JP2012204046A - Photoelectric conversion device and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion device capable of increasing the area of a semiconductor layer which contributes to the photoelectric conversion (power generation) in the photoelectric conversion device.SOLUTION: A photoelectric conversion device comprises: (A) a first substrate 21 and a second substrate 22; and (B) a semiconductor layer 31, a first collector 51 having a first face 51a opposed to the first substrate and a second face 51b opposed to the second substrate, an electrolyte layer 41, a catalyst layer 32 and a second collector 61 which are sequentially arranged from the first substrate side between the first substrate 21 and the second substrate 22. The first substrate 21 and the second substrate 22 are sealed together at their outer edges. The first collector 51 is made of a conductive material with a number of through-holes formed thereon. Part in the thickness direction of the semiconductor layer formed on the first face 51a of the first collector 51 enters the through-holes formed on the first collector 51.

Description

  The present disclosure relates to a photoelectric conversion device and a manufacturing method thereof.

  In recent years, awareness of environmental protection has increased, and the importance of photovoltaic power generation has further increased. A dye-sensitized solar cell (DSSC) includes, for example, a transparent conductive layer, a semiconductor layer carrying a sensitizing dye, an electrolyte layer, and a first substrate, between a first substrate and a second substrate. The counter electrode has a configuration in which the counter electrodes are sequentially provided. In the dye-sensitized solar cell, electrons excited in the dye by the sunlight passing through the first base material made of the transparent substrate are injected into the semiconductor layer, and the transparent conductive layer passes through an external circuit including a load. A current flows through the counter electrode and functions as a battery. Compared to silicon solar cells, dye-sensitized solar cells have fewer resource constraints on the raw materials required for production, and can be manufactured by printing and flow production methods without the need for vacuum equipment. There is an advantage that the cost and the equipment cost are low.

  Incidentally, the semiconductor layer is usually provided so as to cover the transparent conductive layer formed on the first substrate. The transparent conductive layer is made of, for example, ITO (Indium Doped Tin Oxide), FTO (Fluorine Doped Tin Oxide), or the like, and is subject to certain restrictions on low electrical resistance. Therefore, the larger the area of the dye-sensitized solar cell, the more difficult it is to efficiently collect electrons generated by photoelectric conversion in the semiconductor layer. Therefore, as a countermeasure, for example, a method of lowering the electric resistance by providing a current collecting wiring layer on the transparent conductive layer is used. However, such a method has a problem that the area of the semiconductor layer is reduced and the conversion efficiency per unit area is lowered.

  A dye-sensitized solar cell for solving such a problem is known, for example, from JP-A-2009-245750. The dye-sensitized solar cell disclosed in this patent publication is disposed on a transparent substrate, a porous semiconductor layer adsorbing a dye disposed on the transparent substrate, and a surface of the porous semiconductor layer opposite to the transparent substrate. A conductive metal layer having a number of deep through-holes formed by processing performed in advance and electrically connected to an external electrode; and a conductive substrate provided opposite to the transparent substrate. And an electrolyte between the conductive substrate.

JP2009-245750

  In this patent publication, a large number of deep through holes are formed in the conductive metal layer in contact with the porous semiconductor layer. And a porous semiconductor layer is formed by apply | coating the material of a porous semiconductor layer on the electroconductive metal layer in which the through-hole was formed, and baking. By the way, when the porous semiconductor layer is formed based on the coating method, the porous semiconductor layer is filled in the through holes, and the surface of the conductive metal layer facing the transparent substrate is exposed. In such a state, the transparent substrate not only faces the porous semiconductor layer but also faces the surface of the conductive metal layer. That is, a part of the light incident through the transparent substrate is incident on the porous semiconductor layer, but the remaining part collides with the conductive metal layer, and the photoelectric conversion (photosensitizing solar cell) The substantial area of the semiconductor layer (porous semiconductor layer) that contributes to power generation is reduced.

  Accordingly, an object of the present disclosure is to provide a photoelectric conversion device having a configuration and a structure that can increase the area of a semiconductor layer that contributes to photoelectric conversion (power generation) in the photoelectric conversion device, and a method for manufacturing the photoelectric conversion device.

The method for manufacturing a photoelectric conversion device according to the first aspect or the second aspect of the present disclosure for achieving the above object is as follows:
(A) 1st base material and 2nd base material,
(B) Between the first base material and the second base material, provided sequentially from the first base material side, facing the semiconductor layer, the first surface facing the first base material, and the second base material. A first current collector having a second surface, an electrolyte layer, a catalyst layer, and a second current collector,
The first base material and the second base material are sealed at the outer edge portion,
A 1st electrical power collector is a manufacturing method of the photoelectric conversion apparatus which consists of an electrically-conductive material provided with many through-holes.

  And in the manufacturing method of the photoelectric conversion apparatus which concerns on the 1st aspect of this indication, the semiconductor layer precursor layer which consists of ceramic green sheets is transcribe | transferred to the 1st surface of a 1st electrical power collector using a press apparatus. Then, the semiconductor layer is obtained by firing the semiconductor layer precursor layer.

  Moreover, in the manufacturing method of the photoelectric conversion device according to the second aspect of the present disclosure, the semiconductor layer is formed on the first surface of the first current collector, and the first current collector is provided. A part of the semiconductor layer in the thickness direction is made to enter the through hole.

In order to achieve the above object, a photoelectric conversion device of the present disclosure is provided.
(A) 1st base material and 2nd base material,
(B) Between the first base material and the second base material, provided sequentially from the first base material side, facing the semiconductor layer, the first surface facing the first base material, and the second base material. A first current collector having a second surface, an electrolyte layer, a catalyst layer, and a second current collector,
The first base material and the second base material are sealed at the outer edge portion,
The first current collector is made of a conductive material provided with a large number of through holes,
A portion of the semiconductor layer formed on the first surface of the first current collector in the thickness direction penetrates into a through hole provided in the first current collector.

  In the method for manufacturing a photoelectric conversion device according to the first aspect of the present disclosure, the semiconductor layer precursor layer made of a ceramic green sheet is transferred to the first surface of the first current collector using a press device. A semiconductor layer is formed by the method, and in the method for manufacturing a photoelectric conversion device according to the second aspect of the present disclosure or the photoelectric conversion device of the present disclosure, the semiconductor layer is formed on the first surface of the first current collector. And a part of the thickness direction of the semiconductor layer enters the through hole provided in the first current collector, so that the first base material that is the light incident surface faces only the semiconductor layer, It is possible to obtain a state in which the first surface of one current collector is covered with the semiconductor layer. Therefore, the area of the semiconductor layer contributing to the photoelectric conversion (power generation) in the photoelectric conversion device can be increased more than the conventional photoelectric conversion device without depending on the aperture ratio and the opening area of the first current collector. In addition, it is easy to control the formation position of the semiconductor layer in the first current collector. Moreover, it is not necessary to use a transparent conductive layer, and the resistance of the first current collector can be reduced.

1A and 1B are a cross-sectional conceptual diagram before assembly of the photoelectric conversion device of Example 1 and an end-face conceptual diagram after assembly, respectively. 2A is a partial schematic plan view of a first current collector in the photoelectric conversion device of Example 1. FIGS. 2B and 2C are photoelectric conversions of Example 1. FIG. It is a typical partial end view of the 1st current collector etc. in an apparatus. 3A and 3B are photomicrographs obtained by photographing the first laminated structure in the photoelectric conversion device of Example 1 from the first base material side and the second base material side. FIG. 4 is a graph showing the results of evaluating the IV characteristics of the photoelectric conversion devices of Example 1A, Example 1B, and Comparative Example 1. FIG. 5 is a conceptual cross-sectional view of the photoelectric conversion device of Example 2 before assembly. 6A and 6B are a conceptual cross-sectional view before assembly of the photoelectric conversion device of Example 3, and a schematic partial end view of the first current collector and the like, respectively. (C) is a conceptual cross-sectional view of the photoelectric conversion device of Example 4 before assembly. FIGS. 7A and 7B are a cross-sectional conceptual diagram before assembly of the photoelectric conversion device of Example 5 and an end surface conceptual diagram after assembly, respectively. FIG. 8 is a conceptual cross-sectional view of the photoelectric conversion device of Example 6 before assembly. FIGS. 9A and 9B are a cross-sectional conceptual diagram before assembly of the photoelectric conversion device of Example 7 and an end-face conceptual diagram after assembly, respectively. FIG. 10 is a conceptual cross-sectional view of the photoelectric conversion device according to the eighth embodiment before assembly. 11A and 11B are a cross-sectional conceptual diagram before assembly of the photoelectric conversion device of Example 9 and an end-face conceptual diagram after assembly, respectively. FIGS. 12A and 12B are a schematic plan view of the photoelectric conversion device of Example 9 and a schematic cross-sectional view taken along arrow BB in FIG. is there. FIG. 13 is a schematic plan view of the first current collector, the semiconductor layer, and the first lead member in the photoelectric conversion device of Example 9 as viewed from the second base material side. FIG. 14 is a schematic plan view of the second current collector, the catalyst layer, and the second lead member in the photoelectric conversion device of Example 9 as viewed from the first base material side. 15A is a schematic end view of the photoelectric conversion device of Example 10, and FIGS. 15B and 15C are schematic views of a modification of the photoelectric conversion device of Example 10. FIG. FIG. 15D is an end view and a schematic plan view when the first lead member is expanded, and FIG. 15D is an expanded second lead member in another modification of the photoelectric conversion device of Example 10. It is a typical top view at the time. FIG. 16 is a schematic plan view of the first current collector, the semiconductor layer, and the first lead member in the photoelectric conversion device of Example 11 as viewed from the second base material side. FIG. 17 is a schematic plan view of the second current collector, the catalyst layer, and the second lead member in the photoelectric conversion device of Example 11 as viewed from the first base material side. FIG. 18 is a schematic plan view of a first current collector, a semiconductor layer, and a first lead member in a modification of the photoelectric conversion device of Example 11 as viewed from the second base material side. FIG. 19 is a schematic plan view of a second current collector, a catalyst layer, and a second lead member in a modification of the photoelectric conversion device of Example 11 as viewed from the first base material side. FIG. 20 is a schematic plan view of the first current collector, the semiconductor layer, and the first lead member in the photoelectric conversion device of Example 12 as viewed from the second base material side. FIG. 21 is a schematic plan view of the second current collector, the catalyst layer, and the second lead member in the photoelectric conversion device of Example 12 as viewed from the first base material side. 22A and 22B are a cross-sectional conceptual diagram before assembly of the photoelectric conversion device of Example 13 and an end-face conceptual diagram after assembly, respectively. 23A and 23B are conceptual cross-sectional views before assembly of a modified example of the photoelectric conversion device of the ninth embodiment. FIG. 24 is a roll-to-roll processing method for obtaining a first laminated structure composed of a semiconductor layer / first current collector in which the first current collector and the semiconductor layer are integrated in a roll shape in Example 1. It is a conceptual diagram for demonstrating the outline | summary.

Hereinafter, although this indication is explained based on an example with reference to drawings, this indication is not limited to an example and various numerical values and materials in an example are illustrations. The description will be given in the following order.
1. 1. General description of photoelectric conversion device and manufacturing method thereof of the present disclosure Example 1 (photoelectric conversion device of the present disclosure and manufacturing method thereof)
3. Example 2 (Modification of Example 1)
4). Example 3 (another modification of Example 1)
5. Example 4 (Modification of Example 3)
6). Example 5 (another modification of Example 1)
7). Example 6 (Modification of Example 5)
8). Example 7 (a further modification of Example 1)
9. Example 8 (Modification of Example 7)
10. Example 9 (Modification of Examples 1 to 8)
11. Example 10 (modification of Example 9)
12 Example 11 (modification of Example 9 to Example 10)
13. Example 12 (modification of Example 9 to Example 11)
14 Example 13 (modification of Example 9 to Example 12), others

[Description of Photoelectric Conversion Device and Manufacturing Method of the Disclosure of the Present Disclosure]
In the method for manufacturing a photoelectric conversion device according to the second aspect of the present disclosure, a semiconductor layer is formed on the first surface of the first current collector, and the semiconductor layer is formed in the through hole provided in the first current collector. The step of intruding a part in the thickness direction of the semiconductor layer is performed by transferring a semiconductor layer precursor layer made of a ceramic green sheet to the first surface of the first current collector using a press device, and then the semiconductor layer precursor layer It can be set as the form which consists of the process of obtaining a semiconductor layer by baking.

In the method for manufacturing a photoelectric conversion device according to the present disclosure including the preferred mode or the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, a part of the semiconductor layer in the thickness direction is a first current collector. In this case, the average thickness of the first current collector is t ₁ , and the semiconductor that has entered the through-hole provided in the first current collector is not reached to the second surface of the body. When the average penetration length of a part of the layer in the thickness direction is s ₁ ,
0 <s ₁ / t ₁ ≦ 1
Preferably,
0.2 ≦ s ₁ / t ₁ ≦ 1
It is desirable to satisfy In particular,
1 × 10 ⁻⁶ m ≦ t ₁ ≦ 1 × 10 ⁻⁴ m
5 × 10 ⁻⁷ m ≦ s ₁ ≦ 1 × 10 ⁻⁴ m
And when the average thickness of the portion of the semiconductor layer formed on the first surface of the first current collector and in contact with the first surface of the first current collector is s ₀ ,
1 × 10 ⁻⁶ m ≦ s ₀ ≦ 3 × 10 ⁻⁵ m
Preferably,
5 × 10 ⁻⁶ m ≦ s ₀ ≦ 1.5 × 10 ⁻⁵ m
It is desirable that Incidentally, the average thickness t ₁ of the first current collector in the above range, to be able to prevent a decrease in open circuit voltage V _oc, collect efficiently electrons generated by photoelectric conversion in the semiconductor layer In addition, the amount of dye (sensitizing dye) used can be reduced.

  In the manufacturing method of the photoelectric conversion device of the present disclosure including the above-described preferable modes and configurations, or the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, the surface of the surface of the semiconductor layer facing the first substrate The roughness Ra is desirably 2 μm or less. The surface roughness Ra is defined in JIS B 0601: 2001. By defining the value of the surface roughness Ra in this manner, for example, it is difficult for an electrolytic solution to enter between the semiconductor layer and the first base material, and the photoelectric conversion efficiency can be improved.

  In the manufacturing method of the photoelectric conversion device of the present disclosure including the preferred mode and configuration described above, or the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, an insulating layer is formed on the second surface of the first current collector. It can be set as the structure currently formed. And an insulating layer can be obtained by transferring an insulating layer precursor layer to the 2nd surface of a 1st electrical power collector using a press apparatus, and baking an insulating layer precursor layer after that. In addition, the electrolyte layer can be constituted by the insulating layer, and the insulating layer can be impregnated with the electrolyte composition. In this way, by forming the electrolyte layer from the insulating layer impregnated with the electrolyte composition, between the first current collector made of a conductive material provided with a large number of through holes and the second current collector It is possible to reliably prevent a short circuit from occurring. However, the present invention is not limited to this, and the electrolyte layer can be made of an electrolyte composition alone, or the electrolyte layer can be made of a woven or non-woven fabric impregnated with the electrolyte composition.

  Here, the insulating layer is formed of at least one material (for example, a metal oxide material layer) selected from the group consisting of a titanium oxide layer, a zirconium oxide layer, silicon oxide (silica), and aluminum oxide. It can be. In some cases, the insulating layer may have a laminated structure of a woven or non-woven fabric and a metal oxide material layer. Synthetic fiber, more specifically, polyethylene, polypropylene, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyvinyl alcohol, aramid, nylon, vinylon, polyolefin, rayon, low density Examples thereof include polyethylene, ethylene vinyl acetate, copolymerized polyamide, copolymerized polyester, etc., natural fiber cotton, cellulose, glass fiber, and synthetic rubber fiber. The basic performance required of the insulating layer is that it does not hinder the movement of the impregnated electrolyte composition, and the insulating layer is made of titanium oxide or the like, which is a porous material in which adjacent pores penetrate (communicate). If the insulating layer is made of woven fabric or non-woven fabric, the movement of the impregnated electrolyte composition is not hindered. The insulating layer may occupy the first current collector and the catalyst layer, or a space may be provided between the first current collector and the insulating layer. A space may be placed between them. When arranging space, you may arrange a spacer as needed.

  Furthermore, in the photoelectric conversion device of the present disclosure including the above-described preferable modes and configurations, or the method for manufacturing the photoelectric conversion device according to the first mode or the second mode of the present disclosure, the semiconductor layer is configured of titanium oxide. be able to.

  More specifically, a method for forming a semiconductor layer composed of semiconductor fine particles (dye-sensitized semiconductor layer) is to prepare a ceramic green sheet (hereinafter simply referred to as “green sheet”) which is a precursor of the semiconductor layer. After the green sheet is placed on the first current collector and partially pushed into the first current collector in the thickness direction, the particles are brought into electronic contact with each other, and the film strength is improved. In order to improve the adhesion to the electric body, it can be formed by a method such as firing. There is no particular limitation on the range of the firing temperature, but if the firing temperature is raised too much, the electrical resistance of the first current collector may increase or melt, so it is usually more preferably 40 ° C to 700 ° C. Is between 40 ° C and 650 ° C. Also, the firing time is not particularly limited, and is usually about 10 minutes to 10 hours. After firing, for the purpose of increasing the surface area of the semiconductor layer made of semiconductor fine particles or increasing the necking between the semiconductor fine particles, for example, chemical plating treatment using a titanium tetrachloride aqueous solution or necking treatment using a titanium trichloride aqueous solution. Alternatively, dip treatment of a semiconductor ultrafine particle sol having a diameter of 10 nm or less may be performed.

Usually, the green sheet is formed on the support member in advance, and the insulating layer precursor layer is formed on the second support member in advance, but the support member and the second support member can be made of any material, For example, a plastic film such as polyethylene terephthalate (PET) can be exemplified. In addition to semiconductor fine particles, the green sheet can contain a binder, a dispersant, a plasticizer, and the like. In addition, the insulating layer precursor layer includes a material constituting the insulating layer, a binder, a dispersant, a plasticizer. Etc. can be included. The green sheet or the insulating layer precursor layer may be formed by a known method. Specifically, for example, a green sheet is prepared by preparing a slurry for forming a green sheet or an insulating layer precursor layer, and applying and drying the slurry on a support member or a second support member using a doctor blade or the like. Or an insulating layer precursor layer. By controlling the type of binder used, the ratio of binder and plasticizer, etc., it is possible to optimize the elastic modulus of the obtained green sheet, whereby a semiconductor is formed on the first surface of the first current collector. It is possible to optimize the state in which a layer is formed and a part of the semiconductor layer in the thickness direction enters the through hole provided in the first current collector. Examples of the press device include a flat plate press device and a calendar press device (roll press device). The pressing temperature, pressing pressure, and pressing time in the pressing device when the semiconductor layer precursor layer (green sheet) is transferred to the first surface of the first current collector using the pressing device are, for example, the above-described s ₁ / t Various tests may be performed and determined so as to satisfy the relationship of ₁ . The press temperature, press pressure, and press time in the press device when the insulating layer precursor layer is transferred to the second surface of the first current collector using the press device may be appropriately determined by performing various tests. .

  The photoelectric conversion device of the present disclosure including the various preferred embodiments and configurations described above, or the method for manufacturing the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure (hereinafter collectively referred to simply as The second current collector may be made of a conductive material provided with a number of through holes, or may be made of a conductive material layer. Can do.

In the present disclosure, the first current collector is made of a conductive material provided with a large number of through-holes. As the conductive material, a wire mesh material, a woven fabric material, a nonwoven fabric material, a sintered material made of a metal or an alloy is used. Examples of the binder material, the porous material, the foam material, the foil material, the sheet material, and the film material can be given. The through hole depends on the form of the first current collector, but is formed when the first current collector is manufactured from a conductive material (for example, a wire mesh material, a woven fabric material, a nonwoven fabric material, a sintered body material). In the case of a porous material, a foam material, a foil material, a sheet material, a film material), or after producing the first current collector from a conductive material, for example, an etching method, a laser processing method, etc. (In the case of foil-like material, sheet-like material, and film-like material). The size of the through holes and the formation pitch of the through holes are essentially arbitrary, but it is necessary to satisfy the condition that the electrons generated in the semiconductor layer reach the first current collector, specifically, The size of the through hole is 1 × 10 ⁻⁴ m or less, preferably 4 × 10 ⁻⁵ m or less, more preferably 2 × 10 ⁻⁵ m or less, and even more preferably 1 × 10 ⁻⁵ m or less. be able to. The shape of the through hole is essentially arbitrary. Specific examples of metals and alloys constituting the first current collector include titanium, titanium oxide, niobium, molybdenum, nickel, tantalum, tungsten, aluminum, copper, alloys thereof, compounds, and stainless steel. it can. When the first current collector is composed of aluminum, copper, alloys thereof, compounds, stainless steel, or the like, the surface of the conductive material has conductivity as required to prevent corrosion and leakage current. Oxides (eg, titanium oxide, zinc oxide, tin oxide, indium tin oxide, fluorine-doped tin oxide), titanium (Ti), niobium (Nb), molybdenum (Mo), nickel (Ni), tantalum (Ta ), A surface treatment layer made of tungsten (W) may be formed. The surface treatment layer is formed by, for example, various physical vapor deposition methods (PVD method) including sputtering method and ion plating method, various chemical vapor deposition methods (CVD method), sol-gel method, etc. can do. Examples of the thickness of the surface treatment layer include 0.1 μm to 0.4 μm. By constituting the first current collector from a conductive material provided with a large number of through holes, the movement of the electrolyte composition constituting the electrolyte layer to the semiconductor layer is not hindered.

  When the second current collector is composed of a conductive material provided with a large number of through holes, the configuration and structure of the second current collector can include the configuration and structure described in the first current collector, However, the present invention is not limited to this, and a configuration including a conductive material layer may be employed.

  When the second current collector is composed of a conductive material layer, it can be composed of any material as long as it is a conductive substance. Specifically, as a material constituting the conductive material layer, stainless steel, titanium (Ti), niobium (Nb), chromium (Cr), molybdenum (Mo), platinum (Pt), gold (Au), silver (Ag) ), Palladium (Pd), ruthenium (Ru), iridium (Ir), copper (Cu), aluminum (Al), carbon black (C) such as carbon black, and conductive polymers. For example, the conductive material layer may be patterned in a comb-teeth shape, or may not be patterned at all. The conductive material layer can be formed on the catalyst layer or the second substrate by a PVD method such as a vacuum deposition method or a sputtering method, a printing method, or the like, or a material shaped in advance into a sheet shape can be used. it can.

In the present disclosure, the electrolyte layer is composed of an electrolyte composition. For example, when the electrolyte composition is composed of an electrolytic solution, examples of the electrolytic solution include various electrolytic solutions containing a cation such as lithium ion and an anion such as iodine ion. It is preferable that an oxidation-reduction pair capable of reversibly taking an oxidized structure and a reduced structure is present in the electrolyte composition. Examples of such a redox pair include an iodine-iodine compound; a bromine-bromine compound; Examples thereof include quinone-hydroquinone; metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ions; sulfur compounds such as sodium polysulfide and alkylthiol-alkyl disulfides; and viologen dyes. Alternatively, the electrolyte composition includes a combination of iodine (I ₂ ) and metal iodide or organic iodide, a combination of bromine (Br ₂ ) and metal bromide or organic bromide, and ferrocyanate / ferricyanic acid. Metal complexes such as salts and ferrocene / ferricinium ions, sulfur compounds such as sodium polysulfide and alkylthiol / alkyl disulfides, viologen dyes, hydroquinone / quinone, and the like can be used. As the cation of the metal compound, Li, Na, K, Mg, Ca, Cs and the like, and as the cation of the organic compound, a quaternary ammonium compound such as tetraalkylammonium, pyridinium, and imidazolium is preferable. It is not limited, and two or more of these can be mixed and used. Among these, an electrolyte composition in which I ₂ and a quaternary ammonium compound such as LiI, NaI, and imidazolium iodide are combined is preferable. The concentration of the salt in the electrolyte composition is preferably 0.05 mol to 5 mol, more preferably 0.2 mol to 3 mol, with respect to the solvent. The concentration of I ₂ or Br ₂ is preferably 0.0005 mol to 1 mol, more preferably 0.001 mol to 0.3 mol. Further, for the purpose of improving the open-circuit voltage V _oc , an additive composed of an amine compound typified by 4-tert-butylpyridine may be added. In addition to the electrolytic solution, as will be described later, the electrolyte composition may be composed of a gel electrolyte, a solid electrolyte, and a molten salt gel electrolyte.

  As a solvent constituting the electrolyte composition (electrolyte solution), water, alcohols, ethers, esters, carbonate esters, lactones, carboxylic acid esters, phosphate triesters, heterocyclic compounds, nitriles, Ketones, amides, nitromethane, halogenated hydrocarbons, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, hydrocarbons and the like can be mentioned, but are not limited thereto. In addition, two or more of these may be mixed and used. Furthermore, it is also possible to use a solution of a quaternary ammonium compound of tetraalkyl, pyridinium, or imidazolium as the solvent.

  Depending on the structure, structure, and form of the electrolyte layer, gelling agents, polymers, cross-linking monomers, etc. are dissolved in the electrolyte composition and inorganic ceramic particles are dispersed in order to reduce leakage and volatilization of the electrolyte composition. It is also possible to use a gel electrolyte composition. In this case, the electrolyte layer has a single layer configuration of the gel electrolyte composition or a multilayer configuration of the insulating layer and the gel electrolyte composition. The ratio between the gel matrix and the electrolyte composition is such that the higher the electrolyte composition, the higher the ionic conductivity, but the lower the mechanical strength. Conversely, when the electrolyte composition is too low, the mechanical strength is high but the ionic conductivity is high. Since the electrical conductivity is lowered, the electrolyte composition is preferably 50% by mass to 99% by mass, and more preferably 80% by mass to 97% by mass of the gel electrolyte composition. It is also possible to realize an all-solid-type photoelectric conversion device by dissolving an electrolyte composition and a plasticizer in a polymer and volatilizing and removing the plasticizer.

  When the electrolyte composition is composed of an electrolytic solution, the electrolytic solution is injected between the semiconductor layer and the catalyst layer. The method for injecting the electrolytic solution is not particularly limited, but a method in which the injection is performed under reduced pressure inside the photoelectric conversion device in which the outer edge portion (outer peripheral portion) is sealed in advance and the injection port is opened is preferable. In this case, a method of dropping several drops of the electrolytic solution into the injection port and injecting it by capillary action is simple. Moreover, injection | pouring can also be performed under pressure reduction or a heating as needed. After the electrolyte is completely injected, the electrolyte remaining in the inlet is removed and the inlet is sealed. There is no restriction | limiting in particular also in this sealing method, If necessary, it can seal by sticking a glass substrate or a plastic substrate with a sealing agent. In addition to this method, an electrolytic solution can be dropped and bonded together under reduced pressure as in a liquid crystal drop injection (ODF) method of a liquid crystal panel. Alternatively, the outer edge portion (outer peripheral portion) of the three sides is sealed in advance, and the electrolyte solution is injected into the photoelectric conversion device in a state where the remaining one side is opened, and then the remaining one side is removed under reduced pressure. A sealing method can also be employed. In the case of a gel electrolyte composition using a polymer or the like, or an all-solid electrolyte composition, for example, on or above the surface of the first current collector facing the catalyst layer, or the first current collector. A polymer solution containing an electrolyte composition and a plasticizer is formed on the surface of the catalyst layer facing the body or above by a casting method, and then volatilized and removed. And after removing a plasticizer completely, what is necessary is just to seal based on the method similar to the method mentioned above. This sealing is preferably performed using a vacuum sealer or the like in an inert gas atmosphere or under reduced pressure. After sealing, in order to fully impregnate the insulating composition or the semiconductor layer with the electrolyte composition, heating and pressurizing operations may be performed as necessary. Alternatively, for example, a method using a dispenser or a printing method including an ink jet printing method can be used. In addition, what is necessary is just to select the various methods demonstrated above suitably, for example depending on the material which comprises a 1st base material and a 2nd base material.

  In the present disclosure, the first base material on which light is incident needs only to be made of a transparent material in the visible light region, and is excellent in moisture and gas barrier properties, solvent resistance, weather resistance and the like entering from the outside. It is preferable to comprise from the material which is. Specifically, as a material constituting the first base material, a glass substrate, a quartz substrate, a transparent inorganic substrate such as a sapphire substrate, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN); a polycarbonate (PC) resin Polyethersulfone (PES) resin; Polyolefin resin such as polystyrene, polyethylene, polypropylene, etc .; Polyphenylene sulfide resin; Polyvinylidene fluoride resin; Tetraacetyl cellulose resin; Brominated phenoxy resin; Aramid resin; Polyimide resins; Polystyrene resin; Resin; Polysulfone resin; Acrylic resin; Epoxy resin; Fluororesin; Silicone resin; Diacetate resin; Triacetate resin; Polyvinyl chloride resin; Plastic substrate or a film can be mentioned. Examples of the glass substrate include a soda glass substrate, a heat resistant glass substrate, and a quartz glass substrate. An antireflection film, an ultraviolet absorption layer, a contamination prevention layer, a hard coat layer, or the like may be formed on the light incident side surface of the first base material. From the surface of the first base material, aluminum, silica, and alumina may be used. A gas barrier layer made of at least one gas barrier material selected from the group consisting of the above may be formed.

What is necessary is just to select the material which comprises a 2nd base material suitably from the material quoted as a material which comprises a 1st base material. The same material may be sufficient as the material which comprises a 1st base material and a 2nd base material, and a different material may be sufficient as it. Alternatively, as the second base material (counter substrate), an opaque plastic sheet or plastic film, or a glass substrate, a ceramic substrate, a quartz substrate, a plastic sheet, or a plastic film on which an opaque metal film is formed may be mentioned. it can. Alternatively, a gas barrier film having an oxygen permeability of 100 (cc / m ² / day / atm) or less and a water vapor permeability of 100 (g / m ² / day) or less can be used. A gas barrier film in which a gas barrier layer made of at least one gas barrier material selected from the group consisting of aluminum, silica and alumina is laminated can also be used. Substrate or foil made of a metal or alloy (for example, stainless steel) containing at least one element selected from the group consisting of Ni, Cr, Fe, Nb, Ta, W, Co, and Zr as the second base material Can be used, the second base material can also serve as the second current collector. The oxygen permeability can be determined based on JIS K7126-2: 2006 “Plastics—Film and Sheet—Gas Permeability Test Method—Part 2: Isobaric Method”, and the water vapor permeability can be determined according to JIS K7129: 2008. It can be determined based on “Plastics—Film and Sheet—How to Obtain Water Vapor Permeability (Measuring Method)”.

In the present disclosure, examples of the material constituting the semiconductor layer include materials generally used for photoelectric conversion materials. When the semiconductor layer is composed of a dye-sensitized semiconductor, the semiconductor layer is typically composed of semiconductor fine particles carrying a dye (sensitizing dye). Examples of materials constituting the semiconductor fine particles include various compound semiconductor materials, compounds having a perovskite structure, and the like in addition to semiconductor materials typified by silicon (Si). These semiconductors are preferably n-type semiconductors in which conduction band electrons become carriers under photoexcitation and give an anode current. Specific examples of these semiconductors include zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), and strontium titanate (SrTiO ₃ ) in addition to the above-described titanium oxide (TiO ₂ ). ), Calcium titanate (CaTiO ₃ ), barium titanate (BaTiO ₃ ), tin oxide (SnO ₂ ), zirconium oxide (ZrO ₂ ), indium oxide (In ₃ O ₃ ), lanthanum oxide (La ₂ O ₃ ), Thallium oxide (Ta ₂ O ₅ ), yttrium oxide (Y ₂ O ₃ ), phosphonium oxide (Ho ₂ O ₃ ), bismuth oxide (Bi ₂ O), cerium oxide (CeO ₂ ), magnesium oxide (MgO), aluminum oxide _{(Al 2 O 3), CdS} , ZnS, PbS, it can be mentioned semiconductor compounds and oxide semiconductors such as Bi ₂ S _3, among these TiO ₂ of anatase type is especially preferred. However, the semiconductor is not limited to these, and two or more of these can be mixed and used. The semiconductor fine particles can take various shapes and forms as necessary, such as particles, needles, tubes, scales, spheres, rods, and the like. The particle size of the semiconductor fine particles is not particularly limited, and the average particle size of primary particles is preferably 1 × 10 ⁻⁹ m to 2 × 10 ⁻⁷ m, particularly preferably 5 × 10 ⁻⁹ m to 1 × 10 ⁻⁷ m. It is. It is also possible to increase the quantum yield by mixing semiconductor fine particles having a large average particle diameter into semiconductor fine particles having such an average particle diameter and scattering incident light by the semiconductor fine particles having a large average particle diameter. In this case, the average particle diameter of the semiconductor fine particles having a large average particle diameter is preferably 2 × 10 ⁻⁸ m to 5 × 10 ⁻⁷ m. The semiconductor layer may have a multilayer structure in which a plurality of semiconductor layers having different particle diameters of semiconductor particles are stacked, or a multilayer structure in which a plurality of semiconductor layers having different mixing ratios of semiconductor particles having different particle diameters are stacked. You can also

In a semiconductor layer composed of semiconductor fine particles and composed of a dye-sensitized semiconductor (dye-sensitized semiconductor layer), the semiconductor fine particles are preferably particles having a large surface area so that a large amount of dye can be adsorbed. Specifically, the surface area of the semiconductor layer in a state where the semiconductor fine particles are formed on the first current collector is preferably 1 × 10 ¹ times or more with respect to the projected area, and preferably 1 × 10 ² times or more. More preferably. The upper limit of the surface area is not particularly limited, and is usually about 1 × 10 ³ times. In general, as the thickness of a semiconductor layer composed of semiconductor fine particles increases, the amount of supported dye increases per unit projected area, and thus the light capture rate increases. Loss due to coupling also increases. Therefore, a preferable thickness exists in the semiconductor layer, and it is desirable that the thickness be a value as described above.

  Examples of the dye supported (adsorbed) on the semiconductor layer and functioning as a photosensitizer include various known compounds having absorption in the visible light region and / or the infrared light region. Organic dyes, metal complex dyes Etc. can be used. Examples of organic dyes include azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes (eg, merocyanine, quinocyanine, cryptocyanine), merocyanine dyes, and triphenylmethane dyes. , Xanthene dyes (eg, rhodamine B, rose bengal, eosin, erythrosine, etc.), porphyrin dyes, phthalocyanine dyes, coumarin compounds, perylene dyes, indigo dyes, naphthalocyanine dyes, acridine dyes, phenylxanthenes Pigments, anthraquinone pigments, basic dyes (eg, phenosafranine, capri blue, thiocin, methylene blue, etc.), porphyrin compounds (eg, chlorophyll, zinc porphyrin, magnesium porphyrin) ) Can be mentioned. Examples of the metal complex dye include ruthenium metal complex dyes such as a ruthenium bipyridine metal complex dye, a ruthenium terpyridine metal complex dye, and a ruthenium quarterpyridine metal complex dye. Two or more of these dyes may be mixed and used. In order to firmly support (adsorb) the dye on the semiconductor layer, an interlock such as a carboxy group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, a sulfonic acid group, an ester group, a mercapto group, or a phosphonyl group is contained in the dye molecule. Those having a group are preferred, and among these, those having a carboxy group (COOH group) are particularly preferred. In general, an interlock group has a function of adsorbing and fixing a dye to the surface of the material constituting the semiconductor layer, and an electrical coupling that facilitates electron transfer between the excited state dye and the conduction band of the semiconductor layer. Supply.

  There are no particular restrictions on the method of supporting (adsorbing) the dye on the semiconductor layer (dye-sensitized semiconductor layer). For example, the dye may be an alcohol, nitrile, nitromethane, halogenated hydrocarbon, ether, dimethyl sulfoxide, or amide. , N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates, ketones, hydrocarbons, a method of immersing a semiconductor layer in a solvent such as water, The method of apply | coating the solution containing a pigment | dye to a semiconductor layer can be mentioned. In addition, when a dye having high acidity is used, deoxycholic acid or the like may be added for the purpose of reducing association between the dye molecules. After supporting the dye, the surface may be treated with amines for the purpose of promoting the removal of the excessively supported dye. Examples of amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these are liquids, they may be used as they are, or may be used after being dissolved in an organic solvent.

In the present disclosure, the catalyst layer may be any catalyst layer that has a catalytic ability to promote the reduction reaction of oxidized redox ions such as I ₃ ⁻ ions in the electrolyte layer and perform the reduction at a sufficient rate. Examples thereof include a layer made of Pt), carbon (C), rhodium (Rh), ruthenium (Ru), iridium (Ir), and the like. Examples of the method for forming the catalyst layer include a wet method in which a solution containing a catalyst or a catalyst precursor is applied or printed, a PVD method such as a sputtering method or a vacuum deposition method, and a dry method such as various CVD methods. it can.

  In the present disclosure, the sealing material for sealing the first base material and the second base material at their outer edges prevents leakage and volatilization of the electrolyte composition, and impurities enter the inside from the outside. prevent. As the sealing material, it is preferable to use a resin having resistance to the electrolyte composition constituting the electrolyte layer. For example, a heat-sealing film, a thermosetting resin, an ultraviolet curable resin, and the like can be used. Specifically, epoxy resin, polyisobutylene resin, urethane resin, silicone resin, polyolefin resin, acrylic adhesive, EVA (ethylene vinyl acetate), ionomer resin, ceramic, glass frit, biaxially stretched polypropylene (CPP) film Various heat-sealing films such as polyethylene or PE film can be used.

  In the present disclosure, in order to manufacture a photoelectric conversion device, a laminated body of a green sheet and a first current collector is fired to obtain a first laminated structure including a semiconductor layer / first current collector. By firing the laminate of the catalyst layer precursor layer (catalyst layer before firing) and the second current collector, a second laminated structure composed of the catalyst layer / second current collector is obtained. Then, the first base material, the first laminated structure, the insulating layer, the second laminated structure, and the second base material are overlapped, and the first base material and the second base material are sealed at the outer edge portion. Stop.

  Alternatively, by firing the laminate of the green sheet and the first current collector, a first laminated structure composed of the semiconductor layer / first current collector is obtained, while the second current collector is formed on the second substrate. By forming the body, a second laminated structure composed of the second current collector / second base material is obtained. And a 1st base material, a 1st laminated structure, an insulating layer, a catalyst layer, and a 2nd laminated structure are overlap | superposed, and a 1st base material and a 2nd base material are sealed in an outer edge part. . Alternatively, a first laminated structure composed of a semiconductor layer / first current collector is obtained by firing a laminated body of the green sheet and the first current collector. And a 1st base material, a 1st laminated structure, an insulating layer, a catalyst layer, a 2nd electrical power collector, and a 2nd base material are piled up, and the 1st base material and the 2nd base material are piled up. Seal at the outer edge.

  Alternatively, a laminate composed of a green sheet / first current collector / insulating layer precursor layer is formed by laminating a green sheet, a first current collector, and an insulating layer precursor layer (insulating layer before firing). On the other hand, the catalyst layer precursor layer and the second current collector are stacked to form a stack of catalyst layer precursor layer / second current collector. And after firing these laminated bodies, after obtaining the 1st laminated structure and the 2nd laminated structure, the 1st substrate, the 1st laminated structure, the 2nd laminated structure, and the 2nd The base material is overlapped, and the first base material and the second base material are sealed at the outer edge portion. Or after laminating | stacking these laminated bodies, a laminated body baked product is obtained by baking. And a 1st base material, a laminated body baked product, and a 2nd base material are piled up, and a 1st base material and a 2nd base material are sealed in an outer edge part. Alternatively, a laminate is formed by laminating the green sheet, the first current collector, the insulating layer precursor layer, the catalyst layer precursor layer, and the second current collector, and by firing the laminate, After obtaining the laminated body fired product, the first base material, the laminated body fired product, and the second base material are overlapped, and the first base material and the second base material are sealed at the outer edge portion.

  Alternatively, by firing the laminate of the green sheet and the first current collector, the first laminated structure composed of the semiconductor layer / first current collector is obtained, while the insulating layer precursor layer and the catalyst layer precursor are obtained. The laminated body of the layer and the second current collector is fired to obtain a second laminated structure composed of an insulating layer / catalyst layer / second current collector. And a 1st base material, a 1st laminated structure, a 2nd laminated structure, and a 2nd base material are piled up, and a 1st base material and a 2nd base material are sealed in an outer edge part.

The photoelectric conversion device of the present disclosure is
It is composed of a lead member main body (hereinafter referred to as “first lead member main body” for convenience) and a lead member extension (hereinafter referred to as “first lead member extension” for convenience). And a lead member for outputting the generated power (hereinafter referred to as “first lead member” for convenience),
A lead member main body (first lead member main body) is attached to the outer edge of the first current collector,
The lead member extending portion (first lead member extending portion) can be configured to protrude to the outside of the photoelectric conversion device. Further, when the second current collector is made of a conductive material provided with a large number of through holes,
The second lead member body portion and the second lead member extending portion are composed of a conductive material piece, and further include a second lead member for outputting generated power,
A second lead member body is attached to the outer edge of the second current collector;
The 2nd lead member extension part can be made into the form which protrudes the outer side of the photoelectric conversion apparatus. These forms may be referred to as “a photoelectric conversion device with a lead member of the present disclosure” for convenience.

  Thus, in the photoelectric conversion device with a lead member of the present disclosure, the first lead member is made of a conductive material piece, the first lead member main body is attached to the outer edge portion of the first current collector, and the first lead If the member extending portion protrudes outside the photoelectric conversion device, a part of the first lead member is appropriately and surely taken out from the mesh-shaped first current collector in contact with the semiconductor layer. And high reliability can be imparted to the photoelectric conversion device. Further, the second lead member is made of a conductive material piece, the second lead member main body is attached to the outer edge of the second current collector, and the second lead member extending portion protrudes outside the photoelectric conversion device. With this structure, a part of the second lead member can be appropriately and reliably taken out from the mesh-shaped second current collector, and high reliability can be imparted to the photoelectric conversion device. .

  Furthermore, in the photoelectric conversion device with a lead member of the present disclosure, the first current collector includes a first current collector main body portion and a first current collector extending portion extending from the first current collector main body portion. The 1st lead member main-body part can be made into the form attached to the 1st electrical power collector extension part. The second current collector includes a second current collector main body and a second current collector extension extending from the second current collector main body, and the second lead member main body Can be in the form of being attached to the second current collector extension.

  Furthermore, the first lead member main body can be configured to be attached to the upper surface of the first current collector extension and the lower surface of the first current collector extension. The first lead member main body can be more reliably attached to the one current collector extension, and the contact resistance can be reduced. Further, the second lead member main body can be attached to the upper surface of the second current collector extending portion and the lower surface of the second current collector extending portion. The second lead member main body can be more reliably attached to the current collector extension, and the contact resistance can be reduced.

  The planar shape of the first current collector is rectangular, and extends along the first side and the third side extending along the first direction, and the second direction orthogonal to the first direction. It has the 2nd side and the 4th side, and it can be set as the composition where the 1st current collector extension part is located along the 1st side. Further, the second side and the fourth side of the first current collector can be configured to be covered with a coating layer, whereby the first current collector, the second current collector, It is possible to reliably prevent occurrence of a short circuit between the two. Further, the coating layer can further be configured to cover the first current collector extension portion and the first lead member main body portion, thereby generating leakage current, and the first current collector. The occurrence of a short circuit between the body and the second current collector can be reliably prevented, and the reliability of the photoelectric conversion device can be further improved. In some cases, the distance between the first current collector and the catalyst layer can be controlled by controlling the thickness of the coating layer. Furthermore, the portion where the second side and the third side of the first current collector intersect and the portion where the fourth side and the third side intersect can be chamfered. The occurrence of a short circuit between the first current collector and the second current collector can be reliably prevented, and the reliability of the photoelectric conversion device can be further improved.

  Here, examples of the material constituting the coating layer include an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin, and a heat fusion resin. More specifically, for example, as a heat fusion resin, Heat-sealable resins such as polyophine-based adhesive resins (for example, Modic [registered trademark] manufactured by Mitsubishi Chemical Corporation) and ionomer-based adhesive resins (for example, High Milan [registered trademark] of Mitsui DuPont Polychemical Co., Ltd.) In addition, a liquid material such as a silicone resin, an acrylic resin, a urethane resin, or an epoxy resin can be used as the ultraviolet curable resin or the thermosetting resin. And, when using a heat-sealable resin, the coating layer is applied at a predetermined position with a dispenser based on a method of heat-sealing a molded product in a desired shape. Thereafter, it can be formed based on a method of curing with ultraviolet rays or heat.

  Further, in the portion where the first base material and the second base material are sealed, between the first base material and the first lead member and between the second base material and the first lead member. It can be set as the structure by which the adhesive bond layer is distribute | arranged and, thereby, the reliability of a photoelectric conversion apparatus can be improved further. Here, as a material constituting the adhesive, a polyophine-based adhesive resin (for example, Modic [registered trademark] manufactured by Mitsubishi Chemical Corporation), an ionomer-based adhesive resin (for example, High Milan of Mitsui DuPont Polychemical Co., Ltd.) [Registered trademark]).

  The planar shape of the second current collector is rectangular, and extends along the first side and the third side extending along the first direction, and the second direction orthogonal to the first direction. It has a 2nd edge and a 4th edge, and it can be set as the form where the 2nd current collector extension part is located along the 3rd edge. In such a configuration, the projected image of the first lead member can be configured not to overlap the projected image of the second lead member. In this case, the first lead member extending portion and the second lead member The lead member extending portion may be configured to protrude outward from the same side of the photoelectric conversion device. Furthermore, in these forms, the second side and the second side of the second current collector The side of 4 can be configured to be covered with a coating layer, thereby reliably preventing the occurrence of leakage current and the occurrence of a short circuit between the first current collector and the second current collector. it can. Further, the coating layer can further be configured to cover the second current collector extension portion and the second lead member main body portion, thereby further improving the reliability of the photoelectric conversion device. Can be made. Furthermore, in the preferred embodiment described above, the portion where the second side and the first side of the second current collector intersect and the portion where the fourth side and the first side intersect are chamfered. In this case, it is possible to reliably prevent the occurrence of a short circuit between the first current collector and the second current collector, and to further improve the reliability of the photoelectric conversion device. . Furthermore, in these forms, in the portion where the first base material and the second base material are sealed, between the first base material and the second lead member, and the second base material, An adhesive layer may be disposed between the second lead member. Here, the material which comprises a coating layer or an adhesive bond layer is as having mentioned above.

  As a material constituting the conductive material piece constituting the first lead member or the second lead member, it is preferable to select a material having corrosion resistance to the electrolyte composition constituting the electrolyte layer. For example, titanium (Ti), Examples include molybdenum (Mo), niobium (Nb), tungsten (W), tantalum (Ta), alloys thereof, stainless steel, and Hastelloy [registered trademark]. In addition, as a method of attaching the first lead member main body or the second lead member main body to the first current collector extension or the second current collector extension, various welding methods such as resistance welding and ultrasonic welding are used. And a soldering method, a method using a conductive adhesive or a conductive paste, a method using a tape, a method using a sealant, a brazing method, and a pressure bonding method using a press. As a planar shape of the first lead member or the second lead member, a rectangular shape or a strip shape can be exemplified. The first lead member extending portion and the second lead member extending portion made of the conductive material piece are connected to an external circuit. In addition, it is not necessary to provide a surface treatment layer in the first current collector extension portion, thereby reducing the contact resistance between the first current collector extension portion and the first lead member main body portion. Can do.

Furthermore, the first base material may be provided with a heat seal layer. In some cases, the second base material may also be provided with a heat seal layer. Alternatively, in the photoelectric conversion device with a lead member of the present disclosure including the preferable modes and configurations described above, at least the first base material is provided with a heat seal layer (that is, the first base material is heat sealed). The first substrate and the second substrate are provided with a heat seal layer); the first substrate and the second substrate are provided continuously; 1. A base material is provided with a window part for allowing light to enter the semiconductor layer; the window part is made of a transparent plastic film or plastic sheet (hereinafter sometimes referred to as a “window part closing member”). It can be set as the structure closed. By using a metal foil laminate material, a high gas barrier property can be realized. Moreover, it becomes unnecessary to provide the sealing material for sealing a 1st base material and a 2nd base material in those outer edge parts separately by having a heat seal layer, and the base material of a simple structure is provided. Obtainable. The heat seal layer is provided on the first current collector side. The water vapor permeability of the window closing member is desirably 1 × 10 ⁻² (g / m ² / day) or less, preferably 1 × 10 ⁻⁴ (g / m ² / day) or less. Exemplifies a transparent film (transparent silica-deposited film. For example, Tech Barrier [registered trademark] manufactured by Mitsubishi Plastics, Inc.) and X-BARRIER manufactured by Mitsubishi Plastics, Inc. on plastic films such as OPET and ONY. be able to.

  As described above, by providing the heat seal layer on the first base material, the semiconductor layer can be adhered to the first base material via the heat seal layer, and there is a gap between the semiconductor layer and the first base material. It can be prevented, and the electrolyte composition can be prevented from entering between the semiconductor layer and the first base material, and the loss of incident light and the undesired absorption of incident light can be prevented.

  Biaxially stretched polypropylene (CPP) film, polyethylene (PE) film, ethylene vinyl alcohol copolymer, polyophine adhesive resin (for example, modic manufactured by Mitsubishi Chemical Corporation [registered] Trademark]] and ionomer resins (for example, High Milan [registered trademark] from Mitsui DuPont Polychemical Co., Ltd.). Examples of the material constituting the transparent plastic film or plastic sheet (window closing member) that closes the window include polyolefin films such as polyethylene, polypropylene, and cycloolefin polymers, and transparent films such as polyester resins such as polyethylene terephthalate. Moreover, it is more desirable that a barrier layer for enhancing gas barrier properties is formed on these plastic films or plastic sheets. In order to close the window portion with the window portion closing member, the window portion closing member may be bonded to the first base material with a heat seal layer, and when the window portion closing member has heat fusion properties. Can be bonded to the first substrate by heating the window closing member.

  The photoelectric conversion device may be manufactured based on various shapes, structures, and configurations depending on the application, and these are not particularly limited. The photoelectric conversion device is most typically used as a solar cell, but can also be used for, for example, a photosensitive sensor. In addition, the electronic device incorporating the photoelectric conversion device may be basically any type, and includes both portable electronic devices and stationary electronic devices, for example, mobile phones, mobile devices, robots, personal computers, and the like. Computers, in-vehicle devices, various home appliances, and the like can be given. In these cases, the photoelectric conversion device is used as a power source for these electronic devices, for example.

  Example 1 relates to a photoelectric conversion device of the present disclosure and a method for manufacturing the photoelectric conversion device according to the first and second aspects of the present disclosure, and more specifically to a dye-sensitized solar cell. A cross-sectional conceptual diagram of the photoelectric conversion device 10A of Example 1 before assembly is shown in FIG. 1A, and an end face conceptual diagram after assembly is shown. Moreover, the partial schematic plan view of the 1st electrical power collector in the photoelectric conversion apparatus of Example 1 is shown to (A) of FIG. 2, and the 1st collector along arrow BB of (A) of FIG. A schematic partial end view of the electric body is shown in FIG. 2B, and a schematic partial view of the first current collector and the semiconductor layer similar to that along the arrow BB in FIG. An end view is shown in FIG. In addition, the state shown to (A)-(C) of FIG. 2 shows a kind and an ideal state.

The photoelectric conversion device obtained by the photoelectric conversion device of Example 1 or the photoelectric conversion device of Example 2 to Example 13 described later, and the photoelectric conversion device of these examples including Example 1,
(A) 1st base material 21 and 2nd base material 22,
(B) Between the first base material 21 and the second base material 22, the semiconductor layer 31, the first surface 51 a facing the first base material 21, and the first layers provided sequentially from the first base material side. 2 a first current collector 51 having a second surface 51b facing the substrate 22, an electrolyte layer 41, a catalyst layer 32, and a second current collector,
The first base material 21 and the second base material 22 are sealed at the outer edge portion,
The first current collector 51 is made of a conductive material provided with a large number of through holes 51c.

  And in the photoelectric conversion apparatus of Example 1 or Example 2 to Example 13 described later, a part of the semiconductor layer 31 formed on the first surface 51a of the first current collector 51 in the thickness direction is The first current collector 51 has penetrated into a through hole 51c.

Specifically, the first base material 21 made of a transparent substrate and allowing sunlight to pass through is composed of a gas barrier material in which a heat seal layer such as polypropylene / polyethylene terephthalate / silica vapor deposition layer / polypropylene having a thickness of about 10 μm is laminated. The second substrate 22 is made of a metal foil laminate material, specifically, an aluminum laminate film. The semiconductor layer (porous semiconductor layer) 31 is composed of an aggregate of anatase-type TiO ₂ fine particles (average particle diameter: 20 nm) carrying Z991 which is a ruthenium-based dye, and the catalyst layer 32 is carbon. (C).

  In Example 1 or Examples 2 to 13 to be described later, the first current collector 51 is made of a wire mesh material made of stainless steel (SUS316), and the surface of the wire mesh material has corrosion prevention, In order to prevent the occurrence of leakage current, a surface treatment layer (not shown) made of titanium is formed based on an ion plating method. Specifically, the first current collector 51 is a wire mesh material (more specifically, made of stainless steel and having a diameter of 20 μm, having a through-hole (opening) 51 c size of 20 μm and a formation pitch of the through-holes 51 c of 40 μm. The wire is stretched vertically and horizontally, so-called 635 mesh wire mesh having an opening of 20 μm. A space surrounded on all sides by the wire corresponds to the through hole 51c. The planar shape of the through hole 51c is ideally substantially rectangular.

  Further, in the photoelectric conversion device 10A of Example 1, the second current collector 61 is made of a conductive material provided with a large number of through holes. Specifically, the same material as the first current collector 51 is used as the second current collector 61. And in the photoelectric conversion apparatus 10A of Example 1, the 2nd laminated structure which consists of a catalyst layer / 2nd electrical power collector by baking the laminated body of a catalyst layer precursor layer and a 2nd electrical power collector. Can be obtained. Specifically, after the carbon paste is printed on the second current collector 61 to form the catalyst layer precursor layer, the carbon paste is subjected to conditions such as 450 ° C. and 0.5 hours in the air. Firing based on In this way, a second laminated structure composed of the catalyst layer / second current collector in which the second current collector 61 and the catalyst layer 32 are integrated can be obtained.

  Furthermore, in the photoelectric conversion device 10 </ b> A of Example 1, the electrolyte layer 41 includes an insulating layer 43 impregnated with the electrolyte composition 42. Specifically, the insulating layer 43 constituting the electrolyte layer 41 includes 0.1 mol of sodium iodide, 0.6 mol of 1-propyl-2,3 dimethylimidazolium iodide, 0.05 mol of iodine, tert-butyl. It is composed of a non-woven fabric made of polyester impregnated with an electrolyte composition 42 made of 0.5 mol of pyridine in acetonitrile.

In the photoelectric conversion device 10A according to the first embodiment, as illustrated in FIG. 2C, a part in the thickness direction of the semiconductor layer 31 is formed on the second surface 51b of the first current collector 51 ((B in FIG. 2). ) Does not reach (shown by a dashed line). The average thickness of the first current collector 51 is t ₁ , the average penetration length of a part of the semiconductor layer 31 in the thickness direction entering the through hole 51c provided in the first current collector 51 is s ₁ , The average thickness of the portion of the semiconductor layer 31 formed on the first surface 51a of the current collector 51 (indicated by a two-dot chain line in FIG. 2B) and in contact with the first surface 51a of the first current collector 51. Is s ₀ ,
s ₀ = 15 μm
s ₁ = 15 μm
t ₁ = 40 μm
It was. Further, the surface roughness Ra of the surface 31a of the semiconductor layer 31 facing the first substrate 21 is
Ra = 0.2 μm
Met.

  In the method of manufacturing the photoelectric conversion device of Example 1, the semiconductor layer precursor layer made of ceramic green sheet (green sheet) is transferred to the first surface 51a of the first current collector 51 using a press device. Thereafter, the semiconductor layer 31 is obtained by firing the semiconductor layer precursor layer. Specifically, a support member on which a semiconductor layer precursor layer made of a green sheet is formed is prepared, and the first current collector 51 is formed on the semiconductor layer precursor layer formed on the support member using a press device. The semiconductor layer 31 is obtained by transferring to the first surface 51a and then firing the semiconductor layer precursor layer.

  Alternatively, in the method for manufacturing the photoelectric conversion device of Example 1, the semiconductor layer 31 is formed on the first surface 51 a of the first current collector 51 and provided on the first current collector 51. A part of the semiconductor layer 31 in the thickness direction is caused to enter the through hole 51c.

Specifically, first, a slurry composed of a mixture of a semiconductor fine particle, a binder, a dispersant, a plasticizer, and a solvent is prepared based on a well-known method. And using a doctor blade etc., a slurry is apply | coated on the support member which consists of plastic films, such as a polyethylene terephthalate (PET), and a green sheet is produced by carrying out hot air drying (drying temperature: 80 degreeC). Then, the green sheet is placed on the first surface 51a of the first current collector 51 with the support member facing up, and the stacked body of the support member, the green sheet, and the first current collector 51 is carried into the flat plate press apparatus. . Then, the pressing temperature is 40 ° C., the pressing pressure is 1 × 10 ⁸ Pa, the pressing time is 2 minutes, the green sheet is partially pushed into the first current collector 51 in the thickness direction, and then the support member is peeled off. . Next, the green sheet is fired in order to bring the particles into electronic contact and to improve the film strength and the adhesion to the first current collector 51. Specifically, the green sheet is fired in air based on conditions such as 510 ° C. and 0.5 hours. In this way, a first stacked structure composed of a semiconductor layer / first current collector in which the first current collector 51 and the semiconductor layer 31 are integrated can be obtained (see FIG. 2C). Thereafter, the semiconductor layer 31 is impregnated with a dye based on a known method.

  When the manufacturing method of the photoelectric conversion device 10A of Example 1 described above is summarized, the first laminate composed of the semiconductor layer / first current collector is formed by firing the laminate of the green sheet and the first current collector. Get a structure. In addition, by firing the laminate of the catalyst layer precursor layer (catalyst layer before firing) and the second current collector, a second laminated structure composed of the catalyst layer / second current collector is obtained. Then, the first base material, the first laminated structure, the insulating layer, the second laminated structure, and the second base material are overlapped, and the first base material and the second base material are sealed at the outer edge portion. Stop.

  In the assembly of the photoelectric conversion device 10A of Example 1, the first base material 21, the first laminated structure, the insulating layer 43 made of nonwoven fabric, the second laminated structure, and the second base material 22 The first base material 21 and the second base material 22 are sealed (bonded) with a sealing material 23 made of a heat-sealing film on the three sides of the outer edge portion. Then, the electrolyte composition 42 is impregnated into the insulating layer 43 and the semiconductor layer 31 made of a nonwoven fabric from the remaining one side that is in an open state. Next, the remaining one side is sealed with the sealing material 23 under reduced pressure. Thus, the photoelectric conversion device 10A illustrated in FIG. 1B can be obtained. A part of the first current collector 51 and the second current collector 61 protrudes from the photoelectric conversion device 10A and can be connected to an external circuit, but this state is not shown. The same applies to Examples 2 to 8 described below.

  In the photoelectric conversion device 10A of Example 1 (referred to as “Example 1A” for convenience) thus obtained, a power generation characteristic of 6.2% was confirmed as a result of power generation by light irradiation of AM1.5. . In addition, as shown in FIGS. 3A and 3B, microscopic photographs taken of the first laminated structure from the first base material side and the second base material side, on the first base material side, The first surface 51a of the first current collector 51 was covered with the semiconductor layer 31, while the second surface 51b of the first current collector 51 was exposed.

When the size of the first laminated structure is 50 mm × 50 mm and the pressing pressure is 0.5 × 10 ⁸ Pa and 1.5 × 10 ⁸ Pa, the results shown in FIGS. 3A and 3B are shown. I was able to get the status. On the other hand, when the press pressure was 3.0 × 10 ⁸ Pa and 6.0 × 10 ⁸ Pa, the first surface 51a and the second surface 51b of the first current collector 51 were exposed. And when the power generation characteristic average when the pressing pressure is 0.5 × 10 ⁸ Pa and 1.5 × 10 ⁸ Pa is 1.0, the pressing pressure is 3.0 × 10 ⁸ Pa, 6.0 ×. When it was 10 ⁸ Pa, the power generation characteristics decreased to 0.85 or less.

  As the first current collector 51, a wire mesh material having a through-hole (opening) 51c size of 26 μm and a formation pitch of 51 μm of the through-holes 51c (more specifically, a wire rod made of stainless steel and having a diameter of 25 μm vertically and horizontally) A photoelectric conversion device (photoelectric conversion device of Example 1B) was produced in the same manner as in Example 1 except that a stretched so-called 500 mesh wire mesh with an opening of 26 μm was used. In the obtained photoelectric conversion device of Example 1B, a power generation characteristic of 5.0% was confirmed as a result of power generation by light irradiation of AM1.5.

  A photoelectric conversion device of Comparative Example 1 was produced in the same manner as in Example 1A except that a commercially available titanium oxide paste was applied to the first current collector 51 of 635 mesh using an applicator. In the obtained photoelectric conversion device of Comparative Example 1, the first surface 51a of the first current collector 51 and the second surface 51b of the first current collector 51 are exposed, and the semiconductor layer 31 has the first current collector. The through-hole 51c provided in the body 51 is in a state of being filled, and as a result of power generation by light irradiation of AM1.5, only 2.8% power generation characteristics were obtained. In Comparative Example 1, the surface roughness Ra of the surface 31a of the semiconductor layer 31 facing the first base material 21 was far greater than 2 μm. In addition, the result of having evaluated the IV characteristic of the photoelectric conversion apparatus of Example 1A, Example 1B, and the comparative example 1 is shown in FIG.

  In the manufacturing method of the photoelectric conversion device of Example 1, the semiconductor layer precursor layer made of a ceramic green sheet is transferred to the first surface of the first current collector using a press device. And a semiconductor layer is formed on the first surface of the first current collector, and a part of the semiconductor layer in the thickness direction is penetrated into the through hole provided in the first current collector. The first substrate can face only the semiconductor layer, and the first surface of the first current collector can be covered with the semiconductor layer. Therefore, the area of the semiconductor layer that contributes to photoelectric conversion in the photoelectric conversion device can be increased without depending on the opening ratio or opening area of the first current collector. In addition, it is easy to control the formation position of the semiconductor layer in the first current collector, it is not necessary to use a transparent conductive layer, and the resistance of the first current collector can be reduced.

  In the photoelectric conversion device of Example 1, since the electrolyte layer is made of an insulating layer (specifically, a nonwoven fabric) impregnated with the electrolyte composition, the electrolyte layer is made of a conductive material having a large number of through holes. It is possible to reliably prevent a short circuit from occurring between the first current collector and the second current collector. In addition, by configuring the first base material and the second base material from the above-described materials, the photoelectric conversion device can be made thin and flexible, and the components of the photoelectric conversion device can be made resin. . Furthermore, the first laminated structure composed of the semiconductor layer / first current collector and the second laminated structure composed of the catalyst layer / second current collector can be obtained by firing at a relatively high firing temperature. Therefore, high performance can be achieved, and the current collection loss can be reduced by configuring the first current collector and the second current collector from the above-described materials, as described below. The so-called roll-to-roll processing can be applied.

  That is, as shown in a conceptual diagram in FIG. 24, the first laminated structure and the second laminated structure can be obtained by a so-called roll-to-roll processing method. Specifically, a surface treatment layer (not shown) made of titanium is continuously formed on a first current collector made of a roll-like wire netting material based on an ion plating method. On the other hand, using a die coater or the like, a slurry is applied on a support member made of a plastic film such as polyethylene terephthalate (PET) and dried to continuously produce green sheets. And a roll-shaped green sheet | seat is continuously mounted in a roll-shaped 1st electrical power collector, and a green sheet is pushed into a roll-shaped 1st electrical power collector using a roll press apparatus. Subsequently, the roll-shaped laminated body of the obtained green sheet and the 1st electrical power collector is baked in a continuous furnace. In this way, a first laminated structure composed of a semiconductor layer / first current collector in which the first current collector 51 and the semiconductor layer 31 are integrated in a roll shape can be obtained. Thereafter, the semiconductor layer 31 is impregnated with a dye based on a known method. Next, the roll-shaped first laminated structure is cut into a rectangular shape. On the other hand, after printing a carbon paste on the roll-shaped second current collector to form a catalyst layer precursor layer, the carbon paste is fired in a continuous furnace. In this way, a second laminated structure composed of the catalyst layer / second current collector in which the second current collector 61 and the catalyst layer 32 are integrated can be obtained. Then, the second laminated structure is cut into a rectangular shape. And a 1st base material, a 1st laminated structure, a 2nd laminated structure, and a 2nd base material are piled up, and a 1st base material and a 2nd base material are sealed in an outer edge part.

  The second embodiment is a modification of the first embodiment. In Example 1, the 2nd electrical power collector 61 was comprised from the electrically-conductive material provided with many through-holes. On the other hand, in the photoelectric conversion device 10B of Example 2, the second current collector 66 is made of a conductive material layer, as shown in FIG. Specifically, the second current collector 66 is made of a titanium foil. After the carbon paste is printed on the titanium foil, the carbon paste is fired in air based on conditions such as 450 ° C. and 0.5 hours. Under such firing conditions, the titanium foil is not significantly oxidized. In this way, a second laminated structure composed of the catalyst layer / second current collector in which the second current collector 66 and the catalyst layer 32 are integrated can be obtained. And what is necessary is just to manufacture and assemble the photoelectric conversion apparatus 10B of Example 2 by the method similar to having demonstrated in Example 1. FIG. The second current collector 66 may be patterned in a comb-tooth shape, for example, or may not be patterned at all.

  In some cases, the sheet-like catalyst layer 32 may be formed in advance, and the second current collector 66 may be formed on the surface of the catalyst layer 32 facing the second base material 22. Alternatively, the second current collector 66 may be formed on the surface of the second base material 22 facing the catalyst layer 32. That is, you may obtain the 2nd laminated structure which consists of a 2nd electrical power collector / a 2nd base material by forming a 2nd electrical power collector on a 2nd base material. In other words, the first laminated structure composed of the semiconductor layer / first current collector is obtained by firing the laminated body of the green sheet and the first current collector, while the second current collector is obtained on the second substrate. After obtaining a second laminated structure composed of the second current collector / second substrate by forming an electric body, the first substrate, the first laminated structure, the insulating layer, the catalyst layer, You may overlap a 2nd laminated structure and seal a 1st base material and a 2nd base material in an outer edge part. Alternatively, a sheet-like catalyst layer 32 is formed in advance, and a part of the second current collector 66 is formed on the surface of the catalyst layer 32 facing the second base material 22. A part of the second current collector 66 may also be formed on the surface of the second base material 22 facing the second base material 22. Alternatively, the sheet-like catalyst layer 32 and the sheet-like second current collector 66 may be formed in advance. In the following description, these forms are referred to as “variations of the second embodiment” for convenience.

  The third embodiment is also a modification of the first embodiment. A cross-sectional conceptual diagram before assembly is shown in FIG. 6A, and a schematic partial end view of the first current collector and the like is shown in FIG. The insulating layer 44 is composed of a titanium oxide layer impregnated with the electrolyte composition 42 described in Example 1, and corresponds to the electrolyte layer 41. The insulating layer 44 is formed on the second surface 51 b of the first current collector 51. Except for the above points, the photoelectric conversion device 10C of Example 3 has the same configuration and structure as the photoelectric conversion device 10A described in Example 1, and thus detailed description thereof is omitted.

  In the photoelectric conversion device 10C of Example 3, a so-called green sheet, which is a precursor of the semiconductor layer, is produced by the method described in Example 1, and the green sheet is placed on the first current collector 51 and pressed. The green sheet is partially pushed into the first current collector 51 in the thickness direction using an apparatus. At the same time, the insulating layer precursor layer made of titanium oxide is transferred to the second surface 51b of the first current collector 51 using a pressing device. Specifically, a second support member on which an insulating layer precursor layer made of titanium oxide is formed is prepared, and the insulating layer precursor layer formed on the second support member is prepared using a press device. Transfer to the second surface 51 b of the first current collector 51. Thus, a laminate composed of the green sheet / first current collector / insulating layer precursor layer can be formed. In addition, since the green sheet and the insulating layer precursor layer are formed on both surfaces of the first current collector, the structure is unlikely to warp. On the other hand, by printing a carbon paste on the second current collector 61, a laminate composed of a catalyst layer precursor layer made of carbon paste / a second current collector can be formed. Then, these laminates are laminated and fired in air under the conditions of 450 ° C. and 0.5 hours, and the semiconductor layer / first current collector / insulating layer / catalyst layer / second current collector A laminated structure is obtained. And what is necessary is just to assemble the photoelectric conversion apparatus 10C of Example 3 by the method similar to having demonstrated in Example 1. FIG. In Example 3, since the laminated structure of the semiconductor layer 31 / first current collector 51 / insulating layer 44 / catalyst layer 32 / second current collector 61 is obtained, handling becomes easy, and the photoelectric conversion device Assembling can be simplified.

  When the manufacturing method of the photoelectric conversion device 10C of Example 3 described above is summarized, a green sheet / first collector and an insulating layer precursor layer (insulating layer before firing) are laminated to form a green sheet / A laminated body composed of a first current collector / insulating layer precursor layer is formed, and a catalyst layer precursor layer / second current collector is formed by laminating a catalyst layer precursor layer and a second current collector. A laminate is formed. And after laminating | stacking and baking these laminated bodies and obtaining the laminated structure of a semiconductor layer / 1st electrical power collector / insulating layer / catalyst layer / 2nd electrical power collector, the 1st base material and this laminated structure The body and the second base material are overlapped, and the first base material and the second base material are sealed at the outer edge portion.

  The fourth embodiment is a modification of the third embodiment. In Example 3, the second current collector 61 was made of a conductive material provided with a large number of through holes. On the other hand, in the photoelectric conversion device 10D of Example 4, the second current collector 66 is formed of a conductive material layer, as shown in FIG. Specifically, in the fourth embodiment, the second current collector 66 is made of a titanium foil as in the second embodiment. Then, a carbon paste is printed on the titanium foil, whereby a laminate composed of the catalyst layer precursor layer / second current collector can be obtained. Then, a laminate composed of the green sheet / first current collector / insulating layer precursor layer and a laminate composed of the catalyst layer precursor layer / second current collector were laminated, as in Example 3, except that The firing is performed in air at 450 ° C. for 0.5 hour. Then, what is necessary is just to assemble photoelectric conversion apparatus 10D of Example 4 by the method similar to having demonstrated in Example 3. FIG. Note that a modification of the second embodiment can be applied to the third embodiment.

  When the manufacturing method of the photoelectric conversion device 10D of Example 4 described above is summarized, the green sheet, the first current collector, the insulating layer precursor layer, the catalyst layer precursor layer, and the second current collector are stacked. After forming a laminate composed of a green sheet / first current collector / insulating layer precursor layer / catalyst layer precursor layer / second current collector, and firing, a semiconductor layer / first current collector / insulating layer After obtaining the laminated structure of / catalyst layer / second current collector, the first base material, the laminated structure and the second base material are overlapped, and the first base material and the second base material are outer edge portions. Seal at.

  The fifth embodiment is also a modification of the first embodiment. 7A is a conceptual cross-sectional view before assembly of the photoelectric conversion device, and a conceptual diagram of an end surface is illustrated in FIG. 7B. In the photoelectric conversion device 10E of Example 5, the photoelectric conversion When the apparatus is assembled, an insulating layer 44 made of titanium oxide is provided on the surface of the catalyst layer 32 facing the first current collector 51. A space is provided between the insulating layer 44 and the first current collector 51. Except for these points, the photoelectric conversion device 10E of Example 5 has the same configuration and structure as the photoelectric conversion device 10A described in Example 1, and thus detailed description thereof is omitted.

  In the assembly of the photoelectric conversion device 10E according to the fifth embodiment, as in the first embodiment, the first current collector 51 and the first current collector made of the semiconductor current 31 and the semiconductor layer 31 are integrated. One laminated structure is obtained. On the other hand, by printing a carbon paste on one surface of the second current collector 61 and printing an insulating layer 44 on the carbon paste, an insulating layer precursor layer / catalyst layer precursor layer / second current collector is printed. A laminate composed of a body can be formed. Then, the catalyst layer precursor layer and the insulating layer precursor layer are fired in air under the conditions of 450 ° C. and 0.5 hours. In other words, by firing the laminate of the insulating layer precursor layer, the catalyst layer precursor layer, and the second current collector, the second current collector 61, the catalyst layer 32, and the insulating layer 44 are integrated with each other. A second laminated structure comprising layer / catalyst layer / second current collector can be obtained.

  In the assembly of the photoelectric conversion device 10E of Example 5, the first substrate 21, the first stacked structure, the second stacked structure, and the second substrate 22 are superposed, 1, the first base material 21 and the second base material 22 are sealed at the outer edge portion by the same method as described in FIG. Thus, the photoelectric conversion device 10E illustrated in FIG. 7B can be obtained. The space is filled with the electrolyte composition 42. In order to provide a space between the insulating layer 44 and the first current collector 51, a spacer (not shown) may be provided.

  When the manufacturing method of the photoelectric conversion device 10E of Example 5 described above is summarized, the first laminate composed of the semiconductor layer / first current collector is obtained by firing the laminate of the green sheet and the first current collector. While obtaining a structure, the laminated body of an insulating layer precursor layer, a catalyst layer precursor layer, and a second current collector is fired to obtain a second laminated structure comprising an insulating layer / catalyst layer / second current collector Get the body. And a 1st base material, a 1st laminated structure, a 2nd laminated structure, and a 2nd base material are piled up, and a 1st base material and a 2nd base material are sealed in an outer edge part.

  The sixth embodiment is a modification of the fifth embodiment. As shown in FIG. 8 which is a conceptual cross-sectional view before assembly, in Example 6, the electrolyte layer 41 includes an insulating layer 43 made of a nonwoven fabric (referred to as a “first insulating layer 43” for convenience), and It has a laminated structure of an insulating layer 44 made of titanium oxide (referred to as “second insulating layer 44” for convenience). The first insulating layer 43 is in contact with the first current collector 51, and the second insulating layer 44 is formed on the catalyst layer 32. Except for the above points, the photoelectric conversion device 10F of Example 6 has the same configuration and structure as the photoelectric conversion device 10E described in Example 5, and thus detailed description thereof is omitted. In Example 6, since the electrolyte layer 41 has a two-layer structure of the first insulating layer 43 and the second insulating layer 44, higher reliability can be achieved.

  The second current collector in Example 5 or Example 6 may be a second current collector 66 made of titanium foil in the same manner as in Example 2 instead of the conductive material provided with a large number of through holes. it can. For example, in Example 5, after printing a carbon paste on a titanium foil, the same as in Example 2, except that the firing conditions are 450 ° C. and 0.5 hours in air. And what is necessary is just to assemble the photoelectric conversion apparatus 10E by the method similar to having demonstrated in Example 5. FIG. Note that the modification of the second embodiment can be applied to the fifth or sixth embodiment.

  The seventh embodiment is also a modification of the first embodiment. 9A shows a conceptual cross-sectional view before assembly of the photoelectric conversion device, and FIG. 9B shows a conceptual diagram of the end face after assembly. When the photoelectric conversion device is assembled, the insulating layer 44 made of titanium oxide is provided on the surface (second surface 51b) of the first current collector 51 facing the catalyst layer 32. A space is provided between the insulating layer 44 and the catalyst layer 32. Except for these points, the photoelectric conversion device 10G of Example 7 has the same configuration and structure as the photoelectric conversion device 10A described in Example 1, and thus detailed description thereof is omitted.

  In assembling the photoelectric conversion device 10G of Example 7, a so-called green sheet, which is a precursor of the semiconductor layer, is produced by a known method, the green sheet is placed on the first current collector 51, and the press device is The green sheet is pushed into the first current collector 51 by using it. In addition, an insulating layer precursor for forming the insulating layer 44 is formed on the surface of the first current collector 51 facing the catalyst layer 32 in the same manner as in Example 3. Thus, a laminate of the green sheet, the first current collector 51, and the insulating layer precursor can be formed. Next, the green sheet and the insulating layer precursor layer are baked in air based on conditions such as 500 ° C. and 0.5 hours, whereby the semiconductor layer 31, the first current collector 51, and the insulating layer 44 are integrated. Thus, the first laminated structure composed of the semiconductor layer / first current collector / insulating layer can be obtained. In addition, since the semiconductor layer and the insulating layer are formed on both surfaces of the first current collector, the first laminated structure is unlikely to warp. On the other hand, by printing a carbon paste on one surface of the second current collector 61 and firing the carbon paste in the same manner as in Example 1, that is, the catalyst layer precursor layer and the second current collector By firing the laminated body, it is possible to obtain a second laminated structure composed of a catalyst layer / second current collector in which the second current collector 61 and the catalyst layer 32 are integrated. In some cases, the second current collector may be provided on the catalyst layer after firing the green sheet / first current collector / insulating layer precursor / catalyst layer precursor laminate.

  In the assembly of the photoelectric conversion device 10G according to the seventh embodiment, the first substrate 21, the first stacked structure, the second stacked structure, and the second substrate 22 are superposed. 1, the first base material 21 and the second base material 22 are sealed at the outer edge portion by the same method as described in FIG. Thus, the photoelectric conversion device 10G illustrated in FIG. 9B can be obtained. The space is filled with the electrolyte composition 42. In order to provide a space between the insulating layer 44 and the catalyst layer 32, a spacer (not shown) may be provided.

  When the manufacturing method of the photoelectric conversion device 10G of Example 7 described above is summarized, the stacked body of the green sheet, the first current collector, and the insulating layer precursor is baked, so that the semiconductor layer / first current collector is fired. / A first laminated structure comprising an insulating layer is obtained, while a laminated body of a catalyst layer precursor layer and a second current collector is fired to obtain a second laminated structure comprising a catalyst layer / second current collector. Get. And a 1st base material, a 1st laminated structure, a 2nd laminated structure, and a 2nd base material are piled up, and a 1st base material and a 2nd base material are sealed in an outer edge part.

  The eighth embodiment is a modification of the seventh embodiment. As shown in FIG. 10, a cross-sectional conceptual diagram before assembly is shown in FIG. 10. In Example 8, as in Example 6, the electrolyte layer 41 includes an insulating layer 43 (first insulating layer 43) made of nonwoven fabric, and , And a laminated structure of an insulating layer 44 (second insulating layer 44) made of titanium oxide. The second insulating layer 44 is formed on the surface (second surface 51 b) facing the catalyst layer 32 of the first current collector 51, and the first insulating layer 43 is in contact with the catalyst layer 32. An insulating layer precursor for forming the second insulating layer 44 is formed in the same manner as in Example 3. Except for the above points, the photoelectric conversion device 10H of the eighth embodiment has the same configuration and structure as the photoelectric conversion device 10G described in the seventh embodiment, and thus detailed description thereof is omitted. In Example 8, since the electrolyte layer 41 has a two-layer structure of the first insulating layer 43 and the second insulating layer 44, higher reliability can be achieved.

  The second current collector in Example 7 or Example 8 may be a second current collector 66 made of titanium foil in the same manner as in Example 2 instead of the conductive material provided with a large number of through holes. it can. For example, in Example 7, after printing the carbon paste on the titanium foil, the same as in Example 2, except that the firing conditions are 450 ° C. and 0.5 hours in air. Then, the photoelectric conversion device may be assembled by the same method as described in the seventh embodiment. Note that the modification of the second embodiment can be applied to the seventh or eighth embodiment.

  Example 9 relates to a photoelectric conversion device with a lead member of the present disclosure. A conceptual cross-sectional view of the photoelectric conversion device 10J of Example 9 before assembly is shown in FIG. 11A, and an end face conceptual diagram after assembly is shown in FIG. Further, a schematic plan view of the photoelectric conversion device of Example 9 and a schematic cross-sectional view along the arrow BB in FIG. 12A are respectively shown in FIGS. ), And a schematic plan view of the first current collector, the semiconductor layer, and the first lead member as viewed from the second base material side is shown in FIG. 13, and the second current collector, the catalyst layer, and the second lead are shown in FIG. FIG. 14 shows a schematic plan view of the member viewed from the first base material side. The photoelectric conversion device of Example 9 has substantially the same configuration and structure as those of the photoelectric conversion devices described in Examples 1 to 8 or their modifications except for the presence or absence of a lead member.

  The photoelectric conversion device 10J of Example 9 includes a lead member main body portion (first lead member main body portion 72) and a lead member extension portion (first lead member extension portion 73). A lead member (first lead member 71) for outputting the generated electric power. And the 1st lead member main-body part 72 is attached to the outer edge part of the 1st electrical power collector 51, and the 1st lead member extension part 73 protrudes the outer side of the photoelectric conversion apparatus 10J. Specifically, the first current collector 51 includes a first current collector main body 52 and a first current collector extending portion 53 extending from the first current collector main body 52. The first lead member main body 72 is attached to the first current collector extension 53 based on a welding method. The planar shape of the first current collector 51 is rectangular, and the first side 51A and the third side 51C extending along the first direction and the second direction orthogonal to the first direction. It has the 2nd edge | side 51B and 4th edge | side 51D which extend, and the 1st collector extension part 53 is located along 51 A of 1st edge | sides.

  Further, the photoelectric conversion device 10J of Example 9 is composed of a second lead member main body portion 82 and a second lead member extending portion 83, is made of a conductive material piece, and is a second lead member for outputting generated power. 81, the second lead member main body 82 is attached to the outer edge of the second current collector 61, and the second lead member extending portion 83 protrudes outside the photoelectric conversion device 10J. Specifically, the second current collector 61 includes a second current collector main body 62 and a second current collector extending portion 63 extending from the second current collector main body 62. The second lead member main body portion 82 is attached to the second current collector extending portion 63 based on a welding method. The planar shape of the second current collector 61 is a rectangle, and extends along the first side 61A and the third side 61C extending along the first direction, and the second direction orthogonal to the first direction. The second current collector extending portion 63 has a second side 61B and a fourth side 61D that extend, and is positioned along the third side 61C.

  Each of the first side 61A, the second side 61B, the third side 61C, and the fourth side 61D of the second current collector 61 is the first side 51A of the first current collector 51, the second side 61D. This corresponds to the second side 51B, the third side 51C, and the fourth side 51D. In addition, the projected image of the first lead member 71 does not overlap the projected image of the second lead member 81. In addition, the first current collector main body 52 and the second current collector main body 62 overlap, but the first current collector extension 53 and the second current collector extension 63 do not overlap. Moreover, the first lead member extending portion 73 and the second lead member extending portion 83 protrude outward from the same side of the photoelectric conversion device 10J. By adopting such a structure, the first lead member extending portion 73 and the second lead member extending portion 83 are not short-circuited, and the handling of wiring or the like is easy or simplified.

  Here, the conductive material pieces constituting the first lead member 71 and the second lead member 81 are specifically made of a thin plate of titanium (Ti).

  And in the part by which the 1st base material 21 and the 2nd base material 22 are sealed, between the 1st base material 21 and the 1st lead member 71, and the 2nd base material 22 and the 1st lead member An adhesive layer 54 is disposed between the two and 71. Similarly, in the portion where the first base material 21 and the second base material 22 are sealed, between the first base material 21 and the second lead member 81 and between the second base material 22 and the second lead. An adhesive layer 64 is disposed between the member 81. Here, the material constituting the adhesive layers 54 and 64 is made of, for example, a polyolefin adhesive resin such as Modic [registered trademark] manufactured by Mitsubishi Chemical Corporation. And thereby, the reliability of a photoelectric conversion apparatus can be improved further.

  In the manufacture of the photoelectric conversion device 10J of Example 9, for example, in the same manner as in Example 1, the first current collector 51 (more specifically, the first current collector body 52, And the first laminated structure composed of the semiconductor layer / first current collector in which the semiconductor layer 31 is integrated. Then, before or after obtaining the first laminated structure including the semiconductor layer / first current collector, the first lead member main body portion 72 is used as the first current collector extending portion 53 to obtain the above-described method. Install based on. In the photoelectric conversion device 10J according to the ninth embodiment, for example, in the same manner as in the first embodiment, the second current collector 61 (more specifically, the second current collector main body 62 is described below). And the like, and a second laminated structure composed of a catalyst layer / second current collector integrated with the catalyst layer 32 can be obtained. Then, before or after obtaining the second laminated structure composed of the catalyst layer / second current collector, or after obtaining the second lead member main body portion 82 as the second current collector extending portion 63, the method described above. Install based on.

  In the assembly of the photoelectric conversion device 10J of Example 9, the first base material 21, the first laminated structure composed of the semiconductor layer / first current collector, the insulating layer 43 composed of the nonwoven fabric, the catalyst The second laminated structure composed of the layer / second current collector and the second base material 22 are overlapped with each other so that the first lead member extending portion 73 protrudes outward, and the second lead member extending portion 83 is formed. Is also projected outward. The adhesive layers 54 and 64 are arranged as described above. And the 1st base material 21 and the 2nd base material 22 are sealed (bonded together) with the sealing material 23 which consists of a heat-fusion film in the three sides of those outer edge parts. Thereafter, the nonwoven fabric and the semiconductor layer 31 are impregnated with the electrolyte composition 42 from the remaining one side that is open. Next, the remaining one side is sealed with the sealing material 23 under reduced pressure. Thus, the photoelectric conversion device 10J illustrated in FIG. 11B can be obtained. The same applies to Example 10 to Example 13 described below.

  In the manufacturing method of the photoelectric conversion device 10J of Example 9 described above, except for the attachment of the first lead member, the second lead member to the first current collector extension portion, and the second current collector extension portion, It can be the same as that of the summary of the manufacturing method of the photoelectric conversion apparatus of Example 1- Example 8.

  In the photoelectric conversion device of Example 9, the first current collector is made of a conductive material provided with a large number of through holes, the first lead member is made of a conductive material piece, and the first current collector is formed on the outer edge portion of the first current collector. Since the lead member main body is attached and the first lead member extending portion protrudes outside the photoelectric conversion device, a part of the first lead member is removed from the mesh-shaped first current collector in contact with the semiconductor layer. Appropriately and reliably output to the outside. The second current collector is also made of a conductive material provided with a large number of through holes, the second lead member is made of a conductive material piece, and the second lead member main body is attached to the outer edge of the second current collector. Since the second lead member extending portion protrudes outside the photoelectric conversion device, a part of the second lead member can be appropriately and reliably taken out from the mesh-like second current collector. Can do. As a result, high reliability can be imparted to the photoelectric conversion device.

  The tenth embodiment is a modification of the ninth embodiment. In the photoelectric conversion device 10K according to the tenth embodiment, as shown in a schematic end view of FIG. 15A, the first lead member main body 72 is an upper surface of the first current collector extension 53. And attached to the lower surface of the first current collector extension portion 53. The “upper surface” refers to the surface (first surface 51a) facing the first base material, and the “lower surface” refers to the surface (second surface 51b) facing the second base material. Specifically, the first lead member 71 is composed of two conductive material pieces 71A and 71B, and the first lead member extending portion 73 is formed by welding these two conductive material pieces 71A and 71B, for example, by welding. It is constituted by being integrated. On the other hand, in the first lead member main body 72, in the state where the first current collector extension portion 53 is sandwiched between the two conductive material pieces 71A and 71B, the two conductive material pieces 71A and 71B are The first current collector extension 53 is attached.

  The second lead member main body 82 is attached to the upper surface of the second current collector extending portion 63 and the lower surface of the second current collector extending portion 63. Specifically, the second lead member 81 is composed of two conductive material pieces 81A and 81B, and the second lead member extending portion 83 is formed by, for example, welding these two conductive material pieces 81A and 81B. It is constituted by being integrated. On the other hand, in the second lead member main body portion 82, these two conductive material pieces 81 </ b> A and 81 </ b> B are in a state where the second current collector extending portion 63 is sandwiched between these two conductive material pieces 81 </ b> A and 81 </ b> B. It is attached to the second current collector extension part 63.

  Alternatively, a schematic end view is shown in FIG. 15B, and a schematic plan view when the first lead member 71 is developed is shown in FIG. Is composed of a first lead member main body portion 72 having a large width and a first lead member extending portion 73 having a small width, and the first lead member main body portion 72 is a first lead member 51 of the first current collector 51. A wide first lead member main body 72 is bent and attached to the first current collector extending portion 53 so as to cover the side 51A and the upper and lower surfaces of the first current collector extending portion 53. Yes.

  Alternatively, as shown in FIG. 15D, a schematic plan view when the second lead member 81 is expanded is shown. The second lead member 81 includes a wide second lead member main body 82 and a width. The second lead member extending portion 83 is narrow, and the second lead member main body portion 82 includes the third side 61C of the second current collector 61 and the second current collector extending portion 63. A wide second lead member main body portion 82 is bent and attached to the second current collector extending portion 63 so as to cover the upper surface and the lower surface.

  By adopting the configuration and structure as described above, the first lead member main body 72 is attached to the first current collector extending portion 53 and the second lead member main body is attached to the second current collector extending portion 63. The part 82 can be attached more reliably.

  Except for the above points, the photoelectric conversion device of Example 10 can have the same configuration and structure as the photoelectric conversion device described in Example 9, and thus detailed description thereof is omitted.

  Example 11 is a modification of Example 9 or Example 10. 16 and 17, for example, in the photoelectric conversion device 10L of Example 11 in which the photoelectric conversion device of Example 9 is modified, the second of the first current collector 51 is shown. The side 51 </ b> B and the fourth side 51 </ b> D are covered with a coating layer 55 made of polyophine-based adhesive resin (specifically, Modic [registered trademark] manufactured by Mitsubishi Chemical Corporation). The second side 61 </ b> B and the fourth side 61 </ b> D of the two current collectors 61 are covered with a coating layer 65 similar to the coating layer 55. As a result, the occurrence of a short circuit between the first current collector 51 and the second current collector 61 can be reliably prevented. The covering layers 55 and 65 are formed on the second sides 51B and 61B and the fourth sides 51D and 61D based on an arbitrary method such as a dipping method in which the above materials are immersed, a printing method, or a method using a dispenser. can do. In some cases, the third side 51C of the first current collector 51 and the first side 61A of the second current collector 61 may be covered with the covering layers 55 and 65. In order to clearly show the coating layers 55 and 65, the coating layers 55 and 65 are hatched.

  Further, in some cases, as shown in FIGS. 18 and 19, schematic plan views, the covering layer 55 further covers the first current collector extension portion 53 and the first lead member main body portion 72. The covering layer 65 may further cover the second current collector extending portion 63 and the second lead member main body portion 82. And thereby, the reliability of a photoelectric conversion apparatus can be improved further.

  Except for the above points, the photoelectric conversion device of Example 11 can have the same configuration and structure as the photoelectric conversion device described in Example 9 or Example 10, and thus detailed description thereof is omitted.

  The twelfth embodiment is a modification of the ninth to eleventh embodiments. For example, in the photoelectric conversion device 10M according to the twelfth embodiment, which is a modification of the photoelectric conversion device according to the ninth embodiment, a schematic plan view of the second side 51B of the first current collector 51 is shown in FIG. The portion where the third side 51C intersects and the portion where the fourth side 51D and the third side 51C intersect are chamfered. Specifically, a portion where the second side 51B and the third side 51C of the first current collector 51 intersect and a portion where the fourth side 51D and the third side 51C intersect are cut out. Similarly, as shown in FIG. 21, a schematic plan view of the second current collector 61 where the second side 61B and the first side 61A intersect and the fourth side 61D and the first side 61A. The intersecting part is chamfered. Specifically, a portion where the second side 61B and the first side 61A of the second current collector 61 intersect and a portion where the fourth side 61D and the first side 61A intersect are cut out. This also makes it possible to further improve the reliability of the photoelectric conversion device.

  Except for the above points, the photoelectric conversion device of Example 12 can have the same configuration and structure as those of the photoelectric conversion devices described in Examples 9 to 11, and thus detailed description thereof is omitted.

  The thirteenth embodiment is a modification of the ninth to twelfth embodiments. As shown in FIGS. 22 (A) and 22 (B), a sectional conceptual diagram before assembly of the photoelectric conversion device 10N of the thirteenth embodiment and an end surface conceptual diagram after the assembly are shown in FIGS. A heat seal layer 24 is provided on the substrate 21. Specifically, a heat seal layer 24 made of a polypropylene (CPP) film biaxially stretched is laminated on the first base material 21. And the outer edge part of the 1st base material 21 and the 2nd base material 22 is sealed with the heat seal layer 24. FIG. In addition, by adhering the semiconductor layer 31 to the first base material 21 via the heat seal layer 24, no gap is generated between the semiconductor layer 31 and the first base material 21. It is possible to prevent the electrolyte composition from entering between the base material 21 and the occurrence of incident light loss and undesired absorption of incident light.

  Except for the above points, the photoelectric conversion device of Example 13 can have the same configuration and structure as those of the photoelectric conversion devices described in Examples 9 to 12, and thus detailed description thereof is omitted. Moreover, the heat seal layer 24 can be applied to the photoelectric conversion devices described in the first to eighth embodiments or the modifications thereof.

  Although the photoelectric conversion device and the manufacturing method thereof according to the present disclosure have been described based on the preferred embodiments, the present disclosure is not limited to these embodiments. The configuration, structure, used materials and specifications, manufacturing method, and the like of the photoelectric conversion device described in the embodiments are examples, and can be appropriately selected and changed.

  For example, in the ninth to thirteenth embodiments, the first lead member is arranged exclusively on the lower surface (second surface 51b) of the first current collector, but the upper surface (first surface 51a) of the first current collector. ). Further, although the second lead member is disposed exclusively on the upper surface of the second current collector, it may be disposed on the lower surface of the second current collector. Further, for example, as shown in a cross-sectional conceptual diagram of the photoelectric conversion device modification 10J ′ of the ninth embodiment before assembly in FIG. 23A, a lead member main body ( A first lead member main body portion 72 may be attached. In the example shown in FIG. 23A, the lead member main body (first lead member main body) 72 is covered with the semiconductor layer 31. Alternatively, as shown in a cross-sectional conceptual diagram of the photoelectric conversion device modification 10J ″ of the ninth embodiment before assembly in FIG. 23B, the second lead member main body portion is formed on the outer edge portion of the second current collector 61. 23, the second lead member body 82 is covered with the catalyst layer 32. Furthermore, the photoelectric conversion device of Example 9 is also possible. It goes without saying that the modified example 10J ′ and the modified example 10J ″ can be combined.

10A, 10B, 10C, 10D, 10E, 10F, 10G, 10H, 10J, 10J ', 10J ", 10K, 10L, 10M, 10N ... photoelectric conversion device, 21 ... first base material, 22 ... -2nd base material, 23 ... sealing material, 31 ... semiconductor layer, 31a ... surface of semiconductor layer, 32 ... catalyst layer, 41 ... electrolyte layer, 42 ... electrolyte composition , 43, 44 ... insulating layer, 51 ... first current collector, 51a ... first surface of the first current collector, 51b ... second surface of the first current collector, 51c ... a through-hole provided in the first current collector, 51A ... first side of the first current collector, 51B ... second side of the first current collector, 51C ... first 3rd side of 1 current collector, 51D ... 4th side of 1st current collector, 52 ... 1st current collector body part, 53 ... 1st current collector extension part, 54, 64 .... Adhesive layer, 55, 65 ... Cover layer, 61, 66 ... Second current collector, 61A ... Second side of second current collector, 61B ... Second current collector The second side of the body, 61C ... the third side of the second current collector, 61D ... the fourth side of the second current collector, 62 ... the second current collector main body, 63 2nd current collector extension part, 71 ... 1st current collector, 71A, 71B, 81A, 81B ... Conductive material piece, 72 ... 1st current collector body part, 73 ..First current collector extension part, 81... Second current collector, 82... Second current collector body part, 83.

Claims (14)

(A) 1st base material and 2nd base material,
(B) Between the first base material and the second base material, provided sequentially from the first base material side, facing the semiconductor layer, the first surface facing the first base material, and the second base material. A first current collector having a second surface, an electrolyte layer, a catalyst layer, and a second current collector,
The first base material and the second base material are sealed at the outer edge portion,
The first current collector is a method for manufacturing a photoelectric conversion device made of a conductive material provided with a large number of through holes,
A photoelectric conversion device for obtaining a semiconductor layer by transferring a semiconductor layer precursor layer made of a ceramic green sheet to a first surface of a first current collector using a pressing device and then firing the semiconductor layer precursor layer. Production method. (A) 1st base material and 2nd base material,
(B) Between the first base material and the second base material, provided sequentially from the first base material side, facing the semiconductor layer, the first surface facing the first base material, and the second base material. A first current collector having a second surface, an electrolyte layer, a catalyst layer, and a second current collector,
The first base material and the second base material are sealed at the outer edge portion,
The first current collector is a method for manufacturing a photoelectric conversion device made of a conductive material provided with a large number of through holes,
A method for manufacturing a photoelectric conversion device, wherein a semiconductor layer is formed on a first surface of a first current collector, and a part of the semiconductor layer in a thickness direction is inserted into a through hole provided in the first current collector.   The step of forming a semiconductor layer on the first surface of the first current collector and causing a part of the thickness of the semiconductor layer to enter the through-hole provided in the first current collector is a ceramic green sheet. 3. The semiconductor layer precursor layer comprising: transferring the semiconductor layer precursor layer to the first surface of the first current collector using a pressing device; and thereafter firing the semiconductor layer precursor layer to obtain the semiconductor layer. Method for manufacturing a photoelectric conversion device.   The method for manufacturing a photoelectric conversion device according to any one of claims 1 to 3, wherein an insulating layer is formed on the second surface of the first current collector.   5. The photoelectric conversion device according to claim 4, wherein the insulating layer precursor layer is transferred to the second surface of the first current collector using a pressing device, and then the insulating layer precursor layer is baked to obtain the insulating layer. Production method.   The method for manufacturing a photoelectric conversion device according to claim 1, wherein the semiconductor layer is made of titanium oxide. (A) 1st base material and 2nd base material,
(B) Between the first base material and the second base material, provided sequentially from the first base material side, facing the semiconductor layer, the first surface facing the first base material, and the second base material. A first current collector having a second surface, an electrolyte layer, a catalyst layer, and a second current collector,
The first base material and the second base material are sealed at the outer edge portion,
The first current collector is made of a conductive material provided with a large number of through holes,
A photoelectric conversion device in which a part of the semiconductor layer formed on the first surface of the first current collector in the thickness direction enters a through-hole provided in the first current collector.   The photoelectric conversion device according to claim 7, wherein a part of the thickness direction of the semiconductor layer does not reach the second surface of the first current collector. The average thickness of the first current collector is t ₁ ,
When the average penetration depth in the thickness direction of a part of the semiconductor layer that has penetrated into the through-hole provided in the first current collector is s ₁ ,
0 <s ₁ / t ₁ ≦ 1
The photoelectric conversion device according to claim 8 satisfying 0.2 ≦ s ₁ / t ₁ ≦ 1
The photoelectric conversion device according to claim 9, wherein:   11. The photoelectric conversion device according to claim 7, wherein the surface roughness Ra of the surface of the semiconductor layer facing the first base material is 2 μm or less.   The photoelectric conversion device according to claim 7, wherein an insulating layer is formed on the second surface of the first current collector.   The photoelectric conversion device according to claim 12, wherein the insulating layer comprises an electrolyte layer, and the insulating layer is impregnated with an electrolyte composition.   The photoelectric conversion device according to claim 7, wherein the semiconductor layer is made of titanium oxide.