JP2013122875A - Photoelectric conversion element, method for manufacturing the same, counter electrode for photoelectric conversion element, electronic device, and building - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a counter electrode excellent in electrolyte resistance and conductivity, and capable of being manufactured at low cost.SOLUTION: A dye-sensitized photoelectric conversion element 10 includes an electrolyte layer 8 filled between a porous electrode 7 on which a photosensitizing dye is adsorbed, and a counter electrode 1. The counter electrode 1 for a dye-sensitized photoelectric conversion element includes a metal substrate 2, a catalyst layer 3, and a conductive film 4. The metal substrate 2 and the catalyst layer 3 are in contact with opposite sides of the conductive film 4, and the coefficient of linear expansion of the conductive film 4 is greater than or equal to 7.3×10Kand smaller than or equal to 10.5×10K.

Description

  The present disclosure relates to a photoelectric conversion element, a manufacturing method thereof, an electronic device, a counter electrode for the photoelectric conversion element, and a building, for example, a photoelectric conversion element suitable for use in a dye-sensitized solar cell, a manufacturing method thereof, and the photoelectric conversion element. The present invention relates to an electronic device to be used, a counter electrode for a photoelectric conversion element suitable for use in a dye-sensitized solar cell, and a building using the photoelectric conversion element.

Solar cells, which are photoelectric conversion elements that convert sunlight into electrical energy, use sunlight as an energy source, and therefore have very little influence on the global environment, and are expected to become more widespread.
As a conventional solar cell, a crystalline silicon solar cell using single crystal or polycrystalline silicon and an amorphous silicon solar cell are mainly used.

  On the other hand, the dye-sensitized solar cell proposed by Gretzell et al. In 1991 can obtain high photoelectric conversion efficiency, and unlike a conventional silicon-based solar cell, it does not require a large-scale device for production, and has a low It is attracting attention because it can be manufactured at low cost (for example, see Non-Patent Document 1).

This dye-sensitized solar cell generally has a porous electrode made of titanium oxide (TiO ₂ ) or the like combined with a photosensitizing dye and a counter electrode made of platinum (Pt) or the like facing each other. In which an electrolyte layer made of an electrolytic solution is filled. As the electrolytic solution, a solution obtained by dissolving an electrolyte containing an oxidizing / reducing species such as iodine (I) or iodide ion (I ⁻ ) in a solvent is often used.

  In general, the solar cell is required to have stable photoelectric conversion characteristics over a long period of time. In particular, a dye-sensitized solar cell generally contains a liquid electrolyte component as a constituent element. For this reason, in order to obtain stable photoelectric conversion characteristics over a long period of time, characteristic deterioration due to corrosion by the electrolyte solution is an important issue. Therefore, conventionally, platinum has been mainly used as a counter electrode of a dye-sensitized solar cell because it has both excellent catalytic action and corrosion resistance to an electrolyte. Platinum is generally excellent in catalytic activity, corrosion resistance, conductivity and the like. However, since platinum, which is a material, is scarce and expensive in terms of resources, using the platinum layer as a counter electrode has a problem that the material cost is very high.

  In order to solve this problem, in recent years, the development of dye-sensitized solar cells that can be manufactured at low cost and has excellent long-term stability by forming a counter electrode with a metal substrate using a metal that is lower in cost than platinum. Has been done.

  For the metal substrate constituting the counter electrode, a titanium-based material having properties excellent in electrical conductivity and corrosion resistance against an electrolyte is generally used. However, since titanium-based materials are also expensive, the problem of high material costs still remains. In order to solve this problem, it is necessary to apply a low-cost general-purpose metal material such as an aluminum (Al) -based material and a stainless steel (SUS) -based material instead of the titanium-based material to the metal substrate.

  However, low-priced general-purpose metal materials such as aluminum and stainless steel have excellent properties in terms of electrical conductivity, but generally have low corrosion resistance to electrolytes, and can withstand practical use as a counter electrode metal substrate. Does not have performance. Therefore, when a metal substrate is constituted by the general-purpose metal material, it is necessary to improve the corrosion resistance by the electrolyte while ensuring the electrical conductivity. Therefore, a proposal has been made to improve the corrosion resistance of the metal substrate against the electrolyte while ensuring electrical conductivity by performing some treatment on the surface of the metal substrate in contact with the electrolyte (see, for example, Patent Documents 1 and 2). ).

JP 2006-318770 A JP 2008-257948 A

Nature, 353, p.737-740,1991

However, although the dye-sensitized solar cells proposed in these documents are excellent in the corrosion resistance against the electrolyte of the counter electrode, it cannot be said that the photoelectric conversion performance and the durability with time are high.
Therefore, a problem to be solved by the present disclosure is to provide a counter electrode for a dye-sensitized photoelectric conversion element that can be manufactured at low cost and has excellent photoelectric conversion performance and durability performance over time.

  Moreover, the other subject which this indication tends to solve is providing the photoelectric conversion element using the above counter electrodes for photoelectric conversion elements.

  Furthermore, still another problem to be solved by the present disclosure is to provide a high-performance electronic device using the excellent photoelectric conversion element as described above.

  Moreover, the other subject which this indication tends to solve is providing the building using the above outstanding photoelectric conversion elements.

In order to solve the above problems, the present disclosure provides:
A porous electrode;
With the counter electrode,
An electrolyte layer provided between the porous electrode and the counter electrode;
The counter electrode is
A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
The photoelectric conversion element has a value of linear expansion coefficient of the conductive film of 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less.

In addition, this disclosure
A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
The counter electrode for a photoelectric conversion element, which is a photoelectric conversion element having a linear expansion coefficient of the conductive film of 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less. It is.

In addition, this disclosure
When manufacturing a photoelectric conversion element having an electrolyte layer between a porous electrode and a counter electrode, the value of linear expansion coefficient is 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 on a metal substrate. This is a method for producing a photoelectric conversion element, in which a conductive film made of a material of × 10 ⁻⁶ [K ⁻¹ ] is formed and a catalyst layer is formed on the conductive film to form the counter electrode.

In addition, this disclosure
Having at least one photoelectric conversion element;
The photoelectric conversion element is
A porous electrode;
With the counter electrode,
An electrolyte layer provided between the porous electrode and the counter electrode;
The counter electrode is
A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
The electronic device is a photoelectric conversion element in which the value of the linear expansion coefficient of the conductive film is 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less.

In addition, this disclosure
Having at least one photoelectric conversion element;
The photoelectric conversion element is
A porous electrode;
With the counter electrode,
An electrolyte layer provided between the porous electrode and the counter electrode;
The counter electrode is
A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
It is a building which is a photoelectric conversion element whose linear expansion coefficient value of the conductive film is 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less.

In the present disclosure, the porous electrode is composed of fine particles made of a semiconductor. The semiconductor preferably comprises titanium oxide (TiO ₂ ), especially anatase TiO ₂ .

As the porous electrode, a so-called core-shell structured fine particle may be used. As the porous electrode, preferably used is one constituted by fine particles comprising a core made of metal and a shell made of a metal oxide surrounding the core. When such a porous electrode is used, when an electrolyte layer is provided between the porous electrode and the counter electrode, the electrolyte in the electrolyte layer does not come into contact with the metal / metal oxide fine metal core. Therefore, dissolution of the porous electrode by the electrolyte can be prevented. For this reason, gold (Au), silver (Ag), copper (Cu), or the like, which has been difficult to use in the past and has a large surface plasmon resonance effect, is used as the metal constituting the metal / metal oxide fine particle core. Thus, the effect of surface plasmon resonance can be sufficiently obtained in photoelectric conversion. In addition, an iodine-based electrolyte can be used as the electrolyte of the electrolytic solution. Platinum (Pt), palladium (Pd), etc. can also be used as the metal constituting the core of the metal / metal oxide fine particles. As the metal oxide constituting the shell of the metal / metal oxide fine particles, a metal oxide that does not dissolve in the electrolyte to be used is used, and is selected as necessary. Such a metal oxide is preferably at least one selected from the group consisting of titanium oxide (TiO ₂ ), tin oxide (SnO ₂ ), niobium oxide (Nb ₂ O ₅ ), and zinc oxide (ZnO). However, the present invention is not limited to these. For example, a metal oxide such as tungsten oxide (WO ₃ ) or strontium titanate (SrTiO ₃ ) can be used. The particle size of the fine particles is appropriately selected, but is preferably 1 [nm] or more and 500 [nm] or less. The particle diameter of the core of the fine particles is also appropriately selected, but is preferably 1 [nm] or more and 200 [nm] or less.

  An electrolyte solution is typically used as a constituent of the electrolyte layer. A conventionally well-known thing can be used as electrolyte solution, It selects as needed. From the viewpoint of preventing volatilization of the electrolytic solution, a low-volatile electrolytic solution, for example, an ionic liquid electrolytic solution using an ionic liquid as a solvent is preferably used. A conventionally well-known thing can be used as an ionic liquid, and it selects as needed.

  Moreover, you may comprise an electrolyte layer with the porous membrane containing electrolyte solution. By doing so, since the electrolyte layer becomes solid, it is possible to prevent the electrolyte from leaking when the photoelectric conversion element is damaged. In addition, incident light that has passed through the porous electrode and entered the photoelectric conversion element is scattered by the porous film that constitutes the electrolyte layer and is incident on the porous electrode again. Therefore, the incident light is collected by the porous electrode. The rate is high. Thereby, a photoelectric conversion element with high short circuit current density and photoelectric conversion efficiency is realizable. Further, since the electrolyte layer can be constituted by a porous film containing an electrolytic solution, the electrolytic solution can be substantially handled as a membrane, and the handling of the electrolytic solution becomes extremely simple. For this reason, a dye-sensitized photoelectric conversion element having excellent characteristics can be easily realized.

  Various types of porous membranes can be used as the electrolyte layer, and the structure and material are selected as necessary. As this porous film, an insulating material is used. Even if this insulating porous film is made of an insulating material, for example, the surface of the void portion of the porous film made of a conductive material is used. Even if the insulator is made into an insulator, the surface of the void portion may be coated with an insulating film. This porous film may be made of an organic material or an inorganic material. As this porous film, various non-woven fabrics are preferably used, and as the material, for example, various organic polymer compounds such as polyolefin, polyester, cellulose and the like can be used, but are not limited thereto. Absent. The porosity of the porous film is selected as necessary, but the porosity (actual porosity) in a state provided between the porous electrode and the counter electrode is preferably 50% or more. This actual porosity is preferably selected from 80 [%] to less than 100 [%] from the viewpoint of obtaining high photoelectric conversion efficiency.

  Electronic devices may be basically any type, including both portable and stationary types, but specific examples include mobile phones, mobile devices, robots, personal computers. , In-vehicle equipment, various home appliances. In this case, the photoelectric conversion element is a solar cell used as a power source for these electronic devices, for example.

  The counter electrode for a photoelectric conversion element is an electrode provided on the positive electrode side of the photoelectric conversion element.

  The photoelectric conversion element is most typically configured as a solar cell. The photoelectric conversion element may be other than a solar cell, for example, an optical sensor, but is not limited to these, and is basically an element that has a negative electrode and a positive electrode and is driven by light. May be anything.

  Buildings are typically large buildings such as buildings and condominiums, but are not limited to this. Basically, any building having an outer wall surface may be used. Also good. Specific examples of the building include a detached house, an apartment, a station building, a school building, a government building, a stadium, a stadium, a hospital, a church, a factory, a warehouse, a shed, a garage, and a bridge. The structure is preferably a built structure having two window parts (for example, glass windows) or a daylighting part, but the building is not limited to those mentioned above.

  Among photoelectric conversion elements provided in buildings and / or photoelectric conversion element modules in which a plurality of photoelectric conversion elements are electrically connected, those provided in a window or daylighting section are sandwiched between two transparent plates However, it is preferable to fix and configure as necessary. Typically, the photoelectric conversion element and / or the photoelectric conversion element module is assembled between two glass plates and fixed as necessary. Is done.

  According to the present technology, by using a novel counter electrode having a conductive film between a metal substrate and a catalyst layer for a photoelectric conversion element, a photoelectric conversion element having excellent photoelectric conversion performance and durability over time can be obtained. It can be manufactured at low cost. Further, by using this photoelectric conversion element, a high-performance electronic device or the like can be realized.

It is sectional drawing which shows the counter electrode for dye-sensitized photoelectric conversion elements by 1st Embodiment. It is sectional drawing which shows the dye-sensitized photoelectric conversion element by 2nd Embodiment. It is a basic diagram which showed the current-voltage output characteristic of the dye-sensitized photoelectric conversion element. It is a basic diagram which showed the current-voltage output characteristic of the dye-sensitized photoelectric conversion element. It is a basic diagram which showed the current-voltage output characteristic of the dye-sensitized photoelectric conversion element. It is a basic diagram which showed transition of the value of the photoelectric conversion efficiency with respect to the elapsed time of the dye-sensitized photoelectric conversion element in a reliability acceleration test. It is a basic diagram which showed the current-voltage output characteristic of the dye-sensitized photoelectric conversion element. It is sectional drawing which shows the conventional dye-sensitized photoelectric conversion element.

FIG. 8 is a cross-sectional view of an essential part showing a dye-sensitized photoelectric conversion element 100 having a conventional configuration in which the substrate of the counter electrode 1 is a metal substrate 102.
As shown in FIG. 8, in the dye-sensitized photoelectric conversion element 100, a transparent electrode 106 that is an FTO layer is provided on one main surface of a transparent substrate 105, and the transparent electrode 106 is composed of a sintered body of TiO _2. A porous electrode 107 is provided. One or more kinds of photosensitizing dyes (not shown) are bonded to the porous electrode 107. On the other hand, a catalyst layer 103 is provided on one main surface of a metal substrate 102 that is a titanium substrate, thereby constituting a counter electrode 101. The porous electrode 107 and the counter electrode 101 are filled with an electrolyte layer 108 made of an electrolytic solution using redox species of I ⁻ / I ₃ ⁻ as a redox pair, and the transparent substrate 105 and the metal substrate 102 The outer periphery is sealed with a sealing body 109.

  When light enters the porous electrode 107, the dye-sensitized photoelectric conversion element 100 operates as a battery having the transparent electrode 106 as a negative electrode and the counter electrode 101 as a positive electrode.

  The present disclosure has intensively studied using the dye-sensitized photoelectric conversion element 100. In the course of the research, it was found that the deterioration with time of photoelectric conversion efficiency in the dye-sensitized photoelectric conversion element 100 was particularly remarkable in the initial stage of power generation from the start of power generation to a certain time. It was also found that the value was due to a large drop in the initial stage of power generation.

  As a result of further research, the present disclosure has found two major factors of the drop in the open-circuit voltage value described above in the course of the research. The first factor is considered to be a decrease in the catalyst performance of the counter electrode 101 and an increase in the surface resistance value. This is considered to be caused by deterioration with time due to a change in the substance constituting the counter electrode 101, and this change is considered to be caused by a reaction with the electrolytic solution in the electrolyte layer 108 or the like. A possible second factor is an increase in DC resistance between the positive and negative electrodes. This includes an increase in contact resistance between the transparent electrode 106 and the porous electrode 107, an increase in contact resistance between the metal substrate 102 and the catalyst layer 103, an increase in resistance due to a change in the electrolyte solution in the electrolyte layer 108, and the like. It is thought to be caused by.

  It is considered that the increase in contact resistance described above is caused by the alteration of the contact interface in each layer by the electrolytic solution. In particular, the contact interface between the metal substrate 102 and the catalyst layer 103 is considered to be greatly altered because the metal substrate 102 is easily affected by the electrolytic solution. Further, it is considered that the direct-current resistance value is also increased by the alteration of the electrolyte solution in the electrolyte layer 108, and the cause thereof is considered to be caused by the substance constituting the counter electrode 101 being eluted into the electrolyte solution or the like by the above reaction or the like. It is done. Such an increase in direct-current resistance causes not only a decrease in open circuit voltage but also a decrease in fill factor, thereby significantly reducing the photoelectric conversion efficiency.

  The present disclosure has further researched to solve these newly discovered problems. In the process, if the counter electrode of the dye-sensitized photoelectric conversion element is configured by providing a conductive film which is a conductive intermediate layer between the catalyst layer and the metal substrate, the above-described problems can be solved, and dye sensitization can be achieved. The present inventors have found that the deterioration with time of the performance of the photoelectric conversion element can be effectively suppressed, and have come up with the present technology.

Hereinafter, modes for carrying out the invention (hereinafter referred to as “embodiments”) will be described. The description will be made in the following order.
1. First Embodiment (Counter Electrode for Dye-sensitized Photoelectric Conversion Element and Method for Producing the Same)
2. Second Embodiment (Dye-sensitized photoelectric conversion element and manufacturing method thereof)
3. Third Embodiment (Counter Electrode for Dye-sensitized Photoelectric Conversion Element and Method for Producing the Same)
4). Fourth Embodiment (Dye-sensitized photoelectric conversion element and method for producing the same)

<1. First Embodiment>
[Counter electrode for dye-sensitized photoelectric conversion element]
First, the first embodiment will be described.
FIG. 1 is a cross-sectional view of an essential part showing a counter electrode 1 for a dye-sensitized photoelectric conversion element according to a first embodiment.
As shown in FIG. 1, the counter electrode 1 for dye-sensitized photoelectric conversion element (hereinafter referred to as counter electrode 1) is provided with a conductive film 4 laminated so as to cover the entire main surface of the metal substrate 2, and is electrically conductive. The catalyst layer 3 is provided on at least a part of the surface of the conductive film 4. The conductive film 4 is in close contact with the metal substrate 2 and the catalyst layer 3, and these constitute the counter electrode 1.

  The material constituting the metal substrate 2 may be basically any material as long as it is a metal, but is preferably a metal having excellent conductivity. Specific examples of the metal include a simple metal, an alloy, and a metal compound. If the metal is simple, for example, gold (Au), silver (Ag), copper (Cu), titanium (Ti), zinc ( Zn), tin (Sn), iron (Fe), platinum (Pt), nickel (Ni), aluminum (Al) and the like, and if an alloy, a binary alloy of the metal materials mentioned above, Examples include ternary alloys, specifically, steel, stainless steel, copper alloy, aluminum alloy, titanium alloy, nickel alloy, and the like. Examples of steel include carbon steel, high alloy steel, low Alloy steel, high-tensile steel, and the like can be used. For stainless steel, for example, stainless steel plate and stainless steel plate can be used. For stainless steel plates, specifically, for example, SUS201, SUS20. SUS301-SUS305, SUS304L, SUS309, SUS309S, SUS310S, SUS311, SUS314, SUS315, SUS321, SUS329, SUS347, SUS403, SUS405, SUS406, SUS410, SUS414, SUS420, SUS430S4, SUS430US SUS440A-C, SUS442, SUS443, SUS444, SUS445, SUS446, SUS447JI, SUS630, SUS631, SUS836, SUS890, SUS JIS35, SUS XM27, SHOMAC30-2, SEA-CURE, HR-8N, etc. If it is a special steel plate, specifically Is, for example, SUS316, SUS316L, SUS316Ti, SUS316LN, SUS316J1, SUS316J2, SUS316J1L, SUS317, SUS317L, SUS317LN, SUS317J1, SUS317J2, SUS444, SUS445, and CARPENT. Moreover, if it is a copper alloy, for example, brass, red brass, silver, bronze, aluminum bronze, white bronze, red copper, constantan, etc. are mentioned, and if it is an aluminum alloy, for example, 1000 series to 7000 series aluminum alloys Examples of the titanium alloy include 6-4 titanium, α titanium, β titanium, and α + β titanium, and examples of the nickel alloy include Hastelloy (registered trademark) and Monel. (Registered Trademark), Inconel (Registered Trademark), Nichrome, etc. are mentioned, but the material constituting the metal substrate 2 is not limited to these.

  The plate thickness of the metal substrate 2 is preferably thin when viewed as a conductive layer, but is preferably thick when viewed as part of the casing of the element. Accordingly, the thickness of the metal substrate 2 has an optimum thickness, and the thickness is preferably 50 [μm] or more and 2000 [μm] or less, and is 100 [μm] or more and 1000 [μm] or less. Is more preferable, and most preferable is 200 [μm] or more and 500 [μm] or less. This is because if the thickness is less than 50 [μm], the strength of the metal substrate 2 is impaired, and if it exceeds 2000 [μm], the weight of the entire device increases remarkably.

The material constituting the conductive film 4 is preferably a simple metal, an alloy, a ternary amorphous material, a metal carbide, a metal nitride, a metal cyanide, a conductive polymer, a conductive oxide, or the like. Gold, platinum, silver, copper, iron, tin, nickel, titanium-based materials, zinc-based materials, tantalum (Ta) -based materials, chromium (Cr) -based materials, tungsten (W) -based materials, molybdenum (Mo) -based materials Vanadium (V) material, niobium (Nb) material, aluminum (Al) material, hafnium (Hf) material, zirconium (Zr) material, ruthenium (Ru) material and iridium (Ir) material, such as lanthanum (La) based material and the like, as long as the titanium-based material, specifically, for example, Ti, TiN, TiC, TiCN , TiBN, TiB 2, TiAlN, Ti iN, and the like TiAlON, also, if zinc-based material, specifically, for example, Zn, ZrN, ZrC, etc. ZnB ₂ and the like, as long as a tantalum-based material, specifically, for example, , Ta, TaN, TaCN, TaC, TaO, TaB ₂ , TaON, TaCNO, TaAlN, TaSiN, and the like. Specific examples of the chromium-based material include Cr, CrN, and Cr ₃ C _2. , CrB ₂ , CrSiN, CrAlN, and the like. Specific examples of tungsten-based materials include W, WN, WC, W ₂ B ₅ , WCN, WBN, WAlN, WSiN, and WTi. Specific examples of molybdenum-based materials include Mo, MoO, MoN, MO ₂ C, Mo ₂ B ₅ , MoSiN, MoAlN, and MoH. fO and the like, and if it is a vanadium-based material, specifically, for example, VN, VC, VB _{2 and the} like are mentioned. If it is a niobium-based material, specifically, for example, Nb , NbN, NbC, NbB ₂ , NbSiN, NbAlN, etc., and if it is an aluminum material, specifically, for example, Al, AlN, etc., and if it is a hafnium material, Specifically, for example, Hf, HfN, HfC, and the like can be given, and if it is a zirconium-based material, specifically, for example, Zr, ZrN, ZrSiN, ZrAlN, and the like can be mentioned. If there are, specifically, for example, Ru, RuO, RuAlO, RuAlN, etc. may be mentioned, and if it is an iridium-based material, specifically, for example, Ir, Ir And the like, also, if the lanthanum-based material, specifically, for example, La, etc. LaB ₂ and the like, also, if the conducting polymer, specifically, for example, polyaniline, polypyrrole, Examples of the conductive oxide include polythiophene and derivatives thereof. Specifically, for example, tin-doped indium oxide (VI) In ₂ O ₃ (ITO), fluorine-doped oxide indium _{(VI) In 2 O 3 (} IFO), 2 indium oxide (VI) In O _3, fluorine-doped tin oxide _{(IV) SnO 2 (FTO)} , tin oxide doped with antimony (IV) SnO ₂ (ATO), tin oxide (IV) SnO _2, zinc oxide indium-doped (II) ZnO (IZO), fluorine-doped zinc oxide (II) Z Examples include O (FZO), zinc oxide (II) ZnO (AZO) doped with aluminum, zinc oxide (II) ZnO (GZO) doped with gallium, and zinc (II) ZnO. The material which comprises 4 is not limited to these. In addition, the conductive film 4 can be configured by combining two or more types from those listed above, or can be configured by stacking two or more types.

  The conductive film 4 is preferably thin when viewed as a conductive layer, but is preferably thick when viewed as a protective layer. Therefore, the thickness of the conductive film 4 has an optimum thickness, and the thickness is preferably 50 [nm] or more and 400 [nm] or less, and is 100 [nm] or more and 350 [nm] or less. More preferably, it is 200 [nm] or more and 300 [nm] or less. If the thickness is less than 50 [nm], pinholes are generated in the conductive film 4 and the uniformity of the film is impaired. If the thickness exceeds 400 [nm], the DC resistance value increases and the conductive film 4 This is because cracks are easily formed.

  The catalyst layer 3 may basically have any configuration as long as it has a catalytic action for the reduction reaction, but includes at least one of materials having a catalytic action for the reducing action at least in part. In addition, a configuration having high physical and electrical affinity with the conductive film 4 is preferable.

The material constituting the catalyst layer 3 may be basically any material as long as it has a catalytic action for the reduction reaction, but it is preferable to use an electrochemically stable material. Specifically, platinum, gold, carbon, ruthenium, rhodium, palladium, osmium, iridium, conductive polymer, and the like can be given. Among the materials listed above, carbon may be basically any material as long as it is a substance composed of simple carbon, and preferably includes conductive carbon particles. Specific examples of the conductive carbon particles include carbon black, and among them, those having a large specific surface area are preferable. Carbon black preferably has a high electric conductivity. Further, carbon black is preferably one that easily forms a structure structure. The average primary particle size of carbon black is preferably 3 [nm] or more and 40 [nm] or less, more preferably 3 [nm] or more and 24 [nm] or less, and more preferably 3 [nm]. It is most preferable that it is 15 [nm] or less. Specific examples of the carbon black include ketjen black, furnace black, lamp black, channel black, acetylene black, and thermal black. Among these, ketjen black that is inexpensive and has a large specific surface area is preferable. In addition to the carbons listed above, carbon is linear or rod-like carbon, sheet-like carbon crystal, graphite, graphite ribbon, graphite, amorphous carbon (glassy carbon), diamond-like carbon, carbon fiber, activated carbon, Petroleum coke, fullerenes such as C ₆₀ and C ₇₀ , single-walled or multi-walled carbon nanotubes may be used, but carbon is not limited to these. Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, and derivatives thereof. However, the conductive polymer is not limited to these, and the material constituting the catalyst layer 3 is also described above. The catalyst layer 3 can also be configured by appropriately combining the materials listed above.

  The catalyst layer 3 may have any shape as long as it has a configuration in contact with the conductive film 4, but is typically provided by being laminated on the conductive film 4. The catalyst layer 3 may be composed of a plurality of catalyst layers, and may be configured by stacking catalyst layers having the same configuration, or may be configured by stacking catalyst layers having different configurations. The thickness of the catalyst layer 3 is preferably 5 [μm] or more and 200 [μm] or less, more preferably 5 [μm] or more and 100 [μm] or less, and 10 [μm]. It is most preferable that it is 100 [μm] or less. This is because when the thickness of the catalyst layer 3 is 5 [μm] or less, the ability to reduce redox species in the electrolytic solution constituting the electrolyte layer 8 is lowered, and the photoelectric conversion efficiency is lowered. Further, when the thickness of the catalyst layer 3 is 200 [μm] or more, the potential movement inside the counter electrode 1 cannot be performed smoothly.

  Further, the catalyst layer 3 is preferably formed so that a fine structure is formed on the surface of the catalyst layer 3 and an actual surface area is increased in order to improve the catalytic action for the reduction reaction. The actual surface area includes mesopores of carbon particles when the catalyst layer 3 is made of conductive carbon. The actual surface area of the catalyst layer 3 is preferably 10 times or more, and particularly preferably 100 times or more the area (projected area) of the outer surface of the catalyst layer 3.

[Method for producing counter electrode for dye-sensitized photoelectric conversion element]
Next, the manufacturing method of the counter electrode 1 for dye-sensitized photoelectric conversion elements according to the first embodiment will be described.
First, a metal plate that is the metal substrate 2 is prepared.
Next, the conductive film 4 is formed on the entire main surface of the metal substrate 2. The method for forming the conductive film 4 is not particularly limited. Specifically, for example, chemical vapor deposition (CVD) such as plasma CVD, and physical vapor deposition (PVD) such as ion plating. , Ionized vapor deposition, sputtering or the like. Further, when the conductive film 4 is formed, the non-conductive layer of the metal substrate 2, for example, a resistance layer component such as an oxide film, is sufficiently removed by etching treatment, plasma treatment using an inert gas, or the like. Is preferred. In addition, the shorter the time from the removal process to the formation process of the conductive film 4 is, the better. The movement space during the formation process is desirably in an environment where it is difficult to form a nonconductive layer such as a nitrogen atmosphere or a vacuum atmosphere.

  Next, the catalyst layer 3 is formed on the surface of the conductive film 4. Although the formation method of the catalyst layer 3 is not specifically limited, For example, when the catalyst layer 3 is a conductive carbon layer, a wet film forming method or the like is used. Further, when the catalyst layer 3 is a metal layer, for example, a sputtering method, a chemical vapor deposition method, an ionization deposition method, or the like is used. Further, when the catalyst layer 3 is, for example, a conductive polymer layer, a wet film forming method or the like is used. In the wet film forming method, it is preferable to prepare a paste-like dispersion and apply or print this dispersion on at least a part of the surface of the conductive film 4.

  The formation method when the catalyst layer 3 is a conductive carbon layer is specifically prepared by preparing a paste-like dispersion liquid in which carbon, an organic binder, and an inorganic binder are uniformly dispersed in a solvent and printing paste And Next, the printing paste is printed as a paint on the surface of the conductive film 4, a coating film is formed on at least a part of the surface of the conductive film 4, and a carbon coating film is formed on the conductive film 4. A metal substrate 2 was obtained. Next, the obtained carbon coating film is baked. This is because by firing the carbon coating film, the carbons are electrically and mechanically connected to each other to improve the conductivity and mechanical strength, and further, the binding property to the conductive film 4 is enhanced. This is because the catalyst layer 3 is obtained. Moreover, the organic binder in the said carbon coating film lose | disappears by baking, a pore is formed in the catalyst layer 3 obtained, and the real surface area of the catalyst layer 3 becomes large. In this way, the catalyst layer 3 is formed on the conductive film 4, and the desired counter electrode 1 for the dye-sensitized photoelectric conversion element is obtained. When the catalyst layer 3 is composed of a plurality of layers, the catalyst layer 3 may be obtained by further forming and baking a carbon coating film on the carbon coating film formed on the metal substrate 2, The catalyst layer 3 may be obtained by firing a carbon coating film formed on the metal substrate 2 and further forming and firing a carbon coating film on the obtained sintered body.

The carbon, inorganic binder, and organic binder blended in the printing paste can be appropriately selected from conventionally known materials. Preferably, carbon black is used as carbon, titanium oxide (TiO ₂ ) is used as the inorganic binder, and organic binder is used. Ethyl cellulose is selected as the binder.

<Example 1>
The counter electrode 1 was manufactured as follows.
First, a SUS304 steel plate having a thickness of 1000 [μm] was prepared as the metal substrate 2.
Next, the entire surface of one main surface of the SUS304 steel plate is etched to remove the nonconductive layer. After removing the nonconductive layer, a TiN film as the conductive film 4 was formed on the entire surface of one main surface of the SUS304 steel plate by sputtering, and the metal substrate 2 having the conductive film 4 was obtained. The thickness of the obtained TiN film was 300 [nm].

  Next, ketjen black and graphite as carbon, titanium oxide as an inorganic binder, and ethyl cellulose as an organic binder were added to terpineol as a solvent, and the mixture was stirred and dispersed to prepare a paste-like dispersion to obtain a printing paste.

  Next, at least a part of the TiN film formed on the SUS304 steel sheet was printed with the printing paste prepared in the previous step as a paint with a printing machine to obtain a carbon coating film on the TiN film. Then, in order to evaporate the solution in the obtained coating film, it heated and dried with a 100 degreeC hotplate, and the metal substrate 2 which has a conductive carbon layer on the conductive film 4 was obtained.

Next, the obtained conductive carbon layer was fired. The temperature was raised to 400 ° C. in 1 hour and 30 minutes, and the mixture was kept at 400 ° C. for 30 minutes and calcined. By this step, ethyl cellulose is completely decomposed and lost.
Next, a carbon coating film is further formed and fired on the fired conductive carbon layer in the same manner. The child process is performed twice to obtain the catalyst layer 3 which is a three-fired carbon layer. Thus, the metal substrate 2 having the catalyst layer 3 on the conductive film 4 was obtained. The obtained catalyst layer 3 had a thickness of about 35 [μm].
Thus, the intended counter electrode 1 for a dye-sensitized photoelectric conversion element was manufactured.

<Example 2>
A counter electrode 1 for a dye-sensitized photoelectric conversion element was manufactured in the same manner as in Example 1 except that a TiCN film was formed instead of the TiN film as the conductive film 4 on the entire main surface of the SUS304 steel plate. The thickness of the obtained TiCN film was 300 [nm].

<Example 3>
After removing the non-conductive layer, an ATO film is formed on the entire main surface of the SUS304 steel plate by sputtering, and an ITO film is further formed on at least a part of the formed ATO film by sputtering. A counter electrode 1 for a dye-sensitized photoelectric conversion element was produced in the same manner as in Example 1 except that an ATO / ITO laminated film as a conductive film was used and the conductive film 4 was used. The film thickness of the obtained ATO / ITO laminated film was 200 [nm].
Otherwise, the counter electrode 1 for a dye-sensitized photoelectric conversion element was produced in the same manner as in Example 1.

<Example 4>
A counter electrode 1 for a dye-sensitized photoelectric conversion element was produced in the same manner as in Example 1 except that the metal substrate 2 was SUS316.

<Example 5>

A counter electrode 1 for a dye-sensitized photoelectric conversion element was produced in the same manner as in Example 2 except that the metal substrate 2 was SUS316.
<Example 6>
A counter electrode 1 for a dye-sensitized photoelectric conversion element was produced in the same manner as in Example 3 except that the metal substrate 2 was SUS316.

<Example 7>
A counter electrode 1 was produced in the same manner as in Example 1 except that a CrN film as the conductive film 4 was formed on the entire main surface of the SUS304 steel plate.

<Example 8>
A counter electrode 1 was produced in the same manner as in Example 1 except that the Cr ₃ C ₂ film as the conductive film 4 was formed on the entire main surface of the SUS304 steel plate.

<Comparative Example 1>
A counter electrode 1 was produced in the same manner as in Example 1 except that the conductive film 4 was not formed on the SUS304 steel plate.

<Comparative example 2>
A titanium (Ti) plate having a thickness of 1000 [μm] was prepared as the metal substrate 2.

  Next, the entire main surface of the titanium plate is etched to remove the non-conductive layer. Next, a printing paste was printed as a paint on at least a part of the metal substrate 2 with a printing machine to obtain a coating film on the metal substrate 2. Then, in order to evaporate the solution in the obtained coating film, it was heated and dried on a 100 ° C. hot plate to obtain a metal substrate 2 having a carbon layer. Other than that, the target counter electrode 1 was obtained in the same manner as in Example 1. The same printing paste as in Example 1 was used. The thickness of the obtained catalyst layer 3 was 35 [μm].

  As described above, according to the first embodiment, the counter electrode 1 for the dye-sensitized photoelectric conversion element has a configuration in which the catalyst layer 3 is laminated on the metal substrate 2 having the conductive film 4. Low-cost general-purpose metal materials such as aluminum (Al) and stainless steel (SUS) can be applied to the metal substrate, and can be manufactured at low cost. In particular, when the catalyst layer 3 is a carbon catalyst layer, a large-scale facility is not required for manufacturing, and an expensive platinum material is not used, so the counter electrode 1 for a dye-sensitized photoelectric conversion element is manufactured at low cost. be able to.

<2. Second Embodiment>
[Dye-sensitized photoelectric conversion element]
Next, the dye-sensitized photoelectric conversion element 10 according to the second embodiment will be described.
In the second embodiment, the counter electrode 1 of the dye-sensitized photoelectric conversion element according to the first embodiment is used as the counter electrode 1 of the dye-sensitized photoelectric conversion element 10.

FIG. 2 is a cross-sectional view of the main part showing the basic configuration of the dye-sensitized photoelectric conversion element 10 according to the second embodiment.
As shown in FIG. 2, the dye-sensitized photoelectric conversion element 10 is provided with a transparent electrode 6 on one main surface of a transparent substrate 5. A porous electrode 7 is provided on at least a part of the transparent electrode 6. One or more kinds of photosensitizing dyes (not shown) are bonded to the porous electrode 7. As the counter electrode 1, the counter electrode 1 according to the first embodiment is used. An electrolyte layer 8 made of an electrolytic solution is filled between the porous electrode 7 on the transparent substrate 5 and the counter electrode 1. The catalyst layer 3 and the porous electrode 7 are opposed to each other with the electrolyte layer 8 interposed therebetween. Between the transparent substrate 5 and the metal substrate 2, a sealing body 9 is provided in contact with the conductive film 4 formed on the metal substrate 2 in a form that does not leak the electrolyte of the electrolyte layer 8.

As the porous electrode 7, a porous semiconductor layer in which semiconductor fine particles are sintered is typically used. The photosensitizing dye is adsorbed on the surface of the semiconductor fine particles. As a material for the semiconductor fine particles, an elemental semiconductor typified by silicon, a compound semiconductor, a semiconductor having a perovskite structure, or the like can be used. These semiconductors are preferably n-type semiconductors in which conduction band electrons become carriers under photoexcitation and generate an anode current. Specifically, for example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), tungsten oxide (WO ₃ ), niobium oxide (Nb ₂ O ₅ ), strontium titanate (SrTiO ₃ ), tin oxide (SnO ₂ ). Such semiconductors are used. Among these semiconductors, it is preferable to use TiO ₂ , especially anatase TiO ₂ . However, the types of semiconductors are not limited to these, and two or more types of semiconductors can be mixed or combined as necessary. Further, the shape of the semiconductor fine particles may be any of a particulate shape, a tube shape, a rod shape, and the like.

  The particle diameter of the semiconductor fine particles is not particularly limited, but the average primary particle diameter is preferably 1 [nm] or more and 200 [nm] or less, particularly 5 [nm] or more and 100 [nm] or less. Is preferred. It is also possible to improve the quantum yield by mixing particles having a size larger than that of the semiconductor fine particles and scattering incident light with these particles. In this case, the average size of the separately mixed particles is preferably 20 [nm] or more and 500 [nm] or less, but the separately mixed particles are not limited thereto.

  The porous electrode 7 preferably has a large actual surface area so that as many photosensitizing dyes as possible can be bonded. The actual surface area includes mesopores of semiconductor particles constituting the porous electrode 7. The actual surface area in a state where the porous electrode 7 is formed on the transparent electrode 6 is preferably 10 times or more with respect to the area (projected area) of the outer surface of the porous electrode 7, and 100 times The above is particularly preferable. This ratio has no particular upper limit, but is usually about 1000 times.

  The shape of the porous electrode 7 may be basically any shape. In particular, when the sealing body 9 is provided between the transparent substrate 5 and the metal substrate 2, the sealing body 9 is formed on at least a part of a portion other than the outer edge portion on the transparent substrate 5 on which 9 is provided. In particular, in the case where the current collector wiring is provided on the transparent substrate 5, the shape of the porous electrode 7 is appropriately selected depending on the shape of the current collector wiring.

  The thickness of the porous electrode 7 is preferably 0.1 [μm] or more and 100 [μm] or less, and more preferably 1 [μm] or more and 50 [μm] or less. And it is most preferable that it is 3 [μm] or more and 30 [μm] or less. This is because when the thickness of the porous electrode 7 is 0.1 [μm] or less, the number of semiconductor fine particles contained per unit projected area is small, so that photosensitization that can be maintained in the unit projected area is possible. This is because the amount of the dye is small and light cannot be absorbed efficiently. Further, when the thickness of the porous electrode 7 exceeds 100 [μm], the distance by which electrons transferred from the photosensitizing dye to the porous electrode 7 diffuse until reaching the transparent electrode 6 increases. This is because the loss of electrons due to charge recombination within 7 also increases.

  The transparent substrate 5 is not particularly limited as long as it has a material and shape that easily transmit light, and various materials can be used, and in particular, a substrate material having a high visible light transmittance is used. Is preferred. In addition, a material having a high blocking performance for blocking moisture and gas from entering the dye-sensitized photoelectric conversion element 10 from the outside and having excellent solvent resistance and weather resistance is preferable. Specific examples of the material for the transparent substrate 5 include transparent inorganic materials, transparent plastics, and the like. Examples of the transparent substrate 5 include quartz glass, borosilicate glass, phosphate glass, and soda glass. For transparent plastics, for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, acetyl cellulose, tetraacetyl cellulose, polyphenylene sulfide, polycarbonate, polyethylene, polypropylene, polyvinylidene fluoride, brominated phenoxy, amides, poly Polyimides such as etherimide, polystyrenes, polyarylates, polysulfones such as polyestersulfone, polyolefins and the like can be mentioned. Further, the thickness of the transparent substrate 5 is not particularly limited, and can be appropriately selected in consideration of the light transmittance and the performance of blocking the inside and outside of the photoelectric conversion element.

  The transparent electrode 6 provided on the transparent substrate 5 is a conductive thin film, and the smaller the sheet resistance, the better. Specifically, it is preferably 1 [Ω / □] or more and 500 [Ω / □] or less, and more preferably 1 [Ω / □] or more and 100 [Ω / □] or less. This is because if it exceeds 100 [Ω / □], the internal resistance of the transparent electrode 6 remarkably increases. Further, the thickness of the transparent electrode 6 which is a thin film is preferably 100 [nm] or more and 500 [nm]. This is because when the thickness is less than 100 [nm], the surface resistance value and the internal resistance increase, and when it exceeds 500 [nm], the transparent electrode 6 is easily cracked. Moreover, a well-known material can be used as a material which comprises the transparent electrode 6, and it selects as needed. Typically, a metal oxide, for example, indium-tin composite oxide (ITO), fluorine-doped tin oxide (IV) SnO2 (FTO), tin oxide (IV) SnO2, zinc oxide (II) Examples thereof include ZnO and indium-zinc composite oxide (IZO). However, the material constituting the transparent electrode 6 is not limited to these, and may be a thin film of metal or mineral. For example, platinum, gold, silver, chromium, copper, tungsten, Aluminum etc. are mentioned. Moreover, it can also be set as the transparent electrode 6 combining two or more types mentioned above.

  The photosensitizing dye to be bonded to the porous electrode 7 is not particularly limited as long as it exhibits a sensitizing action, but those having an acid functional group adsorbed on the surface of the porous electrode 7 are preferable. In general, the photosensitizing dye preferably has a carboxy group, a phosphoric acid group, and the like, and among them, those having a carboxy group are particularly preferable. Specific examples of the photosensitizing dye include xanthene dyes, cyanine dyes, basic dyes, porphyrin compounds, and the like. Examples of xanthene dyes include rhodamine B, rose bengal, eosin, and erythrosine. Examples of cyanine dyes include merocyanine, quinocyanine, and cryptocyanine. Examples of basic dyes include phenosafranine, fog blue, thiocin, and methylene blue, and porphyrin compounds. Then, for example, chlorophyll, zinc porphyrin, magnesium porphyrin and the like can be mentioned. Others applicable to the photosensitizing dye include, for example, azo dyes, phthalocyanine compounds, coumarin compounds, bipyridine complex compounds, anthraquinone dyes, polycyclic quinone dyes, and the like. Among these, the quantum yield is high, the ligand (ligand) includes a pyridine ring or an imidazolium ring, ruthenium (Ru), osmium (Os), iridium (Ir), platinum (Pt), cobalt (Co), A pigment of at least one metal complex selected from the group consisting of iron (Fe) and copper (Cu) is preferred. Further, among these, cis-bis (isothiocyanate) -N, N-bis (2,2′-dipyridyl-4,4′-dicarboxylic acid) -ruthenium (II) or tris (isothione) has a particularly wide absorption wavelength range. Oxanato) -ruthenium (II) -2,2 '.: 6', 2 "-terpyridine-4,4 ', 4" -tricarboxylic acid is preferred as a dye molecule. Is not limited to these. Moreover, as a photosensitizing dye, typically one of these is used, but two or more kinds of photosensitizing dyes may be mixed and used. When two or more kinds of photosensitizing dyes are used in combination, the photosensitizing dye is preferably an inorganic complex dye having a property of causing MLCT (Metal to Ligand Charge Transfer) held in the porous electrode 7. And an organic molecular dye having the property of intramolecular CT (Charge Transfer) held in the porous electrode 7. In this case, the inorganic complex dye and the organic molecular dye are adsorbed on the porous electrode 7 in different conformations. The inorganic complex dye preferably has a carboxy group or a phosphono group as a functional group bonded to the porous electrode 7. The organic molecular dye preferably has a carboxy group or a phosphono group and a cyano group, an amino group, a thiol group, or a thione group as functional groups bonded to the porous electrode 7 on the same carbon. The inorganic complex dye is, for example, a polypyridine complex, and the organic molecular dye is, for example, an aromatic polycyclic conjugated molecule having an electron donating group and an electron accepting group and having intramolecular CT properties.

Examples of the electrolytic solution constituting the electrolyte layer 8 include a solution containing a redox system (redox pair). Specific examples of the redox system include a combination of iodine (I ₂ ) and a metal or organic iodide salt, a combination of bromine (Br ₂ ) and a metal or organic bromide salt, or the like. . The cations constituting the metal salt are, for example, lithium (Li ⁺ ), sodium (Na ⁺ ), potassium (K ⁺ ), cesium (Cs ⁺ ), magnesium (Mg ²⁺ ), calcium (Ca ²⁺ ) and the like. . Further, as the cation constituting the organic salt, quaternary ammonium ions such as tetraalkylammonium ions, pyridinium ions and imidazolium ions are suitable. These may be used alone or in combination of two or more. Can be used.

  In addition to the above, the electrolyte solution constituting the electrolyte layer 8 includes a metal complex such as a combination of ferrocyanate and ferricyanate, a combination of ferrocene and ferricinium ion, sodium polysulfide, alkylthiol, and the like. Sulfur compounds such as combinations with alkyl disulfides, viologen dyes, combinations of hydroquinone and quinone, and the like can also be used.

  If the sealing body 9 has a structure that prevents leakage of the electrolyte of the electrolyte layer 8 to the outside, drying of the electrolyte in the electrolyte layer 8, mixing of substances into the electrolyte layer 8, etc., basically. Any material may be used, and as the material of the sealing body 9, it is preferable to use a material having light resistance, insulation, moisture resistance, and the like. The sealing body 9 may be transparent or opaque, but the sealing body 9 is preferably capable of transmitting light having a wavelength of 340 [nm] or more, and the wavelength is 380 [nm]. It is more preferable that light having a wavelength of 900 [nm] or less can be transmitted, and it is most preferable that light having a wavelength of 400 [nm] or more and 800 [nm] or less can be transmitted. Specific examples of the material constituting the encapsulant 9 are epoxy resin, thermosetting isomeric resin, ultraviolet (UV) curable resin, heat welding resin, acrylic resin, polyisobutylene resin, EVA (ethylene vinyl acetate), ionomer. Resin, ceramic, various heat-sealing films, etc., which may be a mixture of inorganic filler, metal filler, carbon particles, etc. dispersed in the above-mentioned materials, Is not limited to those listed above, and the sealing body 9 can be configured by appropriately combining those listed above. The sealing body 9 is typically provided between the transparent substrate 5 and the metal substrate 2, but is not limited thereto, and the outer peripheral portions of the transparent substrate 5 and the metal substrate 2 are sealed with the sealing body 9. 9 may be sealed.

[Operation of dye-sensitized photoelectric conversion element]
Next, the operation of the dye-sensitized photoelectric conversion element 10 according to the second embodiment will be described.
When the light is incident, the dye-sensitized photoelectric conversion element 10 operates as a battery having the counter electrode 1 as a positive electrode and the transparent electrode 6 as a negative electrode. The principle is as follows. Here, it is assumed that FTO is used as the material of the transparent electrode 6, TiO ₂ is used as the material of the porous electrode 7, and a redox species of I ⁻ / I ₃ ⁻ is used as the redox pair. It is not limited to this configuration. Further, it is assumed that one kind of photosensitizing dye is bonded to the porous electrode 7.

When a photosensitizing dye that has passed through the transparent substrate 5 and the transparent electrode 6 and has entered the porous electrode 7 and has been bonded to the porous electrode 7 is absorbed, electrons in the photosensitizing dye are released from the ground state (HOMO). Excited to an excited state (LUMO). The electrons thus excited are drawn out to the conduction band of TiO ₂ constituting the porous electrode 7 through electrical coupling between the photosensitizing dye and the porous electrode 7, and pass through the porous electrode 7. It reaches the transparent electrode 6.

On the other hand, the photosensitizing dye that has lost the electrons receives electrons from the reducing agent in the electrolyte layer 8, for example, I by the following reaction, and oxidants such as I ₃ ⁻ (I ₂ and I ⁻ Conjugate).
2I ⁻ → I ₂ + 2e ^{−
_{I 2 + I - → I 3}} -

The oxidant thus generated reaches the catalyst layer 3 constituting the counter electrode 1 by diffusion, receives electrons from the catalyst layer 3 by the reverse reaction of the above reaction, and is reduced to the original reducing agent.
^{_{I 3 - → I 2 + I}} -
I ₂ + 2e ^- → 2I ^-

  The electrons sent from the transparent electrode 6 to the external circuit perform electrical work in the external circuit, and then return to the catalyst layer 3 through the metal substrate 2 and the conductive film 4 constituting the counter electrode 1. In this way, light energy is converted into electrical energy without leaving any change in the photosensitizing dye or the electrolyte layer 8.

[Method for producing dye-sensitized photoelectric conversion element]
Next, a method for manufacturing the dye-sensitized photoelectric conversion element 10 according to the second embodiment will be described.
First, a transparent plate is prepared as the transparent substrate 5. Next, the transparent electrode 6 is formed by forming a transparent conductive layer on one main surface of the transparent substrate 5 by sputtering or the like.

  On the transparent electrode 6, a current collecting wiring may be formed by vacuum-depositing metal in a desired pattern. The metal used is preferably aluminum (Al). Further, the current collector wiring protective layer is formed by oxidizing the surface of the current collector wiring by heat treatment, electrical treatment or chemical treatment. The current collector wiring can also be formed by welding, adhesion, fusion, coating, plating, sputtering, various CVD methods, and the like. Further, the current collecting wiring may be formed by printing a mixture of conductive particles and resin on the transparent electrode 6 by screen printing and then firing. The conductive particles are preferably metal particles.

  Next, the porous electrode 7 is formed on the surface on the transparent electrode 6. The method for forming the porous electrode 7 is not particularly limited, but in consideration of physical properties, convenience, manufacturing cost, etc., it is preferable to use a wet film forming method. In the wet film forming method, a paste-like dispersion liquid in which a powder or sol of semiconductor fine particles is uniformly dispersed in a solvent such as water is prepared, and this dispersion liquid is applied or printed on the transparent electrode 6 of the transparent substrate 5. Is preferred. There is no restriction | limiting in particular in the application method or printing method of a dispersion liquid, A well-known method can be used. Specifically, as a coating method, for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or the like can be used. Moreover, as a printing method, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method, etc. can be used.

When anatase-type TiO ₂ is used as the material for the semiconductor fine particles, this anatase-type TiO ₂ may be a commercially available product in the form of powder, sol, or slurry, or is known such as hydrolyzing titanium oxide alkoxide. A material having a predetermined particle diameter may be formed by a method. When using a commercially available powder, it is preferable to eliminate secondary agglomeration of the particles, and it is preferable to pulverize the particles using a mortar, ball mill or the like when preparing the paste-like dispersion. At this time, acetylacetone, hydrochloric acid, nitric acid, a surfactant, a chelating agent, and the like can be added to the paste-like dispersion in order to prevent the particles from which secondary aggregation has been eliminated from aggregating again. In addition, in order to increase the viscosity of the paste-like dispersion, polymers such as polyethylene oxide and polyvinyl alcohol, or various thickeners such as a cellulose-based thickener can be added to the paste-like dispersion.

  The porous electrode 7 is formed by coating or printing semiconductor fine particles on the transparent electrode 6, and then electrically connecting the semiconductor fine particles to improve the mechanical strength of the porous electrode 7, thereby improving adhesion with the transparent electrode 6. In order to improve, it is preferable to form by baking. There is no particular limitation on the range of the firing temperature, but if the temperature is raised too much, the electrical resistance of the transparent electrode 6 increases, and the transparent electrode 6 may melt. 40 ° C. or higher and 650 ° C. or lower is more preferable. Moreover, although there is no restriction | limiting in particular in baking time, Usually, it is about 10 minutes or more and 10 hours or less.

  After the porous electrode 7 is baked, for example, a dip with a titanium tetrachloride aqueous solution or a titanium oxide ultrafine particle sol having a diameter of 10 nm or less in order to increase the surface area of the semiconductor fine particles or increase the necking between the semiconductor fine particles. Processing may be performed. When a plastic substrate is used as the transparent substrate 5 that supports the transparent electrode 6, the porous electrode 7 is formed on the transparent electrode 6 using a paste-like dispersion containing a binder, and the transparent electrode 6 is heated by pressing. It is also possible to pressure-bond to.

  Next, the photosensitizing dye is bonded to the porous electrode 7 by immersing the transparent substrate 5 on which the porous electrode 7 is formed in a solution in which the photosensitizing dye is dissolved in a predetermined solvent.

  The method for adsorbing the photosensitizing dye to the porous electrode 7 is not particularly limited. For example, the photosensitizing dye may be an alcohol, nitrile, nitromethane, halogenated hydrocarbon, ether, dimethyl sulfoxide, amide, It is dissolved in a solvent such as N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates, ketones, hydrocarbons, water, and the porous electrode 7 is immersed in the solution. A solution containing a photosensitizing dye can be applied on the porous electrode 7. Further, deoxycholic acid or the like may be added for the purpose of reducing association between molecules of the photosensitizing dye. Moreover, a ultraviolet absorber can also be used together as needed. Further, after the photosensitizing dye is adsorbed on the porous electrode 7, the surface of the porous electrode 7 may be treated with amines for the purpose of promoting the removal of the excessively adsorbed photosensitizing dye. . Examples of amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine, and the like. When these are liquid, they may be used as they are, or may be used after being dissolved in an organic solvent.

  Next, the counter electrode 1 was manufactured by the manufacturing method shown in the embodiment, and the counter electrode 1 in which the metal substrate 2 and the catalyst layer 3 were bound via the conductive film 4 was obtained. At this time, the catalyst layer 3 is not formed at the end portion on the conductive film 4, and the conductive film 4 is exposed at the end portion of the counter electrode 1.

  Next, the transparent substrate 5 and the metal substrate 2 are arranged so that the porous electrode 7 and the catalyst layer 3 have a predetermined interval. For example, the interval is preferably 1 [μm] or more and 100 [μm] or less, and more preferably 1 [μm] or more and 50 [μm] or less.

And the sealing body 9 is formed in the outer peripheral part of the transparent substrate 5 and the metal substrate 2, and the space in which the electrolyte layer 8 is enclosed is made, for example, the liquid injection port (not shown) previously formed in the transparent substrate 5 in this space The electrolyte layer 8 is formed by injecting an electrolyte solution. Thereafter, the liquid injection port is closed.
Thus, the target dye-sensitized photoelectric conversion element 10 is manufactured.

  Further, the conductive film 4 is exposed at the end of the counter electrode 1, and the sealing body 9 is disposed in contact with the transparent substrate 5 or the transparent electrode 6 and the conductive film 4 exposed at the end of the counter electrode 1. The body 9 may be cured.

  The curing method of the sealing body 9 may be basically any method. Specifically, for example, if the sealing body 9 is an ultraviolet curable resin, a method of curing by irradiating with ultraviolet rays. Moreover, for example, if the sealing body 9 is a thermosetting resin, a method of curing by applying heat or infrared rays may be used. In particular, if the sealing body 9 is a resin in which an ultraviolet (UV) curable resin and a thermosetting resin are combined, the ultraviolet rays that have passed through the sealing body 9 when irradiated with ultraviolet rays are absorbed by the conductive film 4, Is generated, the sealing body 9 is heated, and the binding and curing at the adhesive interface with the conductive film 4 is promoted, so that the binding property with the sealing body 9 is remarkably improved. The stopping performance is also greatly improved. The wavelength of the ultraviolet rays to be used is preferably 360 [nm] or more and 370 [nm] or less, but is not limited thereto. Further, in the case where the sealing body 9 is a heat welding resin, a method of welding the sealing body 9 and the conductive film 4 by irradiating a laser can be mentioned, and the sealing body 9 is transmitted through the laser irradiation. The absorbed laser light is absorbed by the conductive film 4 and generates heat (at 200 ° C. or higher), so that the bonding property between the conductive film 4 and the sealing body 9 is dramatically improved, and the sealing performance is also dramatically improved. To improve. . The laser to be used is typically an infrared laser, and the wavelength is preferably 700 [nm] or more and 1000 [nm] or less, and more preferably 800 [nm] or more and 900 [nm] or less. Although the laser to be used is not limited to this, a visible light laser, an ultraviolet laser, or the like may be used. In addition, the method for curing the sealing body 9 can be appropriately combined with the methods listed above, but is not limited to these methods.

Next, an electrolyte solution is injected into a space formed by the transparent substrate 5, the metal substrate 2, and the sealing body 9, for example, from a liquid injection port (not shown) formed in the transparent substrate 5 in advance. 8 is formed. Thereafter, the liquid injection port is closed.
Thus, the target dye-sensitized photoelectric conversion element 10 is manufactured.

<Example 9>
The dye-sensitized photoelectric conversion element 10 was produced as follows.
First, as the transparent substrate 5 having the transparent electrode 6, a 1.1 [mm] thick Japanese plate glass FTO substrate for amorphous solar cells (sheet resistance 10 [Ω / □]) was prepared.
Next, this FTO substrate was immersed in a 0.2 [mol / l] titanium tetrachloride solution at 70 ° C. for 40 minutes. Thereafter, it was washed with pure water, rinsed with ethanol and sufficiently dried.

Next, a TiO ₂ paste PST-24NRT (Catalyst Chemical Industry Co., Ltd.) was applied onto the FTO layer of this FTO substrate by a screen method using a circular screen mask having a diameter of 5 mm, and a TiO ₂ coating film. Got.

Then overcoated with TiO ₂ paste PST-400C on the resulting TiO ₂ coating film to obtain a laminated TiO ₂ coating. Thereafter, the obtained laminated TiO ₂ coating film was held at 500 ° C. for 60 minutes and fired, and TiO ₂ fine particles were sintered on the FTO layer to obtain a TiO ₂ sintered body to be the porous electrode 7. The obtained TiO ₂ sintered body was a circle having a diameter of 5 [mm] and a thickness of 18 [μm].

Next, for the purpose of removing impurities from the produced TiO ₂ sintered body and enhancing the activity, UV exposure was performed for 3 minutes with an excimer lamp.

Next, a dye soaking solution prepared by dissolving Z991 as a photosensitizing dye and DPA (1-decylphosphonic acid) as a coadsorbent in a tert-butyl alcohol / acetonitrile mixed solvent (volume ratio 1: 1) as a solvent. Prepared. The mixing ratio of Z991 and DPA was a molar ratio of Z991: DPA = 4: 1. Next, the TiO ₂ sintered body was immersed in the prepared dye soaking solution for 24 hours at room temperature to carry the dye. This TiO ₂ sintered body was washed with acetonitrile, and the solvent was evaporated and dried in the dark. Thus, a porous electrode 7 carrying a photosensitizing dye was obtained.

On the other hand, to 3-methoxypropionitrile (abbreviation MPN) as a solvent, 1.0 [mol / l] methoxypropioimidazolium iodide, 0.05 [mol / l] lithium iodide (LiI), An electrolyte solution was prepared by dissolving 0.10 [mol / l] iodine (I ₂ ) and 0.25 [mol / l] N-butylbenzmidazole (NBB) as an additive.

  Next, the counter electrode 1 was manufactured by providing the catalyst layer 3 on the conductive film 4 by the method of Example 1.

Next, the transparent substrate 5 and the metal substrate 2 are arranged so that the porous electrode 7 and the counter electrode 1 face each other with a predetermined interval. And the sealing body (not shown) is formed in the outer peripheral part of the transparent substrate 5 and the metal substrate 2, the space in which the electrolyte layer 8 is enclosed is made, and the liquid injection previously formed in the transparent substrate 5, for example in this space The electrolyte layer 8 was formed by injecting from the mouth by using a liquid feed pump and expelling bubbles inside the device by reducing the pressure. Thereafter, the liquid injection port was sealed with a glass substrate using a sealing resin.
Thus, the intended dye-sensitized photoelectric conversion element 10 was manufactured.

<Example 10>
A dye-sensitized photoelectric conversion element 10 was produced in the same manner as in Example 9, except that the counter electrode 1 produced by the method of Example 2 was used.

<Example 11>
A dye-sensitized photoelectric conversion element 10 was produced in the same manner as in Example 9, except that the counter electrode 1 produced by the method of Example 3 was used.

<Example 12>
A dye-sensitized photoelectric conversion element 10 was produced in the same manner as in Example 9, except that the counter electrode 1 produced by the method of Example 4 was used.

<Example 13>
A dye-sensitized photoelectric conversion element 10 was produced in the same manner as in Example 9 except that the counter electrode 1 produced by the method of Example 5 was used.

<Example 14>
A dye-sensitized photoelectric conversion element 10 was produced in the same manner as in Example 9 except that the counter electrode 1 produced by the method of Example 6 was used.

<Example 15>
A dye-sensitized photoelectric conversion element 10 was produced in the same manner as in Example 9, except that the counter electrode 1 produced by the method of Example 7 was used.

<Example 16>
A dye-sensitized photoelectric conversion element 10 was produced in the same manner as in Example 9 except that the counter electrode 1 produced by the method of Example 8 was used.

<Comparative Example 3>
A dye-sensitized photoelectric conversion element 10 was manufactured in the same manner as in Example 9 except that the counter electrode 1 manufactured by the method of Comparative Example 1 was used.

<Comparative example 4>
A dye-sensitized photoelectric conversion element 10 was manufactured in the same manner as in Example 9 except that the counter electrode 1 manufactured by the method of Comparative Example 2 was used.

Table 1 shows photoelectric conversion when the dye-sensitized photoelectric conversion elements 10 of Examples 9 to 16 and Comparative Examples 3 to 4 immediately after production were irradiated with artificial sunlight (AM1.5, 100 [mW / cm ² ]). Efficiency Eff. [%], DC resistance R _S [Ω] measurement results are shown.

  As shown in Table 1, the photoelectric conversion efficiency Eff. Compared to the dye-sensitized photoelectric conversion elements 10 of Examples 9 to 14 and Comparative Example 4, the dye-sensitized photoelectric conversion elements 10 of Examples 15 and 16 and Comparative Example 3 showed remarkably low values.

  From this result, assuming that the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 has a configuration in which the catalyst layer 3 is directly formed on the metal substrate 2, the photoelectric conversion efficiency Eff. Shows a good value, but when the metal substrate 2 is a SUS substrate, the photoelectric conversion efficiency Eff. Was found to show only extremely low values. On the other hand, the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 has a configuration in which the metal substrate 2 and the catalyst layer 3 are bound via the conductive film 4, and the conductive film 4 is a TiN film, a TiCN film, When any one of the ATO / ITO laminated films is used, even if a SUS substrate is used as the metal substrate 2, the photoelectric conversion efficiency Eff. Was found to show a good value.

In the dye-sensitized photoelectric conversion element 10 of each example and comparative example, the photoelectric conversion efficiency Eff. It is considered that the cause of the large difference in the value of is that the value of the DC resistance R _S , which is one of the internal resistances of the dye-sensitized photoelectric conversion element 10, is greatly related. The DC resistance R _S indicates the difficulty of current flow between the positive electrode and the negative electrode of the dye-sensitized photoelectric conversion element 10, and the lower this value, the photoelectric conversion efficiency Eff. It is because it is thought that shows a favorable value.

When the value of the direct current resistance R _S in the dye-sensitized photoelectric conversion elements 10 of Examples 9 to 14 and Comparative Example 4 and the dye-sensitized photoelectric conversion elements 10 of Examples 15 and 16 and Comparative Example 3 are compared, The dye-sensitized photoelectric conversion elements 10 of 9 to 14 and Comparative Example 4 showed a low value of 35 [Ω] to 41 [Ω], whereas the dye-sensitized dyes of Examples 15 and 16 and Comparative Example 3 The photoelectric conversion element 10 showed a very high value of 65 [Ω] or more and 156 [Ω] or less. As a result, the photoelectric conversion efficiency Eff. It is considered that there is a close correlation between the value of DC and the value of DC resistance R _S. Accordingly, the DC resistance value R _S of the dye-sensitized photoelectric conversion element 10 is preferably 60 [Ω] or less, more preferably 50 [Ω] or less, and 42 [Ω] or less. Is most preferred, but is not limited to this range.

  Table 2 shows the volume resistivity and thermal expansion coefficient (linear expansion coefficient at 20 ° C.) of the material constituting the conductive film 4 in the dye-sensitized photoelectric conversion elements 10 of Examples 9 to 16.

As shown in Table 2, the volume resistivity of TiN, TiCN and ATO / ITO laminates that are the materials constituting the conductive film 4 in Examples 9 to 14 is 25 [μΩ · cm] and 52 [μΩ · cm] and 44 [μΩ · cm]. On the other hand, the volume resistivity of CrN and Cr ₃ C ₂ which are materials constituting the conductive film 4 in Examples 15 and 16 was 640 [μΩ · cm] and 98 [μΩ · cm], respectively. From this result, it is considered that there is a close relationship between the volume resistivity of the material constituting the conductive film 4 and the DC resistance of the dye-sensitized photoelectric conversion element 10. This is because the dye-sensitized photoelectric conversion element 10 in each example has the same configuration except for the counter electrode 1. Accordingly, the conductive film 4 preferably has a volume resistivity of 60 [μΩ · cm] or less, more preferably 57 [μΩ · cm] or less, and 52 [μΩ · cm] or less. However, it is not limited to these ranges.

Further, in Table 1, when the values of DC resistance R _S of Example 15 (CrN film) and Example 16 (Cr ₃ C ₂ film) are compared, the value is the dye-sensitized photoelectric conversion element of Example 15. The dye-sensitized photoelectric conversion element 10 of Example 16 is larger than 10. On the other hand, when the volume resistivity of CrN and Cr3C2 is compared, the value of volume resistivity of CrN is significantly larger than that of Cr ₃ C ₂ . Example 15 and Example 16 have the same configuration except for the conductive film 4, and the film thickness of the conductive film 4 is also the same. Then, from this result, the value of the DC resistance RS of the dye-sensitized photoelectric conversion element 10 not only increases in proportion to the volume resistivity of the material constituting the conductive film 4, but also increases in DC resistance. There appears to be yet another factor that increases R _S.

Another possible factor is a decrease in physical and electrical binding properties at the contact interface due to thermal expansion. In particular, this problem is considered to occur remarkably when the process for producing the counter electrode 1 has a high temperature step such as firing. As a specific example, if the high temperature state of the counter electrode 1 continues, a difference in expansion occurs between the conductive film 4 and the metal substrate 2. As a result, distortion occurs at the contact interface between the conductive film 4 and the metal substrate 2, which leads to a decrease in physical and electrical binding properties at the contact interface. Thereby, the interface resistance value increases at the contact interface such as between the metal substrate 2 and the conductive film 4, and this is considered to increase the value of the DC resistance R _S.

Here, when the thermal expansion coefficients of CrN and Cr ₃ C ₂ are compared with respect to the linear expansion coefficient at 20 ° C., the linear expansion coefficient of CrN is as small as 2.3 × 10 ⁻⁶ [K ⁻¹ ]. On the other hand, the linear expansion coefficient of Cr ₃ C ₂ showed a large value of 11.7 × 10 ⁻⁶ [K ⁻¹ ]. The linear expansion coefficient of TiN is 9.4 (10 ⁻⁶ / K), the linear expansion coefficient of TiCN is 7.6 × 10 ⁻⁶ [K ⁻¹ ], and the linear expansion coefficient of the ATO / ITO laminate is 8. Since it is 4 × 10 ⁻⁶ [K ⁻¹ ], the coefficient of linear expansion of Cr ₃ C ₂ is large with respect to these materials. Since the dye-sensitized photoelectric conversion elements 10 of Example 15 and Example 16 have the same configuration except for the counter electrode 1, this result is due to the difference in the configuration of the counter electrode 1. Conceivable. That is, since the conductive film 4 of the counter electrode 1 is a Cr ₃ C ₂ film having a large linear expansion coefficient, a large strain is generated at the contact interface between the SUS substrate and the Cr ₃ C ₂ film when heat treatment is performed. This is considered to be because the interfacial resistance was remarkably increased along with the decrease in the binding property.

As a result, the dye-sensitized photoelectric conversion element 10 in which the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4 has a value of the DC resistance R _S depending on the linear expansion coefficient of the conductive film 4. Greatly increases and the photoelectric conversion efficiency Eff. Was shown to decrease. Accordingly, the linear expansion coefficient of the conductive film 4 is preferably within a certain range, and the linear expansion coefficient at 20 ° C. of the conductive film 4 is 7.6 × 10 ⁻⁶ [K ⁻¹ ] or more. It is preferably 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less, and more preferably 7.6 × 10 ⁻⁶ [K ⁻¹ ] or more and 9.4 or less. In addition, since the electrical binding property of the contact interface between the conductive film 4 and the metal substrate 2 is considered to be reduced by thermal expansion, the difference in linear expansion coefficient between the conductive film 4 and the metal substrate 2 is constant. A relationship is also considered necessary. This relationship is considered that the linear expansion coefficient at 20 ° C. of SUS304 is 16 × 10 ⁻⁶ [K ⁻¹ ] and the linear expansion coefficient at 20 ° C. of SUS316 is 17.3 × 10 ⁻⁶ [K ⁻¹ ]. The difference in linear expansion coefficient between the conductive film 4 and the metal substrate 2 is preferably 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less, It is more preferably 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 9.0 × 10 ⁻⁶ [K ⁻¹ ] or less, and 5.5 × 10 ⁻⁶ [K ⁻¹ ] or more and 8.4 ×. Most preferably, it is 10 ⁻⁶ [K ⁻¹ ] or less. In the case where the conductive film 4 and the metal substrate 2 have the above-described difference in linear expansion coefficient, the value of the linear expansion coefficient may be larger or smaller. However, it is preferable that the linear expansion coefficient of the conductive film 4 is larger. In addition, it is preferable to select the material of the conductive film 4 from the materials listed above in combination with the above-described volume resistivity R _S condition and thermal expansion coefficient condition. Furthermore, in addition to the above-mentioned conditions, it is preferable to select a material having high electrolytic solution resistance, in particular, high iodine electrolytic solution resistance.

Table 3 shows that among the materials used for the conductive film 4 listed above, the volume resistivity is 90 [μΩ · cm] or less and the linear expansion coefficient at 20 ° C. is 7.6 × 10 ⁻⁶ [K ^−1. ] 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less.

For example, when the metal substrate 2 is a SUS substrate, the material constituting the conductive film 4 is Ti, V, TiN, TiCN, TiB ₂ , TiC, VB ₂ , NbN as shown in Table 3. , NbB ₂ , Mo ₂ B ₅ , Mo ₂ C, W ₂ B ₅ , ATO / ITO laminate, IZO and the like are preferable, and among these materials, a material having high resistance to electrolytic solution is more preferable. , for _{example, TiN, TiCN, TiB 2,} TiC, VB 2, NbN, NbB 2, Mo 2 B 5, Mo 2 C, W 2 B 5, ATO / ITO laminate, IZO and the like, among which, in particular TiN, TiCN, ATO / ITO laminate, IZO, etc., which are highly resistant to iodine electrolyte, are most preferable, but the material used for the conductive film 4 is not limited to these, and the conductive film 4 is Suitable materials listed above In combination, it may be constructed.

  Next, in order to measure a change in characteristics over time with use of the dye-sensitized photoelectric conversion element 10, a reliability acceleration test of the dye-sensitized photoelectric conversion elements 10 of Examples 9 to 14 and Comparative Example 4 was performed and output. The characteristics were compared. In the reliability acceleration test, the dye-sensitized photoelectric conversion element 10 immediately after production is placed in a thermostatic chamber of 60 ° C. or more and 85 ° C. or less, and the dye-sensitized photoelectric conversion element 10 is irradiated with pseudo-sunlight of a certain intensity to be constant. A method of holding time was adopted. The performance evaluation of the dye-sensitized photoelectric conversion element 10 was performed on the dye-sensitized photoelectric conversion elements 10 of Examples 9 to 14.

  As a performance evaluation of the produced dye-sensitized photoelectric conversion element 10, first, the dye-sensitized photoelectric conversion element 10 having a configuration in which the counter electrode 1 is bonded to the SUS substrate and the catalyst layer 3 through a TiN film. went. Specifically, the counter electrode 1 has a configuration in which the SUS substrate and the catalyst layer 3 are bonded via a TiN film, and the dye-sensitized photoelectric conversion element 10 of Example 9 and Example 12, and the counter electrode 1 is Ti. The performance of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 having a configuration in which the catalyst layer is bound to the substrate was compared immediately after the element was produced. Furthermore, a reliability acceleration test was performed under the same conditions, and the performance of both elements was compared. Here, instead of the dye-sensitized photoelectric conversion element 10 of the comparative example 4 using the SUS substrate as the metal substrate 2 of the counter electrode 1 as a comparison target, the dye-sensitized photoelectric of the comparative example 4 using the Ti substrate as the metal substrate 2 is used. The reason why the conversion element 10 is used is that the photoelectric conversion performance of the dye-sensitized photoelectric conversion element 10 of Comparative Example 3 is extremely low at 2.39 [%] immediately after fabrication, and the aging durability performance is 20 hours from the start of measurement. At this level, the counter electrode 1 is destroyed due to corrosion by an electrolytic solution or the like and cannot be measured. For this reason, it is because it was judged that it is unsuitable to employ | adopt the dye-sensitized photoelectric conversion element 10 of the comparative example 3 as a comparison object of performance evaluation. Further, in the following performance evaluation of the dye-sensitized photoelectric conversion element 10, the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 is used for comparison for the same reason.

FIG. 3 shows simulated sunlight (AM1.5, 100 [mW / cm ² ]) in the dye-sensitized photoelectric conversion element 10 of Example 9, Example 12 and Comparative Example 4 immediately after the start of the test, which is immediately after the production of the element. It is a basic diagram which showed the measurement result of each IV output characteristic at the time of irradiating.

Table 4 shows a case where the dye-sensitized photoelectric conversion element 10 of Example 9, Example 12 and Comparative Example 4 immediately before the start of the test was irradiated with artificial sunlight (AM1.5, 100 [mW / cm ² ]). Each open circuit voltage V _OC [V], short circuit current density J _SC [mA / cm ² ], fill factor FF [%], photoelectric conversion efficiency Eff. The measurement results of [%] and DC resistance R _S [Ω] are shown.

  As shown in FIG. 3 and Table 4, the photoelectric conversion efficiency Eff. The dye-sensitized photoelectric conversion element 10 of Example 9 and Example 12 showed a higher value than the dye-sensitized photoelectric conversion element 10 of Comparative Example 4. Specifically, the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 is shown. Was compared to 100 [%], the relative photoelectric conversion efficiencies of the dye-sensitized photoelectric conversion elements 10 of Example 9 and Example 12 were 103 [%] and 111 [%], respectively.

Photoelectric conversion efficiency Eff. The reason _why the value of the dye-sensitized photoelectric conversion element 10 of Example 9 and Example 12 was higher than that of Comparative Example 4 was that the value of the short circuit current density J _SC was higher than that of Comparative Example 4. The dye-sensitized photoelectric conversion element 10 of Example 12 was higher, and the value of the series resistance R _S was lower for the dye-sensitized photoelectric conversion elements 10 of Example 9 and Example 12 than for Comparative Example 4. Can be mentioned. In particular, the dye-sensitized photoelectric conversion element 10 of Example 12 in which the counter electrode 1 is configured by using the metal substrate 2 as SUS316 and the conductive film 4 as TiN has a very low series resistance R _S , and the dye increase in Comparative Example 4 is performed. Compared to the photoelectric conversion element 10, the short-circuit current density J _SC and the photoelectric conversion efficiency Eff. Was 10% or higher. This is because the counter electrode 1 in which the SUS substrate and the catalyst layer 3 are bonded via the TiN film has higher electrical conductivity than the counter electrode 1 in which the catalyst layer 3 is bonded to the Ti substrate. It is thought that it is from. This is because the dye-sensitized photoelectric conversion element 10 of Example 12 and the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 are different only in the configuration of the counter electrode 1.

From these results, the photoelectric conversion efficiency Eff. Values are considered closely related to the value of the series resistor R _S, value of the series resistor R _S is considered as the configuration of the counter electrode and closely related. In particular, the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4, the conductive film is the TiN film, and the metal substrate is the SUS substrate. Then, a high photoelectric conversion efficiency Eff. It was shown that the value of can be obtained.

  Next, in order to evaluate the change in performance over time of the dye-sensitized photoelectric conversion element 10 with respect to the usage time, a sample is taken out 500 hours after the start of the test, and each of the dye-sensitized photoelectric conversion elements 10 after 500 hours from the start of the test. A comparison was made between the dye-sensitized photoelectric conversion element 10 of Example 9, Example 12, and Comparative Example 4 with respect to the change of each output characteristic with respect to each output characteristic immediately after the production of the element.

  Table 5 shows the photoelectric conversion efficiency Eff. 500 after 500 hours from the start of the tests of Example 9, Example 12, and Comparative Example 4. Measurement results and photoelectric conversion efficiency Eff. Photoelectric conversion efficiency Eff. At 500 hours after the start of the test when the value of 100% is taken as 100%. It shows the relative rate of.

  As shown in Table 5, the photoelectric conversion efficiency Eff. Measured after 500 hours from the start of the test. Both values were shown to be lower than those measured immediately before the start of the test. In particular, the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 is shown. The value of is 95% of the value measured immediately before the test, and the value that decreases is large. On the other hand, the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Example 9 and Example 12 was determined. The values of 99 [%] and 97 [%] of the values measured immediately before the start of the test are respectively shown, and the photoelectric conversion efficiency Eff. The value of is maintained. Here, the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 after 500 hours from the start of the test. The values of relative photoelectric conversion efficiency of the dye-sensitized photoelectric conversion elements 10 of Example 9 and Example 12 were 108 [%] and 113 [%], respectively. It was.

As described above, only the difference in the configuration of the counter electrode 1 causes a difference in deterioration with time of the photoelectric conversion efficiency of the dye-sensitized photoelectric conversion element 10. In order to further investigate this factor, the open-circuit voltage V _OC , short-circuit current density J _SC , fill factor FF, and DC resistance R _S of the dye-sensitized photoelectric conversion element 10 after 500 hours from the start of the test are measured and immediately before the start of the test. Each value was compared.

Table 6 shows the open-circuit voltage V _OC , short-circuit current density J _SC , fill factor FF, and DC resistance R after 500 hours from the start of the test of the dye-sensitized photoelectric conversion elements 10 of Example 9, Example 12 and Comparative Example 4. The relative rate when each value measured immediately before the start of the test of _S is set to 100 [%] is shown.

As shown in Table 6, the relative ratio of the value of the open circuit voltage V _OC for the values and the values measured in the test immediately before the open circuit voltage V _OC was measured after 500 hours after the start of testing, the Example 9 and In the dye-sensitized photoelectric conversion element 10 of Example 12, it was 96 [%] and 95 [%], respectively. On the other hand, the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 was 85 [%] of the value of the open circuit voltage V _OC measured immediately after the start of the test.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the catalyst layer 3 is bound on the Ti substrate, the value of the open-circuit voltage V _OC after 500 hours from the start of use. Fell significantly. On the other hand, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via a TiN film, immediately after the start of the test after 500 hours from the start of use. It was shown that the measured value of the open circuit voltage V _OC was maintained.

Further, the relative ratio of the value of short-circuit current density J _SC for the values and the measured values for the test immediately before the measured short-circuit current density J _SC after 500 hours, Example 9, Example 12 and Comparative Example In the dye-sensitized photoelectric conversion element 10 of No. 4, they were 107 [%], 101 [%], and 114 [%], respectively.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via a TiN film, a short-circuit current after 500 hours from the start of use is obtained. It was shown that the value of the density J _SC was maintained immediately after the device was manufactured. Further, when the counter electrode 1 is configured such that the catalyst layer 3 is bound on the Ti substrate, the value of the short-circuit current density J _SC after 500 hours from the start of the test is compared with that immediately before the start of the test. Although the value is greatly increased, the value of the short-circuit current density J _SC itself is the dye-sensitized photoelectric device in which the counter electrode 1 is provided by binding the SUS substrate and the catalyst layer 3 through the TiN film. The result was lower than the short-circuit current density J _SC of the conversion element 10.

  In addition, the relative ratio between the fill factor FF value measured after 500 hours and the fill factor FF value with respect to the value measured immediately before the start of the test is the same as that of Example 9, Example 12, and Comparative Example 4. In the photoelectric conversion element 10, it became 97 [%], 101 [%], and 98 [%], respectively.

  From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via a TiN film, the fill factor after 500 hours has elapsed from the start of use. It was shown that the value of FF was maintained immediately after the device was manufactured.

The relative ratio of the value of the DC resistance R _S for the values and the values measured in the test immediately before the DC resistance R _S, which is measured after lapse of 500 hours, of Example 9, Example 12 and Comparative Example 4 In the dye-sensitized photoelectric conversion element 10, it was 95 [%], 98 [%], and 109 [%], respectively.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via the TiN film, the DC resistance after 500 hours from the start of use is obtained. On the other hand, when the counter electrode 1 has a structure in which the catalyst layer 3 is bound on the Ti substrate, the value of R _S is less than that immediately after the device is manufactured. It has been shown that the value of the DC resistance R _S increases.

From these results, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the catalyst layer 3 is provided on the Ti substrate which is the metal substrate 2, it is opened after 500 hours from use. The value of the voltage V _OC drops significantly, and the DC resistance R _S also increases significantly. It became clear that the value of fell significantly. This is because, as the counter electrode 1 changes over time, the physical and electrical binding properties with the catalyst layer 3 are impaired, and the electrical resistance at the contact interface between the metal substrate 2 and the catalyst layer 3 is lost. May increase. Another factor is that Ti constituting the metal substrate 2 is eluted into the electrolyte solution constituting the electrolyte layer 8 and the composition of the electrolyte solution is changed, so that the transfer of electrons between the cathode and cathode is hindered. This is thought to be due to an increase in static resistance.

On the other hand, when the counter electrode 1 has a configuration in which the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4, the above-described large drop in the value of the open circuit voltage V _OC does not occur. In particular, when the metal substrate 2 is a SUS substrate, the conductive film 4 is a TiN film, and the catalyst layer 3 is a conductive carbon layer, the value of the open circuit voltage V _OC , the photoelectric conversion efficiency Eff. It was shown that the values of both maintained almost the values immediately after fabrication, and the DC resistance R _S further decreased. This is because, since the TiN film as the conductive film 4 and the SUS substrate as the metal substrate 2 are firmly bound, the electrical resistance at the contact interface between them can be lowered. it is conceivable that. Further, it is considered that the strong binding property between the TiN film and the SUS substrate is maintained even after 500 hours have elapsed since the use of the dye-sensitized photoelectric conversion element 10. By maintaining these binding properties, it is possible to greatly reduce the increase in electrical resistance at each interface, which can also greatly reduce the increase in DC resistance. It is considered that a drop in the value of photoelectric conversion efficiency can be suppressed.

  Next, as the second performance evaluation, the counter electrode 1 is similar to the first performance evaluation for the dye-sensitized photoelectric conversion element 10 having a configuration in which the SUS substrate and the catalyst layer 3 are bound via the TiCN film. Went to. Specifically, the dye-sensitized photoelectric conversion element 10 of Example 10 and Example 13 in which the counter electrode 1 has the above configuration, and the dye sensitization in which the counter electrode 1 has a configuration in which a catalyst layer is bound to a Ti substrate. The performance of the comparative example 4 which is the photoelectric conversion element 10 was compared immediately after the production of the element. Further, the performance of the dye-sensitized photoelectric conversion elements 10 of Example 10, Example 13 and Comparative Example 4 was compared by performing a reliability acceleration test under the same conditions.

FIG. 4 shows a case where pseudo-sunlight (AM1.5, 100 [mW / cm ² ]) is irradiated to the dye-sensitized photoelectric conversion elements 10 of Example 10, Example 13 and Comparative Example 4 immediately before the start of the test. It is a basic diagram which showed the measurement result of each IV output characteristic.

Table 7 shows the results when the dye-sensitized photoelectric conversion element 10 of Example 10, Example 13 and Comparative Example 4 immediately before the start of the test was irradiated with artificial sunlight (AM1.5, 100 [mW / cm ² ]). Each open circuit voltage V _OC [V], short circuit current density J _SC [mA / cm ² ], fill factor FF [%], conversion efficiency Eff. The measurement results of [%] and DC resistance R _S [Ω] are shown.

  As shown in FIG. 4 and Table 7, the photoelectric conversion efficiency Eff. The values of the dye sensitized photoelectric conversion elements 10 of Example 10, Example 13, and Comparative Example 4 showed similar values. Specifically, the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 is shown. The relative photoelectric conversion efficiencies of the dye-sensitized photoelectric conversion elements 10 of Example 10 and Example 13 were both 98 [%].

Similar to the first performance evaluation, when the values of the series resistance R _S of the dye-sensitized photoelectric conversion elements 10 of Example 10, Example 13, and Comparative Example 4 are compared, the series resistance of any of the dye-sensitized photoelectric conversion elements is The value of R _S was similar. Thus, the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4, and the conductive film is a TiCN film and the metal substrate is When the SUS substrate is used, the counter electrode 1 is equivalent to the dye-sensitized photoelectric conversion element 10 having a structure in which the catalyst layer is bound to the Ti substrate, and an equivalent high photoelectric conversion efficiency Eff. It was shown that the value of can be obtained.

  Next, in order to evaluate the temporal deterioration performance of the dye-sensitized photoelectric conversion element 10 with respect to the use time, a sample is taken out 500 hours after the start of the test, and each output of the dye-sensitized photoelectric conversion element 10 after 500 hours from the start of the test. The characteristics and the change of each output characteristic with respect to each output characteristic immediately after fabrication of the element were compared in the dye-sensitized photoelectric conversion element 10 of Example 10, Example 13, and Comparative Example 4.

  Table 8 shows the photoelectric conversion efficiency Eff. 500 after 500 hours from the start of the tests of Example 10, Example 13, and Comparative Example 4. Measurement results and photoelectric conversion efficiency Eff. Photoelectric conversion efficiency Eff. At 500 hours after the start of the test when the value of 100% is taken as 100%. It shows the relative rate of.

  As shown in Table 8, the photoelectric conversion efficiency Eff. Of each element measured 500 hours after the start of the test. Although the value of the dye-sensitized photoelectric conversion element 10 of Example 13 decreased with respect to the value measured immediately before the start of the test immediately after the production, it was still 98 [%] of the value measured immediately before the start of the test. The photoelectric conversion efficiency Eff. Is higher than that of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4. The drop in the value of was significantly less. On the other hand, in the dye-sensitized photoelectric conversion element 10 of Example 10, the value was 101 [%] of the value measured immediately before the start of the test, and the photoelectric conversion efficiency Eff. The value of was shown to rise.

In order to further investigate the relationship between the structure of the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 and the deterioration with time of photoelectric conversion efficiency, as in the first performance evaluation, dye sensitization after 500 hours from the start of the test. The open-circuit voltage V _OC , the short-circuit current density J _SC and the fill factor FF of the photoelectric conversion element 10 were measured and compared with the values immediately before the start of the test.

Table 9 shows the open-circuit voltage V _OC , short-circuit current density J _SC , fill factor FF, and DC resistance R after 500 hours from the start of the test of the dye-sensitized photoelectric conversion element 10 of Example 10, Example 13 and Comparative Example 4. The relative rate when each value measured immediately before the start of the test of _S is set to 100 [%] is shown.

As shown in Table 9, the relative ratio of the value of the open circuit voltage V _OC for the values and the values measured in the test immediately before the open circuit voltage V _OC was measured after 500 hours from the start of the test, Examples 10 and In the dye-sensitized photoelectric conversion element 10 of Example 13, it was 100 [%] and 102 [%], respectively. On the other hand, the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 was 85 [%] of the value of the open circuit voltage V _OC measured immediately after the start of the test.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via the TiCN film, the test starts after 500 hours from the start of use. It was shown that the value of the open-circuit voltage V _OC measured immediately after that rises or is maintained.

Further, the relative ratio of the value of short-circuit current density J _SC for the values and the measured values for the test immediately before the measured short-circuit current density J _SC after 500 hours, Example 10, Example 13 and Comparative Example In the dye-sensitized photoelectric conversion element 10 of No. 4, it was 105 [%], 100 [%], and 114 [%], respectively.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via the TiCN film, the short-circuit current after 500 hours from the start of use is obtained. It was shown that the value of the density J _SC was maintained immediately after the device was manufactured.

  In addition, the relative ratio between the value of fill factor FF measured after 500 hours and the value of fill factor FF with respect to the value measured immediately before the start of the test is the dye increase in Examples 10, 13 and Comparative Example 4. In the photoelectric conversion element 10, it became 97 [%], 94 [%], and 98 [%], respectively.

  From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 has a structure in which the SUS substrate and the catalyst layer 3 are bonded via a TiCN film, a fill factor after 500 hours from the start of use is obtained. It was shown that the value of FF was maintained immediately after the device was manufactured.

The relative ratio of the value of the DC resistance R _S for the values and the values measured in the test immediately before the DC resistance R _S, which is measured after lapse of 500 hours, of Example 10, Example 13 and Comparative Example 4 In the dye-sensitized photoelectric conversion element 10, they were 106 [%], 105 [%], and 109 [%], respectively.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via a TiCN film, the DC resistance after 500 hours from the start of use is obtained. Although the value of R _S is higher than the value immediately after fabrication of the element, the DC resistance of the dye-sensitized photoelectric conversion element 10 in which the counter electrode 1 is configured by binding the catalyst layer 3 on the Ti substrate is provided. It was shown to be lower than the rate of increase of R _S.

From these results, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4, the above-described opening is achieved. A large drop in the value of the voltage V _OC does not occur. In particular, when the metal substrate 2 is a SUS substrate, the conductive film 4 is a TiCN film, and the catalyst layer 3 is a conductive carbon layer, the open circuit voltage V _OC , the photoelectric conversion efficiency Eff. In both cases, it was shown that the value immediately after fabrication was almost maintained. This factor is considered to be the same as the case where the conductive film is a TiN film, and the open-circuit voltage V _OC , photoelectric conversion efficiency Eff. It is thought that the fall of the value of can be suppressed.

  Next, as a third performance evaluation, the counter electrode 1 has a structure in which the SUS substrate and the catalyst layer 3 are bound via a laminated film of an ATO film and an ITO film (hereinafter referred to as an ATO / ITO laminated film). About the sensitized photoelectric conversion element 10, the performance comparison was performed similarly to 1st performance evaluation. Specifically, the counter electrode 1 includes the dye-sensitized photoelectric conversion element 10 of Example 11 and Example 14 having a configuration in which the SUS substrate and the catalyst layer 3 are bonded via an ATO / ITO laminated film, and the counter electrode. The performance of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 having a structure in which a catalyst layer is bound to a Ti substrate 1 was compared immediately after the element was produced. Further, the performance of the dye-sensitized photoelectric conversion elements 10 of Example 11, Example 14 and Comparative Example 4 was compared by performing a reliability acceleration test under the same conditions. Here, the ATO / ITO laminated film is a laminated film in which the ATO film is on the SUS substrate side and the ITO film is on the catalyst layer side.

FIG. 5 shows a case where pseudo-sunlight (AM1.5, 100 [mW / cm ² ]) is irradiated to the dye-sensitized photoelectric conversion element 10 of Example 11, Example 14 and Comparative Example 4 immediately before the start of the test. It is a basic diagram which showed the measurement result of each IV output characteristic.

Table 10 shows a case where the dye-sensitized photoelectric conversion element 10 of Example 11, Example 14 and Comparative Example 4 immediately before the start of the test was irradiated with artificial sunlight (AM1.5, 100 [mW / cm ² ]). Each open circuit voltage V _OC [V], short circuit current density J _SC [mA / cm ² ], fill factor FF (%), conversion efficiency Eff. The measurement results of [%] and DC resistance R _S [Ω] are shown.

  As shown in FIG. 5 and Table 10, the photoelectric conversion efficiency Eff. The values of the dye-sensitized photoelectric conversion elements 10 of Example 11 and Example 14 were higher than the values of the dye-sensitized photoelectric conversion elements 10 of Comparative Example 4. Specifically, the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 is shown. The relative photoelectric conversion efficiencies of the dye-sensitized photoelectric conversion elements 10 of Example 11 and Example 14 were 103 [%] and 101 [%], respectively.

Similar to the first performance evaluation, when the values of the series resistance R _S of the dye-sensitized photoelectric conversion elements 10 of Example 11, Example 14, and Comparative Example 4 are compared, the photoelectric conversion efficiency Eff. The dye-sensitized photoelectric conversion element 10 of Example 14 having the highest value exhibited a particularly low series resistance R _S value. From this result, the photoelectric conversion efficiency Eff. The value of is shown to be closely related to the value of the series resistance R _S , and further, the value of the series resistance R _S was shown to be closely related to the configuration of the counter electrode 1. In particular, the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4, and the conductive film 4 is an ATO / ITO laminated film, metal When the substrate 2 is a SUS substrate, the counter electrode 1 is immediately higher in photoelectric conversion than the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 having a configuration in which the catalyst layer 3 is bound to the Ti substrate immediately after the device is manufactured. Efficiency Eff. It was shown that the value of can be obtained.

  Next, in order to evaluate the temporal deterioration performance of the dye-sensitized photoelectric conversion element 10 with respect to the use time, a sample is taken out 500 hours after the start of the test, and each output of the dye-sensitized photoelectric conversion element 10 after 500 hours from the start of the test. The change of each output characteristic with respect to each output characteristic immediately after the fabrication of the element was compared in the dye-sensitized photoelectric conversion element 10 of Example 11, Example 14, and Comparative Example 4.

  Table 11 shows the photoelectric conversion efficiency Eff. 500 after 500 hours from the start of the tests of Example 11, Example 14, and Comparative Example 4. Measurement results and photoelectric conversion efficiency Eff. Photoelectric conversion efficiency Eff. At 500 hours after the start of the test when the value of 100% is taken as 100%. It shows the relative rate of.

  As shown in Table 11, the photoelectric conversion efficiency Eff. After 500 hours from the start of the test. Of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 was significantly reduced, whereas the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Example 11 and Example 14 was significantly reduced. The value of did not drop at all. In particular, the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Example 11 in which the conductive film 4 is an ATO / ITO film and the metal substrate 2 is a SUS304 substrate. The value of 102 was 102% of the value measured immediately before the test, and increased after 500 hours from the start of the test. The photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 after 500 hours from the start of the test. Of the photoelectric conversion efficiency Eff. Of the dye-sensitized photoelectric conversion element 10 of Comparative Example 4. As a result, the relative photoelectric conversion efficiencies of the dye-sensitized photoelectric conversion elements 10 of Example 11 and Example 14 were both 108 [%].

In order to further investigate the relationship between the structure of the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 and the deterioration with time of photoelectric conversion efficiency, as in the first performance evaluation, dye sensitization after 500 hours from the start of the test. The open-circuit voltage V _OC , the short-circuit current density J _SC and the fill factor FF of the photoelectric conversion element 10 were measured and compared with the values immediately before the start of the test.

The relative ratios with the open circuit voltage V _OC measured immediately before the start of the test were 100 [%] and 98 [%] in the dye-sensitized photoelectric conversion elements 10 of Example 11 and Example 14, respectively. . On the other hand, the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 was 85 [%] of the value measured immediately after the start of the test. Therefore, the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is provided with the metal substrate 2 and the catalyst layer 3 bonded to each other through the conductive film 4. In particular, the conductive film 4 is made of ATO. Assuming that the / ITO laminated film and the metal substrate 2 are SUS substrates, the value of the open circuit voltage V _OC measured immediately after the start of the test after 500 hours from the start of use is shown.

Table 12 shows the open-circuit voltage V _OC , short-circuit current density J _SC , fill factor FF, and DC resistance R after 500 hours from the start of the test of the dye-sensitized photoelectric conversion elements 10 of Example 11, Example 14, and Comparative Example 4. The relative rate when each value measured immediately before the start of the test of _S is set to 100 [%] is shown.

As shown in Table 12, the relative ratio of the value of the open circuit voltage V _OC for the values and the values measured in the test immediately before the open circuit voltage V _OC was measured after 500 hours from the start of the test, Examples 11 and In the dye-sensitized photoelectric conversion element 10 of Example 14, it was 100 [%] and 98 [%], respectively. On the other hand, the dye-sensitized photoelectric conversion element 10 of Comparative Example 4 was 85 [%] of the value of the open circuit voltage V _OC measured immediately after the start of the test.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via the ATO / ITO laminated film, 500 hours have elapsed from the start of use. It was shown that the value of the open circuit voltage V _OC measured immediately after the start of the test was maintained.

Further, the relative ratio of the value of short-circuit current density J _SC for the values and the measured values for the test immediately before the measured short-circuit current density J _SC after 500 hours, Example 11, Example 14 and Comparative Example In the dye-sensitized photoelectric conversion element 10 of No. 4, they were 104 [%], 99 [%], and 114 [%], respectively.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via the ATO / ITO laminated film, 500 hours have elapsed from the start of use. It was shown that the value of the short-circuit current density J _SC in FIG.

  The relative ratio between the fill factor FF value measured after 500 hours and the fill factor FF value with respect to the value measured immediately before the start of the test is the dye increase in Examples 11, 14 and Comparative Example 4. In the photoelectric conversion element 10, it became 95 [%], 97 [%], and 98 [%], respectively.

  From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via the ATO / ITO laminated film, 500 hours have elapsed from the start of use. It was shown that the value of the fill factor FF in FIG.

The relative ratio of the value of the DC resistance R _S for values to the value measured for the test immediately before the DC resistance R _S measured after lapse of 500 hours, of Example 11, Example 14 and Comparative Example 4 In the dye-sensitized photoelectric conversion element 10, they were 108 [%], 110 [%], and 109 [%], respectively.

From this result, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the SUS substrate and the catalyst layer 3 are bonded via the ATO / ITO laminated film, 500 hours have elapsed from the start of use. It was shown that the value of the direct current resistance R _S at was higher than that immediately after the device was fabricated.

From these results, when the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is configured such that the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4, the above-described opening is achieved. A large drop in the value of the voltage V _OC does not occur. In particular, when the metal substrate 2 is a SUS substrate, the conductive film 4 is an ATO / ITO laminated film, and the catalyst layer 3 is a conductive carbon layer, the open circuit voltage V _OC , the photoelectric conversion efficiency Eff. In both cases, it was shown that the value immediately after fabrication was almost maintained. This factor is considered to be the same as the case where the conductive film is a TiN film, and the open-circuit voltage V _OC , photoelectric conversion efficiency Eff. It is thought that the fall of the value of can be suppressed.

  As described above, according to the dye-sensitized photoelectric conversion element 10 according to the second embodiment, in addition to the same advantages as the counter electrode 1 for the dye-sensitized photoelectric conversion element according to the first embodiment, the counter electrode 1 Since the structure in which the metal substrate 2 and the catalyst layer 3 are bonded via the conductive film 4, the change with time of the counter electrode 1 can be suppressed for a long period of time. Thereby, the fall of the open circuit voltage by using the dye-sensitized photoelectric conversion element 10 for a long time and the fall of photoelectric conversion efficiency can be suppressed. Further, by covering the entire surface of the metal substrate 2 in contact with the electrolyte solution on the side of the electrolyte layer 8 with the conductive film 4, the conductive film becomes a protective layer, and the metal substrate 2 is made of a metal with low electrolyte resistance. Can do. Thereby, the time-dependent deterioration of the dye-sensitized photoelectric conversion element 10 can be suppressed by suppressing the modification of the electrolyte in the electrolyte layer 8. As described above, according to the second embodiment, an inexpensive material having low resistance to electrolyte can be used for the metal substrate 2, so that the photoelectric conversion efficiency is high at a low cost, and it can be used for a long time. A high-performance dye-sensitized photoelectric conversion element 10 with little performance deterioration can be obtained.

<3. Third Embodiment>
[Counter electrode for dye-sensitized photoelectric conversion element]
Next, a counter electrode for a dye-sensitized photoelectric conversion element according to a third embodiment will be described.
FIG. 6 is a cross-sectional view of an essential part showing a counter electrode 1 for a dye-sensitized photoelectric conversion element according to a third embodiment.
As shown in FIG. 6, the counter electrode 1 for dye-sensitized photoelectric conversion element (hereinafter referred to as counter electrode 1) is a metal substrate of the counter electrode 1 in which a metal substrate 2 and a catalyst layer 3 are provided via a conductive film 4. Further, a conductive buffer film 11 is further provided between 2 and the conductive film 4. The metal substrate 2 and the conductive film 4 are bonded via the conductive buffer film 11. Specifically, the conductive buffer film 11 is provided on the metal substrate 2, the conductive film 4 is provided on the conductive buffer film 11, and the catalyst layer 3 is formed on at least a part of the conductive film 4. These are provided, and these constitute the counter electrode 1. Others are the same as those of the counter electrode 1 for the dye-sensitized photoelectric conversion element of the first embodiment.

  The thickness of the conductive buffer film 11 is preferably thin from the viewpoint of conductivity, but is preferably 10 [nm] or more and 70 [nm] or less, and is 20 [nm] or more and 60 [nm] or less. Is more preferable, and most preferably 30 [nm] or more and 50 [nm] or less. This is because if the thickness is less than 10 [nm], not only the strain between the metal substrate 2 and the conductive film 4 cannot be absorbed, but also the internal resistance increases. The conductive buffer film 11 preferably has a volume resistivity of 60 [μΩ · cm] or less, more preferably 57 [μΩ · cm] or less, and 52 [μΩ · cm] or less. Is most preferred. The reason is the same as the reason for the conductive film 4 described above.

  The conductive buffer film 11 may be basically any film as long as it has conductivity. However, as the material constituting the conductive buffer film 11, the conductive film 4 is mentioned above. Can be used as appropriate. Since the conductive buffer film 11 preferably has a higher electric conductivity, the material constituting the conductive buffer film preferably has a volume resistivity of 90 [μΩ · cm] or less, and 70 [μΩ · cm]. Or less, and most preferably 60 [μΩ · cm] or less.

In addition, since the conductive buffer film 11 is provided to absorb strain due to expansion of the metal substrate 2 and the conductive film 4, attention is paid to the linear expansion coefficient between the metal substrate 2 and the conductive buffer film 11. Then, the linear expansion coefficient difference between the metal substrate 2 and the conductive buffer film 11 is preferably 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less. More preferably, it is 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 9.0 × 10 ⁻⁶ [K ⁻¹ ] or less, and 5.5 × 10 ⁻⁶ [K ⁻¹ ] or more and 8.4. It is most preferable that it is below 10 < ^-6 > [K < ^-1 >]. The difference in linear expansion coefficient between the conductive film 11 and the conductive buffer film is preferably 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less, It is more preferably 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 9.0 × 10 ⁻⁶ [K ⁻¹ ] or less, and 5.5 × 10 ⁻⁶ [K ⁻¹ ] or more and 8.4 ×. Most preferably, it is 10 ⁻⁶ [K ⁻¹ ] or less. Further, when the conductive buffer film 11 and the metal substrate 2 and the conductive buffer film 11 and the conductive film 4 have the above-described difference in linear expansion coefficient, the value of the linear expansion coefficient may be larger or smaller. Although it is preferable, the value of the linear expansion coefficient of the metal substrate 2 is preferably larger than the value of the linear expansion coefficient of the conductive film 4, and the value of the linear expansion coefficient of the conductive buffer film 11 is the line of the conductive film 4. It is preferable that the value is larger than the value of the expansion coefficient, and it is most preferable that the linear expansion coefficient of the conductive buffer film 11 is smaller than the linear expansion coefficient of the metal substrate 2 and larger than the linear expansion coefficient of the conductive film 4. It is not limited to this.

[Method for producing counter electrode for dye-sensitized photoelectric conversion element]
Next, the manufacturing method of the counter electrode 1 for dye-sensitized photoelectric conversion elements according to the third embodiment will be described.
First, a metal plate that is the metal substrate 2 is prepared.
Next, the conductive buffer film 11 is formed on the entire main surface of the metal substrate 2. Although there is no restriction | limiting in particular in the formation method of this electroconductive buffer film 11, Specifically, it forms by sputtering method, a chemical vapor deposition method, an ionization vapor deposition method, etc. In particular, when the conductive film 4 is formed by a sputtering method, an inert gas or the like that is removed as a pre-process for film formation by a sputtering method is used to remove the non-conductive layer as a pre-process for forming the conductive film 4. Since it can be performed simultaneously with the reverse sputtering used, the process can be simplified. Next, the conductive film 4 is formed on the entire surface of the conductive film 4. Others are the same as the manufacturing method of the counter electrode 1 for dye-sensitized photoelectric conversion elements according to the first embodiment.

  According to the third embodiment, in addition to the same advantages as the first embodiment, the conductive buffer film is provided between the metal substrate and the conductive film. As the conductive buffer film effectively absorbs the strain due to the expansion, a counter electrode 1 for a dye-sensitized photoelectric conversion element having good binding properties and high conductivity can be obtained.

<4. Fourth Embodiment>
[Dye-sensitized photoelectric conversion element]
Next, the dye-sensitized photoelectric conversion element 10 according to the fourth embodiment will be described.
FIG. 7 is a cross-sectional view of the main part showing the basic configuration of the dye-sensitized photoelectric conversion element 10 according to the fourth embodiment.
As shown in FIG. 7, in the fourth embodiment, the counter electrode 1 for the dye-sensitized photoelectric conversion element according to the third embodiment is used as the counter electrode 1 for the dye-sensitized photoelectric conversion element 10. Others are the same as those of the dye-sensitized photoelectric conversion element 10 according to the second embodiment.

[Operation of dye-sensitized photoelectric conversion element]
Next, the operation of the dye-sensitized photoelectric conversion element 10 according to the fourth embodiment will be described.
The operation of the dye-sensitized photoelectric conversion element 10 is the same as the operation of the dye-sensitized photoelectric conversion element 10 according to the second embodiment.

[Method for producing dye-sensitized photoelectric conversion element]
Next, a method for manufacturing the dye-sensitized photoelectric conversion element 10 according to the fourth embodiment will be described.
This manufacturing method of the dye-sensitized photoelectric conversion element 10 is the second implementation except that the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 uses the counter electrode 1 for the dye-sensitized photoelectric conversion element according to the third embodiment. It is the same as that of the manufacturing method of the dye-sensitized photoelectric conversion element 10 by the form.

  The dye-sensitized photoelectric conversion element 10 according to the fourth embodiment has the same advantages as those of the second embodiment, and the counter electrode 1 of the dye-sensitized photoelectric conversion element 10 is replaced with the conductive film 4. Since the metal substrate 2 and the catalyst layer 3 are provided, and the conductive buffer film 11 is further provided between the metal substrate 2 and the conductive film 4, the conductive film 4 and the metal substrate 2 are The conductive buffer film 11 effectively absorbs strain due to expansion. Thereby, even if the expansion coefficient between the conductive film 4 and the metal substrate 2 does not satisfy a certain requirement, it is possible to obtain the counter electrode 1 with low interface electrical resistance and high electrical conductivity. As described above, according to the fourth embodiment, even if the expansion coefficient between the conductive film 4 and the metal substrate 2 does not satisfy a certain requirement, the photoelectric conversion efficiency is high, and even if it is used for a long time. A high-performance dye-sensitized photoelectric conversion element 10 with little performance deterioration can be obtained.

  As described above, according to the fourth embodiment, there are advantages similar to those of the dye-sensitized photoelectric conversion element 10 according to the second embodiment, and between the metal substrate 2 and the conductive film 4. Since the conductive buffer film 11 is provided, even if the expansion coefficient difference between the metal substrate 2 and the conductive film 4 is large, the conductive buffer film effectively absorbs the strain generated at the contact interface. An increase in electrical contact resistance that occurs can be suppressed. From this, high photoelectric conversion efficiency can be obtained, and a high-performance dye-sensitized photoelectric conversion element 10 with little deterioration with time can be obtained.

Although the embodiments and examples have been specifically described above, the present disclosure is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present disclosure are possible. .
For example, the numerical values, structures, configurations, shapes, materials, and the like given in the above-described embodiments and examples are merely examples, and different numerical values, structures, configurations, shapes, materials, etc. are used as necessary. Also good.

In addition, this technique can also take the following structures.
(1) It has a porous electrode, a counter electrode, and an electrolyte layer provided between the porous electrode and the counter electrode, and the counter electrode has a metal substrate and a conductive material provided on the metal substrate. And a catalyst layer provided on the conductive film, and the linear expansion coefficient of the conductive film is 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ^−6. [K ⁻¹ ] A photoelectric conversion element which is equal to or less than
(2) The photoelectric conversion element according to (1), wherein the volume resistivity value of the conductive film is 60 [μΩ · cm] or less.
(3) The photoelectric conversion element according to (1) or (2), wherein the conductive film has a thickness of 50 [nm] to 400 [nm].
(4) The difference in linear expansion coefficient between the conductive film and the metal substrate is 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less (1 )-(3) The photoelectric conversion element in any one of.
(5) The photoelectric conversion element according to any one of (1) to (4), wherein a linear expansion coefficient of the metal substrate is larger than a linear expansion coefficient of the conductive film.
(6) The photoelectric conversion element according to any one of (1) to (5), wherein the conductive film is made of a metal nitride or a conductive oxide.
(7) The photoelectric conversion element according to any one of (1) to (6), wherein the conductive film is made of a material having resistance to iodine electrolyte.
(8) The photoelectric conversion element according to any one of (1) to (7), wherein the metal substrate is made of any one of aluminum, an aluminum alloy, and stainless steel.
(9) The photoelectric conversion element according to any one of (1) to (8), wherein the catalyst layer is a conductive carbon layer.
(10) The photoelectric conversion element according to any one of (1) to (9), wherein the conductive film includes at least one layer selected from the group consisting of TiN, TiCN, ITO, ATO, and IZO.
(11) The photoelectric conversion element according to any one of (1) to (10), wherein a conductive buffer film is further provided between the metal substrate and the conductive film.
(12) The photoelectric conversion element according to (11), wherein the conductive film has a thickness of 50 [nm] to 400 [nm].
(13) The photoelectric conversion element according to the above (11) or (12), wherein the volume resistivity of the conductive buffer film is 60 [μΩ · cm] or less.
(14) The photoelectric conversion element according to any one of (11) to (13), wherein the conductive buffer film has a thickness of 10 nm to 70 nm.
(15) The linear expansion coefficient difference between the conductive buffer film and the metal substrate is 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less, and the conductivity is (11) to (14), wherein the difference in thermal expansion coefficient between the buffer film and the conductive film is 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less. The photoelectric conversion element in any one of.
(16) The photoelectric conversion element according to any one of (1) to (15), wherein the photoelectric conversion element is a dye-sensitized photoelectric conversion element in which a photosensitizing dye is adsorbed to the porous electrode.
(17) It has at least one photoelectric conversion element, the photoelectric conversion element has a porous electrode, a counter electrode, and an electrolyte layer provided between the porous electrode and the counter electrode, and the counter electrode Has a metal substrate, a conductive film provided on the metal substrate, and a catalyst layer provided on the conductive film, and the value of linear expansion coefficient of the conductive film is 7.3. An electronic device that is a photoelectric conversion element that is 10 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less.
(18) It has a metal substrate, a conductive film provided on the metal substrate, and a catalyst layer provided on the conductive film, and the value of linear expansion coefficient of the conductive film is 7. The counter electrode for photoelectric conversion elements which is a photoelectric conversion element which is 3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less.
(19) It has at least one photoelectric conversion element, and the photoelectric conversion element has a porous electrode, a counter electrode, and an electrolyte layer provided between the porous electrode and the counter electrode, and the counter electrode Has a metal substrate, a conductive film provided on the metal substrate, and a catalyst layer provided on the conductive film, and the value of linear expansion coefficient of the conductive film is 7.3. × 10 ^-6 [K ^-1] or 10.5 × 10 ^-6 [K ^-1] Architecture is a photoelectric conversion element or less.
(20) The building according to (19), wherein at least one of the photoelectric conversion element and / or the photoelectric conversion element module is sandwiched between two transparent plates.

DESCRIPTION OF SYMBOLS 1 ... Counter electrode, 2 ... Metal substrate, 3 ... Catalyst layer, 4 ... Electroconductive film, 5 ... Transparent substrate, 6 ... Transparent electrode, 7 ... Porous electrode, 8 ... Electrolyte layer, 9 ... Sealing body, 10 ... Dye Sensitized photoelectric conversion element, 11... Conductive buffer film.

Claims (20)

A porous electrode;
With the counter electrode,
An electrolyte layer provided between the porous electrode and the counter electrode;
The counter electrode is
A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
The photoelectric conversion element whose linear expansion coefficient value of the said electroconductive film is 7.3 * 10 < ^-6 > [K < ^-1 >] or more and 10.5 * 10 < ^-6 > [K < ^-1 >] or less.   The photoelectric conversion element according to claim 1, wherein the conductive film has a volume resistivity value of 60 [μΩ · cm] or less.   The photoelectric conversion element according to claim 2, wherein the conductive film has a thickness of 50 [nm] or more and 400 [nm] or less. 4. The linear expansion coefficient difference between the conductive film and the metal substrate is 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less. Photoelectric conversion element.   The photoelectric conversion element according to claim 4, wherein a linear expansion coefficient of the metal substrate is larger than a linear expansion coefficient of the conductive film.   The photoelectric conversion element according to claim 5, wherein the conductive film is made of a metal nitride or a conductive oxide.   The photoelectric conversion element according to claim 6, wherein the conductive film is made of a material having iodine electrolyte resistance.   The photoelectric conversion element according to claim 7, wherein the metal substrate is made of any one of aluminum, an aluminum alloy, and stainless steel.   The photoelectric conversion element according to claim 8, wherein the catalyst layer is a conductive carbon layer.   The photoelectric conversion element according to claim 9, wherein the conductive film includes at least one layer selected from the group consisting of TiN, TiCN, ITO, ATO, and IZO.   The photoelectric conversion element according to claim 1, wherein a conductive buffer film is further provided between the metal substrate and the conductive film.   The photoelectric conversion element according to claim 11, wherein the conductive film has a thickness of 50 [nm] to 400 [nm].   The photoelectric conversion element according to claim 12, wherein a volume resistivity value of the conductive buffer film is 60 [μΩ · cm] or less.   14. The photoelectric conversion element according to claim 13, wherein the conductive buffer film has a thickness of 10 [nm] to 70 [nm]. The linear expansion coefficient difference between the conductive buffer film and the metal substrate is 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less, and the conductive buffer film is The photoelectric conversion element according to claim 14, wherein a difference in thermal expansion coefficient from the conductive film is 5.0 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.0 × 10 ⁻⁶ [K ⁻¹ ] or less.   The photoelectric conversion element according to claim 1, wherein the photoelectric conversion element is a dye-sensitized photoelectric conversion element in which a photosensitizing dye is adsorbed on the porous electrode. Having at least one photoelectric conversion element;
The photoelectric conversion element is
A porous electrode;
With the counter electrode,
An electrolyte layer provided between the porous electrode and the counter electrode;
The counter electrode is
A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
An electronic device that is a photoelectric conversion element in which the value of the linear expansion coefficient of the conductive film is 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less. A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
The counter electrode for a photoelectric conversion element, which is a photoelectric conversion element having a linear expansion coefficient of the conductive film of 7.3 × 10 ⁻⁶ [K ⁻¹ ] or more and 10.5 × 10 ⁻⁶ [K ⁻¹ ] or less. . Having at least one photoelectric conversion element;
The photoelectric conversion element is
A porous electrode;
With the counter electrode,
An electrolyte layer provided between the porous electrode and the counter electrode;
The counter electrode is
A metal substrate;
A conductive film provided on the metal substrate;
A catalyst layer provided on the conductive film,
The building which is a photoelectric conversion element whose linear expansion coefficient value of the said electroconductive film is 7.3 * 10 < ^-6 > [K < ^-1 >] or more and 10.5 * 10 < ^-6 > [K < ^-1 >] or less.   The building according to claim 19, wherein at least one of the photoelectric conversion element and / or the photoelectric conversion element module is sandwiched between two transparent plates.

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