JP2006278299A - Laminate for dye-sensitized solar cell, substrate material for dye-sensitized solar cell with heat resistant substrate, substrate material for dye-sensitized solar cell, and dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate material for dye-sensitized solar cell equipped with a transparent electrode having high chemical resistance and high electric conductivity, a dye-sensitized solar cell cell and a laminate for dye-sensitized solar cell used for manufacturing this, and a substrate material for dye-sensitized solar cell with heat resistant substrate, and to provide a substrate material for dye-sensitized solar cell with flexibility, and dye-sensitized solar cell cell. <P>SOLUTION: The laminate for the dye-sensitized solar cell is comprised of a heat resistant substrate, a porous layer formed on the heat resistant substrate and containing metal oxide semiconductor fine particles, a first transparent electrode layer formed on the heat resistant substrate and comprising a first metal oxide, and a second transparent electrode layer formed on the first transparent electrode layer and comprising a second metal oxide, and the first metal oxide has higher chemical durability than the second metal oxide. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a dye-sensitized solar cell substrate, a dye-sensitized solar cell, a laminate for a dye-sensitized solar cell used for production thereof, and a dye-sensitized solar cell base with a heat-resistant substrate. More specifically, the present invention relates to a dye-sensitized solar cell substrate, a dye-sensitized solar cell having a transparent electrode in which two transparent electrode layers made of different metal oxides are laminated, and production thereof. The present invention relates to a laminate for a dye-sensitized solar cell and a substrate for a dye-sensitized solar cell with a heat-resistant substrate.

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

  A general configuration of the dye-sensitized solar cell is shown in FIG. As shown in FIG. 7, a general dye-sensitized solar cell 7 includes metal oxide semiconductor fine particles carrying a first electrode layer (transparent electrode layer) 2 and a dye sensitizer on a substrate 1. A porous layer 3 containing a redox pair, an electrolyte layer 4 having a redox pair, a second electrode layer 5, and a counter substrate 6 are laminated in this order, and receives sunlight from the substrate 1 side. The excited electrons are conducted to the first electrode layer and conducted to the second electrode layer through an external circuit. Thereafter, electricity is generated by returning the electrons to the ground level of the sensitizing dye via the redox pair. A typical example of such a dye-sensitized solar cell is a Gretcher cell in which the porous layer is made of porous titanium dioxide and the content of the dye sensitizer is increased. It has been widely studied as a sensitized solar cell.

  Here, in the dye-sensitized solar cell, in order to efficiently transport charges, it is necessary to infiltrate the electrolyte into the porous layer. However, if the electrolyte is infiltrated into the porous layer, the transparent electrode The electrolyte comes into contact. For this reason, when ITO with low chemical durability is used as an electrode, there is a problem that the function as an electrode is deteriorated with time due to deterioration due to an oxidation-reduction pair or an electrolyte solvent contained in the electrolyte.

As a solution to the above problem, a method is conceivable in which the transparent electrode layer is made of a transparent metal oxide having excellent chemical durability such as FTO or SnO ₂ instead of ITO. By using such a transparent metal oxide having excellent chemical durability, it is possible to improve the resistance of the transparent electrode layer to the redox couple, thus forming a dye-sensitized solar cell with excellent temporal stability. In general, however, such a transparent metal oxide having excellent chemical durability is inferior to ITO in terms of electrical conductivity, so that the resulting dye-sensitized solar cell has low power generation efficiency. There is a problem.

  Patent Document 1 discloses a transparent electrode substrate characterized in that two or more different transparent electrode films are formed on a substrate, and the upper transparent electrode film has higher heat resistance than the lower transparent electrode film. It is disclosed. According to the method disclosed in Patent Document 1, the transparent electrode layer is formed by laminating a transparent electrode layer made of ITO and a transparent electrode layer made of a transparent metal oxide having excellent chemical durability. It is possible to form a dye-sensitized solar cell that has excellent chemical durability and stability over time.

  However, the method disclosed in Patent Document 1 requires heat treatment at 500 ° C. to 600 ° C. in order to form a transparent electrode layer made of a transparent metal oxide having excellent chemical durability. Therefore, as a base material used for a dye-sensitized solar cell, a material having heat resistance that can withstand such heat treatment can be used, and a general resin film base material can be used. There is a problem that cannot be done. For this reason, when forming the transparent electrode layer which is excellent in chemical durability by the method disclosed in Patent Document 1, only the rigid material such as heat-resistant glass or quartz glass can be used as the base material, which is obtained. As a dye-sensitized solar cell, there is a problem that it is disadvantageous in terms of practicality, such as poor processability and a heavy weight.

  Furthermore, in order to form a porous layer containing the metal oxide semiconductor fine particles, it is generally necessary to perform a baking treatment at 300 ° C. to 1000 ° C. For this reason, when forming the said porous layer on the said transparent electrode after forming the said transparent electrode layer which consists of said 2 layers on a base material according to the method disclosed by patent document 1, a transparent electrode layer is also inevitably It will be exposed to the heating conditions by a baking process. In general, when a metal oxide used for a transparent electrode layer is exposed to heating conditions, oxidative degradation progresses and an electrical resistance value increases. Therefore, in the method disclosed in Patent Document 1, the metal oxide is used. There is a problem in that the excellent electrical conductivity inherent to is impaired.

JP 2003-323818 A

  The present invention has been made in view of the above-mentioned problems, and is a dye-sensitized solar cell substrate, a dye-sensitized solar cell, and a dye-sensitized solar cell provided with a transparent electrode excellent in chemical durability and electrical conductivity. Provided a laminate for a dye-sensitized solar cell, a dye-sensitized solar cell substrate with a heat-resistant substrate, and a substrate for a dye-sensitized solar cell having flexibility, And a dye-sensitized solar cell.

In order to achieve the above object, the present invention provides a heat resistant substrate, a porous layer formed on the heat resistant substrate and containing metal oxide semiconductor fine particles, formed on the porous layer, and formed of a first metal oxide. A laminate for a dye-sensitized solar cell, comprising: a first transparent electrode layer comprising: a second transparent electrode layer formed on the first transparent electrode layer and comprising a second metal oxide;
Provided is a laminate for a dye-sensitized solar cell, wherein the first metal oxide has higher chemical durability than the second metal oxide.

  According to the present invention, the first metal oxide is provided with two transparent electrodes, a first transparent electrode layer made of the first metal oxide and a second transparent electrode layer made of the second metal oxide. However, since the chemical durability is higher than that of the second metal oxide, the first transparent electrode layer serves as a “protective layer” that protects the second transparent electrode layer from being eroded by the redox couple. Can do. Therefore, according to the present invention, a substrate for a dye-sensitized solar cell and a dye-sensitized solar cell excellent in chemical durability are manufactured without losing the electrical conductivity of the second transparent electrode layer over time. A laminate for a dye-sensitized solar cell that can be obtained can be obtained.

In the present invention, the first metal oxide is at least one selected from the group consisting of FTO, SnO ₂ , IZO, ZnO, ATO, fluorine-doped ZnO, aluminum-doped ZnO, gallium-doped ZnO, and boron-doped ZnO. It is preferable that Since such a metal oxide is particularly excellent in chemical durability, the dye-sensitized solar of the present invention can be obtained by using any one metal oxide of such a group as the first metal oxide. This is because the chemical durability of the dye-sensitized solar cell substrate and the dye-sensitized solar cell manufactured using the battery laminate can be further improved.

In the present invention, the second metal oxide is preferably ITO. Since ITO is excellent in translucency and electric conductivity with respect to sunlight, by using ITO as the second metal oxide, the dye sensitization produced using the laminate for the dye-sensitized solar cell of the present invention is used. This is because the substrate for the sensitive solar cell and the dye-sensitized solar cell can be made excellent in chemical durability and electrical conductivity.
In addition, the laminate for a dye-sensitized solar cell of the present invention uses ITO as the second metal oxide because the second transparent electrode layer is not exposed to heating conditions such as baking treatment in the manufacturing process. Even if it exists, it is because there exists an advantage that the outstanding electrical conductivity which ITO originally has can be maintained.

The present invention is a base material for a dye-sensitized solar cell with a heat-resistant substrate, comprising a base material, an adhesive layer made of a heat-meltable resin, and the dye-sensitized solar cell laminate,
For a dye-sensitized solar cell with a heat-resistant substrate, wherein the second transparent electrode layer of the laminate for a dye-sensitized solar cell and the base material are bonded via the adhesive layer. A substrate is provided.

  According to the present invention, by using the laminate for a dye-sensitized solar cell, the dye-sensitized solar cell substrate and the dye-sensitized solar cell excellent in chemical durability and electrical conductivity are obtained. A base material for a dye-sensitized solar cell with a heat-resistant substrate that can be easily produced can be obtained. Further, by using the laminate for a dye-sensitized solar cell, the base material for a dye-sensitized solar cell and the dye-sensitized solar cell according to the present invention can be used. Since the heat treatment is not required in the step of forming the base material, the base material is not limited to a rigid material having heat resistance, and base materials of any material can be used. Therefore, according to the present invention, a dye-sensitized solar cell with a heat-resistant substrate capable of producing a dye-sensitized solar cell substrate and a dye-sensitized solar cell having a substrate having desired physical properties. A substrate for use can be obtained.

  In the present invention, the substrate is preferably a resin film substrate. Since the resin film base material is excellent in flexibility and lightweight, the dye-sensitized solar cell base material and the dye manufactured using the heat-resistant substrate-attached dye-sensitized solar cell base material of the present invention This is because the sensitized solar cell can be made excellent in practicality such as manufacturing suitability and processability.

The present invention includes a base material, an adhesive layer formed on the base material and made of a heat-meltable resin,
A second transparent electrode layer formed on the adhesive layer and made of a second metal oxide, a first transparent electrode layer formed on the second transparent electrode layer and made of the first metal oxide, and the first A substrate for a dye-sensitized solar cell formed on a transparent electrode layer and comprising a porous layer containing metal oxide semiconductor fine particles, wherein the first metal oxide is the second metal oxide. Disclosed is a dye-sensitized solar cell substrate characterized by having higher chemical durability than a product.

According to the present invention, the first metal oxide is provided with two transparent electrodes, a first transparent electrode layer made of the first metal oxide and a second transparent electrode layer made of the second metal oxide. However, since the chemical durability is higher than that of the second metal oxide, the electrical conductivity of the second transparent electrode layer is not impaired over time, and the dye-sensitized solar cell has excellent chemical durability. A substrate can be obtained.
In the present invention, since the first metal oxide has higher chemical durability than the second metal oxide, not only the second transparent electrode layer but also the adhesive layer is formed by a redox pair. Corrosion can also be suppressed. Therefore, according to the present invention, it is possible to obtain a dye-sensitized solar cell substrate that is excellent in adhesion stability and does not lose the adhesive strength of the adhesive layer over time.

In the present invention, the first metal oxide is selected from the group consisting of FTO, SnO ₂ , IZO, ZnO, ATO, fluorine-doped zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and boron-doped zinc oxide. It is preferable that the number is at least one. Since such a metal oxide is particularly excellent in chemical durability, the dye-sensitized solar of the present invention can be obtained by using any one metal oxide of such a group as the first metal oxide. This is because the chemical durability and adhesion stability of the battery substrate can be further improved.

  In the present invention, the second metal oxide is preferably ITO. Since ITO is excellent in translucency and electric conductivity with respect to sunlight, by using ITO as the second metal oxide, the substrate for the dye-sensitized solar cell of the present invention can be bonded to the chemical durability and adhesion. It is because it can be made excellent in electrical conductivity in addition to stability.

  In the present invention, the substrate is preferably a resin film substrate. Since the resin film base material is excellent in flexibility and lightweight, the resin film base material is used as the base material, so that the dye-sensitized solar cell base material of the present invention can be manufactured and processed. It is because it can be made excellent in practicality such as aptitude.

The present invention provides a dye-sensitized solar cell comprising the dye-sensitized solar cell base material, a counter electrode base material including a second electrode layer and a counter base material, and an electrolyte layer including a redox pair. Because
A dye sensitizing method characterized in that a porous layer of the dye-sensitized solar cell substrate and a second electrode layer of the counter electrode substrate are arranged to face each other with the electrolyte layer interposed therebetween. A solar cell is provided.

  According to the present invention, by using the dye-sensitized solar cell substrate, the transparent electrode composed of the first transparent electrode layer and the second transparent electrode layer is eroded by the redox pair. Therefore, the electrical conductivity can be stably maintained for a long time. Therefore, according to the present invention, it is possible to obtain a dye-sensitized solar cell excellent in the temporal stability of power generation efficiency. In addition, according to the present invention, by using the dye-sensitized solar cell base material using a resin film base material as the base material, a flexible dye-sensitized solar cell can be easily obtained. Obtainable.

  ADVANTAGE OF THE INVENTION According to this invention, the base material for dye-sensitized solar cells provided with the transparent electrode excellent in chemical durability and electrical conductivity, a dye-sensitized solar cell, and the dye-sensitized type used for these manufacture There is an effect that a laminate for a solar cell and a dye-sensitized solar cell substrate with a heat-resistant substrate can be obtained.

  Hereinafter, a laminate for a dye-sensitized solar cell, a dye-sensitized solar cell substrate with a heat-resistant substrate, a dye-sensitized solar cell substrate, and a dye-sensitized solar cell according to the present invention will be described in detail. To do.

A. First, the laminate for a dye-sensitized solar cell of the present invention will be described. The laminate for a dye-sensitized solar cell of the present invention includes a heat-resistant substrate, a porous layer formed on the heat-resistant substrate and including metal oxide semiconductor fine particles, and formed on the porous layer. A laminate for a dye-sensitized solar cell, comprising: a first transparent electrode layer made of an oxide; and a second transparent electrode layer formed on the first transparent electrode layer and made of a second metal oxide. The first metal oxide has higher chemical durability than the second metal oxide.

  Next, the laminate for a dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of a laminate for a dye-sensitized solar cell of the present invention. As shown in FIG. 1, the laminate 10 for a dye-sensitized solar cell of the present invention includes a heat resistant substrate 16, a porous layer 15 formed on the heat resistant substrate 16 and containing metal oxide semiconductor fine particles, A first transparent electrode layer 14 formed on the porous layer 15 and made of a first metal oxide; and a second transparent electrode layer 13 formed on the first transparent electrode layer 14 and made of a second metal oxide; The laminate for a dye-sensitized solar cell is characterized in that the first metal oxide has higher chemical durability than the second metal oxide.

  According to the present invention, the first metal oxide is provided with two transparent electrodes, a first transparent electrode layer made of the first metal oxide and a second transparent electrode layer made of the second metal oxide. However, since the chemical durability is higher than that of the second metal oxide, the first transparent electrode layer serves as a “protective layer” that protects the second transparent electrode layer from being eroded by the redox couple. Can do. Therefore, according to the present invention, the electrical conductivity of the second transparent electrode layer is not impaired over time, and the dye-sensitized solar cell substrate and the dye-sensitized solar cell excellent in chemical durability are easily obtained. It is possible to obtain a laminate for a dye-sensitized solar cell, which can be manufactured in a simple manner.

Dye-sensitized solar cells have been widely studied as a clean energy source, but ITO, which is commonly used as a transparent electrode, is poor in chemical durability, so it is eroded by redox couples over time. There is a problem that the function as an electrode is impaired, and there is a problem that it lacks practicality. For such problems, a method of forming a transparent electrode using a metal oxide excellent in chemical durability is also conceivable, but FTO (generally known as a metal oxide excellent in chemical durability, Fluorine-doped tin oxide) and SnO ₂ are inferior in electrical conductivity to ITO, so when a transparent electrode layer is formed with such a metal oxide, chemical durability can be improved, but as a solar cell, power generation is possible. There was a problem of inefficiency. Also, by laminating a transparent electrode layer made of ITO and a transparent electrode layer made of a metal oxide having excellent chemical durability as in the above example on the base material in this order, electrical conductivity and chemical durability In this case, it is necessary to carry out heat treatment when forming the transparent electrode layer made of the metal oxide having excellent chemical durability. There was a problem that deterioration progressed and as a result, conductivity was impaired. Furthermore, since the heat treatment is performed, only the heat-resistant substrate such as heat-resistant glass or quartz glass can be used as the substrate, and a flexible dye-sensitized solar cell can be obtained. It was difficult.

The laminate for a dye-sensitized solar cell of the present invention is suitable for producing a dye-sensitized solar cell having both flexibility of electrical conductivity and chemical durability of a transparent electrode and flexibility. It is used for. That is, according to the present invention, two transparent electrodes (hereinafter referred to as a first transparent electrode layer), which are a first transparent electrode layer made of a first metal oxide and a second transparent electrode layer made of a second metal oxide. And the second transparent electrode layer may be collectively referred to as a first electrode layer.), And the first metal oxide has higher chemical durability than the second metal oxide. The chemical durability of the first electrode layer can be improved.
Moreover, in the laminated body for dye-sensitized solar cells of this invention, after forming the porous layer and 2nd transparent electrode layer which require the heat processing at high temperature so that it may mention later, a 1st transparent electrode layer is formed. Since it forms, the electrical resistance value of the 1st metal oxide which comprises a 1st transparent electrode layer does not increase by heat processing. Therefore, according to the laminate for a dye-sensitized solar cell of the present invention, the first electrode layer excellent in chemical durability and electrical conductivity can be formed.
Furthermore, the pigment | dye which is excellent in flexibility by forming the base material for dye-sensitized solar cells and a dye-sensitized solar cell by the method mentioned later using the laminated body for dye-sensitized solar cells of this invention. The base material for sensitized solar cells and the dye-sensitized solar cell can be easily manufactured.

  Hereinafter, each structure of the laminated body for dye-sensitized solar cells of this invention is demonstrated in detail.

1. 1st transparent electrode layer First, the 1st transparent electrode layer in the laminated body for dye-sensitized solar cells of this invention is demonstrated. The 1st transparent electrode layer in this invention consists of a 1st metal oxide whose chemical durability is higher than the said 2nd metal oxide.

  The thickness of the first transparent electrode layer in the present invention is not particularly limited as long as it is within a range in which the second transparent electrode layer can be protected from erosion by the redox couple, but usually within the range of 5 nm to 500 nm, particularly 30 nm to It is preferably in the range of 350 nm, and more preferably in the range of 100 nm to 350 nm. If the thickness is thicker than the above range, the electrical resistance value of the first transparent electrode layer increases, and the power generation efficiency of the dye-sensitized solar cell manufactured from the dye-sensitized solar cell laminate of the present invention is impaired. If the thickness is smaller than the above range, the redox couple may pass through the first transparent electrode layer and the second transparent electrode layer may be eroded.

  The transparency of the first transparent electrode layer in the present invention is not particularly limited as long as it is within a range in which a desired transmittance with respect to sunlight can be obtained, depending on the transparency of the second transparent electrode layer described later. In the present invention, the transmittance of light having a wavelength of 400 nm to 800 nm is preferably 70% or more, and more preferably 80% or more. When the transparency of the first transparent electrode layer is lower than the above range, when the dye-sensitized solar cell is produced using the laminate for the dye-sensitized solar cell of the present invention, the dye-sensitized solar cell This is because the power generation efficiency may be impaired.

  The electrical conductivity of the first transparent electrode layer in the present invention may be arbitrarily determined according to the electrical conductivity of the second transparent electrode layer, which will be described later. Usually, the sheet resistance is 30Ω / □ or less. Among them, 10Ω / □ or less is more preferable. If the sheet resistance is higher than the above range, a desired power generation efficiency may not be achieved when a dye-sensitized solar cell is produced using the laminate for a dye-sensitized solar cell of the present invention. is there.

The 1st metal oxide used for the said 1st transparent electrode layer will not be specifically limited if chemical durability is higher than the 2nd metal oxide mentioned later. Among these, when producing a dye-sensitized solar cell using the laminate for a dye-sensitized solar cell of the present invention, those having high durability against the solvent and redox couple used in the electrolyte layer are preferable. As the durability against the solvent, for example, those having high durability against methoxyacetonitrile, acetonitrile, propylene carbonate and the like are preferable, and as the durability against redox couple, for example, those having high durability against iodine and the like are preferable.
More specifically, the first metal oxide includes a first metal oxide film made of the first metal oxide and a second metal oxide film made of the second metal oxide on an arbitrary substrate. After forming with the same thickness, both are in a solvent of methoxyacetonitrile, acetonitrile or propylene carbonate, iodine is 0.05 mol / l, lithium iodide is 0.1 mol / l, dimethylpropylimidazolium iodide Is immersed in an electrolyte solution (25 ° C.) in which 0.3 mol / l of tert-butylpyridine is dissolved at 0.5 mol / l, the first metal oxide film is more preferable than the second metal oxide film. However, it is preferable that the metal oxide film breakage such as cracks, cracks and chips is slow, or the surface resistance value (Ω / □) is slow.
Here, the breakage of the metal oxide film such as cracks, cracks and chips was visually evaluated, and the surface resistance value was measured by a four-terminal surface resistance measuring instrument (Loresta-EP, manufactured by Mitsubishi Chemical). Use the value measured by.

  Examples of the first metal oxide used in the first transparent electrode layer include FTO (fluorine-doped tin oxide), antimony-doped tin oxide (ATO), tin oxide, fluorine-doped zinc oxide, aluminum-doped zinc oxide, zinc oxide, and indium. -It is preferable that it is at least 1 selected from the group which consists of zinc oxide (IZO), gallium dope zinc oxide, and boron dope zinc oxide. Since these metal oxides are particularly excellent in chemical durability, the dye-sensitized solar cell substrate and the dye-sensitized solar cell manufactured using the laminate for the dye-sensitized solar cell of the present invention are used. This is because the chemical durability of the cell can be further improved. Moreover, it is because it becomes easy to form a homogeneous 1st transparent electrode layer by using these metal oxides. In particular, in the present invention, it is most preferable to use FTO as the first metal oxide.

2. Second Transparent Electrode Layer Next, the second transparent electrode layer in the present invention will be described. The 2nd transparent electrode layer in this invention consists of a 2nd metal oxide.

  The electrical conductivity of the second transparent electrode layer in the present invention is not particularly limited as long as it is higher than the electrical conductivity of the first transparent electrode layer. Usually, the sheet resistance is preferably 40Ω / □ or less, More preferably, it is 8Ω / □ or less. If the sheet resistance is higher than the above range, a desired power generation efficiency may not be achieved when a dye-sensitized solar cell is produced using the laminate for a dye-sensitized solar cell of the present invention. is there.

  The transparency of the second transparent electrode layer in the present invention is not particularly limited as long as a desired transmittance can be obtained with respect to sunlight, but in the present invention, the transmittance of light having a wavelength of 400 nm to 800 nm. Is preferably 70% or more, and more preferably 80% or more. When the transparency of the second transparent electrode layer is lower than the above range, when a dye-sensitized solar cell is produced using the laminate for a dye-sensitized solar cell of the present invention, the dye-sensitized solar cell This is because the power generation efficiency may be impaired.

  The thickness of the 2nd transparent electrode layer in this invention is the use of the dye-sensitized solar cell manufactured using the laminated body for dye-sensitized solar cells of this invention, and the 1st which comprises the said 1st transparent electrode layer. According to the kind of 1 metal oxide, it will not specifically limit if it is in the range which can make the electrical resistance value of a 1st electrode layer into a desired value. Especially in this invention, when the thickness ratio of the said 1st transparent electrode layer and a 2nd transparent electrode layer makes thickness of a 2nd transparent electrode layer 1, the thickness of a 2nd transparent electrode layer is 0.01- Is preferably in the range of 0.05 to 0.9, and more preferably in the range of 0.1 to 0.8. When the thickness ratio is smaller than the above range, it may be difficult to adjust the electric resistance value of the first electrode layer within a desired range. When the thickness ratio is larger than the above range, the first electrode This is because it may be difficult to achieve both the chemical durability of the layer and the electrical conductivity.

  Although the thickness of the 2nd electrode layer used for this invention will not be specifically limited if it is in the range which satisfies the said thickness ratio, Usually, the inside of the range of 5 nm-1500 nm is preferable, and it is especially within the range of 10 nm-1000 nm. Is preferable, and in particular, it is preferably in the range of 100 nm to 800 nm. If the thickness is larger than the above range, it may be difficult to form a homogeneous second transparent electrode layer. If the thickness is smaller than the above range, the desired electrical conductivity may not be obtained. Because there is.

  The first metal oxide used in the present invention is ITO, FTO (fluorine-doped tin oxide), antimony-doped tin oxide, tin oxide, fluorine-doped zinc oxide, aluminum-doped zinc oxide, zinc oxide, indium / zinc oxide (IZO). ), A metal oxide other than the metal oxide used as the second metal oxide can be used from the group consisting of gallium-doped zinc oxide and boric acid-doped zinc oxide. It is preferable to use ITO as the metal oxide. This is because ITO is excellent in electrical conductivity and excellent in translucency of sunlight. Moreover, since ITO is widely used as a transparent electrode as well as a dye-sensitized solar cell, it can be easily applied to the present invention.

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

(1) Metal oxide semiconductor fine particles The metal oxide semiconductor fine particles used in the present invention 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 can be mentioned. These metal oxide semiconductor fine particles are suitable for forming a porous porous layer, and are preferably used because energy conversion efficiency can be improved and costs can be reduced. Moreover, in this invention, any 1 type may be used among the said metal oxide semiconductor fine particles, and 2 or more types may be mixed and used for it. Further, one of the metal oxide semiconductor fine particles described above may be a core fine particle, and a core-shell structure in which the core fine particle is included to form a shell by another metal oxide semiconductor fine particle. In the present invention, it is most preferable to use TiO ₂ as the semiconductor oxide fine particles.

  The particle size of the metal oxide semiconductor fine particles used in the present invention is not particularly limited as long as it is within a range where a desired surface area can be obtained in the porous layer, but usually within the range of 1 nm to 10 μm is preferable. In particular, the thickness is preferably in the range of 10 nm to 1000 nm. If the particle size is smaller than the above range, the respective metal oxide semiconductor fine particles may aggregate to form secondary particles, and if the particle size is larger than the above range, the porous layer becomes thicker, This is because when the dye-sensitized solar cell is produced from the laminate for the dye-sensitized solar cell of the present invention, the film resistance may be increased more than necessary.

In the present invention, a mixture of a plurality of metal oxide semiconductor particles having different particle diameters may be used as the metal oxide semiconductor particles. By using a mixture of metal oxide semiconductor fine particles having different particle sizes, the light scattering effect in the porous layer can be enhanced, and light absorption by the dye sensitizer can be efficiently performed. It is particularly preferable to use a mixture of metal oxide semiconductor fine particles having different particle sizes.
The mixture of a 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 a mixture of different types of metal oxide semiconductor fine particles. Good. Examples of combinations of different particle diameters include a mode in which metal oxide semiconductor fine particles in the range of 10 to 50 nm and metal oxide semiconductor fine particles in the range of 50 to 800 nm are mixed and used. .

(2) Other compounds The porous layer in the invention preferably contains a dye sensitizer. It is because the manufacturing process of the dye-sensitized solar cell using the laminated body for dye-sensitized solar cells of this invention can be simplified because the said porous layer contains a dye-sensitizer. The dye sensitizer used in the present invention is not particularly limited as long as it can absorb light and generate an electromotive force. Examples of such a dye sensitizer include organic dyes and metal complex dyes.

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

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

(3) Porous layer The film thickness of the porous layer in the present invention is the film resistance of the porous layer in the dye-sensitized solar cell produced using the laminate for the dye-sensitized solar cell of the present invention. If it is in the range which can be made into a desired value, it will not specifically limit. In particular, the thickness of the porous layer in the present invention is usually preferably in the range of 1 μm to 100 μm, particularly preferably in the range of 5 μm to 30 μm. When the thickness of the porous layer is larger than the above range, the membrane resistance of the porous layer becomes high when the dye-sensitized solar cell is produced using the laminate for the dye-sensitized solar cell of the present invention. This is because it may be too much, and if it is thinner than the above range, it may be difficult to form a porous layer having a uniform thickness.

  The porous layer in the present invention may be composed of a single layer or may be a structure in which a plurality of layers are laminated. In the present invention, the porous layer preferably has a structure in which a plurality of layers are laminated. The constitution of laminating a plurality of layers is arbitrary depending on the method for producing a dye-sensitized solar cell substrate or a dye-sensitized solar cell from the dye-sensitized solar cell laminate of the present invention. The configuration can be appropriately selected and adopted. Among them, in the present invention, a two-layer structure comprising an intervening layer in contact with the heat-resistant substrate as a porous layer, and an oxide semiconductor layer formed on the intervening layer and having a lower porosity than the intervening layer, It is preferable to do. Since the porous layer has a two-layer structure composed of such an oxide semiconductor layer and an intervening layer, the adhesion between the heat-resistant substrate and the porous layer can be reduced. This is because the laminate for a sensitive solar cell can be made suitable for a method for producing a dye-sensitized solar cell substrate by a transfer method.

  When the porous layer has a two-layer structure of the oxide semiconductor layer and the intervening layer, the thickness ratio of the oxide semiconductor layer to the intervening layer is not particularly limited, and the dye-sensitized solar of the present invention What is necessary is just to determine arbitrarily according to the manufacturing conditions etc. which manufacture the base material for dye-sensitized solar cells from the laminated body for batteries. Especially in this invention, it is preferable that the thickness ratio of the said oxide semiconductor layer and the said intervening layer exists in the range of 10: 0.1-10: 5, Especially, it is 10: 0.1-10: 3. It is preferable to be within the range. If the thickness of the intervening layer is larger than the above range, the porous layer may not contain a desired amount of the dye sensitizer. If the thickness is thinner than the above range, the heat resistant substrate and the porous layer may not be contained. When the substrate for a dye-sensitized solar cell is produced from the laminate for the dye-sensitized solar cell of the present invention, it becomes difficult to peel the heat-resistant substrate from the porous layer. Because there is a possibility.

  The porosity of the oxide semiconductor layer is not particularly limited as long as it is within a range in which a desired amount of a dye sensitizer can be included in the porous layer in the present invention. In particular, in the present invention, the porosity of the oxide semiconductor layer is preferably in the range of 10% to 60%, and more preferably in the range of 20% to 50%. If the porosity of the oxide semiconductor layer is smaller than the above range, the function of conducting the charge generated from the dye sensitizer to the first electrode layer may be impaired, and if larger than the above range, This is because there is a possibility that the oxide semiconductor layer cannot contain a desired amount of the dye sensitizer.

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

  In addition, the porosity in this invention shows the nonoccupancy rate of the metal semiconductor fine particle per unit volume. The porosity is calculated based on the result calculated by calculation from the weight per unit area of the oxide semiconductor layer and the intervening layer and the specific gravity of the metal oxide fine particles.

4). Next, the heat resistant substrate in the present invention will be described. The heat-resistant substrate used in the present invention is not particularly limited as long as it has heat resistance with respect to the heating temperature during the baking treatment described later. Examples of such a heat-resistant substrate include a heat-resistant substrate made of glass, ceramics, a metal plate, or the like. In particular, in the present invention, it is preferable to use a flexible metal plate as the heat-resistant substrate. By using such a heat-resistant substrate, the firing treatment described later can be performed at a sufficiently high temperature, so that the binding property between the metal oxide semiconductor fine particles forming the porous layer can be increased. . The heat-resistant substrate is preferably reused.

5. Method for Producing Dye-Sensitized Solar Cell Laminate The method for producing the dye-sensitized solar cell laminate of the present invention is described later in “D. Dye-sensitized solar cell laminate, dye-sensitized with heat-resistant substrate”. Type solar cell base material, dye-sensitized solar cell base material, and method for producing dye-sensitized solar cell ". Since it demonstrates in the term of the manufacturing method of the laminated body for dye-sensitized solar cells, description here is abbreviate | omitted.

B. Next, the dye-sensitized solar cell substrate with a heat-resistant substrate of the present invention will be described. The substrate for a dye-sensitized solar cell with a heat-resistant substrate of the present invention comprises a substrate, an adhesive layer made of a heat-meltable resin, and the laminate for the dye-sensitized solar cell, and the dye-sensitized type The 2nd transparent electrode layer which the laminated body for solar cells has, and the said base material are joined through the said contact bonding layer, It is characterized by the above-mentioned.

  Next, the base material for dye-sensitized solar cells with a heat-resistant substrate of the invention will be described with reference to the drawings. FIG. 2 is a schematic cross-sectional view showing an example of a dye-sensitized solar cell substrate with a heat-resistant substrate of the present invention. As shown in FIG. 2, the base material 20 for dye-sensitized solar cells with a heat-resistant substrate of the present invention includes a base material 11, an adhesive layer 12 made of a heat-meltable resin, and the above-described laminate for dye-sensitized solar cells. The second transparent electrode layer 13 of the dye-sensitized solar cell laminate 10 and the base material 11 are joined via the adhesive layer 12.

  According to the present invention, the dye-sensitized solar cell laminate including the first transparent electrode layer and the second transparent electrode layer and having the first electrode layer excellent in chemical durability and electrical conductivity. A dye-sensitized solar cell base material with excellent heat generation characteristics over time and a dye-sensitized solar cell base material with a heat-resistant substrate capable of easily producing a dye-sensitized solar cell Obtainable.

  Further, the dye-sensitized solar cell substrate with a heat-resistant substrate of the present invention is mainly used for producing a dye-sensitized solar cell substrate, but the heat-resistant substrate-provided dye-sensitized solar cell of the present invention. When a dye-sensitized solar cell substrate is produced from a substrate for a solar cell, it is formed by simply peeling the heat-resistant substrate from the substrate for a dye-sensitized solar cell with a heat-resistant substrate of the present invention as described later. Therefore, no heat treatment is required. Therefore, the base material used for the dye-sensitized solar cell base material with a heat-resistant substrate of the present invention is not limited to those having heat resistance, and a base material made of any material can be appropriately selected and used. .

  Conventionally, in order to obtain a dye-sensitized solar cell substrate having a transparent electrode made of a metal oxide excellent in chemical durability, a transparent electrode made of the above-described metal oxide excellent in scientific durability is prepared. At this time, since heat treatment at a high temperature is required, the base material that can be used for the base material for the dye-sensitized solar cell has been limited to quartz glass, soda glass, etc. excellent in heat resistance. A transparent electrode having flexibility and excellent chemical durability because such a heat-resistant base material, which is industrially usable, is often a rigid material having no flexibility. It was difficult to obtain a dye-sensitized solar cell substrate comprising:

  According to the present invention, since a base material made of any material can be used as the base material, for example, it can be conventionally manufactured by using a flexible resin film base material as the base material. A dye-sensitized solar cell substrate with a heat-resistant substrate that can easily produce a substrate for a dye-sensitized solar cell having a transparent electrode having flexibility and excellent chemical durability. Can be obtained.

  In addition, the porous layer constituting the dye-sensitized solar cell is a porous body and has low mechanical strength. On the other hand, it is responsible for the power generation mechanism of the dye-sensitized solar cell. It is indispensable to handle so as not to damage the porous material in each step until the production of the solar cell, but by using the substrate for a dye-sensitized solar cell with a heat-resistant substrate of the present invention, Since the porous layer can be protected by a heat-resistant substrate until immediately before the production process of the dye-sensitized solar cell, the porous layer may be damaged in the production process of the dye-sensitized solar cell. And a high-performance dye-sensitized solar cell can be manufactured.

  Hereafter, each structure of the base material for dye-sensitized solar cells with a heat-resistant board | substrate of this invention is demonstrated in detail.

1. First, the adhesive layer in the present invention will be described. The adhesive layer used in the present invention is characterized by comprising a heat-meltable resin.

(1) Thermomeltable resin The thermoplastic resin used for the adhesive layer in the present invention is not particularly limited as long as it is a resin that melts at a desired temperature. Among them, in the present invention, the melting point of the thermoplastic resin is preferably in the range of 50 ° C to 200 ° C, particularly preferably in the range of 60 ° C to 180 ° C, and in particular in the range of 65 ° C to 150 ° C. It is preferable that

Examples of the thermoplastic resin having a melting point within the above range include polyethylene, polypropylene, polyisobutylene, polystyrene, polyolefins such as ethylene-propylene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, triacetic acid. Cellulose derivatives such as cellulose, copolymers of poly (meth) acrylic acid and its esters, polyvinyl acetals such as polyvinyl acetate, polyvinyl alcohol and polyvinyl butyral, polyacetals, polyamides, polyimides, nylons, polyester resins, urethane resins, epoxies Examples thereof include a resin, a silicone resin, and a fluororesin. Among these, polyolefin, ethylene-vinyl acetate copolymer, urethane resin, epoxy resin, silane-modified resin, and acid-modified resin are preferable from the viewpoints of adhesiveness, resistance to an electrolytic solution, light transmittance, and transferability.
In the present invention, among the above thermoplastic resins, it is preferable to use a silane-modified resin. This is because the adhesive force exhibited by the adhesive layer can be further strengthened by using the silane-modified resin.

The silane-modified resin used in the present invention is not particularly limited as long as it has the above melting point. Among these, as the silane-modified resin used in the present invention, it is preferable to use a copolymer of a polyolefin compound and an ethylenically unsaturated silane compound.
In the present invention, the copolymer may or may not be crosslinked with a silanol catalyst.

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

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

  The polyethylene resin used in the present invention (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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(2) Adhesive layer The thickness of the adhesive layer used in the present invention is not particularly limited as long as it is within a range in which a necessary adhesive force can be expressed, depending on the type of the thermoplastic resin constituting the adhesive layer. 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 the thermal damage to the base material and the like may increase.

2. Next, the substrate used in the present invention will be described. The base material that can be used in the present invention is not particularly limited as long as it has a desired transparency. Usually, the transmittance for light having a wavelength of 400 nm to 1000 nm is preferably 78% or more, and 80%. More preferably.

Moreover, it is preferable that the base material used for this invention is excellent in heat resistance, a weather resistance, water vapor | steam, and other gas barrier properties among the said transparency. In particular, in the present invention, the oxygen permeability is 1 cc / m ² / day · atm or less under the condition of a temperature of 23 ° C. and a humidity of 90%, and the water vapor permeability is 1 g / day under the condition of a temperature of 37.8 ° C. and a humidity of 100%. It is preferable to use a base material having a gas barrier property of m ² / day or less. In the present invention, in order to achieve such a gas barrier property, a material provided with a gas barrier layer on an arbitrary substrate may be used.

  Examples of the base material having the gas barrier property include transparent flexible materials such as quartz glass, Pyrex (registered trademark) and synthetic quartz plate, ethylene / tetrafluoroethylene copolymer film, biaxially stretched polyethylene terephthalate. Resin films such as film, polyethersulfone (PES) film, polyetheretherketone (PEEK) film, polyetherimide (PEI) film, polyimide (PI) film, polyester naphthalate (PEN), polycarbonate (PC) A substrate can be mentioned.

  In the present invention, it is preferable to use a resin film base material among the above base materials. This is because the resin film base material is excellent in processability, so that it can be easily combined with other devices and the range of applications can be expanded. Moreover, it is because it can contribute also to reduction of manufacturing cost by using a resin-made film base material. Moreover, the base material in this invention may be used individually by 1 type, and may laminate | stack and use 2 or more types. In the present invention, it is particularly preferable to use a biaxially stretched polyethylene terephthalate film (PET), polyester naphthalate (PEN), or polycarbonate (PC) as the substrate.

  The thickness of the substrate used in the present invention is not particularly limited, but it is usually preferably in the range of 50 μm to 2000 μm, particularly preferably in the range of 75 μm to 1800 μm, and more preferably 100 μm to 1500 μm. It is preferable to be within the range.

3. Dye-sensitized solar cell laminate The dye-sensitized solar cell laminate used in the present invention is the same as that described in the above section "A. Dye-sensitized solar cell laminate". Therefore, the description here is omitted.

4). Method for Producing Dye-Sensitized Solar Cell Substrate with Heat Resistant Substrate The method for producing a dye-sensitized solar cell substrate with a heat-resistant substrate according to the present invention is described in “D. Dye-sensitized solar cell laminate, 2. “Dye-sensitized solar cell substrate with heat-resistant substrate, dye-sensitized solar cell substrate, and method for producing dye-sensitized solar cell”. Since it explains in the term of the manufacturing method of a dye sensitizing type photovoltaic cell, explanation here is omitted.

C. Next, the dye-sensitized solar cell substrate of the present invention will be described. The substrate for a dye-sensitized solar cell of the present invention includes a substrate, an adhesive layer formed on the substrate and made of a heat-meltable resin,
A second transparent electrode layer formed on the adhesive layer and made of a second metal oxide, a first transparent electrode layer formed on the second transparent electrode layer and made of the first metal oxide, and the first A porous layer formed on a transparent electrode layer and containing metal oxide semiconductor fine particles, wherein the first metal oxide has higher chemical durability than the second metal oxide. To do.

  Next, the base material for dye-sensitized solar cells of this invention is demonstrated, referring a figure. FIG. 3 is a schematic cross-sectional view showing an example of the dye-sensitized solar cell substrate of the present invention. As shown in FIG. 3, the dye-sensitized solar cell substrate 30 of the present invention includes a substrate 11, an adhesive layer 12 formed on the substrate 11 and made of a heat-meltable resin, and the adhesive layer 12. A second transparent electrode layer 13 made of a second metal oxide, and a first transparent electrode layer 14 made of the first metal oxide and formed on the second transparent electrode layer 13; A substrate for a dye-sensitized solar cell formed on the transparent electrode layer 14 and comprising a porous layer 15 containing metal oxide semiconductor fine particles, wherein the first metal oxide is the second metal oxide. It is characterized by higher chemical durability than metal oxides.

According to the present invention, the first metal oxide is provided with two transparent electrodes, a first transparent electrode layer made of the first metal oxide and a second transparent electrode layer made of the second metal oxide. However, since the chemical durability is higher than that of the second metal oxide, the electrical conductivity of the second transparent electrode layer is not impaired over time, and the dye-sensitized solar cell has excellent chemical durability. A substrate can be obtained.
In the present invention, since the first metal oxide has higher chemical durability than the second metal oxide, not only the second transparent electrode layer but also the adhesive layer is formed by a redox pair. Corrosion can also be suppressed. Therefore, according to the present invention, it is possible to obtain a dye-sensitized solar cell substrate that is excellent in adhesion stability and does not lose the adhesive strength of the adhesive layer over time.

The redox couple used in dye-sensitized solar cells is responsible for the power generation mechanism of dye-sensitized solar cells, but is rich in oxidation and reduction. Those with poor durability have a problem of being eroded by the redox couple.
As such a compound with poor chemical durability, there is a metal oxide constituting a transparent electrode represented by ITO. Since the porous layer used in the dye-sensitized solar cell is porous, it passes through the oxidation-reduction pair, so that the transparent electrode is exposed to the oxidation-reduction pair. One of the problems of dye-sensitized solar cells is that the function is impaired and the power generation characteristics are deteriorated.

  In addition, the oxidation-reduction pair has been confirmed to pass through the transparent electrode, and in a dye-sensitized solar cell using a dye-sensitized solar cell substrate having an adhesive layer, There is a problem that the adhesive layer deteriorates and the adhesive strength stability is impaired.

According to the present invention, the first metal oxide is provided with two transparent electrodes, a first transparent electrode layer made of the first metal oxide and a second transparent electrode layer made of the second metal oxide. However, since the chemical durability is higher than that of the second metal oxide, the second transparent electrode layer can be prevented from being eroded by the redox couple. Therefore, according to the present invention, a dye-sensitized solar cell substrate having excellent temporal stability can be obtained.
Moreover, according to this invention, since it can also suppress that an adhesive layer deteriorates by a redox pair, the base material for dye-sensitized solar cells excellent in the adhesive stability of each layer can be obtained.

  Furthermore, the dye-sensitized solar cell substrate of the present invention can be easily manufactured by using the above-mentioned dye-sensitized solar cell substrate with a heat-resistant substrate. It is also possible to use a resin film substrate having the same. Therefore, according to the present invention, it is possible to obtain a substrate for a dye-sensitized solar cell that includes a transparent electrode that has been difficult to manufacture and has flexibility and excellent chemical durability. it can.

  Hereinafter, each structure of the base material for dye-sensitized solar cells of this invention is demonstrated in detail.

1. 2. Base Material The base material used in the present invention is the above-mentioned “B. Base material for dye-sensitized solar cell with heat-resistant substrate”. Since it is the same as that described in the section of the base material, explanation here is omitted.

2. Adhesive Layer The adhesive layer used in the present invention is the same as that in “B. Dye-sensitized solar cell substrate with heat-resistant substrate” described above. Since it is the same as that described in the section of the adhesive layer, the description here is omitted.

3. 2nd transparent electrode layer The 2nd transparent electrode layer used for this invention is 2 above-mentioned "A. laminated body for dye-sensitized solar cells". Since it is the same as what was described in the term of the 2nd transparent electrode layer, explanation here is omitted.

4). 1st transparent electrode layer The 1st transparent electrode layer used for this invention is 1. above-mentioned "A. laminated body for dye-sensitized solar cells." Since it is the same as what was described in the term of the 1st transparent electrode layer, explanation here is omitted.

5. Porous layer The porous layer used in the present invention is described in “A. Dye-sensitized solar cell substrate” above. Since it is the same as that described in the paragraph of the porous layer, the description here is omitted.

6). Dye-sensitized solar cell substrate The porous layer in the dye-sensitized solar cell substrate of the present invention is preferably patterned. This is because the dye-sensitized solar cell substrate of the present invention can be made suitable for producing a dye-sensitized solar cell having a high module electromotive force by patterning the porous layer. The patterning of the porous layer in the present invention will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing an example of the patterning mode of the porous layer in the present invention. In the patterning of the porous layer in the present invention, it is sufficient that at least the porous layer 15 is patterned as shown in FIG. Moreover, as shown in FIG. 4, when the porous layer 15 consists of the oxide semiconductor layer 15a and the intervening layer 15b, it is preferable that both layers are patterned by the same shape.
Furthermore, as a patterning aspect of the porous layer in the present invention, the porous layer 15, the first transparent electrode layer 14, and the second transparent electrode layer 13 are preferably patterned. When the porous layer 15, the first transparent electrode layer 14, and the second transparent electrode layer 13 are patterned, the patterning shapes may be the same or different.

  In the present invention, when the porous layer is patterned, the pattern can be arbitrarily determined according to the use of the dye-sensitized solar cell substrate of the present invention. Is most preferable.

7). Method for Producing Dye-Sensitized Solar Cell Substrate The method for producing the dye-sensitized solar cell substrate of the present invention is described later in “D. Dye-sensitized solar cell laminate, dye-sensitized with heat-resistant substrate”. Type solar cell substrate, dye-sensitized solar cell substrate, and method for producing dye-sensitized solar cell ", 3. Since it demonstrates in the term of the manufacturing method of the base material for dye-sensitized solar cells, description here is abbreviate | omitted.

D. Next, the dye-sensitized solar cell of the present invention will be described. The dye-sensitized solar cell according to the present invention includes the above-described dye-sensitized solar cell base material, a counter electrode base material including a second electrode layer and a counter base material, and an electrolyte layer including a redox pair. A dye-sensitized solar cell, wherein the porous layer of the dye-sensitized solar cell substrate and the second electrode layer of the counter electrode substrate are opposed to each other with the electrolyte layer interposed therebetween. It is characterized by being arranged.

  Next, the dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view showing an example of the dye-sensitized solar cell in the present invention. As shown in FIG. 5, the dye-sensitized solar cell 40 according to the present invention includes the dye-sensitized solar cell substrate 30, a counter electrode substrate 50 including the second electrode layer 18 and the counter substrate 19. The porous layer 15 included in the dye-sensitized solar cell base material 30 and the second electrode layer 18 included in the counter electrode base material 50. It is disposed so as to face the electrolyte layer 17.

  According to the present invention, by using the dye-sensitized solar cell substrate, the transparent electrode composed of the first transparent electrode layer and the second transparent electrode layer is eroded by the redox pair. Therefore, the electrical conductivity can be stably maintained for a long time. Therefore, according to the present invention, it is possible to obtain a dye-sensitized solar cell excellent in the temporal stability of power generation efficiency. Further, according to the present invention, by using the dye-sensitized solar cell base material using a resin film base material as the base material, it has been difficult to manufacture conventionally, and has flexibility. In addition, a dye-sensitized solar cell including a transparent electrode that is excellent in chemical durability can be easily obtained.

  Hereafter, each structure of the dye-sensitized solar cell of this invention is demonstrated in detail.

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

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

(2) Other compounds The electrolyte layer in the present invention preferably contains a polymer compound that retains the redox couple. It is because the distribution of the redox couple in the electrolyte layer can be made uniform by containing such a polymer compound. The polymer compound holding the redox pair is not particularly limited as long as it has a hole transporting property, and for example, CuI, polypyrrole, or polythiophene can be used.

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

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

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

(1) 2nd electrode layer The 2nd electrode layer in this invention is 2. above-mentioned "A. laminated body for dye-sensitized solar cells." Since it is the same as what was described in the term of the 2nd transparent electrode layer, explanation here is omitted.

(2) Opposite base material The second electrode layer in the present invention is the same as that described in “B. Base material for dye-sensitized solar cell with heat-resistant substrate”. Since it is the same as that described in the section of the base material, explanation here is omitted.

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

3. Dye-sensitized solar cell substrate The dye-sensitized solar cell substrate in the present invention is the same as that described in the above section "C. Dye-sensitized solar cell substrate". The description in is omitted.

4). Method for Producing Dye-Sensitized Solar Cell The method for producing the dye-sensitized solar cell of the present invention is described later in “D. Dye-sensitized solar cell laminate, for dye-sensitized solar cell with heat-resistant substrate”. 4. “Substrate, dye-sensitized solar cell substrate, and method for producing dye-sensitized solar cell”. Since it explains in the term of the manufacturing method of a dye sensitizing type photovoltaic cell, explanation here is omitted.

  D. Dye-sensitized solar cell laminate, dye-sensitized solar cell substrate with heat-resistant substrate, dye-sensitized solar cell substrate, and method for producing dye-sensitized solar cell

  Next, a laminate for a dye-sensitized solar cell, a dye-sensitized solar cell substrate with a heat-resistant substrate, a dye-sensitized solar cell substrate, and a method for producing a dye-sensitized solar cell according to the present invention Will be described. The base material for dye-sensitized solar cells of the present invention can be used for producing the base material for dye-sensitized solar cells with a heat-resistant substrate of the present invention. Moreover, the base material for dye-sensitized solar cells with a heat-resistant board | substrate of this invention can be used for manufacture of the base material for dye-sensitized solar cells of this invention. Furthermore, the base material for dye-sensitized solar cells of this invention can be used for manufacture of the dye-sensitized solar cell of this invention. Therefore, hereinafter, from the laminate for the dye-sensitized solar cell of the present invention, a dye-sensitized solar cell substrate with a heat-resistant substrate, a dye-sensitized solar cell substrate, and a dye-sensitized solar cell Each manufacturing method will be described in detail in order.

1. First, the manufacturing method of the laminated body for dye-sensitized solar cells of this invention is demonstrated. The method for producing the laminate for the dye-sensitized solar cell of the present invention is not particularly limited as long as each layer constituting the laminate for the dye-sensitized solar cell can be formed uniformly, but usually on a heat-resistant substrate. A porous layer forming layer forming step of applying a porous layer forming coating liquid containing organic matter and metal oxide semiconductor fine particles, and solidifying to form a porous layer forming layer; and
A porous body is formed by firing the porous layer forming layer, and a firing step for forming a porous layer;
A first transparent electrode layer forming step of forming a first transparent electrode layer made of a first metal oxide on the porous layer;
A second transparent electrode layer forming step of forming a second transparent electrode layer made of a second metal oxide on the first transparent electrode layer;
It is preferable to produce a laminate for a dye-sensitized solar cell by a production method comprising: This is because according to such a method, it is possible to produce a laminate for a dye-sensitized solar cell in which each layer is uniformly formed with high productivity.

Further, in the method for producing the laminate for a dye-sensitized solar cell, the porous layer forming layer forming step is performed in order to make the porous layer into a two-layer structure including the intervening layer and the oxide semiconductor layer. However, the intermediate layer forming layer forming step of forming an intervening layer forming layer by applying and solidifying a coating liquid for forming an intervening layer containing an organic substance and metal oxide semiconductor fine particles on a heat-resistant substrate,
On the intervening layer forming layer, an oxide semiconductor layer forming coating solution having a higher concentration in the solid content of the metal oxide semiconductor fine particles than the intervening layer forming coating solution is applied and solidified to form an oxide. And an oxide semiconductor layer forming layer forming step of forming a semiconductor layer forming layer.

Next, the manufacturing method of the said laminated body for dye-sensitized solar cells is demonstrated, referring a figure. FIG. 6 is a process diagram showing an example of a method for producing a laminate for a dye-sensitized solar cell of the present invention. As shown in FIG. 6 (a), the method for producing a laminate for a dye-sensitized solar cell is such that an intervening layer forming coating solution is applied on a heat-resistant substrate 16 and solidified to solidify the intervening layer forming layer. An intermediate layer forming layer forming step for forming 25b;
As shown in FIG. 6 (b), an oxide semiconductor layer forming layer 25a is formed by applying an oxide semiconductor layer forming coating solution onto the intervening layer forming layer 25b and solidifying it. Layer forming step,
As shown in FIG. 6C, the intervening layer, which is a porous body having communication holes, is obtained by heating and baking the heat-resistant substrate on which the intervening layer forming layer 25b and the oxide semiconductor layer forming layer 25a are laminated. A baking step of forming 15b and the oxide semiconductor layer 15a;
As shown in FIG.6 (d), the 1st transparent electrode layer formation process which forms the 1st transparent electrode layer 14 on the oxide semiconductor layer 15a,
As shown in FIG. 6 (e), the dye-sensitized solar cell laminate 10 is formed by the second transparent electrode layer forming step of forming the second transparent electrode layer 13 on the first transparent electrode layer 14. It is a manufacturing method.

  Hereinafter, the manufacturing method of the laminated body for dye-sensitized solar cells of the present invention will be described separately for each step.

(1) Interlayer Forming Layer Forming Step First, the intervening layer forming layer forming step in the present invention will be described. The intervening layer forming layer forming step in the present invention is a step of forming an intervening layer forming layer by applying and solidifying the intervening layer forming coating solution on the heat-resistant substrate.

  The intervening layer forming layer here means a layer formed by applying and solidifying an intervening layer forming coating solution. Moreover, the intervening layer mentioned later means what was formed as a porous body by baking the said layer for intervening layer formation. In the present invention, the intervening layer means either a case where a dye sensitizer described later is contained or a case where a dye sensitizer described later is not contained.

(1-1) Intervening Layer Forming Coating Liquid First, the intervening layer forming coating liquid used in this step will be described. The intervening layer forming coating solution used in this step contains at least metal oxide semiconductor fine particles and an organic substance.

a. Metal Oxide Semiconductor Fine Particles The metal oxide semiconductor fine particles used in the coating liquid for forming the intervening layer in this step are the same as those described in “A. Dye-sensitized solar cell laminate”. Since it is the same as that described in the paragraph of the porous layer, the description here is omitted.

  The concentration of the metal oxide semiconductor fine particles in the solid content of the intervening layer forming coating solution may be lower than the concentration of the metal oxide semiconductor fine particles in the solid content of the oxide semiconductor layer forming coating solution described later. Although not particularly limited, specifically, it is preferably in the range of 20% by mass to 80% by mass, and more preferably in the range of 30% by mass to 70% by mass. If the coating liquid for forming an intervening layer contains metal oxide semiconductor fine particles in the above range, the oxide semiconductor is interposed through the layer for forming an intervening layer formed using such a coating liquid for forming an intervening layer. This is because by forming the layer forming layer, appropriate adhesion and excellent peelability can be imparted between the heat-resistant substrate and the oxide semiconductor layer forming layer.

  Further, the concentration of the metal oxide semiconductor fine particles in the intervening layer forming coating solution may be arbitrarily determined according to the application method of the intervening layer forming coating solution described later, but is usually 0.01. It is preferable to be in the range of 30% by mass to 30% by mass, and it is particularly preferable to be in the range of 0.1% to 15% by mass.

b. Organic Material Next, the organic material used for the intervening layer forming coating solution will be described. The organic substance used in the intervening layer forming coating solution is not particularly limited as long as it is easily decomposed in the baking step described later. In particular, in the present invention, it is preferable to use a synthetic resin as the organic substance. This is because the synthetic resin can obtain a compound having a desired thermal decomposability by arbitrarily selecting the molecular weight and material, and thus has advantages such as less restrictions on the processing conditions of the baking treatment described later.

  The synthetic resin is not particularly limited as long as it is difficult to dissolve in the solvent used in the oxide semiconductor layer forming coating liquid described later. Among them, in the present invention, the weight average molecular weight of the synthetic resin is preferably in the range of 2000 to 600000, particularly preferably in the range of 5000 to 300000, and in particular in the range of 10000 to 200000. . When the molecular weight of the synthetic resin is larger than the above range, thermal decomposition in the baking step described later may be insufficient, and when the molecular weight is smaller than the above range, the viscosity of the coating liquid for forming the intervening layer is low. This is because the metal oxide semiconductor fine particles may be aggregated.

  Specific examples of the synthetic resin used in the present invention include cellulose resins such as ethyl cellulose, methyl cellulose, nitrocellulose, acetyl cellulose, acetyl ethyl cellulose, cellulose propionate, hydroxypropyl cellulose, butyl cellulose, benzyl cellulose, and nitrocellulose, or An acrylic resin comprising a polymer or copolymer such as methyl methacrylate, ethyl methacrylate, tertiary butyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, 2-ethyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, Examples thereof include polyhydric alcohols such as polyethylene glycol. In the present invention, one kind of these synthetic resins may be used as a simple substance, or two or more kinds of synthetic resins may be mixed and used.

  The content of the organic substance in the coating liquid for forming the intervening layer should be within a range that can provide the intervening layer with a porous property that can peel off the heat-resistant substrate with a desired peeling force in the heat-resistant substrate peeling step described later. There is no particular limitation. Among these, the content of the organic substance in the intervening layer forming coating liquid in the present invention is preferably within a range of 0.01% by mass to 30% by mass with respect to the intervening layer forming coating liquid. It is preferably in the range of 1% by mass to 15% by mass. If the content of the organic substance is less than the above range, the peeling load of the heat-resistant substrate in the peeling step described later is high, which may be disadvantageous in terms of productivity, and the content is more than the above range. This is because the intervening layer may be peeled off from the heat-resistant substrate after heating and baking.

c. Solvent The coating liquid for forming the intervening layer may be a coating liquid that does not contain a solvent, or may be a coating liquid that contains a solvent. When a solvent is contained in the coating liquid for forming the intervening layer, it is preferable that the solvent is a good solvent with respect to the organic substance to be used. The appropriate selection is made in consideration of the above. Specifically, ketones, hydrocarbons, esters, alcohols, halogenated hydrocarbons, glycol derivatives, ethers, ether esters, amides, acetates, ketone esters, glycol ethers, sulfones And sulfoxides. These may be used alone or in combination of two or more. Among these, organic solvents such as acetone, methyl ethyl ketone, toluene, methanol, isopropyl alcohol, normal propyl alcohol, normal butanol, isobutanol, terpineol, ethyl cellosolve, butyl cellosolve, and butyl carbitol are preferable. This is because the coating liquid for forming the intervening layer is applied onto the heat-resistant substrate, and therefore can be applied onto the heat-resistant substrate with good wettability by using the organic solvent.

d. Additives In addition, various additives may be used in the coating liquid for forming the intervening layer in order to improve the coating suitability for the heat-resistant substrate. As the additive, for example, a surfactant, a viscosity modifier, a dispersion aid, a pH adjuster and the like can be used. Examples of the pH adjuster include nitric acid, hydrochloric acid, acetic acid, dimethylformamide, ammonia and the like. Examples of the dispersion aid include polymers such as polyethylene glycol, hydroxyethyl cellulose, and carboxymethyl cellulose, surfactants, acids, and chelating agents.

(1-2) Heat-resistant substrate As the heat-resistant substrate used in this step, the “A. Dye-sensitized solar cell laminate” described in “4. Since it is the same as that described in the section of the heat-resistant substrate, explanation here is omitted.

(1-3) Formation method of intervening layer forming layer In this step, the method for applying the intervening layer forming coating liquid onto the heat-resistant substrate is not particularly limited as long as it is a known application method. Specifically, die coat, gravure coat, gravure reverse coat, roll coat, reverse roll coat, bar coat, blade coat, knife coat, air knife coat, slot die coat, slide die coat, dip coat, micro bar coat, micro bar reverse coat And screen printing (rotary method). Using such a coating method, the intervening layer forming layer can be adjusted to a desired film thickness by repeating coating and solidification one or more times.

(1-4) Intervening Layer Forming Layer The thickness of the intervening layer forming layer obtained by this step is not particularly limited, but when it is formed as a porous body in the firing step described below, “ It is preferable to adjust and determine the film thickness as described in “(3) Firing step”. Specifically, it is preferably within a range of 0.01 μm to 30 μm, and more preferably within a range of 0.05 μm to 6 μm.

(2) Oxide Semiconductor Layer Formation Layer Formation Step Next, the oxide semiconductor layer formation layer formation step will be described. The oxide semiconductor layer forming layer forming step in the present invention includes an oxide semiconductor layer having a higher concentration in the solid content of the metal oxide semiconductor fine particles than the intermediate layer forming coating liquid on the intermediate layer forming layer. In this step, a forming coating solution is applied and solidified to form an oxide semiconductor layer forming layer.

  The oxide semiconductor layer forming layer here means a layer formed by applying and solidifying an oxide semiconductor layer forming coating solution. In addition, in this invention, an oxide semiconductor layer means in any case of containing the dye sensitizer mentioned later, when not containing the dye sensitizer mentioned later.

(2-1) Oxide semiconductor layer forming coating solution The oxide semiconductor layer forming coating solution used in this step will be described. The coating solution for forming an oxide semiconductor layer used in this step contains at least metal oxide semiconductor fine particles and a resin, and the solid content of the metal oxide semiconductor fine particles is higher than that of the coating solution for forming an intervening layer. The density inside is adjusted high.

a. Metal Oxide Semiconductor Fine Particles The metal oxide semiconductor fine particles used in the oxide semiconductor layer forming coating solution in this step are the same as those described in “A. Dye-sensitized solar cell laminate” above. Since it is the same as that described in the paragraph of the porous layer, the description here is omitted.

  The content of the metal oxide semiconductor fine particles in the oxide semiconductor layer forming coating solution is not particularly limited as long as the desired amount of the dye sensitizer can be contained in the porous layer. In the present invention, the content of the metal oxide semiconductor fine particles is usually preferably in the range of 50% by mass to 100% by mass, particularly 65% by mass to 90% by mass in the solid content of the coating liquid for forming an oxide semiconductor layer. % Is preferable. By using such a coating liquid for forming an oxide semiconductor layer, a sufficient amount of a dye sensitizer is supported on the pore surface of the oxide semiconductor layer formed as a porous body obtained after the firing step. This is because, in the finally obtained oxide semiconductor layer, the function of conducting charges generated from the dye sensitizer by light irradiation can be sufficiently obtained.

  Further, the concentration of the metal oxide semiconductor fine particles with respect to the coating solution for forming an oxide semiconductor layer may be arbitrarily determined depending on the application method of the coating solution for forming an oxide semiconductor layer, which will be described later. It is preferable to be in the range of 10% by mass to 40% by mass.

b. Resin The resin used in this step is used for imparting pores of the porous body by the firing step described later. Moreover, the viscosity of the coating liquid for oxide semiconductor layer formation can be adjusted by changing the usage-amount of resin.

  The content of the resin in the coating solution for forming an oxide semiconductor layer is not particularly limited as long as the desired porosity can be obtained. In the present invention, it is usually preferably in the range of 0.1% by mass to 30% by mass, particularly in the range of 0.5% by mass to 20% by mass with respect to the coating solution for forming an oxide semiconductor layer. Among them, the range of 1% by mass to 10% by mass is preferable.

  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.

c. Solvent The coating liquid for forming an oxide semiconductor layer used in this step may be a coating liquid that does not contain a solvent, or may be a coating liquid that contains a solvent. When a solvent is used in the coating solution for forming an oxide semiconductor layer, the above-described resin dissolves, and the organic substance used to form the above-described intervening layer-forming layer is difficult to dissolve. There is no particular limitation. Specific examples include water or various solvents such as methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, terpineol, dichloromethane, acetone, acetonitrile, and ethyl acetate. Among these, water or an alcohol solvent is preferable. This is because water or an alcohol-based solvent is not mixed with the organic solvent used for the intervening layer forming coating solution, and thus can prevent the intervening layer forming layer and the oxide semiconductor layer forming layer from mixing. .

d. Additives In this step, various additives may be used in order to improve the coating suitability of the coating solution for forming an oxide semiconductor layer. For example, as the additive, a surfactant, a viscosity modifier, a dispersion aid, a pH adjuster, and the like can be used. Since there is, explanation here is omitted. In this step, it is particularly preferable to use polyethylene glycol as a dispersion aid. This is because, by changing the molecular weight of polyethylene glycol, the viscosity of the dispersion can be adjusted, and an oxide semiconductor layer that does not easily peel off can be formed, and the porosity of the oxide semiconductor layer can be adjusted.

(2-2) Method for Forming Oxide Semiconductor Layer Forming Layer In this step, the method for coating the oxide semiconductor layer forming coating liquid on the intervening layer forming layer may be a known coating method. Although not particularly limited, it is specifically the same as that described in “(1) Layer forming step for forming an intervening layer”, and therefore the description thereof is omitted here.

(2-3) Oxide semiconductor layer forming layer The film thickness of the oxide semiconductor layer forming layer obtained in this step is dye sensitization by light irradiation when it is finally formed as an oxide semiconductor layer. There is no particular limitation as long as the function of conducting charges generated by the agent can be sufficiently obtained. For example, when it is formed as a porous body in a firing step described later, it is preferably adjusted and determined so as to have the film thickness described in “(3) firing step” described later. Specifically, it is preferably in the range of 1 μm to 65 μm, and more preferably in the range of 5 μm to 30 μm.

(3) Firing step Next, the firing step in the present invention will be described. The firing step in the present invention is a step of forming the intervening layer and the oxide semiconductor layer by firing the intervening layer forming layer and the oxide semiconductor layer forming layer into a porous body. By this step, an intervening layer and an oxide semiconductor layer formed as a porous body having communication holes can be formed.

  The firing temperature in the firing step is not particularly limited as long as it is within a range in which the organic matter and the resin contained in the intervening layer forming layer and the oxide semiconductor layer forming layer can be thermally decomposed. It is preferable to be within the range of ° C., and it is particularly preferable to be within the range of 350 ° C. to 600 ° C. In the present invention, since a heat-resistant substrate having excellent heat resistance is used, firing in a high temperature range within the above range is possible, and the binding property between the metal oxide semiconductor fine particles in the intervening layer and the oxide semiconductor layer. It is because it can form well.

  In this step, as a heating method for firing the intermediate layer forming layer and the oxide semiconductor layer forming layer, the intermediate layer forming layer and the oxide semiconductor layer forming layer are uniformly fired without heating unevenness. There is no particular limitation as long as it can be performed. Specifically, a known heating method can be used.

  In addition, the film thickness and film thickness ratio of the intervening layer and the oxide semiconductor layer formed as a porous body by this step are the same as those described in “3. Since it is the same as that described in the paragraph of the porous layer, the description here is omitted.

(4) First Transparent Electrode Layer Forming Step Next, the first transparent electrode layer forming step in the present invention will be described. The 1st transparent electrode layer formation process in this invention is a process of forming the 1st transparent electrode layer which consists of a 1st transparent electrode layer on the said oxide semiconductor layer.

  The method for forming the first transparent electrode layer is not particularly limited as long as it is a method for forming a homogeneous first transparent electrode layer on the oxide semiconductor layer. For example, a vacuum deposition method is used. Examples thereof include PVD methods such as sputtering method and ion plating method, dry film forming methods such as CVD methods such as plasma CVD, thermal CVD, and atmospheric pressure CVD, and spray pyrolysis methods. Of these, the spray pyrolysis method is preferred in the present invention. This is because the spray pyrolysis method is an atmospheric process, so it is low-cost. Further, when the spray pyrolysis method is similarly performed in the second transparent electrode layer forming step described later, it is easy to simplify the process. is there.

(4-1) Spray pyrolysis method The spray pyrolysis method in this step will be described. Specifically, the spray pyrolysis method in this step includes heating the oxide semiconductor layer to a temperature equal to or higher than the first transparent electrode layer formation temperature, and including a metal salt or metal containing the metal element contained in the first metal oxide. In this method, the first transparent electrode layer is formed on the oxide semiconductor layer by contacting with the first transparent electrode layer forming coating solution in which the complex is dissolved.

  In the present invention, the “first transparent electrode layer forming temperature” means a metal constituting the first transparent electrode layer by combining a metal element contained in a first transparent electrode layer forming coating liquid described later with oxygen. This refers to the temperature at which an oxide film can be formed. Kinds of metal ions, etc. formed by dissolving metal salts or metal complexes (hereinafter sometimes referred to as metal sources), for forming the first transparent electrode layer It varies greatly depending on the composition of the coating solution. In this step, such “first transparent electrode layer forming temperature” can be measured by the following method. That is, a first transparent electrode layer is prepared by preparing a first transparent electrode layer-forming coating solution in which a desired metal source is actually dissolved, and changing the heating temperature of the oxide semiconductor layer to make contact. The lowest heating temperature at which the metal oxide film can be formed is measured. This minimum heating temperature can be used as the “first transparent electrode layer forming temperature” in the present invention. At this time, whether or not the metal oxide film is formed is usually judged from the result obtained from an X-ray diffraction apparatus (Rigaku, RINT-1500). In the case of an amorphous film having no crystallinity, photoelectron spectroscopy is performed. It shall judge from the result obtained from the analyzer (the product made by VG Scientific, ESCALAB 200i-XL).

a. First Transparent Electrode Layer Forming Coating Liquid The first transparent electrode layer forming coating liquid used in the spray pyrolysis method will be described. The first transparent electrode layer forming coating solution used in the spray pyrolysis method is obtained by dissolving a metal source having a metal element constituting the first transparent electrode layer in a solvent. The first transparent electrode layer forming coating solution preferably contains at least one of an oxidizing agent and a reducing agent. This is because the first transparent electrode layer can be obtained at a lower heating temperature by containing at least one of the oxidizing agent and the reducing agent.

i) Metal source The metal source used in the spray pyrolysis method may be a metal salt or a metal complex as long as it has the metal element contained in the first metal oxide. The “metal complex” in the present invention includes a metal ion coordinated with an inorganic substance or an organic substance, or a so-called organometallic compound having a metal-carbon bond in the molecule.

  The concentration of the metal source with respect to the first transparent electrode layer forming coating solution is not particularly limited as long as it is a concentration capable of obtaining the first transparent electrode layer, but usually when the metal source is a metal salt. 0.001-1 mol / l, preferably 0.01-0.5 mol / l. When the metal source is a metal complex, it is usually 0.001-1 mol / l. It is preferable that it is -0.5 mol / l. If the concentration is less than the above range, it may take too much time to form the first transparent electrode layer. If the concentration exceeds the above range, a first transparent electrode layer having a uniform thickness can be obtained. This is because it may not be possible.

  Examples of the metal element constituting the first transparent electrode layer include those described in 1. A. Laminate for Dye-Sensitized Solar Cell. Since the metal oxide described in the section of the first transparent electrode layer and (1) the first metal oxide has, description thereof is omitted here.

  Examples of the metal salt that gives the metal element included in the first metal oxide include chlorides, nitrates, sulfates, perchlorates, acetates, phosphates, bromates, and the like containing the metal elements. Can be mentioned. Among these, in the present invention, it is preferable to use chloride, nitrate, and acetate. This is because these compounds are easily available as general-purpose products.

In the spray pyrolysis method, the first transparent electrode layer forming coating solution may contain two or more kinds of the metal sources. When the first metal oxide is FTO, the fluorine doping source is not particularly limited as long as it is a fluorine compound that is thermally decomposed at a desired temperature. In the present invention, ammonium fluoride (NH ₄ F) is used. Can be suitably used. Examples of tin raw materials include chlorides such as tin (II) chloride and other nitrates, sulfates, perchlorates, acetates, phosphates, bromates, etc. Products, nitrates and acetates are preferred.

ii) Oxidizing agent The oxidizing agent used in the spray pyrolysis method has a function of promoting the oxidation of metal ions and the like formed by dissolving the above-described metal source. By changing the valence of metal ions or the like, an environment in which the first transparent electrode layer (metal oxide film) is easily generated can be obtained, and the first transparent electrode layer can be obtained at a lower heating temperature.

  The concentration of such an oxidizing agent is not particularly limited as long as it is a concentration capable of obtaining the second transparent electrode layer at a lower heating temperature, but is usually 0.001 to 1 mol / l, It is preferable that it is 0.01-0.1 mol / l. This is because if the concentration is less than the above range, the oxidizing agent may not exhibit the effect, and if the concentration exceeds the above range, the obtained effect is not greatly different and is not preferable in terms of cost.

  The oxidizing agent is not particularly limited as long as it can be dissolved in a solvent described later and promote the oxidation of the metal ions and the like. Examples thereof include sodium, potassium nitrite, sodium bromate, potassium bromate, silver oxide, dichromic acid, potassium permanganate and the like. Among them, hydrogen peroxide and sodium nitrite are preferably used.

iii) Reducing agent The reducing agent used in the spray pyrolysis method emits electrons by a decomposition reaction and generates hydroxide ions by water electrolysis or the like, and the first transparent electrode layer-forming coating solution. It has a function of raising the pH. When the pH of the first transparent electrode layer forming coating solution is increased, the second transparent electrode layer (metal oxide film) can be easily generated and the second transparent electrode can be formed at a lower heating temperature. A layer can be obtained.

  The concentration of such a reducing agent is not particularly limited as long as the first transparent electrode layer can be obtained at a lower heating temperature. However, when the metal source is a metal salt, the concentration is usually 0.001. 1 to 1 mol / l, preferably 0.01 to 0.1 mol / l. When the metal source is a metal complex, it is usually 0.001 to 1 mol / l, and particularly 0.01 to 0.1 mol / l. It is preferably 1 mol / l. This is because when the concentration is less than the above range, the reducing agent may not exhibit an effect, and when the concentration exceeds the above range, a large difference is not seen in the obtained effect, which is not preferable in terms of cost.

  Further, such a reducing agent is not particularly limited as long as it can be dissolved in a solvent described later and can emit electrons by a decomposition reaction. For example, a borane-tert-butylamine complex, Examples include borane complexes such as borane-N, N diethylaniline complex, borane-dimethylamine complex, borane-trimethylamine complex, sodium cyanoborohydride, sodium borohydride, etc., among which borane complex is used. Is preferred.

  Moreover, in this process, even if it uses combining a reducing agent and the oxidizing agent mentioned above, it can be set as the environment where a 1st transparent electrode layer (metal oxide film) is easy to form. Such a combination of a reducing agent and an oxidizing agent is not particularly limited. For example, a combination of hydrogen peroxide or sodium nitrite and an arbitrary reducing agent, or an arbitrary oxidizing agent and a borane complex. The combination etc. are mentioned, Especially, the combination of hydrogen peroxide and a borane-type complex is preferable.

iv) Additive The second transparent electrode layer forming coating solution used in the spray pyrolysis method may contain an additive. Examples of such additives include auxiliary ion sources and surfactants. The auxiliary ion source reacts with electrons to generate hydroxide ions, and raises the pH of the first transparent electrode layer forming coating solution so that the first transparent electrode layer can be easily formed. Can do. The amount of the auxiliary ion source used is preferably selected and used in accordance with the metal salt and reducing agent used. Specific examples of such auxiliary ion sources include chlorate ions, perchlorate ions, chlorite ions, hypochlorite ions, bromate ions, hypobromate ions, nitrate ions, and nitrite ions. Ionic species selected from the group consisting of

  The surfactant acts on the interface between the first transparent electrode layer forming coating solution and the oxide semiconductor layer, and has a function of easily forming a metal oxide film on the surface of the first transparent electrode layer. It is. The amount of the surfactant used is preferably appropriately selected according to the metal salt and reducing agent to be used. Such surfactants are specifically Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 504, Surfinol GA, Surfinol 104A, Surfinol 104BC, Surfinol 104PPM, Surfinol 104E, Surfynol series such as Surfinol 104PA (all manufactured by Nissin Chemical Industry Co., Ltd.), NIKKOL AM301, NIKKOL AM313ON (all manufactured by Nikko Chemical Co., Ltd.) and the like can be mentioned.

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

b. Next, a contact method between the first transparent electrode layer forming coating solution and the oxide semiconductor layer in the spray pyrolysis method will be described. . The contact method in the spray pyrolysis method is not particularly limited as long as it is a method of bringing the first transparent electrode layer forming coating liquid and the oxide semiconductor layer into contact with each other. When the coating solution for forming 1 transparent electrode layer and the oxide semiconductor layer are in contact with each other, it is preferable that the temperature of the heated oxide semiconductor layer is not lowered. This is because if the temperature of the oxide semiconductor layer is lowered, a desired first transparent electrode layer may not be obtained.

  A method for not lowering the temperature is not particularly limited. For example, a method of bringing the oxide semiconductor layer into contact with the first transparent electrode layer by spraying the first transparent electrode layer forming coating liquid as droplets. And a method of passing the oxide semiconductor layer through a space in which the first transparent electrode layer forming coating solution is mist-shaped.

  Although the method of making it contact by spraying the said coating liquid for 1st transparent electrode layer formation is not specifically limited, For example, the method of spraying using a spray apparatus etc. is mentioned. As such a method, for example, the oxide semiconductor layer is heated to a temperature equal to or higher than the first transparent electrode layer forming temperature, and the first transparent electrode layer forming coating liquid is sprayed using a spray device, thereby Examples thereof include a method of forming one transparent electrode layer.

  When spraying using the said spray apparatus, the diameter of a droplet is 0.1-1000 micrometers normally, It is preferable that it is 0.5-300 micrometers especially. This is because if the diameter of the droplet is within the above range, the temperature drop can be suppressed and a uniform first transparent electrode layer can be obtained. Moreover, as spray gas of the said spray apparatus, air, nitrogen, argon, helium, oxygen etc. can be mentioned, for example. In addition, the injection amount of the injection gas is preferably 0.1 to 50 l / min, and more preferably 1 to 20 l / min.

  On the other hand, as a method for allowing the oxide semiconductor layer to pass through the space in which the first transparent electrode layer forming coating liquid is made mist, the first transparent electrode layer forming coating liquid is made mist, for example. A method of forming the first transparent electrode layer by passing an oxide semiconductor layer heated to a temperature equal to or higher than the first transparent electrode layer forming temperature through the space. In such a method, the diameter of the droplet is usually 0.1 to 300 μm, and preferably 1 to 100 μm. This is because when the diameter of the droplet is within the above range, the temperature drop of the oxide semiconductor layer can be suppressed, and a uniform first transparent electrode layer can be obtained.

  Further, in the spray pyrolysis method, when the first transparent electrode layer forming coating solution and the heated oxide semiconductor layer are brought into contact with each other, the oxide semiconductor layer has a “first transparent electrode layer forming temperature”. It is heated to a temperature above that. Such “first transparent electrode layer forming temperature” varies greatly depending on the type of metal ions and the like formed by dissolving the metal source, the composition of the first transparent electrode layer forming coating solution, and the like. It can be set within the range of from 380C to 600C, and it is particularly preferable to be within the range of from 380C to 550C.

  In addition, the heating method is not particularly limited, and examples thereof include a heating method such as a hot plate, an oven, a baking furnace, an infrared lamp, and a hot air blower. A method capable of contacting the first transparent electrode layer forming coating solution while maintaining the temperature at the above temperature is preferable, and specifically, a hot plate or the like is preferably used.

(5) Second Transparent Electrode Layer Forming Step Next, the second transparent electrode layer forming step in the present invention will be described. The second transparent electrode layer forming step in the present invention is a step of providing a second transparent electrode layer on the first transparent electrode layer.

  In this step, the method of providing the second transparent electrode layer on the first transparent electrode layer is not particularly limited as long as it is a method that is excellent in conductivity and can form a homogeneous second transparent electrode layer. Instead, for example, PVD methods such as vacuum deposition, sputtering, and ion plating, and dry film formation methods such as plasma CVD, thermal CVD, and atmospheric pressure CVD, and spray pyrolysis, etc. Among them, the spray pyrolysis method is preferable in the present invention. This is because a second transparent electrode layer having better denseness can be formed.

(5-1) Spray pyrolysis method The spray pyrolysis method in this step will be described. Specifically, in the spray pyrolysis method in this step, the first transparent electrode layer is heated to a temperature equal to or higher than the second transparent electrode layer formation temperature, and a metal salt or metal containing a metal element contained in the second metal oxide In this method, the second transparent electrode layer is formed on the first transparent electrode layer by contacting with the coating solution for forming the second transparent electrode layer in which the complex is dissolved.

In the present invention, the “second transparent electrode layer forming temperature” means a metal constituting the first transparent electrode layer by combining a metal element contained in a second transparent electrode layer forming coating liquid described later with oxygen. The temperature at which the oxide film can be formed refers to a temperature that varies greatly depending on the type of metal ion or the like in which the metal source is dissolved, the composition of the second transparent electrode layer forming coating solution, and the like.
In addition, such “second transparent electrode layer forming temperature” is obtained by preparing a coating solution for forming a second transparent electrode layer in which a desired metal source is actually dissolved. It can be determined by the same method as the measurement method described in “Electrode layer forming step”.

a. Second Transparent Electrode Layer Forming Coating Liquid The second transparent electrode layer forming coating liquid used in the spray pyrolysis method will be described. The second transparent electrode layer forming coating solution used in the spray pyrolysis method is a solution in which a metal salt or metal complex containing a metal element contained in the second metal oxide is dissolved in a solvent. In the spray pyrolysis method, the second transparent electrode layer forming coating solution preferably contains at least one of an oxidizing agent and a reducing agent. This is because the second transparent electrode layer can be obtained at a lower heating temperature by containing at least one of the oxidizing agent and the reducing agent.

i) Metal source The metal source used in the spray pyrolysis method is not particularly limited as long as it contains the metal element contained in the second metal oxide, and may be a metal salt or a metal complex. good.

  In addition, the concentration of the metal source with respect to the second transparent electrode layer forming coating solution is not particularly limited as long as it is a concentration capable of obtaining the second transparent electrode layer, but the metal source is a metal salt. In general, it is 0.001-1 mol / l, preferably 0.01-0.5 mol / l. When the metal source is a metal complex, it is usually 0.001-1 mol / l, especially 0. It is preferable that it is 0.01-0.5 mol / l. When the concentration is less than the above range, it may take too much time to form the second transparent electrode layer. When the concentration exceeds the above range, a second transparent electrode layer having a uniform film thickness can be obtained. This is because it may not be possible.

  Examples of the metal element constituting the second transparent electrode layer are those described in “2. A. Dye-sensitized solar cell laminate”. Since the metal oxide described in the section of the second transparent electrode layer and (1) the second metal oxide has, description thereof is omitted here.

When the second metal oxide is ITO, metal sources include tris (acetylacetonate) indium (III), 2-ethylhexanoate indium (III), tetraethyltin, dibutyltin oxide (IV), tricyclohexyltin ( IV) Hydroxide and the like can be used.
When the metal oxide is ZnO, zinc acetylacetonate, zinc lactate trihydrate, zinc salicylate trihydrate, zinc stearate, or the like can be used as the metal source.
When the metal oxide is FTO, tetraethyltin, dibutyltin oxide (IV), tricyclohexyltin (IV) hydroxide, or the like can be used as the metal source, and ammonium fluoride or the like can be used as the fluorine doping agent. Can be used.
When the metal oxide is ATO, antimony (III) butoxide, antimony (III) ethoxide, tetraethyltin, dibutyltin oxide (IV), tricyclohexyltin (IV) hydroxide, etc. should be used as the metal source. Can do.
When the metal oxide is SnO ₂ (TO), tetraethyltin, dibutyltin oxide (IV), tricyclohexyltin (IV) hydroxide, or the like can be used as the metal source.

ii) Oxidizing agent, reducing agent, and additive The oxidizing agent, reducing agent, and other additives used in the second transparent electrode layer forming coating solution in the spray decomposition method are described in “(4) First Since it is the same as that described in the section “Transparent electrode layer forming step”, the description thereof is omitted here.

iii) Solvent The solvent used in the spray pyrolysis method is the same as that described in the above “(4) First transparent electrode layer forming step”, and therefore description thereof is omitted here.

b. Next, a contact method between the second transparent electrode layer forming coating solution and the first transparent electrode layer. Next, a contact method between the second transparent electrode layer forming coating solution and the first transparent electrode layer in the spray pyrolysis method. explain. The contact method in the spray pyrolysis method is not particularly limited as long as it is a method of bringing the above-described second transparent electrode layer forming coating solution into contact with the above-described first transparent electrode layer. Since it is the same as the method in the above “(4) first transparent electrode layer forming step”, description thereof is omitted here.

  Further, in the spray pyrolysis method, when the second transparent electrode layer forming coating solution and the heated first transparent electrode layer are brought into contact with each other, the first transparent electrode layer is a “second transparent electrode layer”. It is heated to a temperature equal to or higher than the “forming temperature”. Such “second transparent electrode layer forming temperature” varies greatly depending on the type of metal ions and the like formed by dissolving the metal source, the composition of the second transparent electrode layer forming coating solution, and the like. When an oxidizing agent and / or a reducing agent is not added to the coating solution for forming a transparent electrode layer, it can usually be in the range of 400 to 600 ° C, and it is preferably in the range of 450 to 550 ° C. On the other hand, when adding an oxidizing agent and / or a reducing agent to the first transparent electrode layer forming coating solution, it can usually be in the range of 150 to 600 ° C, and in particular, in the range of 250 to 400 ° C. Is preferred. In particular, when the second transparent electrode layer of the ITO film is formed using the above method, it is usually preferably in the range of 300 to 500 ° C, and more preferably in the range of 350 to 450 ° C. Is more preferable.

2. Method for Producing Dye-Sensitized Solar Cell Substrate with Heat Resistant Substrate Next, a method for producing a dye-sensitized solar cell substrate with a heat-resistant substrate of the present invention will be described. The substrate for a dye-sensitized solar cell with a heat-resistant substrate of the present invention is on the second transparent electrode layer of the laminate for a dye-sensitized solar cell produced by the method for producing a laminate for a dye-sensitized solar cell. In addition, the substrate is formed by a substrate forming step in which a substrate is formed through an adhesive layer. As a method of forming a base material in such a base material forming step, the second transparent electrode layer of the dye-sensitized solar cell laminate manufactured by the method for manufacturing a dye-sensitized solar cell laminate, If it is a method which can join a base material with sufficient adhesiveness through an contact bonding layer, it will not specifically limit. As such a method, after forming an adhesive layer made of a thermoplastic resin on a base material in advance and arranging the base material having the adhesive layer so that the adhesive layer and the second transparent electrode layer adhere to each other , A method of heating and heat-sealing (first method), a heat-meltable film made of a thermoplastic resin, and the second transparent electrode layer, a substrate, and the like through the heat-meltable film And a method of laminating (second method).

  The heat-meltable resin used in this step is 1. “B. Dye-sensitized solar cell base material with heat-resistant substrate”. Since it is the same as that described in the section of the adhesive layer, the description here is omitted.

  In the first method, the method for forming the adhesive layer on the substrate is not particularly limited as long as the adhesive layer having a desired thickness and flatness can be formed. Examples of such a method include a method of forming a film by applying a coating solution for forming an adhesive layer containing at least a heat-meltable resin and a solvent on a substrate and drying and solidifying it, or heat-melting a heat-meltable resin. Then, after forming a liquid, a method of forming a film by applying the liquid heat-meltable resin on a substrate and cooling it can be mentioned. In this step, a uniform adhesive layer can be formed by any method. In any of the above cases, a known method can be used as the coating method.

  In the second method, the method for producing a heat-meltable film made of a heat-meltable resin is not particularly limited as long as it can produce a heat-meltable film having a uniform film thickness. As such a method, a known solution casting method or melt casting method generally used for forming a resin film can be mentioned.

  The base material used in this step is the above-mentioned “B. Base material for dye-sensitized solar cell with heat-resistant substrate”. Since it is the same as that described in the section of the base material, explanation here is omitted.

3. Method for Producing Dye-Sensitized Solar Cell Substrate The method for producing a dye-sensitized solar cell substrate according to the present invention is a heat-resistant substrate obtained by the above-described method for producing a dye-sensitized solar cell substrate with a heat-resistant substrate. A method of producing a dye-sensitized solar cell substrate can be suitably used by a peeling step of peeling the heat-resistant substrate 1 from the dye-sensitized solar cell substrate.

(1) Stripping step In the stripping step of stripping the heat-resistant substrate of the dye-sensitized solar cell substrate with a heat-resistant substrate from the intervening layer, the heat-resistant substrate can be stripped as a method of peeling the heat-resistant substrate and the intervening layer. The heat-resistant substrate is flexible, and for example when the roll-to-roll method is used, the heat-resistant substrate of the dye-sensitized solar cell substrate with the heat-resistant substrate and Examples include a method of laminating the base materials with separate heat rolls, and then winding the heat resistant substrate and the dye-sensitized solar cell base material separately. Further, for example, when the heat-resistant substrate is rigid, the substrate of the dye-sensitized solar cell base material with the heat-resistant substrate is bonded with a heat roll, and the dye-sensitized solar cell base material is wound up, etc. Is mentioned. In the present invention, when the heat-resistant substrate and the intervening layer are peeled off, depending on the type of the heat-resistant substrate and the intervening layer, the heat-resistant substrate and the intervening layer cause interfacial peeling, and the intervening layer causes cohesive failure, A part of the intervening layer may remain on the heat resistant substrate.
In this step, the heat-resistant substrate can be peeled off by mechanical polishing or chemical removal such as etching.

(2) Other steps The method for producing a dye-sensitized solar cell substrate of the present invention may include other steps in addition to the above steps. Another process used in the present invention includes a patterning process in which the porous layer is patterned after the heat-resistant substrate is peeled off.

  The method for patterning the porous layer in the patterning step is not particularly limited as long as it can accurately pattern the porous layer into a desired pattern. Examples of the patterning method used in the present invention include laser scribe, wet etching, lift-off, dry etching, mechanical scribe, etc. Among them, laser scribe and mechanical scribe are preferable.

4). Next, a method for producing a dye-sensitized solar cell of the present invention will be described. The method for producing a dye-sensitized solar cell according to the present invention includes a dye-sensitized solar cell substrate obtained by the above-described method for producing a dye-sensitized solar cell substrate, a second electrode layer, and a counter substrate. Forming a dye-sensitized solar cell substrate pair using the counter electrode substrate provided, and pores of the intervening layer and the oxide semiconductor layer of the dye-sensitized solar cell substrate pair After the dye sensitizer carrying step for carrying the dye sensitizer on the surface, and the dye sensitizer carrying step, between the second electrode layer and the intervening layer, and the oxide semiconductor layer and the intervening layer. A method of forming a dye-sensitized solar cell by performing a filling process in which an electrolyte layer forming step for forming an electrolyte layer that transmits charges generated by light irradiation is performed inside the pores of the porous body is preferable. Hereinafter, the dye-sensitized solar cell substrate pair used in the present invention and the filling treatment will be described in detail.

(1) Dye-sensitized solar cell substrate pair A method of forming a dye-sensitized solar cell substrate pair will be described. The method for forming the dye-sensitized solar cell base material pair is not particularly limited as long as it is a method capable of obtaining a dye-sensitized solar cell with good energy conversion efficiency. Can be roughly classified as follows according to the time when this step is performed with respect to the electrolyte layer forming step of the filling treatment described later. That is, this process is performed before the electrolyte layer forming process and when the process is performed after the electrolyte layer forming process.

  When this step is performed prior to the electrolyte layer formation step, the electrolyte layer is not formed, so that there is a gap in which the electrolyte layer is formed between the intervening layer and the second electrode. It is necessary to form a dye-sensitized solar cell substrate pair. In this case, the method for forming the dye-sensitized solar cell substrate pair is not particularly limited as long as it is a method capable of obtaining the dye-sensitized solar cell substrate pair having the gap. However, for example, a method using a spacer can be used. Examples of the spacer include a glass spacer, a resin spacer, or an olefin-based porous film. Further, the gap is not particularly limited as long as it has a width capable of forming an electrolyte layer, but is generally within a range of 0.01 to 100 μm, especially 0.1. It is preferable to be within a range of ˜50 μm.

  On the other hand, when this step is performed after the electrolyte layer forming step, the electrolyte layer has already been formed on the intervening layer, so there is no need to provide a gap as described above. In this case, the method for forming the dye-sensitized solar cell substrate pair is not particularly limited as long as it is a method capable of obtaining a desired dye-sensitized solar cell. Can include a method of bonding the counter electrode substrate.

(2) Filling process Next, the filling process in this invention is demonstrated. The filling treatment in the present invention refers to a dye sensitizer carrying step and an electrolyte layer forming step performed after the dye sensitizer carrying step. In the present invention, the above-described filling treatment is performed for a dye-sensitized solar cell laminate, a dye-sensitized solar cell substrate with a heat-resistant substrate, a dye-sensitized solar cell substrate, or a dye-sensitized solar cell. A dye-sensitized solar cell is manufactured by performing on the pair of base materials. Hereinafter, the dye sensitizer carrying process and the electrolyte layer forming process, which are filling processes in the present invention, will be described.

a. Dye sensitizer carrying process First, the dye sensitizer carrying process in the filling process will be described. The dye sensitizer carrying step includes the laminate for the dye-sensitized solar cell, the dye-sensitized solar cell substrate with a heat-resistant substrate, the dye-sensitized solar cell substrate, or the dye-sensitized solar cell. This is a step of carrying a dye sensitizer on the intervening layer of these members and the pore surface of the oxide semiconductor layer.

  The dye sensitizer used in this step is the “A. Dye-sensitized solar cell laminate” described in “3. Since it is the same as that described in the paragraph of the porous layer, the description here is omitted.

  In this step, the method for supporting the dye sensitizer on the pore surfaces of the intervening layer and the oxide semiconductor layer is not particularly limited. For example, the oxide semiconductor is added to a solution of the dye sensitizer. A method in which the layer and the intervening layer are immersed and dried, or a member having no heat-resistant substrate and exposing the intervening layer, such as a dye-sensitized solar cell base material, a dye sensitizer And a method of applying a solution in which is dissolved and drying it.

b. Electrolyte Layer Forming Step Next, the electrolyte layer forming step in the filling process will be described. The electrolyte layer forming step is a step of forming an electrolyte layer that transmits charges generated by light irradiation by processing the intervening layer.

  The electrolyte layer obtained by this step is located between the intervening layer and the second electrode layer of the dye-sensitized solar cell, and the dye sensitizer carried on the intervening layer and the oxide semiconductor layer and the first The charge transport between the two electrode layers is performed. Examples of the redox couple used in this step include 1. of the above “D. Dye-sensitized solar cell”. Since it is the same as that described in the section of the electrolyte layer, description thereof is omitted here.

  Next, a method for forming the electrolyte layer will be described. The method for forming the electrolyte layer is not particularly limited as long as it is a method capable of obtaining a dye-sensitized solar cell with good energy conversion efficiency. Specifically, the above-described counter electrode group is described above. It can be divided roughly as follows according to the time when this process is performed with respect to the material forming process. That is, it is a case where this process is performed before the said counter electrode base material formation process, and a case where this process is performed after the said counter electrode base material formation process.

  When this step is performed prior to the counter electrode substrate forming step, the dye-sensitized solar cell substrate pair is not formed, and the electrolyte layer is formed directly on the intervening layer. Therefore, it is necessary to form an electrolyte layer having self-supporting properties. The method for forming such an electrolyte layer is not particularly limited. Specifically, the electrolyte layer forming coating solution containing the constituent components of the electrolyte layer is applied to the intervening layer and solidified. The method (coating method) etc. which form an electrolyte layer by making it equal etc. are mentioned. In the coating method, a solid electrolyte layer can be obtained mainly, and when the solid electrolyte layer is obtained, the electrolyte layer forming coating solution usually holds the redox couple and this. Contains the above polymer.

  The coating method in the above coating method is not particularly limited, and a known coating method can be used. Specifically, die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating, bar coating can be used. , Blade coating, knife coating, air knife coating, slot die coating, slide die coating, dip coating, micro bar coating, micro bar reverse coating, screen printing (rotary method), and the like.

  Further, in the coating method, when the electrolyte layer forming coating solution contains a crosslinking agent, a photopolymerization initiator, etc., after applying the electrolyte layer forming coating solution, active light or the like is applied. A solid electrolyte layer can be formed by irradiation and curing.

  On the other hand, if this step is performed prior to the counter electrode substrate forming step, a dye-sensitized solar cell substrate pair having a predetermined gap has already been formed, so an electrolyte layer is formed in this gap. To do. In this case, the method of forming the electrolyte layer is not particularly limited. Specifically, the electrolyte layer forming coating solution containing the constituent components of the electrolyte layer is used as the intervening layer and the second electrode. By injecting between the layers, a method of forming an electrolyte layer (injection method) can be exemplified. In the above injection method, a solid, gel, or liquid electrolyte layer can be formed.

  The injection method in the above injection method is not particularly limited as long as it is a method that can inject the electrolyte forming coating solution into the gap between the intervening layer and the second electrode layer. For example, the capillary phenomenon A method of injecting using can be used.

  In the above injection method, when the electrolyte layer forming coating solution contains the gelling agent, after the electrolyte layer forming coating solution is injected, for example, temperature adjustment, ultraviolet irradiation, electron beam irradiation By performing the above, a gel-like or solid electrolyte layer having a two-dimensional or three-dimensional crosslinked structure can be formed.

c. Timing of performing the filling process Next, the timing of performing the filling process will be described. The filling treatment includes the dye sensitizer carrying step and the electrolyte layer forming step, and the two steps are divided into a laminate for a dye-sensitized solar cell and a substrate for a dye-sensitized solar cell with a heat-resistant substrate. Then, the dye-sensitized solar cell is manufactured by performing on the dye-sensitized solar cell substrate or the dye-sensitized solar cell substrate pair.

  In the present invention, the two steps may be performed continuously, or the two steps may be performed separately. Hereinafter, the method for producing the dye-sensitized solar cell of the present invention will be exemplified with reference to the timing of the dye-sensitizer carrying step first performed in the filling process.

(C-1) When performing a dye sensitizer carrying process with respect to the laminated body for dye-sensitized solar cells When performing a dye sensitizer carrying process with respect to the laminated body for dye-sensitized solar cells Examples of the method for producing a dye-sensitized solar cell include the following methods (i) and (ii).

(I) The dye-sensitized solar cell laminate is subjected to the dye-sensitizer carrying step, and then the substrate forming step, the peeling step, the counter electrode substrate forming step, and the electrolyte layer. A method for producing a dye-sensitized solar cell for forming a dye-sensitized solar cell by performing the forming steps in this order (ii) The dye-sensitizer for the dye-sensitized solar cell laminate Dye sensitization for forming a dye-sensitized solar cell by performing a supporting step and then performing the substrate forming step, the peeling step, the electrolyte layer forming step, and the counter electrode substrate forming step in this order. Type solar cell manufacturing method

(C-2) When performing dye sensitizer carrying | support process with respect to the base material for dye-sensitized solar cells with a heat-resistant substrate Dye sensitizer with respect to the base material for dye-sensitized solar cells with a heat-resistant substrate Examples of the method for producing a dye-sensitized solar cell when performing the supporting step include the following methods (iii) and (iv).

  (Iii) The dye-sensitized solar cell substrate with the heat-resistant substrate is subjected to the dye-sensitizer carrying step, and then the peeling step, the counter electrode substrate forming step, and the electrolyte layer forming step are performed. By performing in this order, a method for producing a dye-sensitized solar cell forming a dye-sensitized solar cell

  (Iv) The dye-sensitized solar cell substrate with the heat-resistant substrate is subjected to the dye-sensitizer carrying step, and then the peeling step, the electrolyte layer forming step, and the counter electrode substrate-forming step. By performing in this order, a method for producing a dye-sensitized solar cell forming a dye-sensitized solar cell

(C-3) When a dye sensitizer carrying step is performed on a dye-sensitized solar cell substrate A dye sensitizer carrying step is performed on a dye-sensitized solar cell substrate with a heat-resistant substrate. Examples of the method for producing a dye-sensitized solar cell in the case of carrying out include the following methods (v) and (vi).

  (V) The dye-sensitized solar cell base material is subjected to the dye-sensitized agent supporting step, and then the counter electrode base material forming step and the electrolyte layer forming step are performed in this order. Method for producing dye-sensitized solar cell for forming dye-sensitized solar cell

  (Vi) By performing the dye sensitizer carrying step on the dye-sensitized solar cell substrate, and then performing the electrolyte layer forming step and the counter electrode substrate forming step in this order, Method for producing dye-sensitized solar cell for forming dye-sensitized solar cell

(C-4) When a dye sensitizer carrying step is performed on the dye-sensitized solar cell substrate pair A dye sensitizer carrying step is carried out on the dye-sensitized solar cell substrate pair Examples of the method for producing a dye-sensitized solar cell include the following method (vii).

  (Vii) By performing the dye sensitizer carrying step on the dye-sensitized solar cell substrate pair, and then performing the counter electrode substrate forming step and the electrolyte layer forming step in this order. , Method for producing dye-sensitized solar cell for forming dye-sensitized solar cell

  In the present invention, among the above (i) to (vii), the method for producing a dye-sensitized solar cell shown in (vi) is particularly preferable.

  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.

(Example)
1. Production of Dye-Sensitized Solar Cell Laminate (1) Formation of Intervening Layer Forming Layer 1% by mass of TiO ₂ fine particles having a primary particle diameter of 20 nm (P25 manufactured by Nippon Aerosil Co., Ltd.) as a coating solution for forming an intervening layer The acrylic resin is dissolved in methyl ethyl ketone and toluene using a homogenizer so that the acrylic resin (molecular weight 25000, glass transition temperature 105 ° C.) (Mitsubishi Rayon BR87) 10 mass% is polymethyl methacrylate, and then TiO 2 is used. _A coating liquid for forming an intervening layer was prepared by dispersing _two fine particles. This intervening layer forming coating solution was coated on a non-alkali glass substrate (thickness 0.7 mm) prepared as a heat-resistant substrate with a wire bar and dried.

(2) Formation of oxide semiconductor layer forming layer 37.5% by mass of TiO ₂ fine particles having a primary particle size of 20 nm (P25 manufactured by Nippon Aerosil Co., Ltd.), 1.25% by mass of acetylacetone, as the coating solution for forming an oxide semiconductor layer A slurry was prepared by dissolving and dispersing in water and isopropyl alcohol using a homogenizer such that polyethylene glycol (average molecular weight 3000) was 1.88% by mass. The slurry was applied with a doctor blade onto the substrate on which the intervening layer forming layer had been formed, then allowed to stand at room temperature for 20 minutes, and then dried at 100 ° C. for 30 minutes.

(3) Firing of Intervening Layer Forming Layer and Oxide Semiconductor Layer Forming Layer Next, the intervening layer forming layer and the oxide semiconductor layer forming layer are formed at 500 ° C., 30 using an electric muffle furnace (P90 manufactured by Denken). Baking for 5 minutes under atmospheric pressure. Thus, an intervening layer and a porous oxide semiconductor layer formed as a porous body were obtained.

(4) Formation of first transparent electrode layer After that, a coating liquid in which NH ₄ F 0.1 mol / l and tin chloride 0.005 mol / l were dissolved in ethanol was prepared as a first transparent electrode layer forming coating liquid. . Thereafter, the baked oxide semiconductor layer is heated by a hot plate (400 ° C.), and the first transparent conductive layer forming coating liquid is ultrasonically sprayed on the heated oxide semiconductor layer. By spraying, a 100 nm FTO film was produced and a first transparent electrode layer was formed.

(5) Formation of 2nd transparent electrode layer Furthermore, the coating liquid which melt | dissolved 0.1 mol / l of indium chloride and 0.005 mol / l of tin chloride in ethanol was prepared as a coating liquid for 2nd transparent electrode layer formation. Thereafter, the first transparent electrode layer is heated by a hot plate (400 ° C.), and the above-described second transparent electrode layer forming coating solution is sprayed on the heated first transparent electrode layer by an ultrasonic sprayer, An ITO film as a second transparent electrode layer was formed to a thickness of 300 nm to obtain a laminate for a dye-sensitized solar cell.

2. Preparation of dye-sensitized solar cell base material with heat-resistant substrate A PET film (Toyobo A5100: thickness 125 μm) was used as the base material, a heat sealant (Toyobo MD1985) was applied on the base material, and the substrate was air-dried. An adhesive layer was formed on the material. The base material having such an adhesive layer and the second transparent electrode layer of the dye-sensitized solar cell laminate produced in “1. Production of dye-sensitized solar cell laminate” above at 120 ° C. A base material for a dye-sensitized solar cell with a heat-resistant substrate was obtained by heat sealing.

3. Preparation of dye-sensitized solar cell base material From the base material for dye-sensitized solar cell with heat-resistant substrate prepared in "2. Preparation of dye-sensitized solar cell base material with heat-resistant substrate" above, heat-resistant group The base material for dye-sensitized solar cells was obtained by transferring the oxide semiconductor layer, the first transparent electrode layer, and the second transparent electrode layer to the base material side by peeling the material.

4). Dye sensitizer support Ruthenium complex (RuL ₂ (NCS) ₂ ) as a dye sensitizer is dissolved in an absolute ethanol solution to a concentration of 3 × 10 ⁻⁴ mol / l and adsorbed dye solution Was made. Thereafter, the dye-sensitized solar cell substrate prepared in “3. Preparation of dye-sensitized solar cell substrate” is immersed in the adsorption dye solution, whereby the sensitizing dye is added to the oxide semiconductor layer. A supported dye-sensitized solar cell substrate was obtained.

5. Production of dye-sensitized solar cell Using the dye-sensitized solar cell substrate carrying the dye-sensitized agent obtained by “4. A dye-sensitized solar cell was produced.
First, 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, and tarsha at a concentration of 0.5 mol / l. A solution in which butyl pyridine was dissolved was used as an electrolyte layer forming coating solution.
After trimming the dye-sensitized solar cell substrate on which the dye sensitizer is supported to 1 cm × 1 cm, the opposing substrate is bonded with Surlyn having a thickness of 20 μm, and an electrolyte layer-forming coating solution is added therebetween. What was impregnated was used as an element. As a counter substrate, a second electrode layer made of a platinum film having a thickness of 50 nm is applied by sputtering on a counter substrate having an ITO sputter layer having a film thickness of 150 nm and a surface resistance of 7Ω / □. Was used. In this way, a dye-sensitized solar cell was produced.

(Comparative example)
A dye-sensitized solar cell is produced in the same manner as in Example 1 except that (3) the first transparent electrode layer is not formed in “1. Production of dye-sensitized solar cell laminate”. Was made.

(Evaluation)
Evaluation of the produced dye-sensitized solar cell is made to enter from the substrate side having the oxide semiconductor layer adsorbed with dye, using AM1.5, artificial sunlight (incident light intensity of 100 mW / cm ² ) as a light source, Current-voltage characteristics were measured by applying voltage with a source measure unit (Caseley 2400 type).

As a result of measuring the current-voltage characteristics of the dye-sensitized solar cells produced in the examples and comparative examples by the above method, in the examples, the short-circuit current was 13, 8 mA / cm ² , the open-circuit voltage was 720 mV, and the conversion efficiency was 6 In the comparative example, the short-circuit current was 12.5 mA / cm ² , the open-circuit voltage was 680 mV, and the conversion efficiency was 5.1%.

It is a schematic sectional drawing which shows an example of the laminated body for dye-sensitized solar cells of this invention. It is a schematic sectional drawing which shows an example of the base material for dye-sensitized solar cells with a heat-resistant board | substrate of this invention. It is a schematic sectional drawing which shows an example of the base material for dye-sensitized solar cells of this invention. It is a schematic sectional drawing which shows the other example of the base material for dye-sensitized solar cells of this invention. It is a schematic sectional drawing which shows an example of the dye-sensitized solar cell of this invention. It is process drawing which shows an example of the manufacturing process of the laminated body for dye-sensitized solar cells of this invention. It is a schematic sectional drawing which shows an example of the general structure of a dye-sensitized solar cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... 1st electrode layer 3 ... Porous layer 4 ... Electrolyte layer 5 ... 2nd electrode layer 6 ... Opposite base material 7 ... Dye-sensitized solar cell 10 ... Laminate for dye-sensitized solar cell DESCRIPTION OF SYMBOLS 11 ... Base material 12 ... Adhesion layer 13 ... 2nd transparent electrode layer 14 ... 1st transparent electrode layer 15 ... Porous layer 15a ... Oxide semiconductor layer 15b ... Interposition layer 16 ... Heat-resistant board | substrate 17 ... Electrolyte layer 18 ... 2nd electrode Layer 19 ... Counter substrate 20 ... Dye-sensitized solar cell substrate with heat-resistant substrate 25a ... Oxide semiconductor layer forming layer 25b ... Intervening layer forming layer 30 ... Dye-sensitized solar cell substrate 40 ... Dye Sensitization type solar cell 50 ... Counter electrode base material

Claims (10)

A heat-resistant substrate,
A porous layer formed on the heat-resistant substrate and containing metal oxide semiconductor fine particles;
A first transparent electrode layer formed on the porous layer and made of a first metal oxide;
A second transparent electrode layer formed on the first transparent electrode layer and made of a second metal oxide;
A laminate for a dye-sensitized solar cell comprising:
The laminate for a dye-sensitized solar cell, wherein the first metal oxide has higher chemical durability than the second metal oxide. The first metal oxide is at least one selected from the group consisting of FTO, SnO ₂ , IZO, ZnO, ATO, fluorine-doped ZnO, aluminum-doped ZnO, gallium-doped ZnO, and boron-doped ZnO. The laminate for a dye-sensitized solar cell according to claim 1.   The laminate for a dye-sensitized solar cell according to claim 1 or 2, wherein the second metal oxide is ITO. A substrate;
An adhesive layer made of a heat-meltable resin;
A laminate for a dye-sensitized solar cell according to any one of claims 1 to 3,
A dye-sensitized solar cell substrate with a heat-resistant substrate, comprising:
The dye-sensitized solar cell with a heat-resistant substrate, wherein the second transparent electrode layer of the laminate for the dye-sensitized solar cell and the base material are bonded via the adhesive layer. Substrate for use.   The base material for a dye-sensitized solar cell with a heat-resistant substrate according to claim 4, wherein the base material is a resin film base material. A substrate;
An adhesive layer formed on the substrate and made of a heat-meltable resin;
A second transparent electrode layer formed on the adhesive layer and made of a second metal oxide;
A first transparent electrode layer formed on the second transparent electrode layer and made of a first metal oxide;
A porous layer formed on the first transparent electrode layer and containing metal oxide semiconductor fine particles;
A dye-sensitized solar cell substrate comprising:
The dye-sensitized solar cell substrate, wherein the first metal oxide has higher chemical durability than the second metal oxide. The first metal oxide is at least one selected from the group consisting of FTO, SnO ₂ , IZO, ZnO, ATO, fluorine-doped ZnO, aluminum-doped ZnO, gallium-doped ZnO, and boron-doped ZnO. The dye-sensitized solar cell substrate according to claim 6.   The substrate for a dye-sensitized solar cell according to claim 6 or 7, wherein the second metal oxide is ITO.   The dye-sensitized solar cell substrate according to any one of claims 6 to 8, wherein the substrate is a resin film substrate. A dye-sensitized solar cell substrate according to any one of claims 6 to 9, a counter electrode substrate comprising a second electrode layer and a counter substrate,
An electrolyte layer comprising a redox couple;
A dye-sensitized solar cell comprising:
A dye sensitizing method characterized in that a porous layer of the dye-sensitized solar cell substrate and a second electrode layer of the counter electrode substrate are arranged to face each other with the electrolyte layer interposed therebetween. Type solar cell.

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