles in the first precursor part 18A and the transparent conductive film 15 are melted. do it. Specifically, the first precursor portion 18A may be heated to 400 to 600 ° C.

In order to form the gap A between the current collector wiring 316 and the transparent conductive film 15, the amount of the solvent in the first precursor portion 18A and the amount of the inorganic binder 53 may be adjusted.

Furthermore, in order to form the gap A3 in the current collecting wiring 316, an inorganic binder having a melting point lower than that of silver particles is used. In this case, since the inorganic binder is melted before the silver particles 51, the inorganic binder can be directed to the transparent conductive film 15 by the action of gravity. As a result, a gap A3 is formed in the current collecting wiring 316.

The silver paste for forming the first and second current collector wiring portions may further include an organic binder such as polyethylene glycol, if necessary, in addition to the silver particles 51 and 61, the inorganic binders 53 and 63, and the solvent.

In order to make the porosity in the 2nd current collection wiring part 19 smaller than the porosity in the 1st current collection wiring part 18, volatile components, such as an organic binder in a silver paste for the 2nd current collection wiring part formation, and a solvent, for example May be made smaller than the content of the volatile component in the silver paste for forming the first current collector wiring portion. By doing in this way, it becomes possible to make the 2nd current collection wiring part 19 denser than the 1st current collection wiring part 18.

As a method for applying the silver paste for forming the first and second current collecting wiring portions, for example, a screen printing method, a doctor blade method, a bar coating method, or the like can be used.

The drying temperature of the silver paste for forming the first and second current collector wiring portions varies depending on the composition of the silver paste for forming the first and second current collector wiring portions, but it may be usually 100 to 200 ° C. The drying time also varies depending on the composition of the silver paste for forming the first and second current collector wiring portions, but is usually 0.1 to 2 hours.

The firing temperature of the first precursor portion 18A and the second precursor portion 19A may be 300 to 600 ° C., and the firing time may be 0.5 to 2 hours.

Further, as described above, the first current collector wiring portion 18 and the second current collector wiring portion 19 are formed in a first batch after the first precursor portion 18A and the second precursor portion 19A are formed. The main part C including the contact part B and the first current collector wiring part 18 and the second current collector wiring part 19 is simultaneously formed by firing the part 18A and the second precursor part 19A. After forming the first precursor portion 18A and firing the first precursor portion 18A to form the contact portion B and the first current collecting wiring portion 18, the second precursor portion is formed on the first current collecting wiring portion 18. 19A may be formed, and the second current collector wiring portion 19 may be formed by firing the second precursor portion 19A. At this time, the conditions for forming the first precursor portion 18A and the second precursor portion 19A are the same as the conditions for forming the first current collecting wiring portion 18 and the second current collecting wiring portion 19 simultaneously.

The wiring protective layer 17 may be made of a material that covers the current collecting wiring 316 and protects it from the electrolyte 30.

When forming the wiring protective layer 17, the wiring protective layer forming material includes a resin such as polyethylene glycol and a solvent such as terpineol in addition to the inorganic material or resin material described in the first embodiment. But you can.

The thickness of the wiring protective layer 17 may be 1 to 10 μm, for example.

The wiring protective layer forming material is a paste containing the above-described inorganic material or heat-resistant resin.

When the paste includes an inorganic material, the heat treatment is a treatment in which the paste 17A applied on the second current collector wiring portion 19 is dried and then baked as shown in FIG. The firing temperature varies depending on the paste composition, but is usually 300 to 600 ° C. The firing time also varies depending on the paste composition, but is usually 0.5 to 2 hours.

When the paste includes a heat resistant resin, the heat treatment is a treatment for drying the paste by heating. The drying temperature varies depending on the paste composition, but is usually 100 to 200 ° C. The drying time also varies depending on the paste composition, but is usually 0.5 to 2 hours. As described above, the manufacturing of the working electrode 310 is completed (FIG. 5). If the paste contains a reactive heat-resistant resin, it may be further heated as necessary to complete the reaction. Although this condition varies depending on the composition of the paste, it may be performed, for example, at 200 to 400 ° C. for 0.5 to 4 hours.

<Photosensitizing dye supporting step>
Next, the photosensitizing dye is adsorbed on the surface of the porous oxide semiconductor layer 12 of the working electrode 310 in the same manner as the photosensitizing dye supporting step of the first embodiment.

As the photosensitizing dye, the same one as the photosensitizing dye of the first embodiment can be used.

<Sealing part forming material fixing step>
Next, an annular sealing part forming material for forming the sealing part 40 is prepared. The annular sealing portion forming material can be obtained, for example, by preparing a sealing resin film and forming a rectangular opening in the sealing resin film.

Then, the sealing portion forming material is fixed on the working electrode 310 by bonding. At this time, the porous oxide semiconductor layer 12 is arranged inside the opening of the sealing portion forming material. Adhesion of the sealing portion forming material to the working electrode 310 can be performed by heating and melting the sealing portion forming material.

At this time, in the working electrode 310, the first current collector wiring portion 18 and the second current collector wiring portion 19 each have a gap A3, and the porosity of the second current collector wiring portion 19 is the first current collector wiring portion 18. It is smaller than the porosity. For this reason, for example, when the sealing part 40 is bonded to the working electrode 310 by heating and melting, the air contained in the gap A3 of the first current collecting wiring part 18 is expanded by the second current collecting wiring part 19. However, the expanded air is sufficiently suppressed from penetrating the wiring protective layer 17. As a result, in the obtained wiring protective layer 17, generation of a path through which the electrolyte 30 can enter is sufficiently suppressed.

<Electrolyte placement process>
Next, the electrolyte 30 is disposed on the porous oxide semiconductor layer 12 in the same manner as the electrolyte disposing step of the first embodiment.

<Counterelectrode preparation process>
Next, the counter electrode 20 is prepared.

<Lamination process>
Next, similarly to the case of the first embodiment, the working electrode 10 and the counter electrode 20 are opposed to each other, and the sealing portion forming material fixed to the working electrode 10 and the counter electrode 20 are bonded together. In other words, the counter electrode 20 is bonded so as to close the opening of the sealing portion 40.

The dye-sensitized solar cell 300 is obtained as described above.

When the dye-sensitized solar cell 300 is manufactured as described above, even when the air contained in the gap A3 of the first current collecting wiring portion 18 is expanded when the wiring protective layer 17 is formed, the second current collecting wiring portion is formed. 19 sufficiently suppresses the expanded air from penetrating the wiring protective layer 17. For this reason, in the wiring protective layer 17, the production | generation of the path | route which the electrolyte 30 can penetrate | invades is fully suppressed. Further, when the sealing portion forming material is bonded to the working electrode 310, even if the air contained in the gap A <b> 3 of the first current collector wiring portion 18 expands, the expanded current is wired by the second current collector wiring portion 19. Penetration through the protective layer 17 is sufficiently suppressed. For this reason, in the wiring protective layer 17, the production | generation of the path | route which the electrolyte 30 can penetrate | invades is fully suppressed. As a result, according to the obtained dye-sensitized solar cell 300, corrosion of the current collection wiring 316 by the electrolyte 30 is sufficiently suppressed, and excellent durability can be achieved.

The present invention is not limited to the first to third embodiments. For example, in the third embodiment, in the wiring portion 313, the second current collecting wiring portion 19 covers the entire surface of the first current collecting wiring portion 18 except for the surface in contact with the conductive substrate 11, and the conductive substrate. 11, the second current collecting wiring portion 19 is a surface of the first current collecting wiring portion 18 except for the surface in contact with the conductive substrate 11 like the wiring portion 413 shown in FIG. It may be only partially covered, and may not be bonded to the conductive substrate 11. In the wiring portion 413, the remaining portion of the first current collecting wiring portion 18 that is not covered with the second current collecting wiring portion 19 and the wiring protective layer 17 are bonded to each other. Here, it is preferable that the wiring protective layer 17 includes an inorganic binder. In this case, since the first current collecting wiring portion 18 includes the inorganic binder 53, the inorganic binder in the wiring protective layer 17 and the inorganic binder 53 in the first current collecting wiring portion 18 are bonded to each other. As a result, it is possible to improve the adhesion between the wiring protective layer 17 and the first current collecting wiring portion 18. Here, as the inorganic binder, glass frit is particularly preferable because it has corrosion resistance to the electrolyte 30 and can sufficiently suppress leakage of volatile substances contained in the electrolyte 30. In FIG. 11, the symbol A <b> 4 represents a gap in the first current collector wiring portion 18 and the second current collector wiring portion 419.

In the third embodiment, the conductive substrate 11 constituting the working electrode 310 is not necessarily transparent. For example, when the counter electrode 20 is a see-through electrode, the conductive substrate 11 can be configured by a non-transparent substrate. As the substrate that is not transparent, for example, a corrosion-resistant metal material such as titanium, nickel, platinum, molybdenum, tungsten, or the like mentioned as the counter electrode substrate 21 of the counter electrode 20 can be used.

Further, in the first to third embodiments, the working electrodes 10 and 310 are bonded to the sealing portion forming material, and the counter electrode 20 is bonded so as to close the opening of the sealing portion forming material. 310, the sealing portion forming material is adhered to the counter electrode 20, and the sealing portion forming material is adhered to the counter electrode 20, and the sealing portion forming materials are adhered to each other, so that the working electrode 310 and the counter electrode 20 are bonded to each other. The sealing part 40 may be formed.

Hereinafter, the content of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
First, an FTO substrate of 20 cm × 20 cm × about 4 mm was prepared. As the FTO substrate, a transparent conductive substrate formed by forming a transparent conductive film made of FTO having a thickness of 0.7 μm on a transparent substrate made of glass and having a thickness of 4 mm was used. Subsequently, a titanium oxide paste (manufactured by Solaronix, Ti nanoi * ide T / sp) was applied to the FTO substrate at 24 locations by a doctor blade method, and then heated at 500 ° C. for 3 hours in a hot air circulation type oven. Baked. Thus, a porous oxide semiconductor layer having a thickness of 17 μm was formed on the FTO substrate.

Then, 70 mass%, 3 mass%, 3 mass%, and 24 mass% of silver particles having an average particle diameter of 0.8 μm, ethylcellulose, glass frit, and dihydroterpineol are blended on the transparent conductive film of the FTO substrate, respectively. The silver paste is applied so as to surround the porous oxide semiconductor layer, and then the silver paste is baked at 500 ° C. for 1 hour to obtain a width of 0.4 mm, a thickness of 0.02 mm, and 20 mm × 5.5 mm. A grid-like current collector wiring having 24 square openings was formed.

Next, a paste for forming a wiring protective layer containing a low-melting glass frit (B20 manufactured by Central Glass Co., Ltd., melting point: 475 ° C.) is applied onto the current collector wiring, and fired by heating at 500 ° C. for 3 hours and firing. Formed body. Thus, a wiring part was formed on the FTO substrate, and a working electrode was produced.

Meanwhile, a counter electrode substrate made of a titanium foil of 19 cm × 17 cm × 0.04 mm was prepared. Then, a platinum catalyst layer made of platinum having a thickness of 6 nm was formed on the counter electrode substrate by sputtering. In this way, a counter electrode was obtained.

Next, in the center of a sheet of 19.5 cm × 17.5 cm × 100 μm made of Nucrel (Mitsui DuPont Polychemical Co., Ltd., melting point: 98 ° C.) which is an ethylene-methacrylic acid copolymer, 18.5 cm × 16. A square annular resin sheet having an opening of 5 cm × 100 μm was prepared. And this resin sheet was arrange | positioned on the wiring part surrounding the porous oxide semiconductor layer of a working electrode. This resin sheet was heated and melted at 180 ° C. for 5 minutes to adhere to the wiring part as a sealing part forming material, and the sealing part forming material was fixed on the wiring part on the FTO substrate.

Next, this working electrode was immersed overnight in a dehydrated ethanol solution in which 0.2 mM of N719 dye as a photosensitizing dye was dissolved, and the working electrode was loaded with the photosensitizing dye.

Meanwhile, a square annular resin sheet having an opening of 18.5 cm × 16.5 cm × 100 μm was prepared in the center of a 19.0 cm × 17.0 cm × 100 μm sheet made of nucler. And this resin sheet was arrange | positioned in the cyclic | annular site | part which is a site | part which is due to adhere | attach with the sealing part forming material fixed to the wiring part of a working electrode among counter electrodes. The resin sheet was heated and melted at 180 ° C. for 5 minutes to adhere to the annular portion as a sealing portion forming material, and the sealing portion forming material was fixed to the annular portion on the counter electrode.

Next, the working electrode is arranged so that the surface of the FTO substrate on the porous oxide semiconductor layer side is horizontal, and inside the sealing portion forming material, a volatile solvent made of methoxypropionitrile is used as a main solvent, A volatile electrolyte containing 0.1M hexylmethylimidazolium iodide, 0.2M iodine, and 0.5M 4-tert-butylpyridine was injected.

Next, the counter electrode to which the sealing portion forming material is fixed is opposed to the working electrode, and the sealing portion forming material fixed to the working electrode and the sealing portion forming material fixed to the counter electrode are stacked under atmospheric pressure. Combined. Then, under a reduced pressure of 800 Pa, using a press machine, the sealing portion forming materials were heated and melted at 148 ° C. while being pressurized at 5 MPa through the counter electrode to obtain a sealing portion. Thus, a dye-sensitized solar cell was obtained.

About the obtained dye-sensitized solar cell, when the cross section of current collection wiring was observed by SEM, it was confirmed that the glass frit part as an inorganic binder and the space | gap were formed in current collection wiring. .

It was also confirmed that a gap was formed between the current collector wiring and the transparent conductive film.

Further, the average particle diameter and porosity of the silver particles were determined. The results are shown in Table 1.

Further, when the contact portion was subjected to element mapping analysis using an element mapping device (manufactured by ZEISS, ULTRA 55), it was confirmed that the contact portion had a silver-tin alloy portion made of an alloy of silver and tin. It was done.

(Example 2)
As shown in Table 1, the average particle diameter of silver particles was changed from 0.8 μm to 10 μm, and the porosity and inorganic binder content in the main body of the current collector wiring were changed from 15% to 35% as shown in Table 1. Except that, a dye-sensitized solar cell was obtained in the same manner as in Example 1.

For the obtained dye-sensitized solar cell, the cross section of the current collector wiring was observed in the same manner as in Example 1. As a result, it was confirmed that a glass frit portion and a void were formed in the current collector wiring.

It was also confirmed that a gap was formed between the current collector wiring and the transparent conductive film.

Furthermore, element mapping analysis was performed on the contact portion in the same manner as in Example 1. As a result, it was confirmed that the contact portion had a silver-tin alloy portion made of an alloy of silver and tin.

(Example 3)
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that no silver frit was added to the silver paste and the porosity in the current collector wiring was changed from 15% to 10% as shown in Table 1.

Regarding the obtained dye-sensitized solar cell, the cross section of the current collector wiring was observed in the same manner as in Example 1. As a result, although the air gap was formed in the current collector wiring, the glass frit portion was not formed. confirmed.

It was also confirmed that a gap was formed between the current collector wiring and the transparent conductive film.

Further, it was confirmed that the contact portion did not have a glass frit portion.

Further, element mapping analysis was performed on the contact portion in the same manner as in Example 1. As a result, it was confirmed that the contact portion had a silver-tin alloy portion made of an alloy of silver and tin.

(Example 4)
Example 3 except that the average particle diameter of the silver particles was changed from 0.8 μm to 2.0 μm as shown in Table 1, and the porosity in the current collector wiring was changed from 10% to 11% as shown in Table 1. A dye-sensitized solar cell was produced in the same manner as described above.

For the obtained dye-sensitized solar cell, the cross section of the current collector wiring was observed in the same manner as in Example 1. As a result, a gap was formed in the current collector wiring, but no glass frit portion was formed. Was confirmed.

It was also confirmed that a gap was formed between the current collector wiring and the transparent conductive film.

Further, it was confirmed that the contact portion did not have a glass frit portion.

Furthermore, element mapping analysis was performed on the contact portion in the same manner as in Example 1. As a result, it was confirmed that the contact portion had a silver-tin alloy portion made of an alloy of silver and tin.

(Example 5)
Example 3 except that the average particle diameter of the silver particles was changed from 0.8 μm to 0.4 μm as shown in Table 1, and the porosity in the current collector wiring was changed from 10% to 14% as shown in Table 1. A dye-sensitized solar cell was produced in the same manner as described above.

For the obtained dye-sensitized solar cell, the cross section of the current collector wiring was observed in the same manner as in Example 1. As a result, a gap was formed in the current collector wiring, but no glass frit portion was formed. Was confirmed.

It was also confirmed that a gap was formed between the current collector wiring and the transparent conductive film.

Further, it was confirmed that the contact portion did not have a glass frit portion.

Furthermore, element mapping analysis was performed on the contact portion in the same manner as in Example 1. As a result, it was confirmed that the contact portion had a silver-tin alloy portion made of an alloy of silver and tin.

(Example 6)
Example 3 except that the average particle diameter of the silver particles was changed from 0.8 μm to 3.5 μm as shown in Table 1, and the porosity in the current collector wiring was changed from 10% to 13% as shown in Table 1. A dye-sensitized solar cell was produced in the same manner as described above.

For the obtained dye-sensitized solar cell, the cross section of the current collector wiring was observed in the same manner as in Example 1. As a result, a gap was formed in the current collector wiring, but no glass frit portion was formed. Was confirmed.

It was also confirmed that a gap was formed between the current collector wiring and the transparent conductive film.

Further, it was confirmed that the contact portion did not have a glass frit portion.

Furthermore, element mapping analysis was performed on the contact portion in the same manner as in Example 1. As a result, it was confirmed that the contact portion had a silver-tin alloy portion made of an alloy of silver and tin.

(Comparative Example 1)
The silver paste was fired at 350 ° C. for 1 hour to form a current collecting wiring, and the porosity in the current collecting wiring was changed from 15% to 40% as shown in Table 1 in the same manner as in Example 1. Thus, a dye-sensitized solar cell was obtained.

For the obtained dye-sensitized solar cell, the cross section of the current collector wiring was observed in the same manner as in Example 1. As a result, it was confirmed that voids and glass frit portions were formed in the current collector wiring.

Also, a gap was formed between the current collector wiring and the transparent conductive film.

Furthermore, it was confirmed that the contact part had a glass frit part. However, when element mapping analysis was performed on the contact portion in the same manner as in Example 1, a silver-tin alloy portion made of an alloy of silver and tin was not confirmed.

(Example 7)
First, a transparent conductive substrate was prepared by forming a transparent conductive film made of FTO having a thickness of 1 μm on a transparent substrate made of glass having a thickness of 1 mm. Next, after applying a paste of titanium oxide nanoparticles (21NR manufactured by JGC Catalysts & Chemicals Co., Ltd.) to four places on the transparent conductive film, it was fired at 150 ° C. for 3 hours in a hot air circulation type oven. Thus, a porous oxide semiconductor layer having a thickness of 6 μm was formed.

Next, the silver paste containing silver particles having a particle size of 200 nm or less (trade name XA-9053, manufactured by Fujikura Kasei Co., Ltd.) has a glass frit content in the inorganic material in the first current collector wiring portion after firing. Glass frit was blended so as to be 1% by mass to prepare a silver paste for forming a first current collector wiring portion. And this 1st current collection wiring part formation silver paste was printed on the transparent conductive film by the screen-printing method, and it dried at 150 degreeC, and formed the 1st precursor part.

Next, a silver paste (trade name XA-9053, manufactured by Fujikura Kasei Co., Ltd.) is printed on the first precursor portion as a second current collector wiring portion forming silver paste by screen printing, and 150 The second precursor part was formed by drying at ° C.

And the 1st precursor part and the 2nd precursor part were baked at 500 ° C for 1 hour, and the 1st current collection wiring part and the 2nd current collection wiring part were formed, respectively. At this time, the 2nd current collection wiring part covered only a part of surface except the surface which touches a transparent conductive film among the 1st current collection wiring parts. That is, the remaining part of the surface of the first current collecting wiring part excluding the surface in contact with the transparent conductive film was not covered with the second current collecting wiring part. Moreover, the thickness of the 1st current collection wiring part and the 2nd current collection wiring part was 10 micrometers, respectively. Here, the porosity in each of the 1st current collection wiring part and the 2nd current collection wiring part was measured. The results are shown in Table 2.

Further, the content (% by mass) of the inorganic binder made of glass frit in the first current collecting wiring part and the second current collecting wiring part is as shown in Table 2.

Also, the maximum diameter of the gap in the second current collector wiring part was measured. The results are shown in Table 2.

Next, a glass frit (B20 manufactured by Asahi Glass Co., Ltd., melting point: 470 ° C.), an organic binder made of ethylcellulose, and a solvent made of terpineol are included so as to cover the first current collecting wiring portion and the second current collecting wiring portion. A wiring protective layer forming paste was printed by a screen printing method.

The wiring protective layer forming paste was baked at 500 ° C. for 1 hour to form a wiring protective layer having a thickness of 5 μm. Thus, a working electrode was obtained.

Next, the working electrode was immersed in the dye solution for 24 hours, then taken out from the dye solution and dried, and the photosensitizing dye was supported on the porous oxide semiconductor layer. The dye solution was prepared by dissolving black dye (N749) in a mixed solvent obtained by mixing acetonitrile and tert-butanol at a volume ratio of 1: 1 so that the concentration was 0.0002 mol / L. .

Next, the same electrolyte as in Example 1 was applied and disposed on the porous oxide semiconductor layer.

Next, an annular sealing part forming material for forming the sealing part was prepared. An annular sealing portion forming material is prepared by preparing a sealing resin film made of a 6 cm × 6 cm × 60 μm ionomer resin (trade name: High Milan, Mitsui, manufactured by DuPont Polychemical Co., Ltd.). It was obtained by forming a square opening in the film. At this time, the opening was made to have a size of 5 cm × 5 cm × 60 μm. As a result, an annular sealing part forming material having a width of 5 mm was obtained.

Then, after this sealing part forming material was placed on the working electrode, it was fixed by adhering to the working electrode by heating and melting.

Next, a counter electrode was prepared. As the counter electrode, a counter electrode substrate made of a titanium foil of 6 cm × 6 cm × 50 μm was prepared. And it prepared by forming the catalyst layer which consists of platinum of thickness 10nm on this counter electrode board | substrate by sputtering method. In addition, another annular sealing portion forming material was prepared, and this sealing portion forming material was adhered and fixed to the surface of the counter electrode facing the working electrode in the same manner as described above.

Then, the sealing portion forming material fixed to the working electrode and the sealing portion forming material fixed to the counter electrode were opposed to each other, and the sealing portion forming materials were overlapped with each other. In this state, the sealing portion forming material was heated and melted at 200 ° C. while pressurizing at 0.15 MPa through the counter electrode using a press under a reduced pressure of 500 Pa. Thus, a sealing portion was formed between the working electrode and the counter electrode, and a dye-sensitized solar cell was obtained.

Regarding the obtained dye-sensitized solar cell, the cross section of the current collector wiring was observed by SEM, and it was confirmed that a glass frit portion and a void were formed in the current collector wiring.

It was also confirmed that a gap was formed between the current collector wiring and the transparent conductive film.

Further, the average particle diameter of silver particles in the current collector wiring was determined. The results are shown in Table 2.

Further, when the contact portion was subjected to element mapping analysis using an element mapping device (manufactured by ZEISS, ULTRA 55), it was confirmed that the contact portion had a silver-tin alloy portion made of an alloy of silver and tin. It was done.

(Examples 8 to 13)
Inorganic binder content ratio A in the first current collector wiring section, porosity in the first current collector wiring section, inorganic binder content ratio B in the second current collector wiring section, porosity in the second current collector wiring section, The maximum diameter of the voids in the second current collector wiring portion, the difference (AB) between the inorganic binder content A in the first current collector wiring portion and the inorganic binder content B in the second current collector wiring portion; A dye-sensitized solar cell was obtained in the same manner as in Example 7 except that the average particle diameter of the silver particles was as shown in Table 2.

(Example 14)
Example 7 except that the second current collecting wiring part was not formed, the thickness of the first current collecting wiring part was 20 μm, and the porosity in the first current collecting wiring part was changed as shown in Table 2. A dye-sensitized solar cell was produced in the same manner as described above.

(Example 15)
Inorganic binder content A in the first current collector wiring section, porosity in the first current collector wiring section, inorganic binder content ratio A in the first current collector wiring section, and inorganic binder in the second current collector wiring section A dye-sensitized solar cell was obtained in the same manner as in Example 7 except that the difference (AB) with respect to the content B was changed as shown in Table 2.

<Durability evaluation>
For the dye-sensitized solar cells of Examples 1 to 15 and Comparative Example 1, durability evaluation was performed as follows.

[Evaluation of photoelectric conversion characteristics of dye-sensitized solar cell: Evaluation 1]
For the dye-sensitized solar cells obtained in Examples 1 to 15 and Comparative Example 1, the initial photoelectric conversion efficiency (η ₀ ) was measured. Subsequently, the photoelectric conversion efficiency (η) after a temperature cycle test based on JIS C8938 A-1 was measured for the dye-sensitized solar cell. And the following formula:
Retention rate of photoelectric conversion efficiency (%) = η / η ₀ × 100
Based on the above, the maintenance ratio of photoelectric conversion efficiency was calculated. Tables 1 and 2 show the results of the initial photoelectric conversion efficiency (η ₀ ) and the maintenance ratio of the photoelectric conversion efficiency.

[Peeling of current collector wiring from transparent conductive film]
The dye-sensitized solar cells obtained in Examples 1 to 15 and Comparative Example 1 were subjected to a temperature cycle test in accordance with JIS C8938 A-1, and then SEM was used to determine whether the current collector wiring was peeled off from the FTO substrate. Observed at. The results are shown in Tables 1 and 2. In Tables 1 and 2, a dye-sensitized solar cell in which no peeling was observed is indicated as “A”, and a dye-sensitized solar cell in which partial peeling has been confirmed is indicated as “B”. The dye-sensitized solar cell in which peeling was completely confirmed was indicated as “C”. The dye-sensitized solar cells labeled “A” and “B” were accepted, and the dye-sensitized solar cells labeled “C” were rejected.

From the results shown in Tables 1 and 2, the dye-sensitized solar cells of Examples 1 to 15 included an example in which peeling of the current collector wiring from the FTO substrate was partially confirmed. The separation of the current collector wiring from the substrate was sufficiently suppressed. In contrast, in the dye-sensitized solar cell of Comparative Example 1, the current collector wiring was completely peeled from the FTO substrate.

Then, it was found that the dye-sensitized solar cells of Examples 1 to 15 had a higher photoelectric conversion efficiency maintenance rate than the dye-sensitized solar cell of Comparative Example 1.

Therefore, it was confirmed that the photoelectric conversion element electrode of the present invention can sufficiently suppress peeling of the current collector wiring from the conductive film, and can impart excellent durability to the photoelectric conversion element.

10 ... Working electrode (electrode for photoelectric conversion element)
13, 113, 213, 313, 413 ... wiring part 14 ... transparent substrate (substrate)
15 ... Transparent conductive film (conductive film)
DESCRIPTION OF SYMBOLS 16,216,316,416 ... Current collection wiring 17 ... Wiring protective layer 18 ... 1st current collection wiring part 19 ... 2nd current collection wiring part 51, 61 ... Silver particle 52 ... Silver tin alloy part 53, 63 ... Inorganic binder 100, 300 ... Dye-sensitized solar cell (photoelectric conversion element)
A, A3, A4 ... gap B ... contact part C ... body part

Claims (15)

A substrate, and a conductive substrate provided on the substrate and having a conductive film containing tin; and
A wiring portion provided on the conductive film of the conductive substrate, and having a current collector wiring containing silver particles;
The current collector wiring has a contact portion in contact with the conductive film;
The contact portion has a silver-tin alloy portion made of an alloy of silver and tin,
A gap is formed adjacent to the contact portion between the current collector wiring and the conductive film,
Electrode for photoelectric conversion element. The electrode for a photoelectric conversion element according to claim 1, wherein the contact portion further includes an inorganic binder. The electrode for a photoelectric conversion element according to claim 1 or 2, wherein the current collecting wiring further includes a gap. The current collecting wiring further includes a main body portion provided on the opposite side of the conductive film with respect to the contact portion, and the main body portion further includes an inorganic binder. Electrode for photoelectric conversion element. The electrode for a photoelectric conversion element according to any one of claims 1 to 4, wherein the wiring portion further includes a wiring protective layer that covers and protects the current collecting wiring. The current collector wiring further has a main body provided on the opposite side of the conductive film with respect to the contact portion;
The main body is
A first current collector wiring portion provided on the contact portion and including an inorganic binder and silver particles;
A second current collecting wiring part provided on the first current collecting wiring part and containing silver particles;
The said 1st current collection wiring part and the said 2nd current collection wiring part have a space | gap, The porosity of the said 2nd current collection wiring part is smaller than the porosity of the said 1st current collection wiring part. Electrode for photoelectric conversion element. The photoelectric conversion element electrode according to claim 6, wherein a content ratio of the inorganic binder in the second current collecting wiring portion is smaller than a content ratio of the inorganic binder in the first current collecting wiring portion. The difference between the content of the inorganic binder in the first current collector wiring portion and the content of the inorganic binder in the second current collector wiring portion is 0.1 to 3% by mass. Electrode for photoelectric conversion element. The photoelectric conversion element electrode according to any one of claims 6 to 8, wherein the maximum diameter of the gap in the second current collector wiring portion is 1 to 10 µm. A photoelectric conversion element comprising the photoelectric conversion element electrode according to any one of claims 1 to 9. A wiring part forming step of forming a wiring part on a conductive substrate provided with a conductive film on the substrate;
The wiring part forming step includes
A current collector wiring forming step of forming a current collector wiring on the conductive substrate;
In the current collector wiring forming step,
The current collector wiring has a contact portion that contacts the conductive film, and the contact portion is formed to have a silver-tin alloy portion made of an alloy of silver and tin,
The manufacturing method of the electrode for photoelectric conversion elements in which a space | gap is formed adjacent to the said contact part between the said current collection wiring and the said electrically conductive film. The wiring part forming step includes
A wiring protective layer forming step of forming a wiring protective layer by covering the current collector wiring with a wiring protective layer forming material and heat-treating the wiring protective layer forming material;
In the current collector wiring forming step, the current collector wiring is:
A first current collector wiring portion provided on the conductive substrate and including an inorganic binder and silver particles;
A second current collecting wiring part provided on the first current collecting wiring part and containing silver particles;
The first current collector wiring part and the second current collector wiring part have a gap,
The method for producing an electrode for a photoelectric conversion element according to claim 11, wherein the porosity of the second current collector wiring portion is formed to be smaller than the porosity of the first current collector wiring portion. The method for producing an electrode for a photoelectric conversion element according to claim 12, wherein the content of the inorganic binder in the second current collecting wiring portion is smaller than the content of the inorganic binder in the first current collecting wiring portion. The difference between the content of the inorganic binder in the first current collector wiring portion and the content of the inorganic binder in the second current collector wiring portion is 0.1 to 3% by mass. Manufacturing method of electrode for photoelectric conversion elements. The method for producing an electrode for a photoelectric conversion element according to any one of claims 12 to 14, wherein the maximum diameter of the gap in the second current collecting wiring portion is 1 to 10 µm.

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