JP2012174382A - Photoelectric conversion device and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion device having such configuration and structure as power can be led out appropriately from a mesh-like electrode in contact with a semiconductor layer.SOLUTION: The photoelectric conversion device 10A comprises a first substrate 21 and a second substrate 22, and a semiconductor layer 31, a first collector 51, an electrolyte layer 41, a catalyst layer 32, and a second collector 61 provided sequentially from the first substrate side between the first substrate 21 and the second substrate 22 which are sealed at the outer edge. The first collector 51 is composed of a conductive material provided with many through holes, and consists of a lead member body 52 and a lead member extension. A lead member consisting of a conductive material piece and outputting generated power is also provided. A lead member body 62 is attached to the outer edge of the first collector 51, and the lead member extension projects to the outside of the photoelectric conversion device 10A.

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.

  For example, JP-A-2009-245750 and JP-A-2005-196982 disclose a dye-sensitized solar cell for solving such a problem.

  A dye-sensitized solar cell disclosed in Japanese Patent Application Laid-Open No. 2009-245750 includes a transparent substrate, a porous semiconductor layer that adsorbs 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. There is an electrolyte between the layer and the conductive substrate.

  Further, a dye-sensitized solar cell disclosed in Japanese Patent Application Laid-Open No. 2005-196982 includes a translucent substrate 1, a substrate 2 disposed opposite to the translucent substrate 1, and the translucent substrate 1 and the substrate 2. Between the semiconductor electrode 3 having a sensitizing dye, the catalyst electrode 4 provided on the surface of the substrate 2, and at least a part of the semiconductor electrode 3, disposed on the side of the transparent substrate 1 between A semiconductor layer 31 having a sensitizing dye provided on at least a part of the surface of the metal linear body 61, comprising an electrolyte 5 filled at least between the semiconductor electrode 3 and the catalyst electrode 4. And at least one of the semiconductor layers 32 having a sensitizing dye provided on at least a part of the surface of the metal network 71.

JP2009-245750 JP 2005-196982 A

  In these patent publications, the electrode in contact with the semiconductor layer (porous semiconductor layer or semiconductor electrode) is composed of a conductive metal layer in which a large number of deep through holes are formed (Japanese Patent Laid-Open No. 2009-245750), or It is comprised from the metal linear body 61 and the metal net-like body 71 (Unexamined-Japanese-Patent No. 2005-196982). In addition, the electrode which contact | connects the semiconductor layer disclosed by these patent publication gazettes is called a mesh electrode for convenience. By the way, if the mesh electrode is pulled out of the dye-sensitized solar cell as it is, connection to an external circuit is often difficult. However, these patent publications do not mention an optimum means for extracting electric power from the mesh electrode to the outside of the dye-sensitized solar cell.

  Therefore, an object of the present disclosure is to provide a photoelectric conversion device having a configuration and a structure that can appropriately draw electric power from a mesh electrode in contact with a semiconductor layer to the outside, and a manufacturing method thereof.

The photoelectric conversion device according to the first aspect of the present disclosure for achieving the above object is as follows.
A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
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,
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) protrudes outside the photoelectric conversion device.

The photoelectric conversion device according to the second aspect of the present disclosure for achieving the above object is as follows:
A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
The first base material and the second base material are sealed at the outer edge portion,
The second current collector is made of a conductive material provided with a large number of through holes,
A conductive material piece composed of a lead member main body (hereinafter referred to as “second lead member main body” for convenience) and a lead member extension (hereinafter referred to as “second lead member extension” for convenience). And a lead member (hereinafter referred to as “second lead member” for convenience) for outputting the generated power.
A lead member main body (second lead member main body) is attached to the outer edge of the second current collector,
The lead member extending portion (second lead member extending portion) protrudes outside the photoelectric conversion device.

A method for manufacturing a photoelectric conversion device according to the first aspect of the present disclosure for achieving the above object is as follows.
A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
With
A lead member (first lead member) that is composed of a lead member main body (first lead member main body) and a lead member extending portion (first lead member extending portion), is composed of a conductive material piece, and outputs generated power. A lead member),
The first current collector is made of a conductive material provided with a large number of through holes,
While obtaining a photoelectric conversion device assembly in which the lead member main body (first lead member main body) is attached to the outer edge of the first current collector,
The first base material provided with the heat seal layer and the second base material are bonded to one side of the first base material and one side of the second base material,
The first base material and the second base material are folded so that the photoelectric conversion device assembly is sandwiched therebetween and the lead member extending portion (first lead member extending portion) protrudes outward, and the first base The outer edge part of a material and a 2nd base material is sealed with a heat seal layer.

A method for manufacturing a photoelectric conversion device according to the second aspect of the present disclosure for achieving the above object is as follows:
A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
With
A lead member (first lead member) that is composed of a lead member main body (first lead member main body) and a lead member extending portion (first lead member extending portion), is composed of a conductive material piece, and outputs generated power. A lead member),
The first current collector is made of a conductive material provided with a large number of through holes,
While obtaining a photoelectric conversion device assembly in which the lead member main body (first lead member main body) is attached to the outer edge of the first current collector,
It is the 1st base material provided with the heat seal layer, and the 2nd base material, Comprising: The 1st base material and the 2nd base material are provided continuously, and light is given to the semiconductor layer in the 1st base material. A window portion is provided for incidence, and the window portion is provided with a first base material and a second base material that are closed by a transparent plastic film or plastic sheet,
The photoelectric conversion device assembly is sandwiched therebetween, the lead member extending portion (first lead member extending portion) protrudes outside, and the first base material and the semiconductor layer are positioned below the window portion. The second base material is folded, and the outer edges of the first base material and the second base material are sealed with a heat seal layer.

  In the photoelectric conversion device according to the first aspect of the present disclosure, the first current collector is made of a conductive material provided with a plurality of through holes, the first lead member is made of a conductive material piece, and the first current collector Since the first lead member main body is attached to the outer edge and the first lead member extending portion protrudes outside the photoelectric conversion device, the first lead from the mesh-shaped first current collector in contact with the semiconductor layer. A part of the member can be appropriately and reliably exposed to the outside, and high reliability can be imparted to the photoelectric conversion device. Moreover, it is not necessary to use a transparent conductive layer, and the resistance of the first current collector can be reduced. In the method for manufacturing a photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, in addition to the effects exhibited by the photoelectric conversion device according to the first aspect of the present disclosure, 2 The base material is integrated in advance, or alternatively, it is produced in a continuous manner, the photoelectric conversion device assembly is sandwiched therebetween, and the lead member extending portion (first lead member extending portion) is The first base material and the second base material are folded so as to protrude outward, and the outer edge portion of the first base material and the second base material is sealed with a heat seal layer, so that photoelectric conversion is performed with a simple process. The device can be manufactured. Further, in the photoelectric conversion device according to the second aspect of the present disclosure, the second current collector is made of a conductive material provided with a plurality of through holes, the second lead member is made of a conductive material piece, and the second current collector The second lead member main body is attached to the outer edge of the body, and the second lead member extending portion protrudes to the outside of the photoelectric conversion device, so that the second lead member extends from the mesh-like second current collector. A part can be appropriately and reliably exposed to the outside, and high reliability can be imparted to the photoelectric conversion device.

1A and 1B are a schematic cross-sectional view before assembly of the photoelectric conversion device of Example 1 and a schematic end view after assembly, respectively. FIGS. 2A and 2B are a schematic plan view of the photoelectric conversion device of Example 1 and a schematic cross-sectional view taken along arrow BB in FIG. is there. FIG. 3 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 1 as viewed from the second base material side. FIG. 4 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 1 as viewed from the first base material side. FIG. 5A is a schematic end view of the photoelectric conversion device of Example 2, and FIGS. 5B and 5C are schematic views of a modification of the photoelectric conversion device of Example 2. FIG. FIG. 5D is an end view and a schematic plan view when the first lead member is developed. FIG. 5D is a diagram illustrating the second lead member in another modification of the photoelectric conversion device according to the second embodiment. It is a typical top view at the time. FIG. 6 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 3 as viewed from the second base material side. FIG. 7 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 3 as viewed from the first base material side. FIG. 8 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 3 as viewed from the second base material side. FIG. 9 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 3 as viewed from the first base material side. FIG. 10 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 4 as viewed from the second base material side. FIG. 11 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 4 as viewed from the first base material side. FIGS. 12A and 12B are a schematic cross-sectional view before assembly of the photoelectric conversion device of Example 5 and a schematic end view after assembly, respectively. FIGS. 13A and 13B are schematic cross-sectional views of the first base material and the like for explaining the method of manufacturing the photoelectric conversion device of Example 6. FIG. FIG. 14 is a schematic end view of the first base material and the like for explaining the manufacturing method of the photoelectric conversion device of Example 6 following FIG. FIGS. 15A and 15B are schematic cross-sectional views of the first base material and the like for explaining the photoelectric conversion device of Example 7 and the method for manufacturing the modification, respectively. FIG. 16 is a schematic cross-sectional view of the photoelectric conversion device according to the eighth embodiment before assembly. 17A and 17B are schematic cross-sectional views before assembly of the photoelectric conversion devices of Example 9 and Example 10, respectively. 18A and 18B are a schematic cross-sectional view before assembly of the photoelectric conversion device of Example 11 and a schematic end view after assembly, respectively. FIG. 19 is a schematic cross-sectional view of the photoelectric conversion device of Example 12 before assembly. 20A and 20B are a schematic cross-sectional view before assembly of the photoelectric conversion device of Example 13 and a schematic end view after assembly, respectively. FIG. 21 is a schematic cross-sectional view of the photoelectric conversion device according to Example 14 before assembly. 22A and 22B are schematic cross-sectional views before assembly of a modification of the photoelectric conversion device of Example 1. FIG. FIG. 23 is a roll-to-roll processing method for obtaining a first laminated structure composed of a semiconductor layer / first current collector in which a first current collector and a semiconductor layer are integrated in a roll shape in Example 6. 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 the photoelectric conversion device according to the first and second aspects of the present disclosure, and the method for manufacturing the photoelectric conversion device according to the first and second aspects of the present disclosure. Example 1 (photoelectric conversion device according to first and second aspects of the present disclosure)
3. Example 2 (Modification of Example 1)
4). Example 3 (Modification of Example 1 to Example 2)
5. Example 4 (Modification of Examples 1 to 3)
6). Example 5 (Modification of Examples 1 to 4)
7). Example 6 (Method for Manufacturing Photoelectric Conversion Device According to First Aspect of Present Disclosure)
8). Example 7 (Method for Manufacturing Photoelectric Conversion Device According to Second Embodiment of Present Disclosure)
9. Example 8 (modification of photoelectric conversion device in Examples 1 to 7)
10. Example 9 (modification of photoelectric conversion device in Examples 1 to 7)
11. Example 10 (Modification of photoelectric conversion device in Examples 1 to 7)
12 Example 11 (Modification of photoelectric conversion device in Examples 1 to 7)
13. Example 12 (Modification of photoelectric conversion device in Examples 1 to 7)
14 Example 13 (Modification of photoelectric conversion device in Examples 1 to 7)
15. Example 14 (modification of photoelectric conversion device in Examples 1 to 7), others

[Photoelectric Conversion Device According to First and Second Aspects of Present Disclosure, and Manufacturing Method of Photoelectric Conversion Device According to First and Second Aspects of Disclosure, General Description]
In the photoelectric conversion device according to the first aspect of the present disclosure,
The first current collector is composed of a first current collector body portion and a first current collector extension portion extending from the first current collector body portion,
The lead member main body (first lead member main body) can be configured to be attached to the first current collector extension.

On the other hand, in the photoelectric conversion device according to the second aspect of the present disclosure, the photoelectric conversion device according to the first aspect of the present disclosure including the preferred embodiment described above, the first aspect or the second aspect of the present disclosure. In the manufacturing method of such a photoelectric conversion device,
The second current collector is composed of a second current collector body portion and a second current collector extension portion extending from the second current collector body portion,
Lead member main body in the photoelectric conversion device according to the second aspect of the present disclosure (the photoelectric conversion device according to the first aspect of the present disclosure, the first in the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, 2 lead member main-body part) can be made into the form attached to the 2nd collector extension part.

  In the photoelectric conversion device according to the first aspect of the present disclosure including the preferred mode described above and the method for manufacturing the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, the lead member main body (first lead member) The main body part) can be configured to be attached to the upper surface of the first current collector extending portion and the lower surface of the first current collector extending portion, whereby the first current collector extending The lead member main body (first lead member main body) can be more reliably attached to the portion, and the contact resistance can be reduced.

  On the other hand, the photoelectric conversion device according to the second aspect of the present disclosure, the photoelectric conversion device according to the first aspect of the present disclosure including the above-described preferred embodiments, the first aspect or the second aspect of the present disclosure In the method for manufacturing a photoelectric conversion device, the lead member main body in the photoelectric conversion device according to the second aspect (the photoelectric conversion device according to the first aspect of the present disclosure, the first aspect of the present disclosure, or the second aspect) The second lead member main body portion in the photoelectric conversion device can be configured to 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 lead member main body (second lead member main body) can be more reliably attached to the second current collector extending portion, and the contact resistance can be reduced.

  In addition, in the photoelectric conversion device according to the first aspect of the present disclosure including the above-described preferable form, and the method for manufacturing the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, the plane of the first current collector The shape is rectangular, the first side and the third side extending along the first direction, and the second side and the fourth side extending along the second direction orthogonal to the first direction The first current collector extending portion can be configured to be located along the first 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 lead member main body portion (first lead member main body portion). Generation and 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. 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, in the preferable configuration described above, a portion where the second side and the third side of the first current collector intersect and a portion where the fourth side and the third side intersect are chamfered. This can also prevent the occurrence of a short circuit between the first current collector and the second current collector, thereby further improving the reliability of the photoelectric conversion device.

  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 to 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.

  In the photoelectric conversion device according to the first aspect of the present disclosure including the preferred embodiment and configuration described above, and the method for manufacturing the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, In the portion where the base material and the second base material are sealed, between the first base material and the lead member (first lead member), and the second base material and the lead member (first lead member) An adhesive layer can be provided between them, whereby the reliability of the photoelectric conversion device can be further improved. 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]).

  Further, in the photoelectric conversion device according to the first aspect of the present disclosure including the preferable mode and configuration described above, the method for manufacturing the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, The current collector is made of a conductive material provided with a large number of through-holes; is composed of a second lead member main body portion and a second lead member extending portion, and is made of a conductive material piece for outputting generated power. A second lead member; a second lead member main body attached to an outer edge of the second current collector; and a second lead member extending portion protruding outside the photoelectric conversion device; can do. And in such a form, in the photoelectric conversion device according to the second aspect of the present disclosure including the preferred form and configuration described above, the planar shape of the second current collector is rectangular. The first side and the third side extending along the first direction, and the second side and the fourth side extending along the second direction orthogonal to the first direction. The second current collector extending portion may be positioned along the third side. 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 may further be configured to cover the second current collector extension portion and the lead member main body portion (second lead member main body portion), thereby, the photoelectric conversion device. Reliability can be further improved. 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. This also makes it 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 lead member (second lead member), and 2 It can be set as the form by which the adhesive bond layer is distribute | arranged between the base material and the lead member (2nd lead member). Here, the material which comprises a coating layer or an adhesive bond layer is as having mentioned above.

Furthermore, in the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure including the preferable form and configuration described above, the first base material is provided with a heat seal layer. Can do. In some cases, the second base material may also be provided with a heat seal layer. And in the photoelectric conversion apparatus which concerns on the 1st aspect or 2nd aspect of this indication containing the preferable form demonstrated above, including such a form, the 2nd base material is a structure which consists of metal foil laminate materials It can be. Alternatively, in the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure including the preferred form and configuration described above, at least the first base material is provided with a heat seal layer (that is, The first base material is provided with a heat seal layer, or alternatively, the first base material and the second base material are provided with a heat seal layer); the first base material and the second base material are continuous. The first base member is provided with a window part for allowing light to enter the semiconductor layer; the window part is a transparent plastic film or plastic sheet (hereinafter referred to as “window part closing member”). It may be a closed structure. 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.

  Furthermore, the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure including the preferred embodiment and configuration described above, and the manufacture of the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure. In the method, the electrolyte layer can be in the form of an electrolyte composition, or the electrolyte layer can be in the form of an insulating layer impregnated with the electrolyte composition. By configuring the electrolyte layer from an insulating layer impregnated with an electrolyte composition as in the latter, 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. In this case, the insulating layer is made of woven fabric or non-woven fabric, or the insulating layer is at least one material selected from the group consisting of a titanium oxide layer, a zirconium oxide layer, silicon oxide (silica), and aluminum oxide. (For example, it can be set as the form comprised from the metal oxide material layer).

  Here, as a material constituting the woven or non-woven fabric, synthetic fiber, more specifically, polyethylene, polypropylene, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyvinyl alcohol, aramid, nylon, vinylon, polyolefin, rayon Examples thereof include low-density polyethylene, ethylene vinyl acetate, copolymerized polyamide, and copolymerized polyester, and natural fibers such as cotton, cellulose, glass fiber, and synthetic rubber. Note that the insulating layer may have a laminated structure of a woven or non-woven fabric and a metal oxide material layer. The basic performance required of the insulating layer is that it does not hinder the movement of the impregnated electrolyte composition. When the insulating layer is composed of a woven or non-woven fabric, the movement of the impregnated electrolyte composition is hindered. Furthermore, if the metal oxide material layer is made of titanium oxide or the like, which is a porous material in which adjacent pores penetrate (communicate) as described above, the movement of the impregnated electrolyte composition is also hindered. I can't. 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.

In the photoelectric conversion device according to the first aspect of the present disclosure including the preferred embodiment and configuration described above, the first current collector in the method for manufacturing the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure Consists of a conductive material provided with a large number of through-holes, but as such a conductive material, a wire mesh material, a woven fabric material, a non-woven fabric material, a sintered body material, a porous material, Examples thereof include foam materials, foil materials, sheet materials, and film materials. 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. 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. The second current collector in the photoelectric conversion device according to the second aspect of the present disclosure including the preferable modes and configurations described above can also basically have the same configuration and structure.

  In the photoelectric conversion device according to the first aspect of the present disclosure and the manufacturing method of the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, the second current collector is provided with a plurality of through holes. In the case of a material, the structure and structure of the second current collector can include the structure and structure described in the first current collector, but the present invention is not limited to this. You can also

  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.

  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.

The photoelectric conversion device according to the first aspect or the second aspect of the present disclosure including the preferred embodiment and configuration described above, and the method for manufacturing the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure (hereinafter referred to as the following) In some cases, these are collectively referred to simply as “this disclosure”), and 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% to 99% by weight, more preferably 80% to 97% by weight 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 photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, it is sufficient that the first base material on which light enters is made of a transparent material in the visible light region. It is preferable to use a material excellent in gas barrier properties, solvent resistance, weather resistance, and the like. 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.

Moreover, in the photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, the material constituting the second base material may be appropriately selected from the materials listed as the material constituting the first base material. Good. 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 photoelectric conversion device according to the first aspect or the second aspect of the present disclosure, the sealing material for sealing the first base material and the second base material at their outer edges is leakage of the electrolyte composition. Prevents volatilization and impurities from entering the inside from the outside. 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 addition, as a material constituting the heat seal layer, a biaxially stretched polypropylene (CPP) film, a polyethylene (PE) film, an ethylene vinyl alcohol copolymer, a polyolefin-based adhesive resin (for example, Modic manufactured by Mitsubishi Chemical Corporation) [Registered Trademark]), ionomer resin (for example, High Milan [Registered Trademark] of Mitsui DuPont Polychemical Co., Ltd.), and among the materials constituting the metal foil laminate material, Aluminum (Al), titanium, copper, etc. can be mentioned. In some cases, an insulating film may be formed on the surface of the metal foil. Specifically, for example, when aluminum (Al) is used as the metal foil, the insulating film may be formed by anodizing the surface. In the method for manufacturing a photoelectric conversion device according to the second aspect of the present disclosure, the first base material and the second base material may be made of a metal foil laminate material. 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.

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 titanium oxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), strontium titanate (SrTiO ₃ ), and 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, can be mentioned semiconductor compounds and oxide semiconductors such as Bi ₂ S _3, among these, the anatase type iO ₂ is particularly 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

  There is no particular limitation on the method of forming a semiconductor layer (dye-sensitized semiconductor layer) composed of semiconductor fine particles, but in consideration of physical properties, convenience, production cost, etc., a so-called green sheet that is a precursor of the semiconductor layer is produced, The green sheet is placed on the first current collector, pushed into the first current collector, the adhesion between the green sheet and the first current collector is improved, and then the particles are brought into electronic contact with each other, and the film In order to improve the strength and the adhesion with the first current collector, 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. The green sheet may be produced by a well-known method.

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. Accordingly, there is a preferred thickness for the semiconductor layer, which is generally 1 × 10 ⁻⁷ m to 1 × 10 ⁻⁴ m, and 1 × 10 ⁻⁶ m to 5 × 10 ^−5. m is more preferable, and 3 × 10 ⁻⁶ m to 3 × 10 ⁻⁵ m is particularly preferable.

  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, 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 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 the photoelectric conversion device according to the first and second aspects of the present disclosure, and more specifically, relates to a dye-sensitized solar cell. FIG. 1A shows a schematic cross-sectional view of the photoelectric conversion device 10A of Example 1 before assembly, and FIG. 1B shows a schematic end view after assembly. Further, a schematic plan view of the photoelectric conversion device of Example 1 and a schematic cross-sectional view taken along arrow BB in FIG. 2A are respectively shown in FIGS. 3 is 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, and FIG. 3 shows the second current collector, the catalyst layer, and the second lead. FIG. 4 shows a schematic plan view of the member viewed from the first base material side.

The photoelectric conversion devices of Example 1 or Example 2 to Example 5 and Example 8 to Example 14 described later are as follows.
A first base material 21 and a second base material 22, and
The semiconductor layer 31, the first current collector 51, the electrolyte layer 41, the catalyst layer 32, and the first base material 21 and the second base material 22, which are sequentially provided from the first base material side, The second current collector,
With
The first base material 21 and the second base material 22 are sealed at the outer edge,
The first current collector 51 is made of a conductive material provided with a large number of through holes,
The electrolyte layer 41 is made of an insulating layer impregnated with the electrolyte composition 42.

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 14 described later, the first current collector 51 is made of a wire mesh material made of stainless steel, and the surface of the wire mesh material has corrosion prevention and leakage current. In order to prevent occurrence, 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 netting material (more specifically, a wire rod having a diameter of 25 μm and made of stainless steel having a through-hole (opening) size of 26 μm and a through-hole formation pitch of 25 μm. Is formed from a so-called 500 mesh wire mesh having an opening of 26 μm. A space surrounded on all sides by the wire corresponds to the through hole. The planar shape of the through hole is generally rectangular. Further, in the photoelectric conversion device 10A of Example 1, the second current collector 61 is also 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.

  Furthermore, in the photoelectric conversion device 10A of Example 1, the electrolyte layer 41 is composed of an insulating layer 43 impregnated with an electrolyte composition. Here, the insulating layer 43 is specifically composed of 0.1 mol of sodium iodide, 0.6 mol of 1-propyl-2,3 dimethylimidazolium iodide, 0.05 mol of iodine, tert-butylpyridine,. It consists of a nonwoven fabric made of polyester impregnated with an electrolyte composition 42 consisting of a 5 molar acetonitrile solution. In this way, by forming the electrolyte layer 41 from the insulating layer 43 impregnated with the electrolyte composition, the first current collector 51 and the second current collector 61 made of a conductive material provided with a large number of through holes are provided. It is possible to reliably prevent a short circuit from occurring between them, and it is not necessary to use a transparent conductive layer, and the resistance of the first current collector 51 can be reduced.

  The photoelectric conversion device 10A according to the first embodiment 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 outside 10A of photoelectric conversion apparatuses. 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.

  In addition, the photoelectric conversion device 10A according to the first embodiment includes the second lead member main body portion 82 and the 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 projects outside the photoelectric conversion device 10A. 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. In addition, 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 10A. 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 10A of the first embodiment, a so-called green sheet that is a precursor of the semiconductor layer is manufactured by a well-known method, and the rectangular first current collector 51 (more specifically, the first 1 is a current collector main body 52, and the same applies to the following, and a rectangular green sheet is placed on the first current collector 51 while heating the green sheet using a hot press machine. The adhesion with the first current collector 51 is increased. Next, the laminate of the obtained green sheet and the first current collector 51 is fired. Specifically, the green sheet is fired in air based on conditions such as 510 ° C. and 0.5 hours. Thus, from the semiconductor layer / first current collector in which the first current collector 51 (more specifically, the first current collector main body 52, the same applies hereinafter) and the semiconductor layer 31 are integrated. A first laminated structure can be obtained. 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.

  Further, in the photoelectric conversion device 10A of Example 1, the second laminated structure composed of the catalyst layer / the second current collector is obtained by firing the laminated body of the catalyst layer precursor layer and the second current collector. You can get a body. Specifically, the catalyst layer precursor layer is formed on the second current collector 61 having a rectangular shape (more specifically, the second current collector main body 62, and the same applies hereinafter). For this purpose, after printing the carbon paste, the carbon paste is fired in air under the conditions of 450 ° C. and 0.5 hours. Thus, from the catalyst layer / second current collector in which the second current collector 61 (more specifically, the second current collector main body 62, the same applies hereinafter) and the catalyst layer 32 are integrated. The 2nd laminated structure which consists of 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 10A of Example 1, 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 10A illustrated in FIG. 1B can be obtained. The same applies to Examples 2 to 5 and Examples 8 to 14 described below.

  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. While obtaining a structure, the laminated body of the catalyst layer precursor layer (catalyst layer before firing) and the second current collector is fired to form the second laminated structure comprising the catalyst layer / second current collector. Get. 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 summary description of the manufacturing method of the photoelectric conversion device, the description of attaching the first lead member and the second lead member to the first current collector extension portion and the second current collector extension portion is omitted. . The same applies to the summary of the manufacturing method of the photoelectric conversion device described in the following embodiments.

  In the photoelectric conversion device of Example 1, 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 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.

  In the photoelectric conversion device of Example 1, the electrolyte layer is made of an insulating layer (specifically, non-woven fabric) impregnated with the electrolyte composition, so that the first current collector made of a conductive material provided with a large number of through-holes is used. It is possible to reliably prevent a short circuit from occurring between the body and the second current collector. Moreover, it is not necessary to use a transparent conductive layer, and the resistance of the first current collector can be reduced. Further, 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 constituent elements 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, it is possible to achieve high performance, and by configuring the first current collector and the second current collector from the above-described materials, it is possible to apply so-called roll-to-roll processing, Current collection loss can be reduced.

  The second embodiment is a modification of the first embodiment. In the photoelectric conversion device 10B of Example 2, as shown in FIG. 5A, a schematic end view shows that the first lead member main body 72 is an upper surface of the first current collector extending portion 53. And attached to the lower surface of the first current collector extension portion 53. The “upper surface” refers to the surface facing the first base material, and the “lower surface” refers to the surface 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. 5B, 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. 5D, a schematic plan view when the second lead member 81 is expanded is shown in FIG. 5D. 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 2 can have the same configuration and structure as the photoelectric conversion device described in Example 1, and thus detailed description thereof is omitted.

  The third embodiment is a modification of the first or second embodiment. 6 and 7, for example, in the photoelectric conversion device 10C of Example 3 in which the photoelectric conversion device of Example 1 is modified, the second of the first current collector 51 is used. 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.

  In some cases, as shown in schematic plan views in FIGS. 8 and 9, the covering layer 55 further covers the first current collector extension portion 53 and the first lead member main body 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 3 can have the same configuration and structure as the photoelectric conversion device described in Example 1 or Example 2, and thus detailed description thereof is omitted.

  The fourth embodiment is a modification of the first to third embodiments. For example, in the photoelectric conversion device 10D according to the fourth embodiment, which is a modification of the photoelectric conversion device according to the first 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. 11, 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 4 can have the same configuration and structure as the photoelectric conversion device described in Examples 1 to 3, and thus detailed description thereof is omitted.

  The fifth embodiment is a modification of the first to fourth embodiments. As shown in FIGS. 12A and 12B, a schematic cross-sectional view before assembly of the photoelectric conversion device 10E of Example 5 and a schematic end view after assembly are shown in FIG. The first base material 21 is provided with a heat seal layer 24. 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 5 can have the same configuration and structure as the photoelectric conversion device described in Examples 1 to 4, and thus detailed description thereof is omitted.

  Example 6 relates to a method for manufacturing a photoelectric conversion device according to the first aspect of the present disclosure. Hereinafter, the manufacturing method of the photoelectric conversion device of Example 6 will be described with reference to FIGS. 13A, 13A, and 14 which are schematic cross-sectional views and end views of the first base material and the like. The photoelectric conversion device finally obtained by the method for manufacturing the photoelectric conversion device of Example 6 has substantially the same configuration and structure as the photoelectric conversion device 10E described in Example 5.

[Step-600]
In the manufacturing method of the photoelectric conversion device of Example 6, first, a photoelectric conversion device assembly is obtained. Here, the photoelectric conversion device aggregate is
A first substrate 121 and a second substrate 124, and
The semiconductor layer 31, the first current collector 51, the electrolyte layer 41, the catalyst layer 32, and the first base material 121 and the second base material 124, which are sequentially provided from the first base material side, Second current collector 61,
With
A lead member (a first lead member main body) 72 and a lead member extending portion (first lead member extending portion) 73, which is made of a conductive material piece and outputs the generated electric power ( A first lead member) 71,
The first current collector 51 is made of a conductive material provided with a large number of through holes,
A first lead member main body 72 is attached to the outer edge of the first current collector 51, specifically, to the first current collector extension 53 of the first current collector 51.

  More specifically, as shown in a conceptual diagram in FIG. 23, a so-called roll-to-roll processing method is used to form a first current collector made of a so-called 500-mesh wire mesh based on an ion plating method. A surface treatment layer (not shown) made of titanium is continuously formed. As the wire mesh, the same wire mesh as that described in Example 1 was used. Next, the roll-shaped green sheet is continuously placed on the first current collector main body of the roll-shaped first current collector, and the roll-shaped first sheet is heated while heating the green sheet using a hot roll press machine. The adhesive is pushed into the current collector to enhance the adhesion between the roll-shaped green sheet and the roll-shaped first current collector. Subsequently, the roll-shaped laminated body of the obtained green sheet and the 1st electrical power collector is baked in a continuous furnace. Thus, the first stack of the semiconductor layer / first current collector in which the first current collector 51 (more specifically, the first current collector main body 52) and the semiconductor layer 31 are integrated in a roll shape. A structure can be obtained. Thereafter, the semiconductor layer 31 is impregnated with a dye. Next, the roll-shaped first laminated structure is cut into a rectangular shape. And the 1st lead member main-body part 72 is attached to the 1st electrical power collector extension part 53 based on the welding method.

  On the other hand, after the carbon paste is printed on the second current collector main body of the roll-shaped second current collector to form the catalyst layer precursor layer, the carbon paste is fired in a continuous furnace. In this way, the second laminated structure composed of the catalyst layer / second current collector in which the second current collector 61 (more specifically, the second current collector main body portion 62) and the catalyst layer 32 are integrated. Obtainable. And after cutting a 2nd laminated structure into a rectangular shape, the 2nd lead member main-body part 82 is attached to the 2nd collector extension part 63 based on a welding method.

  In addition, the first base 121 having the heat seal layer 122 made of a biaxially stretched polypropylene (CPP) film and the second base 124 made of the metal foil laminate material described in Example 1 are used as the first base. One side of the material 121 and one side of the second base material 124 are bonded via the heat seal layer 122 (see FIG. 13A). In addition, as the 1st base material 121, the same material as the 1st base material 21 demonstrated in Example 1 was used. The heat seal layer 122 may be disposed not only on the first substrate 121 but also on the second substrate 124.

[Step-610]
Then, the first base material 121 and the second base material 124 are folded so that the photoelectric conversion device assembly is sandwiched therebetween and the first lead member extending portion 73 protrudes to the outside. The outer edge part of 121 and the 2nd base material 124 is sealed by the heat seal layer 122.

  Specifically, the semiconductor layer 31 of the first laminated structure including the rectangular semiconductor layer / first current collector to which the first lead member is attached is bonded to the first base 121 via the heat seal layer 122. (Refer to FIG. 13B). Next, the first lead member extending portion 73 and the second lead member extending portion 83 protrude outward from the first stacked structure and the rectangular second stacked structure to which the second lead member is attached. As described above, the first base material 121 and the second base material 124 are sandwiched between the first base material 121 and the second base material 124. The adhesive layer 54 is disposed between the first lead member 71 and between the second base material 124 and the first lead member 71, and similarly between the first base member 121 and the second lead member 81. The adhesive layer 64 is disposed between the second base material 124 and the second lead 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 the 1st base material 121 and the 2nd base material 124 are sealed (bonded together) by the heat seal layer 122 in the two sides which those outer edge parts oppose. Then, the nonwoven fabric and the semiconductor layer 31 are impregnated with the electrolyte composition 42 from the remaining one side that is in an open state. Next, the remaining one side is sealed with the heat seal layer 122 under reduced pressure. Thus, the photoelectric conversion device 10E shown in FIG. 14 can be obtained.

  In the manufacturing method of the photoelectric conversion device of Example 6 or Example 7 described later, the first base material and the second base material are integrated in advance, the photoelectric conversion device assembly is sandwiched therebetween, and The first base member and the second base member are folded so that the lead member extension portion (first lead member extension portion) protrudes outward, and the outer edge portion of the first base member and the second base member is formed. Since it seals with a heat seal layer, a photoelectric conversion apparatus can be manufactured with a simple process. In addition, it cannot be overemphasized that the photoelectric conversion apparatus demonstrated in Example 1- Example 4 can be manufactured in the manufacturing method of the photoelectric conversion apparatus of Example 6 or Example 7 mentioned later.

  Example 7 relates to a method for manufacturing a photoelectric conversion device according to the second aspect of the present disclosure. Hereinafter, the manufacturing method of the photoelectric conversion device of Example 7 will be described with reference to FIG. 15A which is a schematic cross-sectional view of the first base material and the like. The photoelectric conversion device 10E ′ finally obtained by the method also has substantially the same configuration and structure as the photoelectric conversion device 10E described in the fifth embodiment.

[Step-700]
In the manufacturing method of the photoelectric conversion device of Example 7, first, the same process as [Process-600] of Example 6 is performed.

[Step-710]
On the other hand, it is the 1st base material 221 provided with the heat seal layer 222, and the 2nd base material 224, Comprising: The 1st base material 221 and the 2nd base material are provided continuously, and the 1st base material 221 is provided. Is provided with a window portion 225 for allowing light to enter the semiconductor layer 31, and the window portion 225 is closed by a transparent plastic film or plastic sheet (window portion closing member). And the 2nd base material 224 is prepared (refer (A) of FIG. 15).

  Specifically, the first base material 221 and the second base material 224 made of the same metal foil laminate material described in Example 1 are integrated, and the first base material 221 and the second base material 224 have a heat seal layer. 222 is provided. The same material as the heat seal layer 222 described in Example 6 was used as the heat seal layer 222. A portion corresponding to the first base material 221 is punched to provide a window portion 225. Next, a transparent layer such as a polyolefin resin such as polyethylene, polypropylene, cycloolefin polymer, or a polyester resin such as polyethylene terephthalate, or a barrier layer that enhances gas barrier properties is formed on the plastic film or plastic sheet. It closes through the heat seal layer (not shown) with the window part closing member 223 which consists of a thing. Specifically, the window closing member 223 is placed on a portion corresponding to the first base material 221 of the metal foil laminate material so as to cover the window 225 with the window closing member 223 larger than the window 225, and the window The outer peripheral part of the part closing member 223 is bonded to the metal foil laminate material through a heat seal layer.

[Step-720]
Next, the first substrate 221 and the first substrate 221 are arranged so that the photoelectric conversion device assembly is sandwiched therebetween, the first lead member extending portion 73 protrudes outward, and the semiconductor layer 31 is positioned below the window portion 225. 2 The base material 224 is folded, and the outer edges of the first base material 221 and the second base material 224 are sealed by the heat seal layer 222. Specifically, a step substantially similar to [Step-610] in Example 6 may be performed.

As shown in a schematic cross-sectional view before assembly in FIG. 15B, in the modified example 10E ″ of the photoelectric conversion device of Example 7, the first base material provided with the heat seal layer 222 221 and the second base material 224, the first base material 221 and the second base material are provided continuously, and the first base material 221 has a window portion for allowing light to enter the semiconductor layer. 225 is provided, and the first base 221 and the second base 224 may be prepared in which the window is closed by a window closing member (specifically, the first base 221). Specifically, a mask layer (not shown) covering a portion corresponding to the window portion 225 is formed on the first base material 221 and the second base material 224 made of a continuous transparent plastic film by a known method. based formed. then, based on the sputtering method, SiO ₂ layer and Arumini Two layers of beam layer (SiO ₂ layer is in contact with the first substrate 221) to form a gas barrier layer 226 made of the first substrate 221, second substrate 224 and a mask layer. Thereafter, the mask layer is removed Thus, based on the so-called lift-off method, the first base material 221 and the second base material 224 can be obtained, and then the heat seal layer 222 is formed on the entire surface, thus forming the first base material 221 and the second base material. An area where the gas barrier layer 226 and the heat seal layer 122 are laminated on the upper part 224, and an area where the window 225 and the heat seal layer 122 are formed above the first base material 221 can be obtained. [Step-700] and [Step-720] may be executed using the first base material 221 and the second base material 224.

  The eighth embodiment is a modification of the first to seventh embodiments. In Example 1 to Example 7, 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 10F of Example 8, the second current collector 66 is made of a conductive material layer as shown in a schematic cross-sectional view before assembly 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. Thus, a catalyst layer / second current collector second laminated structure in which the second current collector 66 and the catalyst layer 32 are integrated can be obtained. And what is necessary is just to assemble the photoelectric conversion apparatus 10F of Example 8 by the method similar to having demonstrated in Example 1- Example 7. 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, 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 laminate is formed on the second substrate. By forming a current collector, a second laminated structure composed of the second current collector / second base material was obtained. Next, the first base material, the first laminated structure, the insulating layer, the catalyst layer, and the second laminated structure are overlaid, and the first base material and the second base material are sealed at the outer edge portion. May be. 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 eighth embodiment” for convenience.

  The ninth embodiment is also a modification of the first to seventh embodiments. As shown in a schematic cross-sectional view before assembly in FIG. 17A, in the photoelectric conversion device 10G of Example 9, the insulating layer 44 is oxidized with the electrolyte composition 42 described in Example 1 impregnated. It is composed of a titanium layer. Except for this point, the photoelectric conversion device 10G of the ninth embodiment has the same configuration and structure as the photoelectric conversion device 10A described in the first to seventh embodiments, and thus detailed description thereof is omitted.

  In the photoelectric conversion device 10G of Example 9, 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 a hot press machine is used. Then, the green sheet is pushed into the first current collector 51 while heating, and the adhesion between the green sheet and the first current collector 51 is improved. Further, a titanium oxide layer (insulating layer precursor layer) on the surface of the first current collector 51 facing the catalyst layer 32 is formed by a printing method. Thus, a laminate composed of the green sheet / first current collector / insulating layer precursor layer can be formed. 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 10G of Example 9 by the method similar to having demonstrated in Example 1- Example 7. In Example 9, since a laminated structure of a semiconductor layer / first current collector / insulating layer / catalyst layer / second current collector is obtained, handling becomes easy and the assembly of the photoelectric conversion device is simplified. be able to.

  When the manufacturing method of the photoelectric conversion device 10G of Example 9 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 tenth embodiment is a modification of the ninth embodiment. In Example 9, 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 10H of Example 10, the second current collector 66 is formed of a conductive material layer as shown in a schematic cross-sectional view before assembly in FIG. Specifically, in the tenth embodiment, the second current collector 66 is made of a titanium foil as in the eighth 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 9, except that The firing is performed in air at 450 ° C. for 0.5 hour. Then, what is necessary is just to assemble the photoelectric conversion apparatus 10H of Example 10 by the method similar to having demonstrated in Example 9. FIG. Note that a modification of the eighth embodiment can be applied to the ninth embodiment.

  When the manufacturing method of the photoelectric conversion device 10H of Example 10 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 eleventh embodiment is also a modification of the first to seventh embodiments. A schematic cross-sectional view before the assembly of the photoelectric conversion device is shown in FIG. 18A, and a schematic end view after the assembly is shown in FIG. 18B, as shown in FIG. 18B. In this case, the insulating layer 44 made of titanium oxide is provided on the surface of the catalyst layer 32 facing the first current collector 51 when the photoelectric conversion device is assembled. Except for this point, the photoelectric conversion device 10J of Example 11 has the same configuration and structure as the photoelectric conversion device 10A described in Examples 1 to 7, and thus detailed description thereof is omitted.

  In assembling the photoelectric conversion device 10J according to the eleventh embodiment, for example, in the same manner as in the first embodiment, the first current collector 51 and the semiconductor layer 31 are integrated into a semiconductor layer / first current collector. A first 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 10J of Example 11, the first substrate 21, the first stacked structure, the second stacked structure, and the second substrate 22 are superposed. 1-The 1st base material 21 and the 2nd base material 22 are sealed in an outer edge part by the method similar to having demonstrated in Example 7. FIG. Thus, the photoelectric conversion device 10J illustrated in FIG. 18B can be obtained. 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 10J of Example 11 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. 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 twelfth embodiment is a modification of the eleventh embodiment. As shown in a schematic cross-sectional view before assembly in FIG. 19, in Example 12, the electrolyte layer 41 is an insulating layer 43 made of a nonwoven fabric (referred to as “first insulating layer 43” for convenience), And it is comprised from the laminated structure of the insulating layer 44 (it is called "the 2nd insulating layer 44" for convenience) consisting of titanium oxide. 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 10K of Example 12 has the same configuration and structure as the photoelectric conversion device 10J described in Example 11, and thus detailed description thereof is omitted. In Example 12, 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 11 or Example 12 may be a second current collector 66 made of a titanium foil in the same manner as in Example 8 instead of the conductive material provided with a large number of through holes. it can. For example, in Example 11, after printing the carbon paste on the titanium foil, the same as in Example 8, 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 eleventh embodiment. A modification of the eighth embodiment can be applied to the eleventh or twelfth embodiment.

  The thirteenth embodiment is also a modification of the first to seventh embodiments. A schematic cross-sectional view before assembly of the photoelectric conversion device is shown in FIG. 20A, and a schematic end view after assembly is shown in FIG. 20B, as shown in FIG. 20B. In this case, the insulating layer 44 made of titanium oxide is provided on the surface of the first current collector 51 facing the catalyst layer 32 when the photoelectric conversion device is assembled. Except for this point, the photoelectric conversion device 10L of Example 13 has the same configuration and structure as the photoelectric conversion device 10A described in Examples 1 to 7, and thus detailed description thereof is omitted.

  In assembling the photoelectric conversion device 10L of the thirteenth embodiment, a so-called green sheet that is a precursor of the semiconductor layer is manufactured by a well-known method, the green sheet is placed on the first current collector 51, and a hot press machine is used. The green sheet is pushed into the first current collector 51 while heating to improve the adhesion between the green sheet and the first current collector 51. Further, the insulating layer 44 is formed on the surface of the first current collector 51 facing the catalyst layer 32 based on a printing method. Thus, a laminate of the green sheet, the first current collector 51, and the insulating layer precursor (a laminate composed of the green sheet / first current collector / insulating layer precursor) can be formed. Next, the green sheet and the insulating layer precursor layer are fired in air based on conditions such as 510 ° 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 composed of the semiconductor layer / first current collector / insulating layer 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 10L of Example 13, the first base material 21, the first stacked structure, the second stacked structure, and the second base 22 are superposed, 1-The 1st base material 21 and the 2nd base material 22 are sealed in an outer edge part by the method similar to having demonstrated in Example 7. FIG. Thus, the photoelectric conversion device 10L illustrated in FIG. 20B can be obtained. 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 10L of Example 13 described above is summarized, the stacked body of the green sheet, the first current collector, and the insulating layer precursor is fired, 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 fourteenth embodiment is a modification of the thirteenth embodiment. As shown in FIG. 21, a schematic cross-sectional view before assembly is shown in FIG. 21. In Example 14, as in Example 12, the electrolyte layer 41 is composed of an insulating layer 43 (first insulating layer 43) made of nonwoven fabric. , 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 of the first current collector 51 that faces the catalyst layer 32, and the first insulating layer 43 is in contact with the catalyst layer 32. Except for the above points, the photoelectric conversion device 10M of Example 14 has the same configuration and structure as the photoelectric conversion device 10L described in Example 13, and thus detailed description thereof is omitted. In Example 14, 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 13 or Example 14 may be a second current collector 66 made of a titanium foil in the same manner as in Example 8 instead of the conductive material provided with a large number of through holes. it can. For example, in Example 13, after printing the carbon paste on the titanium foil, the same as in Example 8, except that the firing conditions are 450 ° C. and 0.5 hours in air. And what is necessary is just to assemble a photoelectric conversion apparatus by the method similar to having demonstrated in Example 13. FIG. A modification of the eighth embodiment can be applied to the thirteenth or fourteenth embodiment.

  Although the photoelectric conversion device of the present disclosure has been described based on the preferred embodiments, the present disclosure is not limited to these embodiments. The configuration, structure, materials used, specifications, and the like of the photoelectric conversion device described in the embodiments are examples, and can be appropriately selected and changed. Moreover, the manufacturing method of the photoelectric conversion apparatus demonstrated in the Example is also an illustration, and can be changed suitably. In Example 1 to Example 7, a photoelectric conversion device in which the photoelectric conversion device according to the first aspect of the present disclosure and the photoelectric conversion device according to the second aspect of the present disclosure are applied together has been described. However, it is needless to say that the photoelectric conversion device according to the first aspect of the present disclosure and the photoelectric conversion device according to the second aspect of the present disclosure can be independently applied. In the embodiment, the first lead member is exclusively disposed on the lower surface of the first current collector, but may be disposed on the upper surface 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 FIG. 22A, a schematic cross-sectional view before the assembly of the modification 10A ′ of the photoelectric conversion device of the first embodiment is performed, the lead member main body is disposed on the outer edge portion of the first current collector 51. A portion (first lead member main body portion) 72 may be attached. In the example shown in FIG. 22A, the lead member main body (first lead member main body) 72 is covered with the semiconductor layer 31. Alternatively, as shown in FIG. 22B, a schematic cross-sectional view of the photoelectric conversion device modification 10A ″ of the first embodiment before assembly, a lead member main body portion on the outer edge portion of the second current collector 61 (Second lead member main body portion) 82 may be attached.In the example shown in Fig. 22B, the lead member main body portion (second lead member main body portion) 82 is covered with the catalyst layer 32. Furthermore, it goes without saying that the modification 10A ′ and the modification 10A ″ of the photoelectric conversion device of the first embodiment can be combined.

10A, 10A ′, 10A ″, 10B, 10C, 10D, 10E, 10E ′, 10E ″, 10F, 10G, 10H, 10J, 10K, 10L, 10M... Photoelectric conversion device, 21, 121, 221. 1st base material, 22,124,224 ... 2nd base material, 122,222 ... heat seal layer, 23 ... sealing material, 223 ... window part closing member, 225 ... window Part, 226 ... gas barrier layer, 31 ... semiconductor layer, 32 ... catalyst layer, 41 ... electrolyte layer, 42 ... electrolyte composition, 43, 44 ... insulating layer, 51 ... First current collector, 51A ... first side of the first current collector, 51B ... second side of the first current collector, 51C ... third of the first current collector Side, 51D: Fourth side of first current collector, 52: First current collector body, 53: First current collector extension Part, 54, 64 ... adhesive layer, 55, 65 ... coating layer, 61, 66 ... second current collector, 61A ... second side of second current collector, 61B .... Second side of second current collector, 61C ... Third side of second current collector, 61D ... Fourth side of second current collector, 62 ... Second current collector Electric body body part, 63 ... second current collector extension part, 71 ... first current collector, 71A, 71B, 81A, 81B ... conductive material piece, 72 ... first current collector Body main body part 73 ... 1st current collector extension part, 81 ... 2nd current collector, 82 ... 2nd current collector body part, 83 ... 2nd current collector extension Part

Claims (20)

A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
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,
It is composed of a lead member main body part and a lead member extending part, is made of a conductive material piece, and further comprises a lead member for outputting generated power,
A lead member main body is attached to the outer edge of the first current collector,
The lead member extending portion is a photoelectric conversion device protruding outside the photoelectric conversion device. The first current collector is composed of a first current collector body portion and a first current collector extension portion extending from the first current collector body portion,
The photoelectric conversion device according to claim 1, wherein the lead member main body is attached to the first current collector extension.   The photoelectric conversion device according to claim 1, wherein the lead member main body is attached to an upper surface of the first current collector extension and a lower surface of the first current collector extension. The planar shape of the first current collector is a rectangle, the first side and the third side extending along the first direction, and the second side extending along the second direction orthogonal to the first direction. And a fourth side,
4. The photoelectric conversion device according to claim 1, wherein the first current collector extending portion is located along the first side. 5.   The photoelectric conversion device according to claim 4, wherein the second side and the fourth side of the first current collector are covered with a coating layer.   The photoelectric conversion device according to claim 5, wherein the coating layer further covers the first current collector extension portion and the lead member main body portion.   In the portion where the first base material and the second base material are sealed, between the first base material and the first current collector and between the second base material and the first current collector. The photoelectric conversion device according to any one of claims 1 to 6, wherein an adhesive layer is disposed. 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 photoelectric conversion device according to any one of claims 1 to 7, wherein the second lead member extending portion protrudes outside the photoelectric conversion device. The planar shape of the second current collector is rectangular, the first side and the third side extending along the first direction, and the second side extending along the second direction orthogonal to the first direction. And a fourth side,
The photoelectric conversion device according to claim 8, wherein the second current collector extending portion is located along the third side.   The photoelectric conversion device according to claim 8 or 9, wherein the projected image of the first lead member does not overlap with the projected image of the second lead member.   The photoelectric conversion device according to claim 10, wherein the first lead member extending portion and the second lead member extending portion protrude outward from the same side of the photoelectric conversion device.   In the portion where the first base material and the second base material are sealed, between the first base material and the second current collector and between the second base material and the second current collector. The photoelectric conversion device according to claim 8, wherein an adhesive layer is disposed.   The photoelectric conversion device according to claim 1, wherein the first base material is provided with a heat seal layer. At least the first base material is provided with a heat seal layer,
The first base material and the second base material are provided continuously,
The first base material is provided with a window for allowing light to enter the semiconductor layer,
The photoelectric conversion device according to claim 1, wherein the window portion is closed by a transparent plastic film or plastic sheet.   The photoelectric conversion device according to claim 1, wherein the electrolyte layer includes an insulating layer impregnated with an electrolyte composition.   The photoelectric conversion device according to claim 15, wherein the insulating layer is made of a woven fabric or a non-woven fabric.   The photoelectric conversion device according to claim 15, wherein the insulating layer is made of at least one material selected from the group consisting of a titanium oxide layer, a zirconium oxide layer, silicon oxide, and aluminum oxide. A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
The first base material and the second base material are sealed at the outer edge portion,
The second current collector is made of a conductive material provided with a large number of through holes,
It is composed of a lead member main body part and a lead member extending part, is made of a conductive material piece, and further comprises a lead member for outputting generated power,
A lead member main body is attached to the outer edge of the second current collector,
The lead member extending portion is a photoelectric conversion device protruding outside the photoelectric conversion device. A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
With
It is composed of a lead member main body part and a lead member extending part, is made of a conductive material piece, and further comprises a lead member for outputting generated power,
The first current collector is made of a conductive material provided with a large number of through holes,
While obtaining a photoelectric conversion device assembly in which the lead member body portion is attached to the outer edge portion of the first current collector,
The first base material provided with the heat seal layer and the second base material are bonded to one side of the first base material and one side of the second base material,
The first base material and the second base material are folded so that the photoelectric conversion device assembly is sandwiched therebetween and the lead member extending portion protrudes to the outside. A method for manufacturing a photoelectric conversion device in which an outer edge portion is sealed with a heat seal layer. A first substrate and a second substrate, and
A semiconductor layer, a first current collector, an electrolyte layer, a catalyst layer, and a second current collector, which are sequentially provided from the first base material side between the first base material and the second base material,
With
It is composed of a lead member main body part and a lead member extending part, is made of a conductive material piece, and further comprises a lead member for outputting generated power,
The first current collector is made of a conductive material provided with a large number of through holes,
While obtaining a photoelectric conversion device assembly in which the lead member body portion is attached to the outer edge portion of the first current collector,
It is the 1st base material provided with the heat seal layer, and the 2nd base material, Comprising: The 1st base material and the 2nd base material are provided continuously, and light is given to the semiconductor layer in the 1st base material. A window portion is provided for incidence, and the window portion is provided with a first base material and a second base material that are closed by a transparent plastic film or plastic sheet,
Fold the first base material and the second base material so that the photoelectric conversion device assembly is sandwiched therebetween, the lead member extending portion protrudes outward, and the semiconductor layer is located below the window portion, The manufacturing method of the photoelectric conversion apparatus which seals the outer edge part of 1 base material and a 2nd base material with a heat seal layer.