JP2008091162A - Oxide semiconductor electrode and dye-sensitized solar cell using the same - Google Patents

Abstract

An object of the present invention is to provide an oxide semiconductor electrode that is excellent in the efficiency of use of incident light.
The present invention provides a substrate, a first electrode layer formed on the substrate and made of a metal oxide, and a porous layer formed on the first electrode layer and including metal oxide semiconductor fine particles. An oxide semiconductor electrode having a layer, wherein the base material contains a light scattering material, thereby solving the above-mentioned problem.
[Selection] Figure 1

Description

  The present invention relates to an oxide semiconductor electrode suitably used for a dye-sensitized solar cell and the like, and more particularly to an oxide semiconductor electrode excellent in incident light utilization efficiency.

In recent years, environmental problems such as global warming caused by an increase in carbon dioxide have become serious, and countermeasures are being promoted worldwide. In particular, active research and development on solar cells using solar energy as a clean energy source with a low environmental impact is underway. As such solar cells, single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, compound semiconductor solar cells and the like have already been put into practical use, but these solar cells have high production costs, etc. There is a problem. Therefore, as a solar cell that has a small environmental load and can reduce the manufacturing cost, a dye-sensitized solar cell has attracted attention and research and development has been promoted.
In such a dye-sensitized solar cell, an oxide semiconductor electrode having a porous layer containing metal oxide semiconductor fine particles is used.

  An example of a general configuration of the dye-sensitized solar cell is shown in FIG. As illustrated in FIG. 4, a general dye-sensitized solar cell 120 includes a porous layer including metal oxide semiconductor fine particles supporting a first electrode layer 102 and a dye sensitizer on a substrate 101. A structure in which an electrolyte layer 104 having a redox pair, a second electrode layer 105, and a counter substrate 106 are stacked in this order on the porous layer 103 of the oxide semiconductor electrode 110 in which the layers 103 are stacked in this order. It is what has. Then, the dye sensitizer adsorbed on the surface of the metal oxide semiconductor fine particles is excited by receiving sunlight from the substrate 101 side, and the excited electrons are conducted to the first electrode layer, and are passed through the external circuit. Conducted to two electrode layers. Thereafter, electricity is generated by returning the electrons to the ground level of the dye sensitizer through the redox pair. A typical example of such a dye-sensitized solar cell is a Gretcher cell in which the porous layer is made of porous titanium dioxide and the content of the dye sensitizer is increased. It has been widely studied as a sensitized solar cell.

  At present, various attempts have been made to more effectively utilize light incident on a dye-sensitized solar cell. For example, Patent Document 1 discloses a solar cell in which a light-transmitting light diffusion layer is provided on a light receiving surface of a solar cell element. This solar cell is intended to improve the conversion efficiency of the solar cell by providing a translucent light diffusion layer so that light is diffusely incident and the optical path length is increased. However, the solar cell of Patent Document 1 has a translucent light diffusion layer disposed on the outer surface of the substrate, and the distance to the porous layer on which the dye sensitizer is supported is long, and diffused light is porous. There is a problem that it is difficult to effectively reach the layer, and the utilization efficiency of incident light is reduced.

  For example, Patent Documents 2 to 4 disclose a dye-sensitized solar cell or the like in which a reflective layer or the like is provided on the counter electrode side. Such a dye-sensitized solar cell improves the power generation efficiency by reflecting the light incident from the substrate side and passing through the porous layer using a reflective layer or the like and passing through the porous layer again. Is intended. However, when the reflective layer is provided on the counter electrode side, there is a problem in that incident light loss due to absorption of visible light such as iodine in the electrolyte occurs, and the utilization efficiency of incident light is reduced.

JP 2002-222974 A JP 2000-348784 A JP 2003-142171 A JP 2005-158379 A

  The present invention has been made in view of the above problems, and a main object of the present invention is to provide an oxide semiconductor electrode excellent in incident light utilization efficiency.

  To achieve the above object, the present invention provides a base material, a first electrode layer formed on the base material and made of a metal oxide, and a metal oxide semiconductor fine particle formed on the first electrode layer. An oxide semiconductor electrode comprising: a porous layer including an oxide semiconductor electrode, wherein the base material contains a light scattering material.

  According to the present invention, the light scattering material is included in the base material disposed in the vicinity of the porous layer, so that the incident light scattered by the light scattering material passes through the porous layer. The optical path can be lengthened. Thereby, according to this invention, the oxide semiconductor electrode excellent in the utilization efficiency of incident light can be obtained.

  In the oxide semiconductor electrode of the present invention, the base material includes a base body and an adhesive layer formed on the base body and containing a light scattering material, and the first electrode layer is formed on the adhesive layer. It is preferable. The base material has an adhesive layer containing a light scattering material, and the first electrode layer is formed on the adhesive layer, so that the incident light can be used efficiently, and further, the productivity by the transfer method can be improved. This is because an excellent oxide semiconductor electrode can be obtained.

  The present invention also provides a porous layer, a second electrode layer, and a counter group of the oxide semiconductor electrode of the present invention in which a dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. Provided is a dye-sensitized solar cell, in which a second electrode layer of a counter electrode substrate made of a material is disposed so as to face each other through an electrolyte layer containing a redox pair.

  ADVANTAGE OF THE INVENTION According to this invention, a dye-sensitized solar cell with high electric power generation efficiency can be obtained by using the oxide semiconductor electrode of the said this invention excellent in the utilization efficiency of incident light as an oxide semiconductor electrode.

  ADVANTAGE OF THE INVENTION According to this invention, there exists an effect that the oxide semiconductor electrode excellent in the utilization efficiency of incident light can be obtained.

  Hereinafter, the oxide semiconductor electrode and the dye-sensitized solar cell of the present invention will be described in detail.

A. Oxide Semiconductor Electrode First, the oxide semiconductor electrode of the present invention will be described. The oxide semiconductor electrode of the present invention is a porous material including a base material, a first electrode layer made of a metal oxide formed on the base material, and metal oxide semiconductor fine particles formed on the first electrode layer. And a light scattering material is included in the base material.

  Next, the oxide semiconductor electrode of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of an oxide semiconductor electrode of the present invention. As illustrated in FIG. 1, an oxide semiconductor electrode 10 of the present invention includes a base material 1 including a light scattering material 4, a first electrode layer 2 formed on the base material 1 and made of a metal oxide, It has a porous layer 3 formed on the first electrode layer 2 and containing metal oxide semiconductor fine particles.

  FIG. 2 is a schematic sectional view showing another example of the oxide semiconductor electrode of the present invention. As shown in FIG. 2, in the oxide semiconductor electrode 11 of the present invention, the base material 1 ′ is composed of the base body 1a and the adhesive layer 1b including the light scattering material 4, and the first layer on the adhesive layer 1b. The one electrode layer 2 and the porous layer 3 may be configured to be laminated in this order.

  As shown in FIG. 1 and FIG. 2, the oxide semiconductor electrode of the present invention includes a light scattering material having a function of scattering incident light on a base material, whereby the present invention uses the incident light. The effect is that an oxide semiconductor electrode having excellent efficiency can be provided.

The reason why the use efficiency of incident light can be improved by including a light scattering material in the base material will be described below.
The oxide semiconductor electrode of the present invention is used for a device having a photoelectric conversion function represented by a dye-sensitized solar cell. In such an oxide semiconductor electrode, usually, metal oxide semiconductor fine particles are used. The photoelectric conversion function is expressed in the porous layer containing. Therefore, in order to efficiently use the light incident on the oxide semiconductor electrode for the photoelectric conversion function, the optical path length in the porous layer when the light incident on the oxide semiconductor electrode passes through the porous layer is increased. Doing is the most direct and effective means. In the oxide semiconductor electrode of the present invention, a light scattering material is contained in a base material, and incident light is forward scattered by the light scattering material, so that light incident on the porous layer is a method of the porous layer. By making the light incident obliquely with respect to the linear direction, the optical path length in the porous layer is lengthened, thereby improving the utilization efficiency of incident light.

Conventionally, incident light utilization efficiency has been improved by using such a scattering phenomenon. In addition to the oxide semiconductor electrode, a light scattering layer having a light scattering function is formed outside the oxide semiconductor electrode. Has been used. However, in such an embodiment, there is a problem that the scattered light cannot be effectively used because the distance between the porous layer that expresses the photoelectric conversion function by incident light and the light scattering layer is increased.
In this regard, according to the oxide semiconductor electrode of the present invention, the porous semiconductor layer is formed by forming the oxide semiconductor electrode and including the light scattering material in the base material disposed close to the porous layer. Since incident light can be scattered at a position close to the layer, the utilization efficiency of incident light can be further improved.

  The oxide semiconductor electrode of this invention has a base material, a 1st electrode layer, and an oxide semiconductor layer. Hereinafter, each structure of the oxide semiconductor electrode of this invention is demonstrated in detail.

1. Base material First, the base material used for the oxide semiconductor electrode of this invention is demonstrated. The base material used for this invention has a function which scatters the light which injects into the oxide semiconductor electrode of this invention by including a light-scattering material. Moreover, the base material used for this invention has a function which supports the 1st electrode layer and porous layer which are mentioned later.
For example, when a dye-sensitized solar cell is manufactured using the oxide semiconductor electrode of the present invention, the base material serves as a sunlight receiving surface.

  The base material used in the present invention is not particularly limited as long as it has a base having a self-supporting property that supports at least a first electrode layer and a porous layer described later. Therefore, the base material used in the present invention may be composed only of such a base, or may have a structure in which the base and other layers are laminated. Especially, it is preferable that the base material used for this invention has the structure which the said base | substrate and the contact bonding layer laminated | stacked. This is because the oxide semiconductor electrode of the present invention can be made excellent in productivity by the transfer method when the substrate has a structure in which the substrate and the adhesive layer are laminated.

  In the case where a substrate having a structure in which the substrate and the adhesive layer are laminated is used as the substrate, it is sufficient that a light scattering material is included in at least one of the substrate and the adhesive layer. As such a mode, a mode in which a light scattering material is included only in the base body, a mode in which a light scattering material is included only in the adhesive layer, and a light scattering material is included in the base body and the adhesive layer. There are three modes. In the present invention, any of the above three modes can be used preferably, but it is preferable to use a mode in which a light scattering material is contained in at least the adhesive layer.

  Hereinafter, the light scattering material, the substrate, and the adhesive layer used for the substrate will be described.

(1) Light-scattering material The light-scattering material contained in the base material used for this invention is demonstrated. The light scattering material used in the present invention has a function of scattering light incident on the base material forward by being contained in the base material.

  The light scattering material used in the present invention has a function of scattering light incident on the base material forward by being present in the base material. For this reason, the light scattering material used in the present invention needs to have a refractive index different from that of the material constituting the substrate. The light-scattering material used for this invention will not be specifically limited if it has a refractive index different from the material which comprises a base material. In particular, in the present invention, fine particles, spherulites, and bubbles can be preferably used as the light scattering material. Hereinafter, each of such light scattering materials will be described.

a. First, the fine particles used as the light scattering material in the present invention will be described. The refractive index of the fine particles used in the present invention is appropriately selected according to the use of the oxide semiconductor electrode of the present invention so that the difference from the refractive index of the material constituting the substrate is within a desired range. Can be used. In particular, when the oxide semiconductor electrode of the present invention is used in a dye-sensitized solar cell, the difference in refractive index between the fine particles and the material constituting the substrate is 0.01 or more, more preferably 0. It is preferable to use one that is .05 or more.

  The refractive index of the specific fine particles used in the present invention is not particularly limited as long as the difference from the refractive index of the material constituting the substrate is within the above range, but from the viewpoint of ease of material selection. Is preferably within the range of 1.0 to 3.0, more preferably within the range of 1.2 to 2.8, and particularly preferably within the range of 1.3 to 2.5.

  Further, the refractive index of the fine particles used in the present invention may be larger or smaller than the refractive index of the material constituting the substrate.

  Examples of the fine particles used in the present invention include organic fine particles made of an organic material and inorganic fine particles made of an inorganic material. In the present invention, any of the organic fine particles and the inorganic fine particles is preferable. Can be used.

  Examples of the organic fine particles used in the present invention include polyolefin resins such as polyethylene and polypropylene, polyvinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, and polyvinyl formal, and polyethylene glycol. Polyether resins such as acrylic resins, styrene resins, phenol resins, urea resins, melamine resins, urethane resins, epoxy resins, fluorine resins, polyester resins, unsaturated polyester resins, saturation Examples thereof include fine particles composed of a copolyester resin, an alkyd resin, a polyamide resin, and a natural polymer resin. In particular, in the present invention, among these organic fine particles, fine particles composed of a styrene resin or an acrylic resin can be preferably used.

Examples of the inorganic fine particles used in the present invention include SiO ₂ , TiO ₂ , Al ₂ O ₃ , ZrO ₂ , B ₂ O ₃ , Na ₂ O, K ₂ O, Li ₂ O, Rb ₂ O, Fine particles made of oxides such as Cs ₂ O, SnO ₂ , In ₂ O ₃ , ZnO, fluorides such as AlF ₃ , CaF ₂ , MnF ₂ , BeF ₂ , LiF, and other nitrides, chlorides, sulfides, etc. Can be mentioned. In particular, in the present invention, among these inorganic fine particles, fine particles composed of SiO ₂ , TiO ₂ , or ZrO ₂ can be preferably used.

  The fine particles used in the present invention may be only one type, or a mixture of two or more types.

  The shape of the fine particles used in the present invention is not particularly limited as long as the light incident on the substrate can be scattered forward, but spherical fine particles are preferably used. This is because by using spherical fine particles, incident light can be scattered forward regardless of the angle of light incident on the substrate.

  When the fine particles are used as the light scattering material, the content of the fine particles in the substrate is determined so that the light scattering property of the substrate is within a desired range depending on the type of fine particles and the use of the oxide semiconductor electrode of the present invention. If it is in the range which can do, it will not specifically limit. In particular, in the present invention, it is preferable that the amount of haze of the substrate is in the range of 1% to 50%, more preferably in the range of 5% to 30% by adding fine particles.

  Furthermore, the amount of fine particles contained in the substrate is such that the light transmittance of the substrate can be within a desired range depending on the type of fine particles and the use of the oxide semiconductor electrode of the present invention. An amount is preferred. More specifically, it is preferable that the total light transmittance of the base material is 70% or more, more preferably 85% or more by adding fine particles.

  Further, in the case where the substrate used in the present invention has a configuration in which a substrate and an adhesive layer are laminated, as an aspect in which fine particles are used as the light scattering material, at least one of the substrate or the adhesive layer is used. There is no particular limitation as long as it contains fine particles. As such an embodiment, an embodiment in which the fine particles are contained only in the substrate, an embodiment in which the fine particles are contained only in the adhesive layer, and the fine particles are contained in the substrate and the adhesive layer. Can be mentioned. In particular, in the present invention, it is preferable to use an embodiment in which fine particles are contained in at least the adhesive layer, and it is particularly preferable to use an embodiment in which fine particles are contained only in the adhesive layer.

When the fine particles are used as the light scattering material, the method for incorporating the fine particles in the substrate is not particularly limited as long as it is a method capable of uniformly containing a certain amount of fine particles. As such a method, for example, a method for forming a substrate by a known method such as a casting method using a composition for forming a substrate containing a material constituting the substrate described later and the fine particles described above. Can be used.
In the case where the base material used in the present invention is an embodiment in which the base and the adhesive layer are laminated as described above, examples of the method for causing the adhesive layer to contain fine particles include, for example, an adhesive layer on the base. A method of applying an adhesive layer forming composition containing the adhesive resin used for the adhesive layer and the fine particles and applying the adhesive layer forming composition onto the substrate. it can.

b. Spherulite Next, the spherulite used as the light scattering material in the present invention will be described. The spherulite used in the present invention is not particularly limited as long as it has a refractive index different from that of the material constituting the base material. Usually, a material in which the material constituting the base material is partially spherulite is used.

  When spherulites are used as the light scattering material in the present invention, the amount of spherulites in the substrate is not particularly limited as long as it is within a range in which desired light scattering properties can be imparted to the substrate. In particular, in the present invention, the abundance of the spherulites is preferably within a range that allows the haze and light transmittance of the substrate to be within the desired ranges. Such a range of haze and light transmittance is the same as the range described in the above-mentioned section “a. Fine particles”, and thus the description thereof is omitted here.

  In the case where the substrate used in the present invention has a configuration in which a substrate and an adhesive layer are laminated, a spherulite is used as the light scattering material, and at least one of the substrate or the adhesive layer is a sphere. There is no particular limitation as long as the crystal is formed. As such an embodiment, there are an embodiment in which spherulites are formed only on the substrate, an embodiment in which spherulites are formed only on the adhesive layer, and an embodiment in which spherulites are formed on the substrate and the adhesive layer. Can be mentioned. In particular, in the present invention, it is preferable to use an embodiment in which spherulites are formed in at least the adhesive layer, and it is particularly preferable to use an embodiment in which spherulites are formed only in the adhesive layer.

  In the case where spherulites are used as the light scattering material, the method for forming spherulites in the base material is, for example, by controlling the cooling temperature after film formation when preparing the base material, Examples thereof include a method of controlling, and a method of controlling the size of spherulites by adding a nucleating agent when forming a substrate or an adhesive layer.

c. Bubble Next, the bubble used as the light scattering material in the present invention will be described. The bubble used in the present invention is not particularly limited as long as it is a bubble composed of a substrate having a refractive index different from that of the material constituting the substrate, but it is usually preferable to use a bubble composed of air.

  When bubbles are used as the light scattering material in the present invention, the amount of bubbles present in the substrate is not particularly limited as long as it is within a range in which a desired light scattering property can be imparted to the substrate. In particular, in the present invention, the abundance of the spherulites is preferably within a range that allows the haze and light transmittance of the substrate to be within the desired ranges. Such a range of haze and light transmittance is the same as the range described in the above section “a. Fine particles”, and thus the description thereof is omitted here.

  Further, the specific size of the bubbles used in the present invention is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.5 μm to 5 μm.

  In the case where the substrate used in the present invention has a configuration in which a substrate and an adhesive layer are laminated, as an embodiment in which bubbles are used as the light scattering material, at least one of the substrate or the adhesive layer is a spherulite. If it is the aspect in which was formed, it will not specifically limit. Examples of such an embodiment include an embodiment in which bubbles are formed only in the substrate, an embodiment in which bubbles are formed only in the adhesive layer, and an embodiment in which bubbles are formed in the substrate and the adhesive layer. it can. In the present invention, any of these embodiments can be suitably used.

  When bubbles are used as the light scattering material, the method for incorporating bubbles in the substrate is not particularly limited as long as it is a method that can uniformly contain a certain amount of bubbles. As such a method, for example, a method of heating and foaming the base material, a method of adding a foaming agent to the base material, and the like can be mentioned. Here, about the said foaming agent, generally well-known foaming agent can be used.

(2) Substrate Next, the substrate used in the present invention will be described. The substrate used in the present invention is not particularly limited as long as it has a self-supporting property capable of supporting the first electrode layer and the porous layer described later, and is a flexible material having flexibility. It may be a rigid material that does not have flexibility, such as quartz glass, Pyrex (registered trademark), and synthetic quartz plate. In particular, in the present invention, it is preferable to use the flexible material, and among the flexible materials, a film base material is preferable. This is because the film substrate is excellent in processability and can reduce the manufacturing cost.

  Examples of the film substrate include an ethylene / tetrafluoroethylene copolymer film, a biaxially stretched polyethylene terephthalate film, a polyethersulfone (PES) film, a polyetheretherketone (PEEK) film, and a polyetherimide (PEI). Examples thereof include resin film substrates such as films, polyimide (PI) films, polyester naphthalate (PEN), and polycarbonate (PC). Among them, biaxially stretched polyethylene terephthalate film (PET), polyester naphthalate (PEN) Polycarbonate film (PC) is preferred.

  The thickness of the substrate varies depending on the application of the oxide semiconductor electrode of the present invention, but is in the range of 50 μm to 2000 μm, in particular in the range of 75 μm to 1800 μm, particularly in the range of 100 μm to 1500 μm. Is preferred. This is because if the thickness of the substrate is too small, there is a possibility that sufficient mechanical strength cannot be imparted to the oxide semiconductor electrode of the present invention. Further, if the thickness of the substrate is too large, the processability of the oxide semiconductor electrode of the present invention may be impaired.

The substrate is preferably excellent in heat resistance, weather resistance, water vapor, and other gas barrier properties. This is because when the substrate has gas barrier properties, for example, when the oxide semiconductor electrode of the present invention is used in a dye-sensitized solar cell, the temporal stability of the dye-sensitized solar cell can be improved. In particular, in the present invention, the oxygen transmission rate is 1 cc / m ² / day · atm or less under conditions of a temperature of 23 ° C. and a humidity of 90%, and the water vapor transmission rate is 1 g under the conditions of a temperature of 37.8 ° C. and a humidity of 100%. It is preferable to use a substrate having a gas barrier property of / m ² / day or less. In the present invention, in order to achieve such gas barrier properties, a substrate provided with a gas barrier layer on an arbitrary substrate may be used.

(3) Adhesive layer The adhesive layer used for this invention is demonstrated. The adhesive layer used in the present invention is not particularly limited as long as it is made of a material capable of adhering a first electrode layer to be described later and the substrate. Especially, in this invention, a thermoplastic resin is used suitably as a material which comprises the said contact bonding layer.

  The thermoplastic resin used for the adhesive layer is not particularly limited as long as it is a resin that melts at a desired temperature. In particular, in the present invention, the melting point of the thermoplastic resin is preferably in the range of 50 ° C to 200 ° C, particularly preferably in the range of 60 ° C to 180 ° C, particularly in the range of 65 ° C to 150 ° C. It is preferable to be within. When the melting point is lower than the above range, for example, when a dye-sensitized solar cell produced using the oxide semiconductor electrode of the present invention is used outdoors, the adhesion between the substrate and the first electrode layer is low. If the melting point is higher than the above range, for example, when the oxide semiconductor electrode of the present invention is produced by a transfer method, a heating step higher than the melting point is required in the transfer step. Therefore, depending on the type of the substrate, the substrate itself may be damaged by heat.

  In the present invention, the thermoplastic resin is preferably an adhesive resin. Examples of such adhesive resins include polyethylene, polypropylene, polyisobutylene, polystyrene, polyolefins such as ethylene-propylene rubber, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethyl cellulose, and cellulose triacetate. Cellulose derivatives, copolymers of poly (meth) acrylic acid and its esters, polyvinyl acetals such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyamide, polyimide, nylon, polyester resin, urethane resin, epoxy resin, silicone Examples thereof include resins and fluororesins. Of these, polyolefins, ethylene-vinyl acetate copolymers, urethane resins, epoxy resins, silane-modified resins, and acid-modified resins are preferable from the viewpoints of adhesiveness, resistance to an electrolytic solution, light transmittance, and transferability.

  Moreover, the following polyolefin compounds can be mentioned as another example of the said adhesive resin. Examples of the polyolefin compound include homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, and 1-butene, and those α-olefins and ethylene, propylene, 1-butene, and 3-methyl-. Other α-olefins having about 2 to 20 carbon atoms such as 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, vinyl acetate, (meth) acrylic Examples include acids, copolymers with (meth) acrylic acid esters, (anhydrous) maleic acid-modified resins, silane-modified resins, olefin elastomers, and the like.

  Examples of the α-olefin homo- or copolymer include, for example, ethylene homopolymers such as low / medium / high-density polyethylene (branched or linear), ethylene-propylene copolymers, atactic polypropylene, and propylene alone. Polymer, polyolefin such as 1-butene homopolymer; ethylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1- Hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-ethylene-1-butene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer Polymer or its ionomer, ethylene- (meth) acrylate copolymer such as ethylene-ethyl acrylate copolymer Maleic acid-modified ethylene-vinyl acetate copolymer resin, maleic acid-modified polyolefin resin, (anhydrous) maleic acid-modified resin such as ethylene-ethyl acrylate-maleic anhydride terpolymer, ethylene unsaturated silane compound and polyolefin compound And modified polyolefins such as silane-modified resins made of a copolymer.

  Examples of the olefin-based elastomer include elastomers having polyethylene or polypropylene as hard segments and ethylene-propylene rubber (EPR) or ethylene-propylene-diene rubber (EPDM) as soft segments.

  These polyolefin compounds can be used alone or in combination of two or more.

  In the present invention, among these polyolefin compounds, from the viewpoint of adhesiveness, modified polyolefins, particularly modified ethylene resins (for example, silane-modified resins composed of a copolymer of an ethylenically unsaturated silane compound and a polyolefin compound, ethylene- Vinyl acetate copolymers, ethylene copolymers such as ethylene-ethyl acrylate copolymers, etc.) are preferred. Of these, the case where a silane-modified resin is used as the adhesive layer is most preferable.

  The silane-modified resin is not particularly limited as long as it has the melting point. Among these, as the silane-modified resin used in the present invention, it is preferable to use a copolymer of a polyolefin compound and an ethylenically unsaturated silane compound. By using such a copolymer, for example, it becomes easy to adjust various physical properties of the silane-modified resin within a suitable range according to the method for producing the oxide semiconductor electrode of the present invention. In the present invention, the copolymer may or may not be crosslinked with a silanol catalyst.

  The copolymer of the polyolefin compound and the ethylenically unsaturated silane compound may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. In the present invention, a graft copolymer is preferable, and a graft copolymer obtained by polymerizing a main chain of polyethylene for polymerization and an ethylenically unsaturated silane compound as a side chain is more preferable. This is because such a graft copolymer has a higher degree of freedom of silanol groups that contribute to the adhesive strength, and thus can further strengthen the adhesive strength of the adhesive layer.

  Examples of the polyolefin compound include homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, and 1-butene, and those α-olefins and ethylene, propylene, 1-butene, and 3-methyl-1- Other α-olefins having about 2 to 20 carbon atoms such as butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, vinyl acetate, (meth) acrylic acid, Examples thereof include copolymers with (meth) acrylic acid esters and the like. Specific examples include ethylene homopolymers such as low, medium and high density polyethylene (branched or linear), ethylene-propylene copolymers, and the like. Polymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer ,ethylene- (Meth) acrylic acid copolymers, ethylene resins such as ethylene- (meth) ethyl acrylate copolymers, propylene homopolymers, propylene-ethylene copolymers, propylene-ethylene-1-butene copolymers, etc. Examples thereof include propylene resins and 1-butene resins such as a 1-butene homopolymer, a 1-butene-ethylene copolymer, and a 1-butene-propylene copolymer. Among these, in the present invention, a polyethylene resin is preferable.

  The polyethylene resin (hereinafter referred to as polymerization polyethylene) is not particularly limited as long as it is a polyethylene polymer. Examples of such polyethylene-based polymers include low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, very ultra low density polyethylene, and linear low density polyethylene. In the present invention, one kind of these polyethylene polymers may be used as a simple substance, or two or more kinds may be mixed and used.

In addition, the polyethylene for polymerization preferably has a low density among the polyethylene-based polymers. Specifically, the density is preferably in the range of 0.850 g / cm ^{3 to} 0.960 g / cm ³ , In particular, it is preferably in the range of 0.865 g / cm ^{3 to} 0.930 g / cm ³ . A polyethylene-based polymer having a low density generally contains a large number of side chains and can be suitably used for graft polymerization. Therefore, if the density is higher than the above range, graft polymerization may be insufficient, and a desired adhesive force may not be imparted to the adhesive layer. If the density is lower than the above range, This is because the mechanical strength may be impaired.

  The ethylenically unsaturated silane compound is not particularly limited as long as it can be polymerized with the polymerization polyethylene to form a thermoplastic resin. Examples of such ethylenically unsaturated silane compounds include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl tributoxy silane, vinyl triopentoxy silane, vinyl triphenoxy silane, vinyl tribenzyloxy silane, vinyl It is preferably at least one selected from the group consisting of trimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane.

  Next, the manufacturing method of the graft copolymer of the said polyolefin compound and the said ethylenically unsaturated silane compound is demonstrated. The method for producing such a graft copolymer is not particularly limited as long as a desired yield can be obtained, and can be produced by a known polymerization means. In particular, in the present invention, a method of obtaining a graft copolymer by heating and mixing a silane-modified resin composition comprising the polyolefin compound, the ethylenically unsaturated silane compound, and a free radical generator is preferable. This is because such a method makes it easy to obtain the graft copolymer in a high yield.

  The heating temperature at the time of heating and melting and mixing is not particularly limited as long as it is within a range in which the polymerization reaction can be completed within a desired time, but is usually preferably 300 ° C. or less, particularly preferably 270 ° C. or less. It is preferably within a range of from ℃ to 250 ℃. This is because if the heating temperature is lower than the above range, the polymerization reaction may not sufficiently proceed, and if the heating temperature is higher than the above range, the silanol group portion may be cross-linked and gelled.

  The free radical generator is not particularly limited as long as it is a compound that can contribute to the promotion of the polymerization reaction. Examples of such free radical generators include hydroperoxides such as diisopropylbenzene hydroperoxide and 2,5-dimethyl-2,5-di (hydroperoxy) hexane; di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-peroxy) hexyne- Dialkyl peroxides such as 3; diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dichlorobenzoyl peroxide Oxides; t-butyl-peroxyisobutyrate, -Butyl peroxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyoctoate, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate, Peroxy such as di-t-butylperoxyphthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyne-3 Esters; organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, or azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) it can. These free radical generators may be used alone or as a mixture of two or more.

  The content of the free radical generator in the silane-modified resin composition can be arbitrarily determined according to the type of free radical generator and the polymerization reaction conditions, but in the silane-modified resin obtained by the polymerization reaction. It is preferable that the remaining amount is within a range of 0.001% by mass or less. In the present invention, it is usually preferable that 0.001 part by weight or more is contained with respect to 100 parts by weight of the polyolefin compound in the silane-modified resin composition, particularly 0.01 part by weight to 5 parts by weight. It is preferable.

  The content of the ethylenically unsaturated silane compound in the silane-modified resin composition is preferably in the range of 0.001 part by weight to 4 parts by weight, particularly 0.01 parts by weight with respect to 100 parts by weight of the polyethylene for polymerization. Within the range of parts to 3 parts by weight is preferred. If the content of the ethylenically unsaturated silane compound is more than the above range, there is a possibility that the free ethylenically unsaturated silane compound remains without being polymerized. If the content is less than the above range, the adhesive strength of the adhesive layer This is because the stability of the oxide semiconductor electrode of the present invention may be impaired.

  The adhesive layer used in the present invention can contain other compounds than the silane-modified resin as necessary. In the present invention, it is preferable to use a thermoplastic resin as such another compound, and it is particularly preferable to use a polyolefin compound (hereinafter referred to as a polyolefin compound for addition). Further, when a copolymer of a polyolefin compound and an ethylenically unsaturated silane compound is used as the silane-modified resin contained in the adhesive layer, the polyolefin used in the copolymer as such a polyolefin compound for addition It is preferable to use a compound and a compound.

  In the present invention, the content of the polyolefin compound for addition in the adhesive layer is preferably in the range of 0.01 to 9900 parts by weight, particularly 0.1 parts by weight to 100 parts by weight of the silane-modified resin. More preferably within the range of 2000 parts by weight. If the content of the polyolefin compound for addition is less than the above range, it may be disadvantageous in terms of cost, and if it is more than the above range, the adhesive force of the adhesive layer may be insufficient. Because.

  In the present invention, it is preferable to use a polyethylene-based resin (hereinafter referred to as polyethylene for addition) as the polyolefin compound. In the present invention, it is preferable to use a copolymer of a polyethylene resin and an ethylenically unsaturated silane compound as the silane-modified resin.

  The additive polyethylene is preferably at least one selected from the group consisting of low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, and linear low density polyethylene.

  Moreover, it is preferable that the contact bonding layer used for this invention contains the at least 1 sort (s) of additive chosen from the group which consists of a light stabilizer, a ultraviolet absorber, a heat stabilizer, and antioxidant. By including these additives, it is possible to obtain stable mechanical strength over a long period of time, prevention of yellowing, prevention of cracking, and excellent processability.

  The light stabilizer supplements the active species at the start of photodegradation in the thermoplastic resin used in the adhesive layer and prevents photooxidation. Specific examples include light stabilizers such as hindered amine compounds and hindered piperidine compounds.

  UV absorbers absorb harmful UV rays in sunlight and convert them into innocuous heat energy within the molecule, which excites the active species that initiate photodegradation in the thermoplastic resin used in the adhesive layer. Is to prevent. Specifically, benzophenone-based, benzotriazole-based, salicylate-based, acrylonitrile-based, metal complex-based, hindered amine-based, and ultrafine titanium oxide (particle size: 0.01 μm to 0.06 μm) or ultrafine zinc oxide (particle size) : 0.01 [mu] m to 0.04 [mu] m).

  Thermal stabilizers include tris (2,4-di-t-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite And a lactone heat stabilizer such as a reaction product of 8-hydroxy-5,7-di-t-butyl-furan-2-one and o-xylene. It is preferable to use a phosphorus-based heat stabilizer and a lactone-based heat stabilizer in combination.

  The antioxidant prevents oxidative deterioration of the thermoplastic resin used for the adhesive layer. Specific examples include phenol-based, amine-based, sulfur-based, phosphorus-based, and lactone-based antioxidants.

  These light stabilizers, ultraviolet absorbers, heat stabilizers and antioxidants can be used alone or in combination of two or more.

  The content of the light stabilizer, ultraviolet absorber, heat stabilizer and antioxidant varies depending on the particle shape, density, etc., but is 0.001% by mass to 5% by mass in the material of the adhesive layer, respectively. It is preferable to be within the range.

  Furthermore, as other compounds used in the present invention, in addition to the above, a crosslinking agent, a dispersing agent, a leveling agent, a plasticizer, an antifoaming agent, and the like can be given.

  The thickness of the adhesive layer used in the present invention is not particularly limited as long as it is within a range in which a necessary adhesive force can be expressed, depending on the type of thermoplastic resin constituting the adhesive layer, but is usually within a range of 5 μm to 300 μm. In particular, the range of 10 μm to 200 μm is preferable. If the thickness of the adhesive layer is thinner than the above range, a desired adhesive force may not be obtained, and if the thickness is thicker than the above range, excessive heating is required to sufficiently express the interlayer adhesive strength by the adhesive layer. This is because it may be necessary and thermal damage to the substrate may increase.

(4) Others As for the base material used for this invention, the fine uneven | corrugated shape may be formed in the surface. It is because the light scattering function by a base material can be improved by forming such a fine uneven | corrugated shape.

2. 1st electrode layer Next, the 1st electrode layer used for this invention is demonstrated. The first electrode layer used in the present invention is made of a metal oxide.

(1) Metal oxide The metal oxide used in the present invention is not particularly limited as long as it is a material having excellent conductivity and resistance to a redox pair described later. In particular, in the present invention, it is preferable to use a material having excellent sunlight permeability. For example, when a dye-sensitized solar cell is manufactured using the oxide semiconductor electrode of the present invention, the metal oxide is usually used for the invention that receives sunlight from the base material side. This is because the power generation efficiency of the dye-sensitized solar cell using the oxide semiconductor electrode of the present invention is impaired when the property is poor.

Examples of the metal oxide having excellent sunlight permeability include SnO ₂ , ITO, IZO, and ZnO. In the present invention, among these metal oxides, fluorine doped SnO ₂ (hereinafter referred to as FTO) and ITO are preferably used. This is because FTO and ITO are excellent in both conductivity and sunlight permeability.

(2) 1st electrode layer The structure which consists of a single layer may be sufficient as the 1st electrode layer in this invention, and the structure which laminated | stacked the several layer may be sufficient as it. Examples of the configuration in which a plurality of layers are stacked include an invention in which layers having different work functions are stacked, and an invention in which layers made of different metal oxides are stacked.

The thickness of the 1st electrode layer in this invention will not be specifically limited if it exists in the range which can implement | achieve desired electroconductivity according to the use etc. of the oxide semiconductor electrode of this invention. In particular, the thickness of the first electrode layer in the present invention is usually preferably in the range of 5 nm to 2000 nm, and particularly preferably in the range of 10 nm to 1000 nm. If the thickness is greater than the above range, it may be difficult to form a homogeneous first electrode layer. If the thickness is less than the above range, the oxide semiconductor electrode of the present invention may be used depending on the application. This is because the conductivity of one electrode layer may be insufficient.
In addition, the thickness of the said transparent electrode shall point out the total thickness which added the thickness of all the layers, when a transparent electrode is comprised from a several layer.

  In addition, as the first electrode layer in the present invention, it is also possible to use a layer having a structure in which a metal mesh having a sufficient opening and a light transmitting property is integrated or laminated on the base material. it can.

3. Next, the porous layer used in the present invention will be described. The porous layer used in the present invention includes metal oxide semiconductor fine particles.

(1) Metal oxide semiconductor fine particles The metal oxide semiconductor fine particles used in the porous layer include TiO ₂ , ZnO, SnO ₂ , ITO, ZrO ₂ , MgO, Al ₂ O ₃ , CeO ₂ , and Bi ₂ O _3. , Mn ₃ O ₄ , Y ₂ O ₃ , WO ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , La ₂ O _{3 and the} like. These metal oxide semiconductor fine particles are suitable for forming a porous porous layer, and can be used suitably for the oxide semiconductor electrode of the present invention because energy conversion efficiency can be improved and cost can be reduced. It is done. Moreover, in this invention, any 1 type may be used among the said metal oxide semiconductor fine particles, and 2 or more types may be mixed and used for it. Further, one of the metal oxide semiconductor fine particles described above may be a core fine particle, and a core-shell structure in which the core fine particle is included to form a shell by another metal oxide semiconductor fine particle. In the present invention, it is most preferable to use TiO ₂ as the semiconductor oxide fine particles.

  The particle size of the metal oxide semiconductor fine particles is not particularly limited as long as a desired surface area can be obtained in the porous layer, but is usually preferably in the range of 1 nm to 10 μm, particularly 10 nm to It is preferable to be in the range of 1000 nm. If the particle size is smaller than the above range, the respective metal oxide semiconductor fine particles may aggregate to form secondary particles, and if the particle size is larger than the above range, the porous layer becomes thicker. In addition, the porosity of the porous layer, that is, the specific surface area is reduced. For example, when the oxide semiconductor electrode of the present invention is used in a dye-sensitized solar cell, it is sufficient for photoelectric conversion to the porous layer. This is because it may not be possible to carry a large dye sensitizer.

In the present invention, a mixture of a plurality of metal oxide semiconductor particles having different particle diameters may be used as the metal oxide semiconductor particles. Since the light scattering effect in the porous layer can be enhanced by using a mixture of metal oxide semiconductor fine particles having different particle sizes, for example, when the oxide semiconductor electrode of the present invention is used in a dye-sensitized solar cell In addition, light absorption by the dye sensitizer can be performed efficiently. Therefore, in the present invention, it is particularly preferable to use a mixture of metal oxide semiconductor fine particles having different particle diameters.
The mixture of a plurality of metal oxide semiconductor particles having different particle diameters may be a mixture of the same type of metal oxide semiconductor particles or a mixture of different types of metal oxide semiconductor particles. Good. Examples of combinations of different particle diameters include an invention in which metal oxide semiconductor fine particles within a range of 10 to 50 nm and metal oxide semiconductor fine particles within a range of 50 to 800 nm are mixed and used. .

(2) Other compounds The porous layer in the present invention contains the same metal element as the metal element included in the metal oxide constituting the first electrode layer (hereinafter sometimes referred to as an electrode metal element). It is preferable. This is because when the porous layer contains an electrode metal element, the oxide semiconductor electrode of the present invention can be made excellent in conductivity.

  The distribution of the presence of the electrode metal element in the porous layer can be arbitrarily determined according to the use of the oxide semiconductor electrode of the present invention, but from the surface on the first electrode layer side to the opposite surface. It is preferable to have a distribution with a decreasing concentration gradient. This is because the current collection efficiency of the porous layer can be further improved by such distribution of the electrode metal element in the porous layer.

  In the present invention, the presence of the electrode metal element in the porous layer and the presence distribution described above are determined by mapping the characteristic X-ray intensity of the metal element to be specified using the electron beam as a probe in two dimensions. can do. Specifically, it can be determined by EPMA (Electron Probe Micro Analyzer) manufactured by JEOL. Further, the concentration gradient of the metal element can be determined from the detected intensity profile in the vertical direction (cross-sectional vertical direction) of the cross-sectional element mapping diagram obtained by the EPMA.

Moreover, it is preferable that the porous layer in this invention contains a dye sensitizer. That is, it is preferable that the dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. This is because when the porous layer contains a dye sensitizer, the production process of the dye-sensitized solar cell can be simplified when the oxide semiconductor electrode of the present invention is used for a dye-sensitized solar cell. . The dye sensitizer used in the present invention is not particularly limited as long as it can absorb light and generate an electromotive force. Examples of such a dye sensitizer include organic dyes and metal complex dyes.
In the present invention, the above-mentioned “containing a dye sensitizer” means adsorbing to the surface of the metal oxide semiconductor fine particles contained in the porous layer (intervening layer and oxide semiconductor layer). And

  Examples of the organic dye used in the present invention include acridine, azo, indigo, quinone, coumarin, merocyanine, and phenylxanthene dyes. In the present invention, among these organic dyes, a coumarin dye is preferably used.

  Further, as the metal complex dye used in the present invention, a ruthenium dye is preferable, and a ruthenium bipyridine dye and a ruthenium terpyridine dye which are ruthenium complexes are particularly preferable. This is because such a ruthenium complex has a wide wavelength range of light to be absorbed, so that the wavelength range of light that can be photoelectrically converted can be greatly expanded.

(3) Porous layer The thickness of the porous layer in the present invention is not particularly limited as long as a desired mechanical strength can be imparted to the porous layer according to the use of the oxide semiconductor electrode of the present invention. The thickness of the porous layer in the present invention is usually preferably in the range of 1 μm to 100 μm, particularly preferably in the range of 5 μm to 30 μm. If the thickness of the porous layer is larger than the above range, peeling from the adhesive layer, cohesive failure of the porous layer itself may easily occur, and membrane resistance may easily occur. For example, when the oxide semiconductor electrode of the present invention is used in a dye-sensitized solar cell, the porous layer containing the dye-sensitizer is This is because the light and the like cannot be sufficiently absorbed, and there is a possibility that the performance is deteriorated.

  The porous layer in the present invention may be composed of a single layer or may be a structure in which a plurality of layers are laminated. In the present invention, the porous layer preferably has a structure in which a plurality of layers are laminated. As a structure in which a plurality of layers are stacked, any structure can be appropriately selected and employed in accordance with the oxide semiconductor electrode manufacturing method of the present invention. In particular, in the present invention, an oxide semiconductor layer having a porous layer in contact with the first electrode layer, an intervening layer formed on the oxide semiconductor layer and having a higher porosity than the oxide semiconductor layer, A two-layer structure consisting of By forming the porous layer into a two-layer structure comprising such an oxide semiconductor layer and an intervening layer, the adhesion between the heat-resistant substrate and the porous layer can be increased when the porous layer is formed by a transfer method. This is because an oxide semiconductor electrode that can be reduced and has excellent productivity by a transfer method can be obtained.

  In the present invention, when the porous layer has a two-layer structure including the oxide semiconductor layer and the intervening layer, the intervening layer does not need to be uniformly formed on the oxide semiconductor layer. Further, it may have a thickness distribution, and there may be a portion where no intervening layer exists on the oxide semiconductor layer. This is because even if the intervening layer is present in this manner, an oxide semiconductor electrode excellent in productivity by the transfer method can be obtained.

  When the porous layer has a two-layer structure of the oxide semiconductor layer and the intervening layer, the thickness ratio between the oxide semiconductor layer and the intervening layer depends on the method for manufacturing the oxide semiconductor electrode of the present invention. It can be determined arbitrarily. Especially in this invention, it is preferable that the thickness ratio of the said oxide semiconductor layer and the said intervening layer exists in the range of 10: 0.1-10: 5, Especially, 10: 0.1-10: It is preferable to be within the range of 3. If the thickness of the intervening layer is larger than the above range, cohesive failure of the intervening layer tends to occur, resulting in poor yield when producing the oxide semiconductor electrode of the present invention. For example, the oxide semiconductor of the present invention This is because when the electrode is used in a dye-sensitized solar cell, a desired amount of the dye sensitizer may not be adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. Further, if the thickness is less than the above range, it may not be possible to contribute to the productivity improvement of the oxide semiconductor electrode of the present invention.

  The porosity of the oxide semiconductor layer is preferably in the range of 10% to 60%, and more preferably in the range of 20% to 50%. For example, when the oxide semiconductor electrode of the present invention is used for a dye-sensitized solar cell, if the porosity of the oxide semiconductor layer is smaller than the above range, the specific surface area becomes small. The contained porous layer may not be able to effectively absorb sunlight or the like, and if it is larger than the above range, the oxide semiconductor layer may not be able to contain a desired amount of dye sensitizer. Because.

  The porosity of the intervening layer is not particularly limited as long as it is larger than the porosity of the oxide semiconductor layer, but it is usually preferably in the range of 25% to 65%, and in particular, 30% to It is preferable to be within the range of 60%. If the porosity of the intervening layer is smaller than the above range, the adhesion to the heat-resistant substrate will be high, so productivity may be lost, and if it is larger than the above range, a homogeneous intervening layer will be formed. It may be difficult to do.

  In addition, the porosity in this invention shows the nonoccupancy rate of the metal semiconductor fine particle per unit volume. As a method for measuring the porosity, the pore volume is measured with a gas adsorption amount measuring device (Autosorb-1MP; manufactured by Quantachrome), and is calculated from the ratio to the volume per unit area. About the porosity of an intervening layer, it calculates | requires as a porous layer laminated | stacked with the oxide semiconductor layer, and calculates from the value calculated | required by the oxide semiconductor layer single-piece | unit.

4). Oxide Semiconductor Electrode The porous layer in the oxide semiconductor electrode of the present invention is preferably patterned. This is because the oxide semiconductor electrode of the present invention can be made suitable for producing a dye-sensitized solar cell having a high module electromotive force by patterning the porous layer. The porous layer in the present invention may be patterned as long as at least the porous layer is patterned. Moreover, when a porous layer consists of the said oxide semiconductor layer and the said intervening layer, it is preferable that both layers are patterned by the same shape.

  As an invention for patterning a porous layer in the present invention, the porous layer and the first electrode layer are preferably patterned. In the case where the porous layer and the first electrode layer are patterned in this way, the pattern shape of the porous layer and the first electrode layer is, for example, the pattern shape of the porous layer is the first electrode layer It is preferable that the pattern shapes are different from each other in a manner such as smaller than the pattern shape.

  In the present invention, when the porous layer is patterned, the pattern can be arbitrarily determined according to the use of the oxide semiconductor electrode of the present invention, among others, it can be a stripe pattern. Most preferred.

5. Next, a method for manufacturing an oxide semiconductor electrode of the present invention will be described. The manufacturing method of the oxide semiconductor electrode of the present invention is not particularly limited as long as it is a method capable of manufacturing the oxide semiconductor electrode having the above structure.
Hereinafter, as an example of a method for manufacturing an oxide semiconductor electrode of the present invention, an example of a method for manufacturing an oxide semiconductor electrode in a mode in which the base material has a configuration in which an adhesive layer containing a light scattering material and a base material are stacked will be described. To do.

  The oxide semiconductor electrode of the above aspect can be manufactured by a method of transferring a laminate of a porous layer and a first electrode layer to an adhesive layer side of a substrate having a configuration in which an adhesive layer and a substrate are laminated. . Specifically, a porous layer forming step for forming a porous layer on a heat resistant substrate, a first electrode layer forming step for forming a first electrode layer on the porous layer, and a first electrode layer on the first electrode layer A base material applying step for providing a base material having a structure in which an adhesive layer containing a light scattering material and a base material are laminated, and a base material forming step with a heat resistant substrate for producing an oxide semiconductor electrode with a heat resistant substrate, and The oxide semiconductor electrode with a heat-resistant substrate can be manufactured by a heat-resistant substrate peeling process that peels the heat-resistant substrate from the porous layer. Hereinafter, such a manufacturing method will be described in detail.

(1) Base material forming step with a heat-resistant substrate First, the above-described base material forming step with a heat-resistant substrate will be described. The base material forming step with a heat-resistant substrate is a step of producing an oxide semiconductor electrode with a heat-resistant substrate by a porous layer forming step, a first electrode layer forming step, and a base material applying step.

i. Porous layer forming step In the porous layer forming step, a porous layer forming coating solution containing metal oxide semiconductor fine particles, a resin, and a solvent is applied onto a heat-resistant substrate, and then fired. Thus, a porous layer can be formed on the heat resistant substrate.
Further, in this step, an intermediate layer forming layer forming step for forming an intermediate layer forming layer on the heat-resistant substrate, and an oxide semiconductor layer forming layer for forming the oxide semiconductor layer forming layer on the intermediate layer forming layer And a firing step of firing the intermediate layer forming layer and the oxide semiconductor layer forming layer to form a porous intermediate layer and a porous layer made of the oxide semiconductor layer. Thereby, the porous layer formed by this process can be made into the structure which consists of two layers of an oxide semiconductor layer and an intervening layer as mentioned above.

  The heat-resistant substrate used in this step is not particularly limited as long as it has heat resistance with respect to the heating temperature during the baking treatment described later. “Heat resistance” in the present invention refers to heat resistance against the heating temperature during the baking treatment performed when the porous layer is formed. By using such a heat-resistant substrate having excellent heat resistance, the firing treatment described later can be performed at a sufficiently high temperature, so that the binding property between the metal oxide semiconductor fine particles forming the porous layer is increased. Can do. The heat-resistant substrate is preferably reusable.

  The heat-resistant substrate used in this step is preferably one having further acid resistance among those having heat resistance. Here, “acid resistance” in the present invention means that when the porous layer forming coating solution used for forming the porous layer is acidic, the porous layer forming coating solution does not corrode. Acid resistance to such an extent that the acid decomposition product does not cause alteration or peeling of the porous layer or the like even when it is somewhat corroded.

  The heat-resistant substrate may be a single layer or a plurality of layers as long as it has the acid resistance and heat resistance described above. When the heat-resistant substrate is a single layer, the material of the heat-resistant substrate is not particularly limited as long as it has flexibility, heat resistance, and acid resistance. For example, a single metal, a metal alloy, and a metal Examples thereof include metals such as oxides. Examples of the metal simple substance include Ti, W, Mo, Nb, Cr, Ni, Ag, Zr, Pt, Ta, and Au. Among these, Ti, W, Pt, and Au are preferable. Examples of the metal alloy include SUS, Ti alloy, Fe alloy, Ni alloy, Al alloy, W alloy, Mg alloy, Co alloy, and Cr alloy. Among them, SUS, Ti alloy, and Al alloy are preferable. Examples of the metal oxide include Si oxide, Al oxide, Ti oxide, Zr oxide, Sn oxide, Cr oxide, and W oxide. Ti oxide is preferred.

  On the other hand, when the heat-resistant substrate has a plurality of layers, for example, the heat-resistant substrate has a heat-resistant layer and an acid-resistant layer formed on the surface of at least the porous layer side of the heat-resistant layer. Can be mentioned.

  The heat-resistant layer is not particularly limited as long as the heat-resistant layer has sufficient heat resistance with respect to the heating temperature during the baking treatment performed when the porous layer is formed. Examples of the material for such a heat-resistant layer include metals, glasses, ceramics, and the like, among which metals are preferable. Furthermore, specific examples of the metal include a simple metal, a metal alloy, and a metal oxide. Moreover, since the said metal simple substance, a metal alloy, and a metal oxide generally have sufficient heat resistance, the kind etc. are not specifically limited. In addition, as said metal simple substance, specifically Ti, W, Pt, Au etc. are preferable, As said metal alloy, SUS, Ti alloy, Al alloy etc. are specifically preferable, As said metal oxide, Specifically, Si oxide, Al oxide, Ti oxide and the like are preferable.

  The acid-resistant layer is not particularly limited as long as it has acid resistance and heat resistance. Examples of the material for such an acid-resistant layer include metals, glasses, ceramics, and the like. Among these, metals are preferable. Furthermore, specific examples of the metal include a simple metal, a metal alloy, and a metal oxide. Examples of the metal simple substance include Ti, W, Mo, Nb, Cr, Ni, Ag, Zr, Pt, Ta, and Au. Among these, Ti, W, Pt, and Au are preferable. Examples of the metal alloy include SUS, Ti alloy, Fe alloy, Ni alloy, Al alloy, W alloy, Mg alloy, Co alloy, and Cr alloy. Among them, SUS, Ti alloy, and Al alloy are preferable. Examples of the metal oxide include Si oxide, Al oxide, Ti oxide, Zr oxide, Sn oxide, Cr oxide, and W oxide. Ti oxide is preferred.

  When the heat-resistant substrate used in this step has the heat-resistant layer and the acid-resistant layer, the combination of the heat-resistant layer and the acid-resistant layer is not particularly limited and can be arbitrarily selected. . For example, the combination of the material of the heat resistant layer is metal, glass or ceramics, and the material of the acid resistant layer is metal. Among them, the material of the heat resistant layer and the acid resistant layer is metal. Some combinations are preferred. This is because a heat-resistant substrate having excellent flexibility can be obtained.

  As a combination in which the material of the heat resistant layer and the acid resistant layer is a metal, for example, the material of the heat resistant layer is a simple metal, a metal alloy, or a metal oxide, and the material of the acid resistant layer is the heat resistant layer. The combination which is a metal simple substance, a metal alloy, or a metal oxide other than the metal used for the above can be mentioned. Specifically, as a combination of the material of the heat resistant layer / the material of the acid resistant layer, Ti simple substance / Ti oxide, SUS / Cr simple substance, SUS / Si oxide, SUS / Ti oxide, SUS / Al oxide, Examples thereof include SUS / Cr oxide.

Moreover, when the material of the said heat resistant layer and the said acid resistant layer is a metal, it is preferable that the metal element contained in the said heat resistant layer differs from the metal element contained in the said acid resistant layer. Here, “a metal element contained in the heat-resistant layer” means a metal element contained most in the heat-resistant layer. Therefore, for example, even when SUS contains Cr, Ni or the like, the “metal element contained in the heat-resistant layer” is Fe. The same applies to the “metal element contained in the acid-resistant layer”. As a combination of such a heat-resistant layer and an acid-resistant layer, as a combination of a material of a heat-resistant layer / a material of an acid-resistant layer, SUS / Cr simple substance, SUS / Si oxide, SUS / Ti oxide, SUS / Al Examples thereof include oxides and SUS / Cr oxides.
The heat resistant substrate preferably has flexibility. This is because an oxide semiconductor electrode can be manufactured by the Roll to Roll method.

  The resin used in the porous layer forming coating solution is not particularly limited as long as it is easily decomposed in the firing step. Examples of the resin used in the coating solution for forming the oxide semiconductor layer include cellulose resins, polyester resins, polyamide resins, polyacrylate resins, polyacryl resins, polycarbonate resins, polyurethane resins, polyolefin resins. In addition to polyvinyl acetal resins, fluorine resins, polyimide resins, etc., polyhydric alcohols such as polyethylene glycol can be used.

  The solvent used in the porous layer forming coating solution is not particularly limited as long as it can dissolve the resin in a desired amount. Examples of such a solvent include water and various solvents such as methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, terpineol, dichloromethane, acetone, acetonitrile, ethyl acetate, and tert-butyl alcohol. Among these, water or an alcohol solvent is preferable.

  The method for forming the porous layer forming layer by applying the porous layer forming coating liquid on the heat resistant substrate is not particularly limited, and generally known methods can be used. Further, the method for firing the porous layer forming layer is not particularly limited as long as it is a method capable of forming pores by decomposing the resin. As a method for forming such a layer for forming a porous layer and a method for firing the layer for forming a porous layer, for example, the method described in JP-A-2005-166648 can be suitably used.

ii. First Electrode Layer Forming Step Next, the first electrode layer forming step will be described. The first electrode layer forming step is a step of forming a first electrode layer made of a metal oxide on the porous layer.

  In the first electrode layer forming step, the method of forming the first electrode layer on the porous layer is not particularly limited as long as it is a method capable of forming the first electrode layer having a uniform thickness and excellent flatness. First, for example, a solution processing step of providing a base electrode layer inside or on the surface of the porous layer using a base electrode layer forming coating solution, and an upper electrode layer formation of providing a main first electrode layer on the base electrode layer And a method of forming the first electrode layer in two steps. According to such a method, the porous layer can easily contain a metal element included in the metal oxide constituting the first electrode layer, and a dense first electrode layer can be formed. Further, the surface of the metal oxide semiconductor fine particles forming the porous layer is covered with the metal oxide constituting the first electrode layer, so that the reverse electron transfer from the porous layer into the electrolyte is suppressed.

  In the solution treatment step, a base first electrode layer forming coating solution in which a metal salt or metal complex containing a metal element included in the metal oxide constituting the first electrode layer is dissolved is brought into contact with the porous layer. Thus, it is possible to use a method of providing the base first electrode layer inside or on the surface of the porous layer. The base first electrode layer forming coating solution used in this step is a metal salt or metal complex (hereinafter referred to as “metal source”) containing at least a metal element contained in the metal oxide constituting the first electrode layer. And a solvent, and may contain other compounds as necessary.

  The metal source includes a metal element contained in the metal oxide constituting the first electrode layer, and may be a metal salt or a metal complex. The “metal complex” includes a metal ion coordinated with an inorganic substance or an organic substance, or a so-called organometallic compound having a metal-carbon bond in the molecule.

  Since the metal element constituting the metal source used in this step is a metal element included in the metal oxide described in the above section “2. First electrode layer”, description thereof is omitted here.

  As said metal source used for this process, what was described in Unexamined-Japanese-Patent No. 2005-166648 can be used suitably, for example.

  The solvent used in the base first electrode layer forming coating solution in this step is not particularly limited as long as it can dissolve the metal salt and the like. For example, the metal source is a metal salt. In this case, water, methanol, ethanol, isopropyl alcohol, propanol, butanol and the like can be exemplified by lower alcohols having a total carbon number of 5 or less, toluene, and mixed solvents thereof. When the metal source is a metal complex, The lower alcohol mentioned above, toluene, and these mixed solvents can be mentioned.

  Moreover, the coating solution for base | substrate 1st electrode layer formation used for this process may contain an additive as needed. Examples of the additive used in this step include an oxidizing agent, a reducing agent, an auxiliary ion source, and a surfactant. Specific examples of such additives include those described in JP-A No. 2005-166648.

  In this step, the method for bringing the porous layer and the base first electrode layer forming coating solution into contact with each other is not particularly limited. For example, the dipping method, the single-wafer method, or the solution is atomized. Generally known items such as a coating method can be used. As such a method, for example, a method described in JP-A-2005-166648 can be suitably used.

  In the upper first electrode layer forming step, the upper first electrode layer having a desired density is provided as a method of providing the upper first electrode layer on the base first electrode layer formed by the solution processing step. The method is not particularly limited as long as it is a method that can be used. For example, after the solution treatment step, the base first electrode layer is heated and brought into contact with an upper first electrode layer forming coating liquid to be described later. A method of providing the upper first electrode layer on the base first electrode layer, or a PVD method such as a vacuum deposition method, a sputtering method, or an ion plating method, a CVD method such as plasma CVD, thermal CVD, atmospheric pressure CVD, etc. Can be mentioned. In particular, in the present invention, after the solution treatment step, the base first electrode layer is heated and brought into contact with an upper first electrode layer forming coating liquid to be described later, whereby an upper first electrode is formed on the base first electrode layer. A method of providing an electrode layer is preferred. In this step, as such a method, for example, the method described in JP-A-2005-166648 can be suitably used.

iii. Next, the base material applying step will be described. This step uses a substrate having a structure in which an adhesive layer containing a light scattering material and a substrate are laminated, and the adhesive layer and the first electrode layer are in contact with each other on the first electrode layer. This is a step of applying a base material.

  The method for applying the base material in this step is particularly limited as long as the base material can be applied on the first electrode layer so that the adhesive layer containing the light scattering material and the first electrode layer are in contact with each other. Not. As such a method, after forming an adhesive layer containing a light scattering material on a substrate in advance and arranging a base material having an adhesive layer so that the adhesive layer and the first electrode layer are adhered, Examples thereof include a method of heat-sealing, a method of producing a film made of an adhesive resin containing a light scattering material, and a method of laminating the first electrode layer and a substrate through the film.

  The method of forming the adhesive layer containing the light scattering material on the above differs depending on the type of the light scattering material to be used. For example, when using fine particles as the light scattering material, the adhesive layer containing the fine particles and an adhesive resin is used. It can be formed by coating a forming coating solution on the substrate.

  Since the light scattering material, the substrate, and the adhesive layer used in this step are the same as those described in the above section “1. Base material”, description thereof is omitted here.

(2) Heat-resistant substrate peeling process The method of peeling a heat-resistant board | substrate from the oxide semiconductor electrode with a heat-resistant board | substrate in the said heat-resistant board | substrate peeling process is not specifically limited, A general peeling method can be used. In this step, the heat-resistant substrate can be peeled off by mechanical polishing or chemical removal such as etching.

  In the heat-resistant substrate peeling step, the heat-resistant substrate is peeled from the porous layer, and the peeled state at that time may be peeled from the boundary between the heat-resistant substrate and the porous layer. Further, the porous layer may be peeled off by cohesive failure. In addition, when the porous layer is composed of two layers of an oxide semiconductor layer and an intervening layer, the heat resistant substrate is peeled off from the intervening layer. The interlayer may be peeled off from the boundary, or the intervening layer may be peeled off by cohesive failure.

6). Applications of Oxide Semiconductor Electrode The oxide semiconductor electrode of the present invention is a substrate for a dye-sensitized photocharge capacitor used for a dye-sensitized photocharge capacitor, an electrochromic display substrate used for an electrochromic display, and a photocatalyst. It can be used as a pollutant decomposition substrate capable of decomposing pollutants in the atmosphere using a reaction, and a dye-sensitized solar cell substrate used in dye-sensitized solar cells. It is used suitably for the base material for dye-sensitized solar cells used for a solar cell.

B. Next, the dye-sensitized solar cell of the present invention will be described. The dye-sensitized solar cell of the present invention uses the oxide semiconductor electrode of the present invention, and the dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. The porous layer of the oxide semiconductor electrode and the second electrode layer of the counter electrode base material composed of the second electrode layer and the counter base material are arranged to face each other via the electrolyte layer containing the redox pair. It is a feature.

  The dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of the dye-sensitized solar cell of the present invention. As illustrated in FIG. 3, the dye-sensitized solar cell 20 of the present invention has a configuration in which the oxide semiconductor electrode 10 of the present invention and the second electrode layer 7 are formed on the counter substrate 6. The counter electrode substrate 8 is used, and the electrolyte layer 5 is sandwiched between the porous layer 3 ′ of the oxide semiconductor electrode 10 and the second electrode layer of the counter electrode substrate 8. . Further, a dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer 3 '.

  ADVANTAGE OF THE INVENTION According to this invention, a dye-sensitized solar cell with high electric power generation efficiency can be obtained by using the oxide semiconductor electrode of the said this invention excellent in the utilization efficiency of incident light as an oxide semiconductor electrode.

  The dye-sensitized solar cell of the present invention has an electrolyte layer, a counter electrode base material, and an oxide semiconductor electrode. Hereafter, each structure of the dye-sensitized solar cell of this invention is demonstrated in detail.

1. Electrolyte Layer First, the electrolyte layer used in the present invention will be described. The electrolyte layer in the present invention includes an oxidation-reduction pair.

The redox couple used in the electrolyte layer in the present invention is not particularly limited as long as it is generally used in the electrolyte layer. Specifically, a combination of iodine and iodide and a combination of bromine and bromide are preferable. For example, as a combination of iodine and iodide, a combination of metal iodide such as LiI, NaI, KI, and CaI ₂ and I ₂ can be mentioned. Further, examples of the combination of bromine and bromide include a combination of a metal bromide such as LiBr, NaBr, KBr, and CaBr ₂ and Br ₂ .

  The electrolyte layer in the present invention may contain additives such as a crosslinking agent, a photopolymerization initiator, a thickener, and a room temperature molten salt as other compounds other than the redox couple.

The electrolyte layer may be an electrolyte layer having any form of gel, solid, or liquid. When the electrolyte layer is in a gel form, either a physical gel or a chemical gel may be used. Here, the physical gel is gelled near room temperature due to physical interaction, and the chemical gel is a gel formed by chemical bonding by a crosslinking reaction or the like.
When the electrolyte layer is in a liquid state, for example, acetonitrile, methoxyacetonitrile, propylene carbonate or the like is used as a solvent, and an ionic liquid containing an oxidation-reduction pair or an imidazolium salt as a cation is used as a solvent. can do.
Furthermore, when the electrolyte layer is in a solid state, it may be any material that does not include a redox pair and functions as a hole transporting agent. For example, a hole transporting agent including CuI, polypyrrole, polythiophene, etc. There may be.

2. Next, the counter electrode substrate used in the present invention will be described. The counter electrode base material in this invention consists of a 2nd electrode layer and a counter base material.

(1) Second Electrode Layer The second electrode layer in the present invention is the same as that described in the section of the first electrode layer in “A. Oxide Semiconductor Electrode”, and the description thereof is omitted here. .

(2) Opposite base material The second electrode layer in the present invention is the same as that described in the above-mentioned “A. Oxide semiconductor electrode of the first embodiment” in the section of the base material, and the description here is omitted. To do.

(3) Other layers The counter electrode substrate used in the present invention may contain other layers other than the above, if necessary. Examples of the other layer used in the present invention include a catalyst layer. In the present invention, by forming a catalyst layer on the second electrode layer, the dye-sensitized solar cell of the present invention can be made more excellent in power generation efficiency. Examples of such a catalyst layer include an embodiment in which Pt is vapor-deposited on the second electrode layer, but is not limited thereto.

3. Oxide Semiconductor Electrode The oxide semiconductor electrode in the present invention is the same as that described in the above section “A. Oxide Semiconductor Electrode”, and thus the description thereof is omitted here.

4). Method for Producing Dye-Sensitized Solar Cell Next, an example of a method for producing the dye-sensitized solar cell of the present invention will be described. The dye-sensitized solar cell of the present invention is formed by forming an electrolyte layer between the porous layer of the oxide semiconductor electrode of the present invention and the second electrode substrate of the counter electrode substrate. Can be manufactured.

  In the present invention, as a method of forming an electrolyte layer between the porous layer of the oxide semiconductor electrode of the present invention and the second electrode substrate of the counter electrode substrate, each layer is formed with high thickness accuracy. There is no particular limitation as long as it can be performed. As such a method, after forming an electrolyte layer on the porous layer, a method of forming a second electrode layer on the electrolyte layer (first method), and a second method facing the porous layer A method (second method) of forming an electrolyte layer between the porous layer and the second electrode layer after forming the electrode layer can be mentioned.

  As the first method, for example, an application method of applying a counter electrode substrate after forming an electrolyte layer by applying a composition for forming an electrolyte layer on the porous layer and drying it is used. it can. In addition, as the second method, the porous layer and the second electrode layer of the counter electrode base material are arranged with a predetermined gap so as to face each other, and an electrolyte layer forming electrode is formed in the gap. An injection method for forming an electrolyte layer by injecting the composition can be used.

  As the coating method of the composition for forming a porous layer in the above coating method, a known coating method can be used. Specifically, die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating, bar Examples include coat, blade coat, knife coat, air knife coat, slot die coat, slide die coat, dip coat, micro bar coat, micro bar reverse coat, and screen printing (rotary method).

  Further, when the electrolyte layer is formed by the coating method, the electrolyte layer forming composition for forming the electrolyte layer is not particularly limited as long as it has at least a redox couple and a polymer compound that holds the redox couple. Not.

  When the electrolyte layer is formed by the above injection method, the electrolyte layer forming composition for forming the electrolyte layer is not particularly limited as long as it has at least a redox pair. In this case, it is assumed that a gelling agent is further contained. For example, in the case of a physical gel, examples of the gelling agent include polyacrylonitrile and polymethacrylate. Moreover, in the case of a chemical gel, an acrylic ester type, a methacrylic ester type, etc. can be mentioned.

  The method for injecting the composition for forming an electrolyte layer into the gap between the porous layer and the second electrode layer of the counter electrode base material is not particularly limited, but for example, a method of injecting using a capillary phenomenon In addition, a method may be used in which the gap between the porous layer and the second electrode is in a vacuum state and is injected by releasing the pressure to atmospheric pressure in a state where the composition for forming an electrolyte layer is in contact.

  Moreover, after injecting the composition for forming an electrolyte layer by an injection method, for example, temperature adjustment, ultraviolet irradiation, electron beam irradiation, or the like is performed, and a two-dimensional or three-dimensional crosslinking reaction is caused to generate a gel or solid. The electrolyte layer can be formed.

  In the present invention, the method for forming the second electrode layer on the counter substrate is not particularly limited, and a general method can be used.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the technical idea described in the claims of the present invention has substantially the same configuration and exhibits the same function and effect regardless of the case. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described more specifically with reference to examples.

1. Example 1
A base material (thickness 120 μm) prepared by kneading 1% by mass of light diffusing particles (Gantz pearl average particle size 100 μm: manufactured by Ganz Corporation) on a PET film was prepared. When the haze value of this base material was measured, it was 20% (measuring instrument: haze meter: Suga Test Instruments SM-C).

  Next, a first electrode layer made of tin oxide (ITO) doped with indium was formed on the substrate by sputtering. The surface resistance of the formed first electrode layer was 15Ω / □.

Next, a TiO ₂ dispersion (PECC-K01; Peccell Technologies) was applied onto the first electrode layer by a doctor blade method to form a porous layer having a thickness of 10 μm.
The oxide semiconductor electrode of the present invention was formed by such a method.

After the porous layer of the prepared oxide semiconductor electrode was formed into a 1 cm square, the porous layer was integrated into a dye (N3 (Ruthenium 535): manufactured by Solaronix) solution (3.0 × 10 ⁻³ M in ethanol). The dye was adsorbed inside the pores of the porous layer by dipping in the evening.

  Next, an ITO / PET film (Tobe OTEC (thickness: 25 μm), 10Ω / □) prepared by sputtering platinum on an ITO / PET film as a counter electrode base material was prepared. The electrode base material was bonded at 120 ° C. via a thermoplastic resin (Surlyn; DuPont).

  Next, using methoxyacetonitrile as a solvent, a concentration of 0.1 mol / L lithium iodide, a concentration of 0.05 mol / L iodine, a concentration of 0.3 mol / L dimethylpropylimidazolium iodide, a concentration of 0.5 mol / L A composition for forming an electrolyte layer was prepared by dissolving t-butylpyridine. The composition for forming an electrolyte layer was injected between the oxide semiconductor electrode and the counter electrode base material through an injection hole provided in the counter electrode base material to prepare a dye-sensitized solar cell.

As a result of measuring the conversion efficiency (100 mW / cm ² , AM1.5) of the produced dye-sensitized solar cell, the conversion efficiency was 4.5% (Isc = 9.8 mA, Voc = 710 mV, FF = 0.64). there were.

2. Comparative Example 1
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that a PET film (120 μm) containing no light diffusing agent was used as the substrate.

  About the produced dye-sensitized solar cell, the conversion efficiency was measured by the same method as Example 1. As a result, the conversion efficiency was 4.1% (Isc = 8.9 mA, Voc = 708 mV, FF = 0.66).

3. Example 2
1% by mass of TiO ₂ fine particles having a primary particle size of 20 nm (P25 manufactured by Nippon Aerosil Co., Ltd.) and 10% by mass of an acrylic resin (molecular weight 25000, glass transition temperature 105 ° C .: BR87 manufactured by Mitsubishi Rayon Co., Ltd.) whose main component is polymethyl methacrylate. As described above, an acrylic resin was dissolved in methyl ethyl ketone and toluene using a homogenizer, and then a coating solution for forming an intervening layer was prepared by dispersing TiO ₂ fine particles. This intervening layer-forming coating solution is coated with a wire bar on a titanium substrate (thickness 150 μm, size 10 cm × 10 cm) prepared as a heat-resistant substrate, and dried, whereby an intervening layer-forming layer is formed on the heat-resistant substrate. Formed.

  Next, Ti Nanoxide D made by Solaronix SA was prepared as a coating liquid for forming an oxide semiconductor layer, and the coating liquid for forming an oxide semiconductor layer was applied onto the intermediate layer forming layer with a doctor blade (5 Mil). After that, it was allowed to stand at room temperature for 20 minutes and further dried at 100 ° C. for 30 minutes to form an oxide semiconductor layer forming layer on the intervening layer forming layer.

  Next, using an electric muffle furnace (P90 manufactured by Denken), the heat-resistant substrate on which the intervening layer forming layer and the oxide semiconductor layer forming layer are formed is baked at 500 ° C. for 30 minutes in an atmospheric pressure atmosphere. did. Thereby, the porous layer which consists of an intervening layer and an oxide semiconductor layer was formed on the said heat-resistant board | substrate.

  Next, the heat-resistant substrate on which the porous layer was formed was placed on a hot plate (400 ° C.) so that the porous layer faced upward. Next, a first electrode layer-forming coating solution in which 0.1 mol / L of indium chloride and 0.005 mol / L of tin chloride are dissolved in ethanol is sprayed on the heated porous layer by an ultrasonic sprayer. An ITO film (thickness: 500 nm) as one electrode layer was formed.

Next, 5 parts by mass of silica particles (Fuso Chemical Co., Ltd., SP-0.3B (particle size: 0.3 μm)) is dispersed in a heat sealant (Toyobo MD1985) with a homogenizer, thereby forming an adhesive layer. A composition was obtained. Next, the adhesive layer-forming composition was applied onto a PET film (Toyobo E5100 thickness: 125 μm) and air-dried to form an adhesive layer.
Thereafter, the PET film in which the adhesive layer is laminated on the first electrode layer is bonded at 120 ° C. so that the adhesive layer and the first electrode layer are in contact with each other, thereby providing an oxide semiconductor electrode with a heat-resistant substrate. Was made.

  Next, the oxide semiconductor electrode of the present invention was obtained by peeling the heat-resistant substrate from the oxide semiconductor electrode with a heat-resistant substrate.

  Then, the dye-sensitized solar cell was produced by the method similar to Example 1 using the produced oxide semiconductor electrode.

  About the produced dye-sensitized solar cell, the conversion efficiency was measured by the same method as Example 1. As a result, the conversion efficiency was 6.2% (Isc = 15.2 mA, Voc = 710 mV, FF = 0.57).

4). Comparative Example 2
A dye-sensitized solar cell was produced in the same manner as in Example 2 except that the composition for forming the adhesive layer was not dispersed silica particles.

  About the produced dye-sensitized solar cell, the conversion efficiency was measured by the same method as Example 1. As a result, the conversion efficiency was 5.5% (Isc = 13.2 mA, Voc = 715 mV, FF = 0.57).

It is a schematic sectional drawing which shows an example of the general structure of a dye-sensitized solar cell. It is a schematic sectional drawing which shows an example of the oxide semiconductor electrode of this invention. It is a schematic sectional drawing which shows the other example of the oxide semiconductor electrode of this invention. It is a schematic sectional drawing which shows an example of the dye-sensitized solar cell of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 1 '... Base material 1a ... Base | substrate 1b ... Adhesive layer 2 ... 1st electrode layer 3, 3' ... Porous layer 4 ... Light-scattering material 5 ... Electrolyte layer 6 ... Opposite base material 7 ... 2nd electrode layer 8 ... Counter electrode substrate 10, 11 ... Oxide semiconductor electrode 20 ... Dye-sensitized solar cell

Claims (3)

An oxide semiconductor comprising: a base material; a first electrode layer formed on the base material and made of a metal oxide; and a porous layer formed on the first electrode layer and containing metal oxide semiconductor fine particles. An electrode,
An oxide semiconductor electrode, wherein the base material contains a light scattering material.   The base material is composed of a base and an adhesive layer formed on the base and containing a light scattering material, and the first electrode layer is formed on the adhesive layer. Item 2. The oxide semiconductor electrode according to Item 1.   The porous layer, the second electrode layer, and the counter group of the oxide semiconductor electrode according to claim 1 or 2, wherein a dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. A dye-sensitized solar cell, characterized in that a second electrode layer of a counter electrode substrate made of a material is disposed so as to face each other through an electrolyte layer containing a redox pair.

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