JP2008257893A - Method of manufacturing substrate for dye-sensitized solar cell, method of manufacturing dye-sensitized solar cell, and substrate for dye-sensitized solar cell and dye-sensitized solar cell manufactured by these methods - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a substrate for a dye-sensitized solar cell capable of manufacturing the substrate for the dye-sensitized solar cell having a porous layer having high bonding properties of metal oxide semiconductor fine particles and capable of manufacturing the dye-sensitized solar cell having high power generation efficiency by reduced processes. <P>SOLUTION: The method of manufacturing the substrate includes a porous layer laminate forming process forming a porous laminate by laminating a catalyst layer 2 made of metal, a porous insulating layer 3 made of an insulating substance, a porous layer 4 containing oxide semiconductor fine particles in this order on a heat resistant substrate 1; and a transparent electrode layer forming process forming a transparent electrode layer 5 made of metal oxides on the porous layer of the porous laminate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dye-sensitized solar cell and a method for producing a dye-sensitized solar cell substrate for use in a dye-sensitized solar cell.

  In recent years, environmental problems such as global warming have progressed globally. In recent years, photovoltaic power generation has attracted attention as a clean energy with a low environmental load, and research and development are being actively promoted. 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 are expensive to manufacture, The problem is that the energy consumption at the manufacturing stage is large. Under such circumstances, the dye-sensitized solar cell is attracting attention as a novel solar cell with high possibility of cost reduction, and research and development are being conducted energetically.

A typical dye-sensitized solar cell includes a first electrode layer 112 made of a metal oxide on a substrate 111 and a metal oxide having a dye sensitizer adsorbed on the surface, as exemplified in FIG. A dye-sensitized solar cell electrode substrate 110 having a structure in which a porous layer 113 containing semiconductor fine particles is laminated in this order, and a counter electrode layer 122 made of a metal oxide on a counter substrate 121. Is used, and the porous layer 113 and the counter electrode layer 122 are surrounded by an electrolyte layer 130 made of an electrolytic solution containing an oxidation-reduction pair and surrounded by a sealing material 140. The electrode base material 110 for dye-sensitized solar cells and the counter electrode base material 120 are arranged so as to face each other.
And it has the function to generate electric power in the said porous layer 113 when sunlight injects into the said porous layer 113 from the said base material 111 side.

  Here, the porous layer of the electrode substrate for the dye-sensitized solar cell is a porous body so as to be easily impregnated with the electrolytic solution constituting the electrolyte layer. In order to form a quality layer, a baking treatment at about 600 ° C. is usually required. For this reason, the following two methods have been mainly used as a method for producing the dye-sensitized solar cell substrate.

In the first method, a first electrode layer is produced on a substrate by a sputtering method, and then a material constituting the porous layer is applied on the first electrode layer, and then fired. This is a method for obtaining a porous layer which is a porous body.
On the other hand, in the second method, a porous layer forming coating solution is applied onto a heat resistant substrate, and this is baked to form a porous layer. Then, the porous layer is formed into a heat resistant resin film or the like. This is a method for obtaining a semiconductor electrode by transferring to a low-performance material. (Hereinafter, such a method is referred to as a transfer method). Such a transfer method is disclosed in, for example, Patent Document 1.

However, in the first method, only the substrate having heat resistance can be used as the substrate, and for example, a flexible resin film or the like cannot be used as the substrate.
In the second method, since the substrate usable as the substrate is not particularly limited in heat resistance, for example, a flexible electrode substrate for a dye-sensitized solar cell using a resin film substrate is used. However, there is a problem that the manufacturing method becomes complicated due to the transfer step, and the productivity is not necessarily high.

In order to solve such problems, Patent Document 2 discloses a dye sensitization by using an opaque heat-resistant substrate as the base material and forming a porous layer fired at a sufficient temperature on such a heat-resistant substrate. In a dye-sensitized solar cell using a dye-sensitized solar cell electrode substrate prepared by such a method, sunlight is used as a pair opposite to the conventional one. A method is disclosed in which light is incident from the electrode substrate side.
Certainly, according to such a method, the problems of the conventional manufacturing method described above can be solved, and a dye-sensitized solar cell electrode substrate having a porous layer baked at a sufficient temperature can be obtained with a small number of steps. Can be made. However, if a porous layer is formed on the first electrode layer, the electrical resistance at the interface between the two layers increases, so that the dye using the dye-sensitized solar cell substrate produced by such a method is used. The sensitized solar cell has a problem that the power generation efficiency decreases.
Further, as described above, when the dye-sensitized solar cell is used in a mode in which sunlight is received from the counter electrode base material side, the electrolyte layer is used until the incident sunlight reaches the porous layer that contributes to power generation. Since it must permeate, sunlight cannot be used effectively due to light scattering in the electrolyte layer, and power generation efficiency is reduced.

JP 2002-313443 A US Patent Application Publication No. 2003/0192584

  The present invention has been made in view of such problems, and has a porous layer excellent in binding properties of metal oxide semiconductor fine particles, and produces a dye-sensitized solar cell excellent in power generation efficiency. The main object of the present invention is to provide a method for producing a dye-sensitized solar cell substrate capable of producing a dye-sensitized solar cell substrate that can be produced with a small number of steps.

  In order to solve the above-mentioned problems, the present invention is such that a catalyst layer made of metal, a porous insulating layer made of an insulating material, and a porous layer containing oxide semiconductor particles are laminated in this order on a heat-resistant substrate. A porous laminate forming step of forming a porous laminate, and a transparent electrode layer forming step of forming a transparent electrode layer made of a metal oxide on the porous layer of the porous laminate. The manufacturing method of the board | substrate for dye-sensitized solar cells characterized by these is provided.

According to the present invention, the porous laminate forming step forms the catalyst layer, the porous insulating layer, and the porous layer on the heat-resistant substrate, so that the porous layer is formed at a high temperature. Thus, a dye-sensitized solar cell substrate provided with a porous layer having excellent binding properties of metal oxide semiconductor particles can be produced.
According to the present invention, the transparent electrode layer forming step forms the transparent electrode layer on the porous layer, thereby improving the electrical conductivity between the porous layer and the transparent electrode layer. Therefore, it is possible to produce a dye-sensitized solar cell substrate or a solar cell substrate capable of producing a dye-sensitized solar cell with excellent power generation efficiency.
Further, according to the present invention, since a complicated process is not required as in the conventional transfer method, the dye-sensitized solar cell substrate can be manufactured with a small number of processes.
Therefore, according to the present invention, a dye-sensitized solar cell having a porous layer excellent in the binding property of metal oxide semiconductor fine particles and capable of producing a dye-sensitized solar cell excellent in power generation efficiency The manufacturing method of the board | substrate for dye-sensitized solar cells which can manufacture a battery substrate in few processes can be provided.

In the said invention, it has the translucent board | substrate lamination process which laminates | stacks the translucent board | substrate provided with a light transmittance through the adhesive layer which consists of adhesive resin on the said transparent electrode layer after the said transparent electrode layer formation process. It is preferable. By having such a translucent substrate laminating step, for example, by using a substrate having an arbitrary function as the translucent substrate, the substrate for a dye-sensitized solar cell manufactured according to the present invention can be arbitrarily used. This is because it becomes easy to impart functionality.
Moreover, any kind of translucent board | substrate can be used by the said translucent board | substrate lamination process laminating | stacking the said translucent board | substrate through the said contact bonding layer.

  Moreover, in the said invention, it is preferable after the said transparent electrode layer formation process to have the pigment | dye adsorption process which makes a dye sensitizer adsorb | suck to the surface of the said metal oxide semiconductor fine particle. By having such a dye adsorption step, the dye-sensitized solar cell substrate produced according to the present invention is produced according to the present invention because the dye sensitizer is supported on the porous layer. This is because it becomes easy to produce a colored paper-sensitized solar cell using the dye-sensitized solar cell substrate.

  The present invention uses a dye-sensitized solar cell substrate produced by the method for producing a dye-sensitized solar cell substrate of the present invention, and a porous insulating layer of the dye-sensitized solar cell substrate. Provided is a method for producing a dye-sensitized solar cell, which is impregnated with an electrolytic solution containing a redox couple.

  According to the present invention, by using the dye-sensitized solar cell substrate produced by the method for producing a dye-sensitized solar cell substrate of the present invention, the dye-sensitized solar cell excellent in power generation efficiency is used. A substrate can be manufactured.

  The present invention also provides a heat-resistant substrate, a catalyst layer formed on the heat-resistant substrate and made of metal, a porous insulating layer formed on the catalyst layer and made of an insulating material, and formed on the porous insulating layer. A substrate for a dye-sensitized solar cell, comprising: a porous layer containing metal oxide semiconductor fine particles; and a transparent electrode layer formed on the porous layer and made of a metal oxide, the transparent electrode layer Is provided so as to be the outermost layer. A dye-sensitized solar cell substrate is provided.

  The substrate for a dye-sensitized solar cell according to the present invention has a configuration in which a catalyst layer, a porous insulating layer, a porous layer, and a transparent electrode layer are laminated in this order on the heat-resistant substrate. The dye-sensitized solar cell substrate can be manufactured with a small number of steps. In addition, the substrate for a dye-sensitized solar cell of the present invention is formed so that the top surface of the transparent electrode layer is the outermost layer, for example, a translucent substrate having an arbitrary function on the transparent base material. By giving, there is an advantage that an arbitrary function can be given.

  The present invention also provides a heat-resistant substrate, a catalyst layer formed on the heat-resistant substrate and made of metal, a porous insulating layer formed on the catalyst layer and made of an insulating material, and formed on the porous insulating layer. A porous layer containing metal oxide semiconductor fine particles, a transparent electrode layer formed on the porous layer and made of a metal oxide, and an adhesive layer formed on the transparent electrode layer and made of an adhesive resin There is provided a dye-sensitized solar cell substrate comprising a light-transmitting substrate formed on the adhesive layer and having light transmittance.

The substrate for a dye-sensitized solar cell according to the present invention has a configuration in which a catalyst layer, a porous insulating layer, a porous layer, and a transparent electrode layer are laminated in this order on the heat-resistant substrate. The dye-sensitized solar cell substrate can be manufactured with a small number of steps.
The dye-sensitized solar cell substrate of the present invention is a substrate that can be used as the translucent substrate because the translucent substrate is formed on the transparent electrode layer via the adhesive layer. Since there is no restriction and a substrate having an arbitrary function can be used, a dye-sensitized solar cell substrate having an arbitrary function can be obtained as the translucent substrate.

  In the said invention, it is preferable that the said metal oxide semiconductor microparticles | fine-particles have a dye sensitizer adsorbed on the surface. This is because it becomes easy to produce a dye-sensitized solar cell using the dye-sensitized solar cell substrate of the present invention.

  Further, in the present invention, the dye-sensitized solar cell substrate of the present invention is used, and an electrolyte solution containing a redox pair is formed in the porous insulating layer of the dye-sensitized solar cell substrate. Provided is a dye-sensitized solar cell which is impregnated.

  The dye-sensitized solar cell of the present invention has an arbitrary function by using, for example, a substrate having a translucent substrate having an arbitrary function on the transparent electrode layer as the substrate for the dye-sensitized solar cell. It has the advantage that the dye-sensitized solar cell which has can be obtained.

  The present invention produces a dye-sensitized solar cell substrate that has a porous layer with excellent binding properties of metal oxide semiconductor fine particles and can produce a dye-sensitized solar cell with excellent power generation efficiency in a small number of steps. There is an effect that can be done.

  Hereinafter, the manufacturing method of the dye-sensitized solar cell substrate, the manufacturing method of the dye-sensitized solar cell, the dye-sensitized solar cell substrate, and the dye-sensitized solar cell of the present invention will be described in detail.

A. Method for Producing Dye-Sensitized Solar Cell Substrate First, a method for producing a dye-sensitized solar cell substrate of the present invention will be described. In the method for producing a dye-sensitized solar cell substrate of the present invention, a catalyst layer made of metal, a porous insulating layer made of an insulating material, and a porous layer containing oxide grain semiconductor fine particles are formed on a heat-resistant substrate. A porous laminate forming step for forming a porous laminate laminated in order, and a transparent electrode layer forming step for forming a transparent electrode layer made of a metal oxide on the porous layer of the porous laminate, and , Characterized by having.

  A method for producing such a dye-sensitized solar cell substrate of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an example of the dye-sensitized solar cell substrate of the present invention. As illustrated in FIG. 1, the method for producing a dye-sensitized solar cell substrate of the present invention uses a heat resistant substrate 1 (FIG. 1A), and a catalyst layer 2 made of metal on the heat resistant substrate 1. A porous laminate forming step for forming a porous laminate 30 having a configuration in which a porous insulating layer 3 made of an insulating material and a porous layer 4 containing metal oxide semiconductor fine particles are laminated in this order (FIG. 1). (B)) and a transparent electrode layer forming step (FIG. 1 (c)) for forming a transparent electrode layer 5 made of a metal oxide on the porous layer 4 of the porous laminate 30. A dye-sensitized solar cell substrate 10 in which a catalyst layer 2, a porous insulating layer 3, a porous layer 4, and a transparent electrode layer 5 are laminated in this order on 1 is manufactured.

According to the present invention, the porous laminate forming step forms the catalyst layer, the porous insulating layer, and the porous layer on the heat-resistant substrate, so that the porous layer is sufficiently formed. Since the baking treatment can be performed at a high temperature, a substrate for a dye-sensitized solar cell including a porous layer having excellent binding properties of metal oxide semiconductor fine particles can be produced.
According to the present invention, the transparent electrode layer forming step forms the transparent electrode layer on the porous layer, thereby forming the porous layer on the transparent electrode layer as in the prior art. Compared with the case of the above, the conductivity between the porous layer and the transparent electrode layer can be improved, so that a dye-sensitized solar cell with excellent power generation efficiency can be produced. A substrate can be manufactured.
Furthermore, the present invention has only a step of sequentially laminating each layer on the above heat-resistant substrate, and does not require a complicated step as in the conventional transfer method. Therefore, the substrate for a dye-sensitized solar cell can be formed with fewer steps. Can be manufactured.
Therefore, according to the present invention, a dye-sensitized solar cell having a porous layer excellent in the binding property of metal oxide semiconductor fine particles and capable of producing a dye-sensitized solar cell excellent in power generation efficiency The manufacturing method of the board | substrate for dye-sensitized solar cells which can manufacture a battery substrate in few processes can be provided.

  The manufacturing method of the board | substrate for dye-sensitized solar cells of this invention has the said porous laminated body formation process and the said transparent electrode layer formation process. Hereafter, each process which comprises such this invention is demonstrated in detail.

1. Porous Laminate Formation Step First, the porous laminate formation step in the present invention will be described. This process forms a porous laminate in which a catalyst layer made of metal, a porous insulating layer made of an insulating material, and a porous layer containing metal oxide semiconductor fine particles are laminated in this order on a heat-resistant substrate. It is a process to do.

The method for forming the porous laminate in this step is not particularly limited as long as it is a method capable of forming a porous layer laminate having the above configuration. As such a method, on the heat-resistant substrate, the catalyst layer, the porous insulating layer, and the method of forming the porous layer in order for each layer (first aspect), and the catalyst on the heat-resistant substrate The method (2nd aspect) which forms the porous laminated body which has the said structure by forming simultaneously two or more layers of a layer, the said porous insulating layer, and the said porous layer can be mentioned.
Hereinafter, each of such aspects will be described.

1-1: First Aspect First, the first aspect will be described. The method for forming a porous laminate of this aspect includes a catalyst layer forming step of forming the catalyst layer on the heat-resistant substrate, a porous layer, a porous insulating layer, and the porous layer on the catalyst layer. It is a method of forming a layer in order for each layer, usually a catalyst layer forming step of forming a catalyst layer on a heat-resistant substrate, a porous layer forming step of forming a porous layer on the catalyst layer, and the porous A method of forming the porous laminate by a porous insulating layer forming step of forming a porous insulating layer on the layer is used.

  A method for forming such a porous laminate of this embodiment will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of a method for producing the porous laminate of this embodiment. As illustrated in FIG. 2, the method for manufacturing a porous laminate of this embodiment uses a heat resistant substrate 1 (FIG. 2A), and forms a catalyst layer 2 made of metal on the heat resistant substrate 1. (FIG. 2 (b)), a porous insulating layer forming step (FIG. 2 (c)) for forming a porous insulating layer 3 made of an insulating material on the catalyst layer 2, and on the porous insulating layer 3. By the porous layer forming step (FIG. 2 (d)) for forming the porous layer 4 containing the metal oxide semiconductor fine particles, the catalyst layer 2, the porous insulating layer 3, and the In this method, the porous layered body 30 is formed by sequentially forming the porous layer 4 for each layer.

  Hereinafter, the catalyst layer forming step, the porous insulating layer forming step, and the porous layer forming step used in this embodiment will be described.

(1) Porous layer formation process First, the said porous layer formation process is demonstrated. This step is a step of forming a porous layer containing metal oxide semiconductor fine particles on the porous insulating layer formed by the porous insulating layer forming step described later.

As a method for forming a porous layer in this step, when a dye-sensitized solar cell is produced using the dye-sensitized solar cell substrate produced according to the present invention, a desired amount of a dye sensitizer is added. The method is not particularly limited as long as it is a method that can be formed of a porous body having a porosity that can be supported and that can form a porous layer containing metal oxide semiconductor fine particles. As such a method, usually, a porous layer forming layer forming step of forming a porous layer forming layer by applying a porous layer forming coating liquid on the porous insulating layer, and the porous A method of forming a porous layer by a firing step of firing a layer for forming a porous layer is used.
Hereinafter, a method for forming such a porous layer will be described.

a. First, the layer forming process for forming a porous layer will be described. This step is a step of forming a porous layer forming layer by applying a porous layer forming coating solution on the porous insulating layer.

  The porous layer forming coating solution used in this step is not particularly limited as long as it contains metal oxide semiconductor fine particles, but usually in this step, metal oxide semiconductor fine particles and What contains resin and a solvent is used suitably.

Examples of the metal oxide semiconductor fine particles include TiO ₂ , ZnO, SnO ₂ , ITO, ZrO ₂ , MgO, Al ₂ O ₃ , CeO ₂ , 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 suitably used in this step because energy conversion efficiency can be improved and cost can be reduced. Among these, in this step, it is most preferable to use TiO ₂ as the semiconductor oxide fine particles.

  In this step, only one kind of the metal oxide semiconductor fine particles may be used, or two or more kinds may be mixed and used. Further, among the metal oxide semiconductor fine particles, one having a core-shell structure in which one kind is a core fine particle and the core fine particle is included by another metal oxide semiconductor fine particle can be used.

  The particle diameter of the metal oxide semiconductor fine particles used in this step is not particularly limited as long as it is within a range in which a desired porosity can be imparted to the porous layer formed by this step, but usually 1 nm to 10 μm. Is preferably within the range of 10 nm to 1000 nm. This is because if the particle size is smaller than the above range, the respective metal oxide semiconductor fine particles may aggregate to form secondary particles. On the other hand, if the particle size is larger than the above range, the porous layer formed by this step not only becomes thicker, but also the specific surface area decreases, and a desired amount of dye sensitizer is supported on the porous layer. This is because there are cases where it cannot be done.

  In this step, it is preferable to use a mixture of a plurality of metal oxide semiconductor particles having different particle diameters as the metal oxide semiconductor particles. Since the light scattering property of the porous layer formed by this step can be increased by using a mixture of metal oxide semiconductor fine particles having different particle sizes, the dye-sensitized solar cell substrate produced by the present invention This is because, in a dye-sensitized solar cell using the above, light absorption by the dye sensitizer can be efficiently performed.

The mixture of the plurality of metal oxide semiconductor fine particles having different particle diameters may be a mixture of the same type of metal oxide semiconductor fine particles, or may be a mixture of different types of metal oxide semiconductor fine particles. .
Examples of combinations of different particle diameters include a mode in which metal oxide semiconductor fine particles within a range of 10 nm to 50 nm and metal oxide semiconductor fine particles within a range of 50 nm to 800 nm are mixed and used. Can do.

  The content of the metal oxide semiconductor fine particles in the porous layer forming coating liquid is preferably in the range of 50% by mass to 100% by mass in the solid content of the porous layer forming coating liquid, In particular, it is preferably in the range of 65% by mass to 90% by mass. This is because if the content of the metal oxide semiconductor fine particles is less than the above range, the porous layer formed by this step may not contain a desired amount of the dye sensitizer. Moreover, it is because there exists a possibility that the resistance of the porous layer formed by this process may become large too much when it exceeds the said range.

  Next, the resin used for the porous layer forming coating solution will be described. The resin used in the porous layer forming coating solution is not particularly limited as long as it is thermally decomposed at a baking treatment temperature in the baking step described later. Examples of such resins include cellulose resins, polyester resins, polyamide resins, polyacrylate resins, polyacryl resins, polycarbonate resins, polyurethane resins, polyolefin resins, polyvinyl acetal resins, and fluorine resins. In addition to resins and polyimide resins, polyhydric alcohols such as polyethylene glycol can be used.

  The content of the resin in the coating liquid for forming a porous layer is not particularly limited as long as a desired porosity can be imparted to the porous layer formed by this step. Especially in this process, the inside of the range of 0.1 mass%-30 mass% is preferable, The inside of the range of 0.5 mass%-20 mass% is especially preferable, Especially, the range of 1 mass%-10 mass% is preferable. The inside is preferable. This is because if the resin content is less than the above range, the porosity of the porous layer formed by this step will be low, and it may not be possible to contain the desired amount of dye sensitizer. Further, if the amount is more than the above range, the resistance of the porous layer formed by this step may be excessively increased, or the mechanical strength of the porous layer may be lowered.

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

  Various additives may be included in the coating liquid for forming a porous layer used in this step in order to improve the coating suitability for a porous insulating layer described later. As such an additive, for example, a surfactant, a viscosity adjusting agent, a dispersion aid, a pH adjusting agent and the like can be used. Among these, in this step, it is preferable that polyethylene glycol is contained as a dispersion aid. By changing the molecular weight of such polyethylene glycol, the viscosity of the dispersion can be adjusted, so in this step, it becomes easy to form a porous layer with excellent adhesion to the porous insulating layer, It is also easy to adjust the porosity of the porous layer.

  In this step, the method for applying the coating liquid for forming a porous layer onto the porous insulating layer described later is not particularly limited as long as it is a method capable of forming a coating film having a uniform film thickness and excellent flatness. . Examples of such methods include die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating, bar coating, blade coating, knife coating, air knife coating, slot die coating, slide die coating, dip coating, micro bar coating, Examples thereof include microbar reverse coating and screen printing (rotary method).

  In this step, a porous layer forming layer having a desired thickness can be formed by using such a coating method and repeating coating and solidification as necessary.

  The thickness of the porous layer forming layer formed in this step is usually in the range of 0.5 μm to 100 μm, more preferably in the range of 1 μm to 50 μm, and still more preferably in the range of 5 μm to 25 μm.

b. Next, the firing process will be described. The firing step in this embodiment is a step of firing the porous layer forming layer and thermally decomposing the resin contained in the porous layer forming layer to form a porous layer that is a porous body. It is.

  The firing temperature in this step is not particularly limited as long as it is within a range in which the resin can be thermally decomposed, depending on the type of resin contained in the porous layer forming layer, but is usually 300 ° C to 700 ° C. Within the range, more preferably within the range of 350 ° C to 600 ° C. In this embodiment, since the porous layer forming layer is formed on the heat-resistant substrate, firing at a high temperature range within the above range is possible, and the above porous layer formation is performed at a firing temperature within the above range. By firing the working layer, a porous layer having excellent binding properties between the metal oxide semiconductor fine particles can be formed.

  In this step, the heating method for firing the porous layer forming layer is not particularly limited as long as it is a method capable of firing the porous layer forming layer uniformly without heating unevenness. A known heating method can be used.

(2) Porous insulating layer forming step Next, the porous insulating layer forming step will be described. This step is a step of forming a porous insulating layer made of an insulating material on the catalyst layer formed by the catalyst layer forming step described later.

  As a method for forming a porous insulating layer in this step, electrolysis containing a redox pair is performed when a dye-sensitized solar cell is produced using the dye-sensitized solar cell substrate produced according to the present invention. The method is not particularly limited as long as it is a method that is made of a porous material that can be impregnated with a desired amount of liquid and that can form a porous insulating layer made of an insulating material. As such a method, usually, a porous insulating layer forming layer forming step of forming a porous insulating layer forming layer by applying a porous insulating layer forming coating solution on the catalyst layer; and A method of forming a porous insulating layer by a firing step of firing the porous insulating layer forming layer is used. Hereinafter, a method for forming such a porous insulating layer will be described.

a. First, the layer forming step for forming the porous insulating layer will be described. This step is a step of forming a porous insulating layer forming layer by applying a porous insulating layer forming coating solution onto a catalyst layer formed by a catalyst layer forming step described later.

  The coating liquid for forming a porous insulating layer used in this step is not particularly limited as long as it contains an insulating substance, but usually a liquid containing an insulating substance, a resin, and a solvent is used. It is done.

As the insulating material, when a dye-sensitized solar cell is manufactured using the dye-sensitized solar cell substrate manufactured according to the present invention, the porous electrode layer and the transparent electrode layer formed by this step are used. The catalyst layer is not particularly limited as long as it has an insulating property that does not allow current to flow. Examples of such an insulating material include Al ₂ O ₃ , SiO ₂ , MgO, ZrO ₂ , WO ₃ , In ₂ O ₃ , Bi ₂ O ₃ , CeO ₂ , Nb ₂ O ₅ , and Y ₂ O _3. Etc. In particular, in this step, it is preferable to use Al ₂ O ₃ , SiO ₂ , or In ₂ O ₃ as the insulating material.

  Moreover, in the said coating liquid for porous insulation layer formation, the said insulating substance may contain only 1 type, or 2 or more types may contain.

  The content of the insulating material in the coating liquid for forming a porous insulating layer is not particularly limited as long as a desired porosity can be imparted to the porous insulating layer formed in this step. In particular, in this step, it is preferably in the range of 1% by mass to 60% by mass, particularly preferably in the range of 5% by mass to 3% by mass, and in particular, 7% by mass to 20% by mass. It is preferable to be within the range. This is because if the content of the insulating material is less than the above range, the porosity of the porous insulating layer formed by this step is lowered, and there is a possibility that a desired amount of the electrolytic solution cannot be impregnated. Moreover, it is because the mechanical strength of the said porous insulating layer may fall when more than the said range.

  In addition, the content of the resin in the porous insulating layer forming coating solution is not particularly limited as long as a desired porosity can be imparted to the porous insulating layer formed by this step. Especially in this process, the inside of the range of 0.5 mass%-30 mass% is preferable, The inside of the range of 2 mass%-15 mass% is especially preferable, The inside of the range of 4 mass%-12 mass% is especially preferable. This is because if the resin content is less than the above range, the porosity of the porous insulating layer formed by this step is low, and a desired amount of the dye sensitizer may not be contained. Moreover, it is because there exists a possibility that the mechanical strength of the porous insulating layer formed by this process may fall when more than the said range.

  The resin and the solvent used in the porous insulating layer forming coating solution are the same as the solvent used in the porous layer forming coating solution, and the description thereof is omitted here. .

  In addition to the insulating material, examples of the additive that can be contained in the coating liquid for forming a porous insulating layer include a leveling agent and a surfactant.

  In this step, the method for applying the coating liquid for forming the porous insulating layer onto the catalyst layer is not particularly limited as long as it is a method capable of forming a coating film having a uniform film thickness and excellent flatness. Such a method is the same as that described in the above-mentioned section “1. Porous layer forming step”, and thus description thereof is omitted here.

  The thickness of the porous insulating layer forming layer formed in this step is usually in the range of 0.1 μm to 200 μm, more preferably in the range of 1 μm to 100 μm, and still more preferably in the range of 5 μm to 50 μm. .

b. Firing step The firing step in this embodiment is a step of firing the porous insulating layer forming layer to form a porous insulating layer that is a porous body. In this step, the method for firing the porous insulating layer is the same as the method described in the above section “1. Porous layer forming step”, and thus the description thereof is omitted here.

(3) Catalyst Layer Formation Step Next, the catalyst layer formation step will be described. This step is a step of forming a metal catalyst layer on the heat-resistant substrate.

  In this step, the method for forming the catalyst layer on the heat-resistant substrate is not particularly limited as long as it can form a catalyst layer made of a desired metal. As such a method, a catalyst layer forming layer forming step of forming a catalyst layer forming layer by applying a catalyst layer forming coating solution containing a metal compound on the heat resistant substrate, and the catalyst layer forming described above. And a method (first method) using the firing step of firing the working layer and a method (second method) of sputtering metal ions on the heat-resistant substrate. Hereinafter, these methods will be described.

a. First Method First, the first method will be described. The first method is a catalyst layer forming layer forming step of forming a catalyst layer forming layer by applying a catalyst layer forming coating solution containing a metal compound on the heat resistant substrate, and the catalyst layer forming step. In this method, the catalyst layer is formed by a firing step of firing the layer.

  The catalyst layer forming coating solution used in the catalyst layer forming layer forming step is not particularly limited as long as it contains a metal compound capable of forming a catalyst layer made of a desired metal. As such a coating solution for forming a catalyst layer, a solution containing a metal compound and a solvent is usually used.

  The metal compound is not particularly limited as long as it can form a catalyst layer made of a desired metal. Examples of such a metal compound include carbon (carbon), chloroplatinic (IV) acid, dinitrodiammine platinum (II), tetraamminedichloroplatinum (II), palladium (II) chloride, palladium (II) nitrate, dinitrodiammine. Palladium (II), iridium chloride (IV) acid, ruthenium (III) chloride, rhodium (III) chloride and the like can be mentioned.

  Further, the solvent used in the catalyst layer forming coating solution is not particularly limited as long as it can dissolve the metal compound at a desired concentration. Such a solvent is the same as that described in the above-mentioned section “1. Porous layer forming step”, and thus description thereof is omitted here.

  In this step, the method for applying the catalyst layer forming coating solution onto the heat-resistant substrate is not particularly limited as long as it is a method capable of forming a coating film having a uniform film thickness and excellent flatness. Such a method is the same as that described in the above-mentioned section “1. Porous layer forming step”, and thus description thereof is omitted here.

  The heat-resistant substrate used in this step is not particularly limited as long as it has heat resistance against the heating temperature in the firing step in the porous forming step and the porous insulating layer forming step described above. In particular, the heat resistant substrate used in this step preferably has a melting point of 200 ° C. or higher.

  The substrate used as the heat resistant substrate may be a flexible substrate having flexibility or a rigid substrate having no flexibility, but the flexible substrate is used in this step. It is preferable. By using a flexible substrate, for example, the production method of the dye-sensitized solar cell substrate of the present invention can be made into a Roll to Roll process. Therefore, the production of the dye-sensitized solar cell substrate according to the present invention is possible. It is because it can contribute to the improvement of property.

  Examples of such a heat-resistant substrate include a glass substrate, a ceramic substrate, a metal plate, and a plastic substrate. In particular, in this step, it is preferable to use a metal plate made of titanium, nickel, tungsten, SUS, gold, or platinum, or a plastic substrate made of a high heat resistant resin such as polyimide or polyamide as the heat resistant substrate.

  The heat-resistant substrate used in this step may have a structure in which counter electrode layers made of a conductive material are stacked. By using the heat-resistant substrate having such a configuration, the power generation efficiency of the dye-sensitized solar cell manufactured using the dye-sensitized solar cell substrate manufactured according to the present invention may be improved. is there. In this step, when an insulating substrate is used as the heat-resistant substrate, it is preferable to use a substrate on which such a counter electrode layer is formed.

As the above conductive material, SnO 2 which has been used in the conventional counter electrode, _ITO, IZO, may be used made of a transparent metal oxide such as ZnO, the counter-electrode layer in this step Since it is not necessary to have transparency to sunlight, it is not limited to those made of such metal oxides. For example, a material made of a conductive material opaque to sunlight, such as a metal material, may be used. good.

b. Second Method Next, the second method will be described. The second method is a method of forming a catalyst layer by sputtering metal ions on the heat-resistant substrate.

  The method of sputtering metal ions in this step is not particularly limited as long as it can form a catalyst layer having a desired film thickness, and a sputtering method generally used for the production of a metal thin film is used. be able to.

  Examples of the metal used for forming the catalyst layer by sputtering include Pt, Ti, Ir, Ru, Pd, carbon, and alloys containing these.

  In addition, the thing similar to what is used for the said 1st method can be used for the heat-resistant board | substrate used for the 2nd method.

1-2: Second Aspect Next, the second aspect will be described. The method for forming a porous laminate of this embodiment, on the heat-resistant substrate, by simultaneously forming two or more layers of the catalyst layer, the porous insulating layer, and the porous layer on the heat-resistant substrate, This is a method of forming a porous laminate in which a catalyst layer, a porous insulating layer, and a porous layer are laminated in this order on a heat resistant substrate.

  In this embodiment, as the method for simultaneously forming two or more layers of the catalyst layer, the porous insulating layer, and the porous layer on the heat-resistant substrate, a method of simultaneously firing two or more layers is used. It is done.

Such a method will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of a method for forming a porous laminate of this embodiment. As illustrated in FIG. 3, in this embodiment, the heat-resistant substrate 1 is usually used (FIG. 3A), and the catalyst layer 2 is formed on the heat-resistant substrate 1 (FIG. 3B). Then, a porous insulating layer forming layer 3 ′ is formed on the catalyst layer 2 by applying a coating liquid for forming a porous insulating layer (FIG. 3C).
Next, a porous layer forming layer 4 ′ is formed by applying a porous layer forming coating solution onto the porous insulating layer forming layer 3 ′ (FIG. 3D).
Next, the porous insulating layer forming layer 3 ′ and the porous layer forming layer 4 ′ are fired at the same time, so that the porous insulating layer forming layer 3 ′ and the porous layer forming layer 4 are fired. 'Is a porous insulating layer 3 and a porous layer 4 made of a porous body, respectively (FIG. 3 (e)), so that the catalyst layer 2, the porous insulating layer 3 and the porous layer are formed on the heat-resistant substrate 1. A method of forming a porous laminate 10 in which 4 are laminated in this order is used.

Here, FIG. 3 illustrates a method of simultaneously forming the porous insulating layer and the porous layer by simultaneously firing the porous insulating layer forming layer and the porous layer forming layer. The method for forming the porous laminate of the present embodiment is not limited to such an example, and a plurality of layers can be fired simultaneously in any combination.
As such a combination, in addition to the combination of the porous insulating layer forming layer and the porous layer forming layer, a combination of a catalyst layer forming layer, a porous insulating layer forming layer, and a porous layer forming layer A combination of the catalyst layer forming layer and the porous insulating layer forming layer can be exemplified.

  In this embodiment, the method for forming the catalyst layer forming layer, the porous insulating layer forming layer, and the porous layer forming layer is the same as the method described in the above section “1-1: First embodiment”. Therefore, the description here is omitted. In addition, the method for firing the catalyst layer forming layer, the porous insulating layer forming layer, and the porous layer forming layer is the same as the method described in the section “1-1: First aspect”. Explanation here is omitted.

2. Transparent electrode layer formation process Next, the transparent electrode layer formation process in this invention is demonstrated. This step is a step of forming a transparent electrode layer made of a metal oxide on the porous layer of the porous laminate formed by the porous laminate forming step. In this step, by forming a transparent electrode layer on the porous layer, a transparent electrode layer having excellent conductivity with the porous layer can be formed.

In this step, the method for forming the transparent electrode layer on the porous layer is not particularly limited as long as it can form a transparent electrode layer having a uniform thickness and excellent flatness. As a method for forming such a transparent electrode layer, there are a solution treatment step in which a base electrode layer is provided inside or on the surface of the porous layer using a base electrode layer forming composition, and a main transparent electrode on the base electrode layer. An upper electrode layer forming step for forming a layer, a method for forming a transparent electrode layer in two steps (first method), and a transparent electrode layer on the porous layer in one step using the composition for forming a transparent electrode layer The method (2nd method) which forms can be mentioned.
The first method has an advantage that a dense transparent electrode layer can be formed on the porous layer. Further, the second method has an advantage that the process can be simplified.
Hereinafter, these methods will be described.

(1) First Method First, the first method will be described. The first method is a solution treatment step in which a base electrode layer is provided in or on the surface of a porous layer using a base electrode layer forming composition, and an upper electrode layer formation in which a main transparent electrode layer is provided on the base electrode layer. And forming a transparent electrode layer in two steps.

a. Solution Processing Step First, the solution processing step will be described. In the solution treatment step, by contacting the porous layer with a base transparent electrode layer forming coating solution in which a metal salt or metal complex containing a metal element included in the metal oxide constituting the transparent electrode layer is dissolved, In this step, a base transparent electrode layer is provided inside or on the surface of the porous layer.

  The base transparent electrode layer forming coating solution used in this step is usually a metal salt or metal complex containing a metal element contained in the metal oxide constituting the transparent electrode layer (hereinafter referred to as “metal source”). In some cases) and those containing solvents.

The metal source contains a metal element contained in the metal oxide constituting the transparent electrode layer, and may be a metal salt or a metal complex. Specific examples of the metal source used in this step include those described in JP-A No. 2005-166648.
In this step, only one type of the metal source may be used, or two or more types may be used. In the case where two or more kinds of metal sources are used, in this step, for example, a composite underlying transparent electrode layer such as ITO, Gd—CeO ₂ , Sm—CeO ₂ , Ni—Fe ₂ O ₃ is obtained. be able to.

The solvent used in the base transparent electrode layer forming coating solution is not particularly limited as long as it can dissolve the metal salt and the like. As such a solvent, for example, when a metal salt is used as the metal source, water, methanol, ethanol, isopropyl alcohol, propanol, butanol, etc., a lower alcohol having a total carbon number of 5 or less, toluene, and a mixture thereof A solvent or the like can be used.
Moreover, when using a metal complex as said metal source, the lower alcohol mentioned above, toluene, these mixed solvents, etc. can be used.

  Moreover, the said base transparent electrode layer forming coating liquid may also contain an additive as needed. Examples of such additives include an oxidizing agent, a reducing agent, an auxiliary ion source, and a surfactant.

  In this step, as the method for bringing the porous layer and the base transparent electrode layer forming coating solution into contact, the above-described porous layer can be brought into contact with the above base transparent electrode layer forming coating solution. If it is, it will not specifically limit. Examples of such a method include a dipping method, a single-wafer method, and a method in which a solution is applied in the form of a mist.

  In this step, it is preferable to perform heating when the porous layer and the base transparent electrode layer forming coating solution are brought into contact with each other. This is because the heating rate of the base transparent electrode layer can be improved by heating. In particular, in this step, it is preferable to heat the porous layer, and it is particularly preferable to heat the porous layer and the base transparent electrode layer forming coating solution. This is because the formation reaction of the base transparent electrode layer in the vicinity of the porous layer can be promoted. The heating temperature is preferably in the range of 50 to 150 ° C, and more preferably in the range of 70 to 100 ° C.

b. Upper transparent electrode layer forming step Next, the upper transparent electrode layer forming step will be described. This step is a step of providing the upper transparent electrode layer on the base transparent electrode layer formed by the solution treatment step described above. In this step, a dense transparent electrode layer can be obtained by forming the upper transparent electrode layer on the base transparent electrode layer described above.

The method for forming the upper transparent electrode layer in this step is not particularly limited as long as it is a method capable of forming an upper transparent electrode layer having desired density. Examples of such methods include PVD methods such as spraying, vacuum deposition, sputtering, and ion plating, and CVD methods such as plasma CVD, thermal CVD, and atmospheric pressure CVD. Of these, the spray method is preferably used in this step.
Here, the spray method refers to heating the base transparent electrode layer and bringing the heated base transparent electrode layer into contact with a coating liquid for forming an upper transparent electrode layer, which will be described later, on the base transparent electrode layer. In this process, for example, a method described in JP-A-2005-166648 can be used.

  As the coating liquid for forming the upper transparent electrode layer used in the spray method, a solution containing a metal salt or metal complex containing a metal element contained in a metal oxide constituting the transparent electrode layer and a solvent is usually used. . Here, as the metal source and the solvent, the same ones as those used in the above-mentioned base transparent electrode layer forming coating solution can be used.

  Moreover, the upper transparent electrode layer forming coating solution used in the spray method may contain additives such as an auxiliary ion source and a surfactant.

(2) Second Method Next, the second method will be described. The second method is a method of forming a transparent electrode layer on the porous layer in one step using the transparent electrode layer forming composition. When the transparent electrode layer is formed by such a second method, the solution treatment step in the first method is not performed, and the upper side is formed on the porous layer according to the method described in the upper transparent electrode layer formation step. By forming the transparent electrode layer, the transparent electrode layer in this step can be formed.

3. Other Steps The method for producing a dye-sensitized solar cell substrate of the present invention may have other steps in addition to the porous laminate forming step and the transparent electrode layer forming step. As such other processes, an arbitrary process may be used depending on functions required for the dye-sensitized solar cell produced using the dye-sensitized solar cell substrate produced according to the present invention. it can. In particular, as a process preferably used in the present invention, after the transparent electrode layer forming process, a transparent substrate having a light transmitting property is laminated on the transparent electrode layer through an adhesive layer made of an adhesive resin. After the optical substrate laminating step and the transparent electrode layer forming step, a dye adsorption step for adsorbing a dye sensitizer on the surface of the metal oxide semiconductor fine particles in the porous layer can be raised.
Hereinafter, such a translucent substrate lamination step and a dye adsorption step will be described.

(1) Translucent substrate lamination process First, the said translucent substrate lamination process is demonstrated. This step is a step of laminating a translucent substrate having light transmissivity on the transparent electrode layer through an adhesive layer made of an adhesive resin after the transparent electrode layer forming step.

  Such a translucent substrate lamination process will be described with reference to the drawings. FIG. 4 is a schematic view showing an example of the translucent substrate lamination step. As illustrated in FIG. 4, in the translucent substrate lamination step, the catalyst layer 2, the porous insulating layer 3, the porous layer 4, and the transparent electrode layer 5 are laminated on the heat resistant substrate 1 in this order. A dye-sensitized solar cell substrate 10 having the above-described configuration (FIG. 4A), and a light-transmitting material having light transmissivity on the transparent electrode layer 5 through an adhesive layer 6 made of an adhesive resin. This is a step of forming a dye-sensitized solar cell substrate 11 provided with a translucent substrate 7 by laminating a conductive substrate 7 (FIG. 4B).

Such a translucent board | substrate lamination process provides arbitrary functionality to the board | substrate for dye-sensitized solar cells manufactured by this invention by using the board | substrate which has arbitrary functions as said translucent board | substrate. Has the advantage of being able to.
Moreover, the said translucent board | substrate lamination process has the advantage that the translucent board | substrate of arbitrary materials can be used by laminating | stacking the said translucent board | substrate through the said contact bonding layer.

  The translucent substrate formed on the transparent electrode layer by this step is solar light when a dye-sensitized solar cell is produced using the dye-sensitized solar cell substrate manufactured according to the present invention. It is arranged on the light receiving surface that receives light. Therefore, the translucent substrate is required to have translucency for sunlight.

  The translucent substrate used in this step is not particularly limited as long as it can transmit sunlight corresponding to the absorption wavelength of the dye sensitizer described later, depending on the type of the dye sensitizer described later. In particular, in this step, the transmittance for light having a wavelength of 400 nm to 1000 nm is preferably 78% or more, and more preferably 80% or more. If the transmittance is lower than the above range, the power generation efficiency of the dye-sensitized solar cell produced using the dye-sensitized solar cell substrate produced according to the present invention may be impaired. is there.

The translucent substrate used in this step is not particularly limited as long as it has the above translucency, and any substrate can be used.
Conventionally, the translucent substrate laminated on the transparent electrode layer has been limited to a substrate having heat resistance that can withstand the firing conditions when forming the porous layer, and thus any substrate cannot be used. . However, in the present invention, in the process of producing the dye-sensitized solar cell substrate, the translucent substrate is not exposed to a high-temperature atmosphere such as firing conditions, so there is no restriction on the heat resistance and the like. A translucent substrate made of any material and having any function can be used.

Examples of the translucent substrate used in this process include transparent rigid materials such as quartz glass, Pyrex (registered trademark) and synthetic quartz plate, ethylene / tetrafluoroethylene copolymer films, two Axial stretched polyethylene terephthalate film, polyethersulfone (PES) film, polyetheretherketone (PEEK) film, polyetherimide (PEI) film, polyimide (PI) film, polyester naphthalate (PEN), polycarbonate (PC), etc. Examples of the resin film substrate are as follows.
In particular, in this step, it is preferable to use the resin film substrate. This is because the resin film base material has advantages such as easy combination with other devices because it is excellent in processability. Moreover, it is because it can contribute also to the reduction of manufacturing cost by using a resin-made film base material.
In this step, it is preferable to use a biaxially stretched polyethylene terephthalate film (PET), polyester naphthalate (PEN), or polycarbonate (PC) among the resin film base materials.

  In addition, the base material in this invention may use only 1 type independently, and may laminate | stack and use 2 or more types.

  As the light-transmitting substrate used in this step, a substrate having an arbitrary function can be used as described above. Examples of the functions of the translucent substrate include barrier properties (water, oxygen), UV resistance, antireflection properties, light diffusibility, wavelength conversion function, water repellency function, antifouling function and the like. . In particular, in this step, it is preferable to use a substrate having barrier properties (moisture, oxygen), UV resistance, and antireflection properties as the translucent substrate.

  Next, an adhesive layer for adhering the translucent substrate on the transparent electrode layer in this step will be described. The adhesive layer is not particularly limited as long as it is made of an adhesive resin that can adhere the translucent substrate and the transparent electrode layer according to the type of the translucent substrate. Examples of such adhesive resins include thermoplastic resins, thermosetting resins, and electron beam curable resins. Among these, it is preferable to use a thermoplastic resin in this step. This is because the thermoplastic resin is excellent in adhesiveness and can easily bond the translucent substrate and the transparent electrode layer by heating.

The adhesive resin used in this step is preferably a thermoplastic resin having a melting point in the range of 50 ° C to 200 ° C, particularly preferably in the range of 60 ° C to 180 ° C. Furthermore, what is in the range of 65 to 150 degreeC is preferable. The reason is as follows. That is, when a thermoplastic resin is used as the adhesive resin, the transparent substrate, the transparent electrode layer, and the transparent electrode layer are heated by heating the thermoplastic resin to a melting point or higher when bonding the transparent substrate. This is because if the melting point of the thermoplastic resin is higher than the above range, the translucent substrate may be damaged by heat.
In addition, when the melting point is lower than the above range, when the dye-sensitized solar cell produced by using the dye-sensitized solar cell substrate manufactured according to the present invention is used outdoors, the above-mentioned adhesion may be caused depending on the use environment. This is because the layer may be remelted, and for this reason, for example, the function of the transparent electrode layer formed so as to be in contact with the adhesive layer may be impaired.

Examples of the thermoplastic resin include polyethylene, polypropylene, polyisobutylene, polystyrene, polyolefin such as ethylene-propylene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, cellulose triacetate, etc. Cellulose derivatives, copolymers of poly (meth) acrylic acid and esters thereof, 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.
Among these, in this step, polyolefin, ethylene-vinyl acetate copolymer, urethane resin, epoxy resin, silane-modified resin, and acid-modified resin are used in terms of adhesiveness, resistance to electrolytic solution, light transmittance and transferability. It is preferable to use a silane-modified resin. This is because the adhesive force of the adhesive layer can be further strengthened by using the silane-modified resin.

In this step, it is preferable to use a copolymer of a polyolefin compound and an ethylenically unsaturated silane compound among the silane-modified resins. By using such a copolymer, for example, it is easy to adjust various physical properties of the silane-modified resin within a suitable range according to the method for producing the dye-sensitized solar cell substrate used in the present invention. Because it becomes.
Here, the copolymer may or may not be crosslinked with a silanol catalyst.

  Examples of the polyolefin compound used in the copolymer include homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene and 1-butene, those α-olefins and ethylene, propylene, 1-butene, Other α-olefins having about 2 to 20 carbon atoms such as 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, vinyl acetate, Examples include (meth) acrylic acid, copolymers with (meth) acrylic acid esters, and the like. Specifically, for example, low / medium / high-density polyethylene (branched or linear) ethylene single weight Polymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1- Kuten copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic acid copolymers, ethylene-based resins such as ethylene- (meth) acrylic acid ethyl copolymers, propylene homopolymers, propylene-ethylene copolymers Polymers, propylene resins such as propylene-ethylene-1-butene copolymer, and 1-butene such as 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer Based resins and the like. Of these, a polyethylene resin is preferred in this step.

  Such a 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.

  The ethylenically unsaturated silane compound used in the copolymer of the polyolefin compound and 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.

  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. Is preferably a graft copolymer, and more preferably a graft copolymer obtained by polymerizing the main chain of polyethylene for polymerization and an ethylenically unsaturated silane compound as a side chain. 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. 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 the said adhesive layer, other compounds other than the said adhesive resin can be included as needed. In this step, it is preferable that a thermoplastic resin is included as such other compound, and it is preferable that a polyolefin compound is included among them. Further, when a copolymer of a polyolefin compound and an ethylenically unsaturated silane compound is used as the adhesive resin, it is preferable to use a polyolefin compound used for the copolymer as such other compound. .

  Further, the adhesive layer used in this step is at least selected from the group consisting of a crosslinking agent, a dispersant, a leveling agent, a plasticizer, an antifoaming agent light stabilizer, an ultraviolet absorber, a heat stabilizer, and an antioxidant. It is preferable to contain one type of additive. By including these additives, it is possible to obtain a long-term stable mechanical strength, yellowing prevention effect, cracking prevention effect, and workability.

  In this step, as a method of laminating the translucent substrate on the transparent electrode layer through the adhesive layer, the method is particularly suitable as long as the transparent electrode layer and the translucent substrate can be adhered by the adhesive layer. It is not limited. As such a method, an adhesive layer made of the above-mentioned adhesive resin is formed in advance on a light-transmitting substrate, and the light-transmitting substrate having the adhesive layer is bonded to the adhesive layer and the transparent electrode layer. A method of heat-sealing after placement, a method of producing a heat-meltable film made of an adhesive resin, and laminating the transparent electrode layer and the translucent substrate through the heat-meltable film, and transparent the adhesive resin Examples thereof include an extrusion lamination method in which the electrode layer and the translucent substrate are directly poured and heat-welded.

(2) Dye adsorption process Next, the said dye adsorption process is demonstrated. This step is a step of adsorbing a dye sensitizer on the surface of the metal oxide semiconductor fine particles after the transparent electrode layer forming step. By having such a dye adsorption step, the dye-sensitized solar cell substrate produced according to the present invention can be produced by carrying the dye-sensitizer on the porous layer. It is possible to easily produce a colored paper-sensitized solar cell using the dye-sensitized solar cell substrate.

  In the dye adsorption step, as a method of adsorbing the dye sensitizer on the surface of the metal oxide semiconductor fine particles, the metal oxide semiconductor fine particles contained in the porous layer may be selected according to the porosity of the porous layer. The method is not particularly limited as long as a desired amount of the dye sensitizer can be adsorbed on the surface of the resin. As such a method, for example, the porous layer is formed by a method in which a dye solution containing a dye sensitizer is permeated into the porous layer, a method in which a dye-sensitized solar cell substrate is immersed in the dye solution, or the like. Examples of the method include a method of drying after adding the above dye solution.

  The dye sensitizer is not particularly limited as long as it can absorb light having a wavelength corresponding to sunlight and generate an electromotive force. As such a dye sensitizer, for example, an organic dye or a metal complex dye can be used.

  Examples of the organic dye include acridine dyes, azo dyes, indoline dyes, indigo dyes, quinone dyes, coumarin dyes, merocyanine dyes, and phenylxanthene dyes. Among these, it is preferable to use a coumarin-based dye in this step.

  Moreover, as said metal complex pigment | dye, a ruthenium type pigment | dye can be used suitably, for example. In particular, in this step, it is preferable to use a ruthenium bipyridine dye and a ruthenium terpyridine dye which are ruthenium complexes. 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.

4). Substrate for dye-sensitized solar cell The substrate for dye-sensitized solar cell produced according to the present invention comprises a catalyst layer, a porous insulating layer, a porous layer, and a transparent electrode layer in this order on a heat-resistant substrate. It has a laminated structure. Since such a dye-sensitized solar cell substrate will be described in detail in the section “C. Dye-sensitized solar cell substrate” described later, description thereof is omitted here.

B. Next, a method for producing the dye-sensitized solar cell of the present invention will be described. The method for producing the dye-sensitized solar cell of the present invention is the method for producing the dye-sensitized solar cell substrate of the present invention described in the section “A. Method for producing dye-sensitized solar cell substrate” above. The dye-sensitized solar cell substrate produced by the method is used, and the porous insulating layer of the dye-sensitized solar cell substrate is impregnated with an electrolytic solution containing a redox pair. .

  A method for producing such a dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 5 is a schematic view showing an example of a method for producing the dye-sensitized solar cell of the present invention. As illustrated in FIG. 5, the dye-sensitized solar cell manufacturing method of the present invention is the dye-sensitized solar cell substrate 10 manufactured by the above-described dye-sensitized solar cell substrate manufacturing method of the present invention. (FIG. 5A), the dye-sensitized solar cell 20 is obtained by impregnating the porous insulating layer 3A of the dye-sensitized solar cell substrate 10 with an electrolytic solution containing a redox pair. This is manufactured (FIG. 5B).

  According to the present invention, by using the dye-sensitized solar cell substrate produced by the method for producing a dye-sensitized solar cell substrate of the present invention, the dye-sensitized solar cell excellent in power generation efficiency is used. A substrate can be manufactured.

  In the present invention, the method for impregnating the porous insulating layer of the dye-sensitized solar cell substrate with the electrolytic solution is particularly limited as long as the porous insulating layer can be impregnated with a desired amount of the electrolytic solution. It is not a thing. Examples of such a method include a method of impregnating the porous layer by dropping an electrolytic solution, a method of immersing the dye-sensitized solar cell substrate in the electrolytic solution, or screen printing. And a method of impregnating an electrolytic solution only at a predetermined position by the printing method.

  As the electrolytic solution used in the present invention, one containing a redox couple and a solvent is usually used. The oxidation-reduction pair used in such an electrolytic solution is not particularly limited as long as it is generally used in an electrolyte layer. Such redox pairs can include, for example, a combination of iodine and iodide, and a combination of bromine and bromide.

Examples of the combination of iodine and iodide include a combination of metal iodide such as LiI, NaI, KI, and CaI ₂ and I ₂ . 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 .

  In the present invention, any of the above-mentioned combination of iodine and iodide and the above-mentioned combination of bromine and bromide is preferably used. Among them, the combination of iodine and iodide is preferably used.

  The solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the redox couple at a desired concentration, but usually acetonitrile, methoxyacetonitrile, propylene carbonate, or the like is preferably used.

  Moreover, the electrolyte solution used in the present invention may contain, for example, additives such as a thickener and a room temperature molten salt, in addition to the redox couple and the solvent.

  The dye-sensitized solar cell substrate used in the present invention is manufactured by the method for manufacturing a dye-sensitized solar cell substrate described in the above section “A. Method for manufacturing dye-sensitized solar cell substrate”. It is a thing. Since such a dye-sensitized solar cell substrate will be described in detail in the section “C. Dye-sensitized solar cell substrate” described later, description thereof is omitted here.

  The dye-sensitized solar cell produced by the present invention has a structure in which a catalyst layer, a porous insulating layer, a porous layer, and a transparent electrode layer are laminated in this order on a heat-resistant substrate, and The porous insulating layer is impregnated with an electrolytic solution. Since such a dye-sensitized solar cell will be described in detail in the section “D. Dye-sensitized solar cell” described later, description thereof is omitted here.

C. Next, the dye-sensitized solar cell substrate of the present invention will be described. The dye-sensitized solar cell substrate of the present invention can be broadly divided into two modes depending on its configuration. Hereinafter, the substrate for a dye-sensitized solar cell of the present invention will be described separately for each embodiment.

C-1: Dye-sensitized solar cell substrate of the first aspect First, the dye-sensitized solar cell substrate of the first aspect of the present invention will be described. The dye-sensitized solar cell substrate of this aspect includes a heat-resistant substrate, a catalyst layer formed on the heat-resistant substrate and made of a metal, a porous insulating layer formed on the catalyst layer and made of an insulating material, The transparent electrode includes a porous layer formed on the porous insulating layer and containing metal oxide semiconductor fine particles, and a transparent electrode layer formed on the porous layer and made of a metal oxide. The layer is formed so as to be the outermost layer.

Such a dye-sensitized solar cell substrate of this embodiment will be described with reference to the drawings. FIG. 6 is a schematic view showing an example of the dye-sensitized solar cell substrate of this embodiment. As illustrated in FIG. 6, the dye-sensitized solar cell substrate 10 of this embodiment is formed on the heat-resistant substrate 1, the catalyst substrate 2 made of metal, and formed on the catalyst layer 2. A porous insulating layer 3 made of an insulating material, a porous layer 4 formed on the porous insulating layer 3 and containing metal oxide semiconductor fine particles, and formed on the porous layer 4. And a transparent electrode layer 5 made of
In such an example, the dye-sensitized solar cell substrate 10 of this embodiment is characterized in that the transparent electrode layer 5 is formed as an outermost layer.

  The substrate for a dye-sensitized solar cell according to this aspect has a configuration in which a catalyst layer, a porous insulating layer, a porous layer, and a transparent electrode layer are laminated in this order on the above heat-resistant substrate, thereby The dye-sensitized solar cell substrate can be manufactured with a small number of steps. In addition, the dye-sensitized solar cell substrate of this embodiment is formed so that the transparent electrode layer is the outermost layer, and thus, for example, a translucent substrate having an arbitrary function on the transparent electrode layer By giving, there is an advantage that an arbitrary function can be given.

  The dye-sensitized solar cell substrate of this embodiment has a heat-resistant substrate, a catalyst layer, a porous insulating layer, a porous layer, and a transparent electrode layer. Hereafter, each structure of the board | substrate for dye-sensitized solar cells of such an aspect is demonstrated in detail.

1. Porous layer First, the porous layer used in this embodiment will be described. The porous layer includes metal oxide semiconductor fine particles. Here, the metal oxide semiconductor fine particles are the same as those used in the method for producing a dye-sensitized solar cell substrate described in "A. Method for producing a dye-sensitized solar cell substrate" above. Therefore, the description here is omitted.

  The film thickness of the porous layer in this embodiment is not particularly limited as long as the desired mechanical strength can be imparted to the porous layer. Especially in this aspect, it is preferable to exist in the range of 1 micrometer-100 micrometers, and it is especially preferable to exist in the range of 5 micrometers-30 micrometers. This is because if the thickness of the porous layer is larger than the above range, the porous layer itself is liable to cohesive failure, which may cause membrane resistance. Further, if it is thinner than the above range, it becomes difficult to form a porous layer having a uniform thickness. For example, a dye-sensitized solar cell was produced using the dye-sensitized solar cell substrate of this embodiment. In this case, the porous layer containing the dye sensitizer cannot sufficiently absorb sunlight or the like, which may cause poor performance.

  The porous layer in this embodiment may be composed of a single layer or may be composed of a plurality of layers.

  Further, the porosity of the porous layer in this embodiment is preferably in the range of 10% to 60%, and more preferably in the range of 20% to 50%. This is because if the porosity is smaller than the above range, the specific surface area becomes small, so that the porous layer containing the dye sensitizer may not be able to effectively absorb sunlight or the like. Moreover, it is because the mechanical strength of a porous layer may be impaired when empty efficiency is larger than the said range.

  In the present embodiment, the “porosity” refers to the non-occupancy ratio of the metal semiconductor fine particles per unit volume, and such a porosity indicates the pore volume as a gas adsorption amount measuring device. It can be determined by measuring with (Autosorb-1MP; manufactured by Quantachrome) and calculating from the ratio with the volume per unit area.

  The metal oxide semiconductor fine particles contained in the porous layer in this embodiment are preferably those in which a dye sensitizer is adsorbed on the surface. Since the metal oxide semiconductor fine particles have a dye sensitizer adsorbed on the surface, it is easy to produce a dye-sensitized solar cell using the dye-sensitized solar cell substrate of this embodiment. Because it becomes.

  The dye sensitizer used in this embodiment is not particularly limited as long as it can absorb sunlight and generate an electromotive force. Such a dye sensitizer is the same as that described in the above-mentioned section “A. Method for producing dye-sensitized solar cell substrate”, and the description thereof is omitted here.

2. Next, the porous insulating layer in this embodiment will be described. The porous insulating layer has a porous form and is made of an insulating material. The insulating material is the same as that used in the method for producing a dye-sensitized solar cell substrate described in “A. Method for producing a dye-sensitized solar cell substrate” above. The description in is omitted.

The porosity of the porous insulating layer used in this embodiment is impregnated with a desired amount of electrolyte when a dye-sensitized solar cell is produced using the substrate for a dye-sensitized solar cell of this embodiment. However, in this embodiment, it is preferably in the range of 10% to 80%, and more preferably in the range of 20% to 80%. It is preferable. If the porosity is larger than the above range, the mechanical strength of the porous insulating layer may be impaired. If the porosity is smaller than the above range, a desired amount of electrolyte may not be impregnated. is there.
Here, since the method for measuring the porosity is the same as the method described in the above section “1. Porous layer”, the description is omitted here.

  The thickness of the porous insulating layer determines the distance between the porous layer in the present embodiment and a transparent electrode layer described later. The gap between the electrodes is determined when a sensitive solar cell is produced. Accordingly, the thickness of the porous insulating layer may be appropriately determined according to the use of the dye-sensitized solar cell produced using the dye-sensitized solar cell substrate of this embodiment. In particular, in this embodiment, the thickness of the porous insulating layer is preferably in the range of 0.1 μm to 200 μm, more preferably in the range of 1 μm to 100 μm, and still more preferably in the range of 5 μm to 50 μm. This is because when the thickness of the porous insulating layer is within the above range, the dye-sensitized solar cell produced using the dye-sensitized solar cell substrate of this embodiment can be made excellent in power generation efficiency. .

3. Transparent electrode layer Next, the transparent electrode layer used in this embodiment will be described. The transparent electrode layer used in this embodiment is made of a metal oxide.

  The metal oxide used in this embodiment is not particularly limited as long as it is a material having excellent conductivity and resistance to a redox pair described later. Especially in this aspect, it is preferable to use a material excellent in sunlight permeability. The reason is as follows. That is, since the dye-sensitized solar cell produced using the dye-sensitized solar cell substrate of the present embodiment is usually used in a mode of receiving sunlight from the transparent electrode layer side, the metal oxide This is because, if solar light permeability is poor, the power generation efficiency of the dye-sensitized solar cell using the dye-sensitized solar cell substrate of this embodiment is impaired.

Examples of the metal oxide having excellent sunlight permeability include SnO ₂ , ITO, IZO, and ZnO. In this embodiment, 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.

  The transparent electrode layer in this embodiment may have a single-layer configuration or a configuration in which a plurality of layers are stacked. Examples of the configuration in which a plurality of layers are stacked include a mode in which layers having different work functions are stacked and a mode in which layers made of different metal oxides are stacked.

The thickness of the transparent electrode layer in this embodiment is not particularly limited as long as desired conductivity can be achieved according to the type of the metal oxide. In particular, in this embodiment, it is 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 transparent electrode layer. If the thickness is less than the above range, the dye-sensitized solar cell substrate of this embodiment is used. This is because the conductivity of the transparent electrode layer may be insufficient depending on the case.
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.

4). Next, the catalyst layer will be described. The catalyst layer is not particularly limited as long as it is made of a desired metal. Examples of such metals include Pt, Ti, Ir, Ru, Pd, carbon, and alloys containing these. In particular, in this embodiment, it is preferable to use Pt.

  The thickness of the catalyst layer is usually in the range of 5 nm to 2000 nm, more preferably in the range of 10 nm to 1000 nm.

5. Heat-resistant substrate The heat-resistant substrate used in this embodiment is the same as that described in the above-mentioned section “A. Method for producing dye-sensitized solar cell substrate”, and the description thereof is omitted here.

6). Others The dye-sensitized solar cell substrate of this embodiment may contain other components in addition to the heat-resistant substrate, the catalyst layer, the porous insulating layer, the porous layer, and the transparent electrode layer. Examples of such another configuration include a counter electrode layer made of a conductive material and formed between the heat-resistant substrate and the catalyst layer. By having such a counter electrode layer, there exists an advantage that the electric power generation efficiency of the dye-sensitized solar cell manufactured using the board | substrate for dye-sensitized solar cells of this aspect may be improved. In particular, in this embodiment, it is preferable to have such a counter electrode layer when an insulating substrate is used as the heat-resistant substrate.

  An example in which the dye-sensitized solar cell substrate of this embodiment has the counter electrode layer will be described with reference to the drawings. FIG. 7 is a schematic diagram illustrating an example in which a dye-sensitized solar cell substrate has the counter electrode layer. As illustrated in FIG. 7, in the dye-sensitized solar cell substrate 10 ′ of this embodiment, the counter electrode layer 8 made of a conductive material is formed between the heat-resistant substrate 1 and the catalyst layer 2. It may have a configuration in which the counter electrode layer 8, the catalyst layer 2, the porous insulating layer 3, the porous layer 4, and the transparent electrode layer 5 are laminated on the heat resistant substrate 1.

As the conductive material constituting the counter electrode layer, a material made of a transparent metal oxide such as SnO ₂ , ITO, IZO, ZnO used for the conventional counter electrode can be used. Since the counter electrode layer in the aspect does not have to be transparent to sunlight, for example, a layer made of a conductive material opaque to sunlight such as a metal material may be used.

7). Method for Producing Dye-Sensitized Solar Cell Substrate The method for producing the dye-sensitized solar cell substrate of this embodiment is particularly limited as long as it is a method capable of producing a dye-sensitized solar cell substrate having the above-described configuration. Although not intended, the method described in the above section “A. Method for producing dye-sensitized solar cell substrate” can be preferably used.

C-2: Substrate for dye-sensitized solar cell of the second aspect Next, the substrate for dye-sensitized solar cell of the second aspect of the present invention will be described. The dye-sensitized solar cell substrate of this aspect includes a heat-resistant substrate, a catalyst layer formed on the heat-resistant substrate and made of a metal, a porous insulating layer formed on the catalyst layer and made of an insulating material, Formed on the porous insulating layer, comprising a porous layer containing metal oxide semiconductor fine particles, formed on the porous layer, formed of a transparent electrode layer made of a metal oxide, and formed on the transparent electrode layer; It has an adhesive layer made of an adhesive resin, and a translucent substrate that is formed on the adhesive layer and has optical transparency.

Such a dye-sensitized solar cell substrate of this embodiment will be described with reference to the drawings. FIG. 8 is a schematic view showing an example of the dye-sensitized solar cell substrate of this embodiment. As illustrated in FIG. 8, the dye-sensitized solar cell substrate 11 of this embodiment includes a heat-resistant substrate 1, a catalyst layer 2 made of metal and formed on the heat-resistant substrate 1, and the catalyst layer 2. A porous insulating layer 3 made of an insulating material, formed on the porous insulating layer 3, formed on the porous layer 4 containing metal oxide semiconductor fine particles, and formed on the porous layer 4. A transparent electrode layer 5 made of a material, an adhesive layer 6 formed on the transparent electrode layer 5 and made of an adhesive resin, and a translucent substrate 7 formed on the adhesive layer 6 and having light transmissivity. It is what you have.

According to the dye-sensitized solar cell substrate of this aspect, the above-described book is obtained by having a structure in which a catalyst layer, a porous insulating layer, a porous layer, and a transparent electrode layer are laminated in this order on a heat-resistant substrate. The dye-sensitized solar cell substrate according to the invention can be manufactured in a small number of steps by the method for manufacturing a substrate.
Moreover, the dye-sensitized solar cell substrate of this embodiment is a dye-sensitized solar cell having an arbitrary function by forming the translucent substrate on the transparent electrode layer via the adhesive layer. A substrate can be obtained.

The dye-sensitized solar cell substrate of this embodiment has the above heat-resistant substrate, catalyst layer, porous insulating layer, porous layer, transparent electrode layer, adhesive layer, and translucent substrate. Hereinafter, each configuration of the dye-sensitized solar cell substrate of this embodiment will be described in detail.
The heat-resistant substrate, the catalyst layer, the porous insulating layer, the porous layer, and the transparent electrode layer are described in the section “C-1: Dye-sensitized solar cell substrate of the first aspect”. Since it is the same as that of a thing, description here is abbreviate | omitted.

1. First, the adhesive layer will be described. The said adhesive layer consists of adhesive resin, and has a function which adhere | attaches the translucent board | substrate mentioned later and the said transparent electrode layer.

  The adhesive resin constituting the adhesive layer used in this embodiment is not particularly limited as long as it can adhere a light-transmitting substrate and a transparent electrode layer, which will be described later. Such an adhesive resin is the same as that described in the above-mentioned section “A. Method for producing dye-sensitized solar cell substrate”, and thus the description thereof is omitted here.

  The adhesive layer may contain other compounds in addition to the adhesive resin. Such other compounds are also the same as those described in the above section “A. Method for Producing Dye-Sensitized Solar Cell Substrate”, and thus the description thereof is omitted here.

  The thickness of the adhesive layer used in this embodiment 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 the adhesive resin constituting the adhesive layer. In particular, in this embodiment, the range of 5 μm to 300 μm is preferable, and the range of 10 μm to 200 μm is particularly 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 is necessary and thermal damage to a light-transmitting substrate, which will be described later, may increase.

2. Translucent Substrate The translucent substrate used in this embodiment is the same as that described in the section “A. Manufacturing Method of Dye-Sensitized Solar Cell Substrate” above, and the description thereof is omitted here. To do.

3. Others The dye-sensitized solar cell substrate of this embodiment may contain other components in addition to the heat-resistant substrate, the catalyst layer, the porous insulating layer, the porous layer, and the transparent electrode layer. Examples of such another configuration include a counter electrode layer made of a conductive material and formed between the heat-resistant substrate and the catalyst layer. Such a counter electrode layer is the same as that described in the above section “C-1: Substrate for dye-sensitized solar cell of first aspect”, and the description thereof is omitted here.

4). Method for Producing Dye-Sensitized Solar Cell Substrate The method for producing the dye-sensitized solar cell substrate of this embodiment is particularly limited as long as it is a method capable of producing a dye-sensitized solar cell substrate having the above-described configuration. Although not intended, the method described in the above section “A. Method for producing dye-sensitized solar cell substrate” can be preferably used.

D. Next, the dye-sensitized solar cell of the present invention will be described. The dye-sensitized solar cell of the present invention has the above-mentioned “C-1: dye-sensitized solar cell substrate of the first embodiment” or “C-2: substrate of dye-sensitized solar cell of the second embodiment”. The dye-sensitized solar cell substrate according to any of the above items is used, and the porous insulating layer of the dye-sensitized solar cell substrate is impregnated with an electrolytic solution containing a redox pair It is characterized by being.

  The dye-sensitized solar cell of the present invention includes a first embodiment using the dye-sensitized solar cell substrate described in the section “C-1: Dye-sensitized solar cell substrate of the first embodiment”, and This can be broadly classified into the second embodiment using the dye-sensitized solar cell substrate described in the section “C-2: Substrate for dye-sensitized solar cell of the second embodiment”.

  FIG. 9 is a schematic view showing an example of the dye-sensitized solar cell according to the first aspect of the present invention. As illustrated in FIG. 9, the dye-sensitized solar cell 20 of the first aspect of the present invention is dye-sensitized as described in the section “C-1: Substrate for dye-sensitized solar cell of the first aspect”. The transparent electrode layer has a structure in which a catalyst layer 2, a porous insulating layer 3, a porous layer 4, and a transparent electrode layer 5 are laminated in this order on a substrate for a sensitive solar cell, that is, a heat-resistant substrate 1. 5 is a substrate for a dye-sensitized solar cell formed to be the outermost layer, and the porous insulating layer 3A is impregnated with an electrolytic solution containing a redox pair. is there.

  FIG. 10 is a schematic view showing an example of the dye-sensitized solar cell according to the second aspect of the present invention. As illustrated in FIG. 10, the dye-sensitized solar cell according to the second aspect of the present invention is dye-sensitized as described in the section “C-2: Substrate for dye-sensitized solar cell according to the second aspect” above. Dye solar cell having a catalyst layer 2, a porous insulating layer 3, a porous layer 4, a transparent electrode layer 5, an adhesive layer 6 and a translucent substrate 7 on a substrate for a solar cell, that is, a heat-resistant substrate 1 The porous insulating layer 3A is impregnated with an electrolytic solution containing a redox couple using a substrate for a sensitive solar cell.

  The dye-sensitized solar cell of the present invention has, for example, a dye having an arbitrary function by using a light-transmitting substrate having an arbitrary function on the transparent electrode layer as the dye-sensitized solar cell substrate. It has the advantage that a sensitized solar cell can be obtained.

  Here, regarding the dye-sensitized solar cell substrate used in the present invention, the above-mentioned “C-1: dye-sensitized solar cell substrate of the first aspect” or “C-2: dye of the second aspect”. Since it is the same as that described in the section of “Sensitizing Solar Cell Substrate”, the description is omitted here.

  In the present invention, the electrolytic solution impregnated in the porous insulating layer of the dye-sensitized solar cell substrate contains a redox couple. Such an electrolytic solution is the same as that described in the above-mentioned section “B. Manufacturing method of dye-sensitized solar cell”, and thus the description thereof is omitted here.

  In the present invention, the amount of the electrolyte impregnated in the porous insulating layer is not particularly limited as long as the dye-sensitized solar cell substrate of the present invention is within a range capable of generating power with a desired efficiency. Usually, an amount capable of filling all the pores of the porous insulating layer is impregnated.

  The method for producing the dye-sensitized solar cell of the present embodiment is not particularly limited as long as it is a method capable of producing a dye-sensitized solar cell substrate having the above-described configuration. The method described in the section “Method for producing substrate for solar cell” can be suitably 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. Formation of porous laminate (catalyst layer formation)
A titanium foil having a thickness of 100 μm was used as a heat-resistant substrate, and a catalyst layer was formed by applying a platinum film having a thickness of 300 nm on the titanium foil by sputtering.

(1) Formation of porous insulating layer forming layer (Preparation of coating liquid for forming porous insulating layer)
A slurry was prepared such that silicon dioxide particles having an average particle diameter of 40 nm and rutile-type titanium oxide particles having an average particle diameter of 400 nm were in a mass ratio of 35:65. The composition of the prepared slurry is as follows.
-Particles: 17% by mass of the above mixed particles
・ Solvent: Turpineol (Fluka) 73% by mass
・ Resin: Ethylcellulose (Fluka) 10% by mass

(Formation of porous insulation layer forming layer)
The porous insulating layer-forming coating solution prepared above was applied on the catalyst layer by a screen printing method, and then allowed to stand at room temperature for 20 minutes. Thereafter, the porous insulating layer forming layer was formed by further drying at 100 ° C. for 30 minutes.

(2) Formation of porous layer forming layer As a porous layer forming coating solution, titanium oxide paste Ti-Nanoxide D (manufactured by Solaronix) having a particle size of about 13 nm is used, and such a porous layer forming coating is used. The liquid was applied onto the porous insulating layer forming layer by a doctor blade method. Then, the porous layer forming layer was formed by allowing to stand at room temperature for 20 minutes and further drying at 100 ° C. for 30 minutes.

(3) Firing The porous insulating layer forming layer and the porous layer forming layer were fired at 500 ° C. for 30 minutes in an atmospheric pressure atmosphere using an electric muffle furnace (P90 manufactured by Denken). Thereby, the porous laminated body was formed by making the said layer for porous insulating layer formation and the said layer for porous layer formation into the porous insulating layer and porous layer which consist of a porous body.

2. Formation of transparent electrode layer As a coating solution for forming a transparent electrode layer, a solution prepared by dissolving 0.1 mol / L of indium chloride and 0.005 mol / L of tin chloride in ethanol was prepared.

  The porous laminate is heated by placing it on a hot plate (400 ° C.) so that the porous layer faces upward, and the transparent electrode layer described above is formed on the porous layer of the heated porous laminate. The forming coating solution was sprayed with an ultrasonic sprayer. This formed the transparent electrode layer which consists of an ITO film | membrane with a thickness of 800 nm, and obtained the board | substrate for dye-sensitized solar cells.

3. Application of Dye Sensitizer The above dye-sensitized solar cell substrate is prepared by using a dye solution for adsorption (ruthenium complex (RuL ₂ (NCS) ₂ ), Kojima Chemical Co., Ltd.) in an absolute ethanol solution at a concentration of 3 × 10 ^−4. The dye sensitizer was supported on the porous layer by immersing it in (mol / L dissolved).

4). Preparation of dye-sensitized solar cell Using methoxyacetonitrile as a solvent, lithium iodide at a concentration of 0.1 mol / L, iodine at a concentration of 0.05 mol / L, dimethylpropylimidazolium iodide at a concentration of 0.3 mol / l, concentration 0 A solution in which 5 mol / L of tertiary butyl pyridine was dissolved was used as an electrolytic solution. A dye-sensitized solar cell was produced by impregnating such an electrolytic solution into the porous insulating layer and the porous layer of the dye-sensitized solar cell substrate on which the dye sensitizer was supported.

5. Battery characteristic evaluation About the produced dye-sensitized solar cell, as a result of measuring a current-voltage characteristic using the upper surface and the lower surface as an extraction electrode, the short-circuit current was 14.2 mA / cm ² , the open-circuit voltage was 712 mV, and the conversion efficiency was 6.6%. .

It is the schematic which shows an example of the manufacturing method of the board | substrate for dye-sensitized solar cells of this invention. It is the schematic which shows an example of the porous laminated body formation process in this invention. It is the schematic which shows the other example of the porous laminated body formation process in this invention. It is the schematic which shows an example of the translucent board | substrate lamination process in this invention. It is the schematic which shows an example of the manufacturing method of the dye-sensitized solar cell of this invention. It is the schematic which shows an example of the board | substrate for dye-sensitized solar cells of this invention. It is the schematic which shows the other example of the board | substrate for dye-sensitized solar cells of this invention. It is the schematic which shows the other example of the board | substrate for dye-sensitized solar cells of this invention. It is the schematic which shows an example of the dye-sensitized solar cell of this invention. It is the schematic which shows the other example of the dye-sensitized solar cell of this invention. It is the schematic which shows an example of the conventional dye-sensitized solar cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Heat resistant substrate 2 ... Catalyst layer 3, 3A ... Porous insulating layer 3 '... Porous insulating layer forming layer 4 ... Porous layer 4' ... Porous layer forming layer 5 ... Transparent electrode layer 6 ... Adhesive layer 7 ... Translucent substrate 8 ... Counter electrode layer 10, 11 ... Dye-sensitized solar cell substrate 20, 21 ... Dye-sensitized solar cell 30 ... Porous laminate

Claims (8)

Porous forming a porous laminate in which a catalyst layer made of metal, a porous insulating layer made of an insulating material, and a porous layer containing metal oxide semiconductor fine particles are laminated in this order on a heat-resistant substrate A laminate forming step;
And a transparent electrode layer forming step of forming a transparent electrode layer made of a metal oxide on the porous layer of the porous laminate. A method for producing a dye-sensitized solar cell substrate, comprising:   After the transparent electrode layer forming step, a translucent substrate laminating step of laminating a translucent substrate having light transmissivity via an adhesive layer made of an adhesive resin is provided on the transparent electrode layer. The manufacturing method of the board | substrate for dye-sensitized solar cells of Claim 1.   3. The dye-sensitized solar according to claim 1, further comprising a dye adsorption step of adsorbing a dye sensitizer on the surface of the metal oxide semiconductor fine particles after the transparent electrode layer forming step. A method for manufacturing a battery substrate.   Using the dye-sensitized solar cell substrate manufactured by the method for manufacturing a dye-sensitized solar cell substrate according to claim 3, oxidation-reduction is performed on the porous insulating layer of the dye-sensitized solar cell substrate. A method for producing a dye-sensitized solar cell, comprising impregnating an electrolytic solution containing a pair. A heat-resistant substrate,
A catalyst layer formed on the heat-resistant substrate and made of metal;
A porous insulating layer formed on the catalyst layer and made of an insulating material;
A porous layer formed on the porous insulating layer and containing metal oxide semiconductor fine particles;
A dye-sensitized solar cell substrate having a transparent electrode layer formed on the porous layer and made of a metal oxide,
The dye-sensitized solar cell substrate, wherein the transparent electrode layer is formed to be an outermost layer. A heat-resistant substrate,
A catalyst layer formed on the heat-resistant substrate and made of metal;
A porous insulating layer formed on the catalyst layer and made of an insulating material;
A porous layer formed on the porous insulating layer and containing metal oxide semiconductor fine particles;
A transparent electrode layer formed on the porous layer and made of a metal oxide;
An adhesive layer formed on the transparent electrode layer and made of an adhesive resin;
A dye-sensitized solar cell substrate, comprising: a light-transmitting substrate formed on the adhesive layer and having light transmittance.   The dye-sensitized solar cell substrate according to claim 5 or 6, wherein the metal oxide semiconductor fine particles have a dye sensitizer adsorbed on a surface thereof.   The dye-sensitized solar cell substrate according to claim 7 is used, and the porous insulating layer of the dye-sensitized solar cell substrate is impregnated with an electrolytic solution containing a redox pair. And a dye-sensitized solar cell.

Images