JP2008091084A - Stack for oxide semiconductor electrode, oxide semiconductor electrode, and dye-sensitized solar cell using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stack for an oxide semiconductor electrode used for the oxide semiconductor electrode enhancing durability, productivity, and a photoelectric conversion efficiency when used as the cell of the dye-sensitized solar cell and to provide the oxide semiconductor electrode using the stack. <P>SOLUTION: The stack for the oxide semiconductor electrode has a heat resistant substrate 1 having heat resistance; a porous layer 2 formed on the heat resistant substrate and containing metal oxide semiconductor fine particles; a transparent electrode layer 3 formed on the porous layer and comprising a metal oxide; a first electrode layer 5 comprising a conductive layer 4 formed on the surface of the transparent electrode layer in a pattern shape. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminated body for an oxide semiconductor electrode used for an oxide semiconductor electrode.

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

  A general configuration of the dye-sensitized solar cell is shown in FIG. As shown in FIG. 10, a general dye-sensitized solar cell 60 includes a porous layer 63 including metal oxide semiconductor fine particles carrying a first electrode layer 62 and a dye sensitizer on a base 61. Has a structure in which an electrolyte layer 64 having a redox pair, a second electrode layer 65, and a counter substrate 66 are laminated in this order on the porous layer 63 of the oxide semiconductor electrode 71 laminated in this order. The sensitizing dye adsorbed on the surface of the metal oxide semiconductor fine particles is excited by receiving sunlight from the substrate 61 side, and the excited electrons are conducted to the first electrode layer 62, and the second is transmitted through the external circuit. Conducted to the electrode layer 65. 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.

  In order to form a porous porous layer that is characteristic of the Gretchel cell, it is generally necessary to perform a baking treatment at 300 ° C. to 700 ° C. on the porous layer forming composition. Therefore, the base material cannot be used unless it is a heat-resistant material that can withstand the baking treatment, and a general polymer film cannot be used.

  In order to solve the above problem, Patent Document 1 discloses that an oxide semiconductor film obtained by forming a layer containing an oxide semiconductor and / or a precursor thereof on a heat-resistant substrate and heating and firing the layer is a transferred group. Disclosed is a method for manufacturing an oxide semiconductor electrode, which is characterized by being transferred onto a material. According to such a transfer method, a porous layer made of an oxide semiconductor film can be formed by transferring an oxide semiconductor film fired on a heat-resistant substrate to an arbitrary substrate to be transferred. Therefore, such a transfer method is useful in that an appropriate substrate to be transferred can be selected according to the use of the oxide semiconductor electrode regardless of the material of the substrate to be transferred.

  In the above transfer method, a porous layer is formed by transferring an oxide semiconductor film formed on a heat-resistant substrate to a substrate to be transferred. It is necessary to form an adhesive layer. Therefore, for example, when an oxide semiconductor electrode having a porous layer formed by a transfer method is used in a dye-sensitized solar cell, an adhesive layer is added to the general configuration of the dye-sensitized solar cell shown in FIG. Will be. FIG. 11 shows a configuration of a dye-sensitized solar cell using an oxide semiconductor electrode in which a porous layer is formed by a transfer method. As shown in FIG. 11, when an oxide semiconductor electrode having a porous layer formed by a transfer method is used, the dye-sensitized solar cell 70 has an adhesive layer between the substrate 61 and the first electrode layer 62. A will be formed. It does not specifically limit as an adhesive agent used for the said contact bonding layer, A general various synthetic resin and an inorganic adhesive agent can be used.

  In such a dye-sensitized solar cell, the material for the electrode layer of the first electrode layer or the second electrode layer is made of a transparent material so as not to interfere with incident light from the substrate side. . As such a material, metal oxides such as ITO (indium tin oxide) and FTO (fluorine-doped tin oxide) are used. However, since the electric resistance is not sufficiently low, the dye-sensitized solar cell is used. This is a cause of lowering the photoelectric conversion efficiency of the cell.

  For such a problem, Patent Document 2 discloses a method for improving photoelectric conversion efficiency by providing a conductive layer made of a metal or alloy having a lower resistance value than the electrode layer between the electrode layer and the electrolyte layer. Yes. However, in this method, the photoelectric conversion efficiency is improved by providing a conductive layer made of a metal or alloy having a lower resistance value than the electrode layer. However, the conductive layer is subject to corrosion such as iodine contained in the electrolyte layer. There was a risk of low durability.

  Patent Document 3 discloses a method of installing a conductive layer between an electrode layer and a base material. However, in order to dispose the conductive layer, it is necessary to process the unevenness for disposing the conductive layer on the base material, and to install the conductive layer with respect to the concave portion. Since a non-flexible transparent rigid material such as polycarbonate is used, it is very difficult to perform the above uneven processing with high accuracy. In addition, there is a problem that it is not easy to install a conductive layer in the concave portion, and productivity is low.

JP 2002-184475 A JP 2003-203681 A JP 2004-296669 A

  Therefore, the present invention provides an oxide semiconductor electrode that can be used as an oxide semiconductor electrode that is excellent in durability and productivity and enables high photoelectric conversion efficiency when used as, for example, a dye-sensitized solar cell. It is a main object to provide a laminated body for use, and an oxide semiconductor electrode using the same.

  The present invention has been made in view of the above object, and has a heat resistant substrate having heat resistance, a porous layer formed on the heat resistant substrate and containing metal oxide semiconductor fine particles, and formed on the porous layer. A laminated body for an oxide semiconductor electrode, comprising: a transparent electrode layer made of a metal oxide; and a first electrode layer made of a conductive layer formed in a pattern on the surface of the transparent electrode layer. provide.

  According to the present invention, when the first electrode layer includes the conductive layer, the conductivity of the first electrode layer can be improved. Moreover, the fall of the light transmittance of the said 1st electrode layer can be suppressed because the said conductive layer is formed in pattern shape. Furthermore, the oxide semiconductor electrode laminate of the present invention can be used for manufacturing an oxide semiconductor electrode by forming an oxide semiconductor electrode with a heat-resistant substrate by a transfer method and then peeling the heat-resistant substrate.

  The present invention includes a base material, an adhesive layer formed on the base material and made of a thermoplastic resin, a transparent electrode layer made of a metal oxide, and a conductive layer formed in a pattern on one side of the transparent electrode layer, An oxide semiconductor electrode comprising: a first electrode layer comprising: a porous layer including metal oxide semiconductor fine particles formed on the first electrode layer, wherein the conductive layer of the first electrode layer includes: Provided is an oxide semiconductor electrode formed so as to be in contact with the adhesive layer.

  According to the present invention, the first electrode layer can be made excellent in conductivity by including the conductive layer. Therefore, when the oxide semiconductor electrode of the present invention is used for a dye-sensitized solar cell, high photoelectric conversion efficiency can be obtained. In addition, since the conductive layer is between the adhesive layer and the transparent electrode layer of the first electrode layer, it is not subject to corrosion due to redox pairs such as iodine contained in the electrolyte layer, so that it is stable over time. It can be. Furthermore, since the conductive layer is formed in a pattern, blocking of incident light can be suppressed.

  In the said invention, it is preferable that the conductive layer opening part of the said 1st electrode layer is filled with the said contact bonding layer. Since the conductive layer opening of the first electrode layer is filled with the adhesive layer, the adhesion between the first electrode layer and the adhesive layer can be enhanced. In addition, since the adhesive layer is made of a thermoplastic resin, it is not necessary to process the adhesive layer in advance so as to correspond to the pattern of the conductive layer in order to fill the opening of the conductive layer with the adhesive layer. Therefore, it can be excellent in productivity.

  The present invention also provides an oxide semiconductor electrode with a heat-resistant substrate, comprising a heat-resistant substrate on the porous layer of the oxide semiconductor electrode of the present invention.

  According to the present invention, since the oxide semiconductor electrode has a heat resistant substrate on the porous layer, the oxide semiconductor electrode having excellent adhesion of each layer can be easily formed by peeling the heat resistant substrate. An oxide semiconductor electrode with a heat resistant substrate can be obtained.

  The present invention includes a porous layer of the oxide semiconductor electrode of the present invention, a second electrode layer, and a counter substrate, wherein a dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. Provided is a dye-sensitized solar cell in which the second electrode layer of the counter electrode substrate is opposed to the second electrode layer via an electrolyte layer containing a redox pair.

  According to the present invention, a dye-sensitized solar cell excellent in photoelectric conversion efficiency can be obtained by having the oxide semiconductor electrode of the present invention.

  The present invention includes a porous layer forming step for forming a porous layer on a heat resistant substrate, a transparent electrode layer forming step for forming a transparent electrode layer on the porous layer, and a conductive layer on the transparent electrode layer. A conductive layer forming step, an adhesive layer and a base material applying step for laminating an adhesive layer and a base material on the conductive layer in this order, and a heat resistant substrate peeling step for peeling the heat resistant substrate. A method for manufacturing an oxide semiconductor electrode is provided.

  According to the present invention, by forming the base material after the porous layer forming step of forming the porous layer, the base is not affected by the temperature conditions required in the porous layer forming step. The material of the material can be selected. In addition, after the conductive layer is formed on the transparent electrode layer, the adhesive layer is formed on the conductive layer. When the adhesive layer is made of a thermoplastic resin, the pattern of the conductive layer is formed on the adhesive layer. It is possible to eliminate the need to perform uneven processing corresponding to the above. Therefore, the productivity of the oxide semiconductor electrode can be improved.

  The present invention provides an oxide semiconductor electrode stack that can be used for an oxide semiconductor electrode that is excellent in durability, productivity, and enables high photoelectric conversion efficiency when used as, for example, a dye-sensitized solar cell. And an oxide semiconductor electrode using the same.

The present invention provides an oxide semiconductor electrode stack that can be used for an oxide semiconductor electrode that is excellent in durability, productivity, and enables high photoelectric conversion efficiency when used as, for example, a dye-sensitized solar cell. , Oxide semiconductor electrode using the laminate for oxide semiconductor electrode, oxide semiconductor electrode with heat-resistant substrate, method for producing oxide semiconductor electrode, and dye-sensitized solar cell using the oxide semiconductor electrode It is about.
Hereinafter, the oxide semiconductor electrode laminate, the oxide semiconductor electrode, the oxide semiconductor electrode with a heat-resistant substrate, the dye-sensitized solar cell, and the method for producing the oxide semiconductor electrode of the present invention will be described in detail.

A. First, the laminated body for oxide semiconductor electrodes of this invention is demonstrated. The oxide semiconductor electrode laminate of the present invention includes a heat-resistant substrate having heat resistance, a porous layer formed on the heat-resistant substrate and containing metal oxide semiconductor fine particles, and formed on the porous layer. A transparent electrode layer made of an oxide, and a first electrode layer made of a conductive layer formed in a pattern on the surface of the transparent electrode layer.

  Next, the laminated body for oxide semiconductor electrodes of this invention is demonstrated, referring FIG. FIG. 1 is a schematic cross-sectional view showing an example of the oxide semiconductor electrode laminate of the present invention. As shown in FIG. 1, an oxide semiconductor electrode laminate 10 of the present invention includes a heat resistant substrate 1, a porous layer 2 formed on the heat resistant substrate 1 and containing metal oxide semiconductor fine particles, and the porous material. A transparent electrode layer 3 formed on the layer 2 and made of a metal oxide, and a first electrode layer 5 made of a conductive layer 4 formed in a pattern on the surface of the transparent electrode layer 3.

  According to the present invention, when the first electrode layer includes the conductive layer, the conductivity of the first electrode layer can be improved. Moreover, the fall of the light transmittance of the said 1st electrode layer can be suppressed because the said conductive layer is formed in pattern shape. Furthermore, the oxide semiconductor electrode laminate of the present invention can be used for manufacturing an oxide semiconductor electrode by forming an oxide semiconductor electrode with a heat-resistant substrate by a transfer method and then peeling the heat-resistant substrate.

  The laminate for an oxide semiconductor electrode of the present invention includes a heat-resistant substrate, a porous layer containing metal oxide semiconductor fine particles, a transparent electrode layer formed on the porous layer and made of a metal oxide, and the transparent electrode And a first electrode layer made of a conductive layer formed in a pattern on the surface of the layer. Hereinafter, details of such a stacked body for an oxide semiconductor electrode will be described.

1. First Electrode Layer First, the first electrode layer used for the oxide semiconductor electrode of the present invention will be described. The first electrode layer used in the present invention is composed of a transparent electrode layer made of a metal oxide and a conductive layer formed in a pattern on the surface of the transparent electrode layer. Hereinafter, each configuration of the first electrode layer will be described in detail.

(1) Conductive layer The conductive layer used for this invention is demonstrated. The conductive layer used in the present invention is formed in a pattern on a transparent electrode layer to be described later, and has a function of making the conductivity of the first electrode layer excellent, and the first electrode This suppresses a significant decrease in the light transmittance of the layer.

  As a conductive material used for such a conductive layer, it is more conductive than transparent metal oxides such as ITO (indium tin oxide) and FTO (fluorine doped tin oxide), which are generally used as a transparent electrode layer described later. As long as the property is high, it is not particularly limited. Examples of the conductive material include metals, alloys, and carbon. In the present invention, one or more of Ag, Ag alloy (Ag / Pd, Ag / Nd, Ag / Au), Cu, Cu alloy and the like are used. This is because the conductive material is particularly highly conductive.

The pattern of the conductive layer is not particularly limited as long as it does not significantly reduce the light transmittance of the first electrode layer. Among these, it is preferable that the pattern has a shape with a combination of a number of fine lines and has a high aperture ratio. This is because the light transmittance of the first electrode layer can be made extremely high. In the above pattern, the line width of the fine wire is preferably in the range of 10 μm to 3000 μm, particularly preferably in the range of 100 μm to 1000 μm. In the present invention, the line width of the thin line of the conductive layer is regulated within the above range. If the width is narrower than the above range, the conductivity cannot be improved. This is because the transmittance decreases. Further, the thickness of the fine wire in the conductive layer is preferably in the range of 1 μm to 100 μm, and particularly preferably in the range of 10 μm to 70 μm. In the present invention, the thickness of the thin wire of the conductive layer is defined in the above range because if it is thinner than the above range, the conductivity cannot be improved, and even if it is thicker than the above range, the conductivity does not change. It is.

In the present invention, the aperture ratio of the conductive layer is preferably in the range of 60% to 99%, and particularly preferably in the range of 80% to 99%. In the present invention, the reason why the aperture ratio is defined in the above range is that the conductivity cannot be improved if it is larger than the above range. Further, when the thickness is smaller than the above range, the light transmittance of the first electrode layer is lowered, and when the oxide semiconductor electrode is used as the oxide semiconductor electrode laminate of the present invention, a dye-sensitized solar cell is produced. This is because the power generation efficiency of the dye-sensitized solar cell is impaired because it is usually used in a mode of receiving sunlight from the substrate side.
The aperture ratio is defined as the ratio of the area not shielded by the conductive layer in the unit area of the first electrode layer when the first electrode layer is viewed in plan.

The pattern of the conductive layer used in the present invention is such that when the first electrode layer is viewed in plan, the area shielded by the conductive layer per unit area on the first electrode layer is arranged constant. preferable. This is because the conductivity of the first electrode layer can be made excellent.
Further, the shape of the pattern is not particularly limited, and can be appropriately set according to the line width, aperture ratio, etc. of the fine line forming the pattern of the conductive layer. In the present invention, a lattice shape is preferable. This is because it is easy to uniformly dispose the conductive layer on the transparent electrode layer.

(2) Transparent electrode layer The transparent electrode layer used for this invention consists of a metal oxide which has transparency. The metal oxide used in the present invention is not particularly limited as long as it has transparency, excellent electrical conductivity, and resistance to a redox pair described later. In particular, in the present invention, it is preferable to use a material excellent in sunlight permeability. For example, when using the oxide semiconductor electrode laminate of the present invention as an oxide semiconductor electrode, and creating a dye-sensitized solar cell, it is usually used in a mode of receiving sunlight from the substrate side. This is because the power generation efficiency of the dye-sensitized solar cell is impaired when the metal oxide has poor sunlight permeability.

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

  The thickness of the transparent electrode layer in the present invention is not particularly limited as long as the desired conductivity can be achieved. The thickness of the transparent electrode layer in the present invention is usually preferably in the range of 100 nm to 1500 nm, and particularly preferably in the range of 300 nm to 1000 nm. If the thickness is greater than the above range, it may be difficult to form a homogeneous transparent electrode layer. If the thickness is less than the above range, depending on the use of the oxide semiconductor electrode laminate of the present invention. This is because the conductivity of the transparent electrode layer may be insufficient.

(3) 1st electrode layer The 1st electrode layer in this invention will not be specifically limited if it consists of a transparent electrode layer and the conductive layer formed on the said transparent electrode layer.
As a 1st electrode layer used for this invention, it is good also as what provided the transparent electrode layer further on the transparent electrode layer and the conductive layer formed on the said transparent electrode layer, and the structure which laminated | stacked the several layer It may be. Examples of the configuration in which a plurality of layers are stacked include a mode in which layers having different work functions are stacked and a mode in which layers made of different metal oxides are stacked.

  Further, the first electrode layer used in the present invention is not particularly limited as long as it has a desired transparency depending on the use of the oxide semiconductor electrode laminate of the present invention. The light transmittance for light of ˜1000 nm is preferably 75% or more, and more preferably 80% or more. When the light transmittance of the first electrode layer is lower than the above range, for example, when the oxide semiconductor electrode laminate of the present invention is used to form an oxide semiconductor electrode and a dye-sensitized solar cell is produced. This is because the power generation efficiency may be impaired.

2. Heat-resistant substrate 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 firing treatment for forming the porous layer. 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.

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. Since these metal oxide semiconductor fine particles are suitable for forming a porous porous layer and can improve energy conversion efficiency and reduce costs, the laminate for oxide semiconductor electrodes of the present invention It is suitably used for an oxide semiconductor electrode using 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. In addition, the porosity of the porous layer, that is, the specific surface area is reduced. For example, the oxide semiconductor electrode using the oxide semiconductor electrode laminate of the present invention is converted into a dye-sensitized solar cell. This is because there is a case where a dye sensitizer sufficient for photoelectric conversion in the porous layer may not be supported when used in the above.

In the present invention, a mixture of a plurality of metal oxide semiconductor particles having different particle diameters may be used as the metal oxide semiconductor particles. Since the light scattering effect in the porous layer can be enhanced by using a mixture of metal oxide semiconductor fine particles having different particle diameters, for example, using the oxide semiconductor electrode laminate of the present invention, When this is used in a dye-sensitized solar cell, light absorption by the dye sensitizer can be efficiently performed. Therefore, in the present invention, it is particularly preferable to use a mixture of metal oxide semiconductor fine particles having different particle diameters.
The mixture of a plurality of metal oxide semiconductor 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 present invention contains the same metal element as the metal element included in the metal oxide constituting the first electrode layer (hereinafter sometimes referred to as an electrode metal element). It is preferable. This is because, when the porous layer contains an electrode metal element, the oxide semiconductor electrode laminate of the present invention can be made excellent in conductivity.

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

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

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

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

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

(3) Porous layer Especially if the film thickness of the porous layer in this invention is in the range which can provide desired mechanical strength to a porous layer according to the use of the laminated body for oxide semiconductor electrodes of this invention. It is not limited. The thickness of the porous layer in the present invention is usually preferably in the range of 1 μm to 100 μm, particularly preferably in the range of 5 μm to 30 μm. If the thickness of the porous layer is larger than the above range, peeling from the adhesive layer, cohesive failure of the porous layer itself may easily occur, and membrane resistance may easily occur. It becomes difficult to form a uniform porous layer, for example, when the oxide semiconductor electrode laminate of the present invention is used as an oxide semiconductor electrode and used in a dye-sensitized solar cell, This is because the porous layer containing the dye sensitizer cannot sufficiently absorb sunlight or the like, which may cause poor performance.

  The porous layer in the present invention may be composed of a single layer or may be a structure in which a plurality of layers are laminated. In the present invention, the porous layer preferably has a structure in which a plurality of layers are laminated. As a structure in which a plurality of layers are stacked, any structure can be appropriately selected and employed according to the method for manufacturing the oxide semiconductor electrode laminate of the present invention. Among them, in the present invention, a porous layer is in contact with the first electrode layer, an intervening layer formed on the oxide semiconductor layer and having a higher porosity than the oxide semiconductor layer, A two-layer structure consisting of

  FIG. 2 is a schematic cross-sectional view illustrating an example of such a stacked body for oxide semiconductor electrodes. As shown in FIG. 2, the oxide semiconductor electrode laminate 10 includes a porous layer 2 having an oxide semiconductor layer 2 a in contact with the first electrode layer 5, the oxide semiconductor layer 2 a, and the heat-resistant substrate 1. And an intervening layer 2b having a higher porosity than the oxide semiconductor layer 2a. By making the porous layer into a two-layer structure consisting of such an oxide semiconductor layer and an intervening layer, the adhesion between the heat-resistant substrate and the porous layer is reduced when the porous layer is formed by the transfer method. This is because an oxide semiconductor electrode excellent in productivity can be obtained by a transfer method.

  In the present invention, the porous layer includes an oxide semiconductor layer in contact with the first electrode layer, and an intervening layer formed on the oxide semiconductor layer and having a higher porosity than the oxide semiconductor layer. In the case of a two-layer structure, the intervening layer does not need to be uniformly formed on the oxide semiconductor layer, may have a thickness distribution, and the intervening layer is provided on the oxide semiconductor layer. There may be parts that do not exist. This is because even if the intervening layer exists in such a manner, the oxide semiconductor electrode can be obtained with a high yield by the transfer method.

  When the porous layer has a two-layer structure of the oxide semiconductor layer and the intervening layer, the thickness ratio between the oxide semiconductor layer and the intervening layer was determined using the oxide semiconductor electrode laminate of the present invention. What is necessary is just to determine arbitrarily according to the manufacturing method etc. of an oxide semiconductor electrode. 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. When the thickness of the intervening layer is larger than the above range, the interstitial layer tends to cause cohesive failure, resulting in poor yield when producing the oxide semiconductor electrode using the oxide semiconductor electrode laminate of the present invention. For example, when the oxide semiconductor electrode laminate of the present invention is used as an oxide semiconductor electrode and used in a dye-sensitized solar cell, the surface of the metal oxide semiconductor fine particles contained in the porous layer This is because there is a possibility that a desired amount of the dye sensitizer cannot be adsorbed. Further, if the thickness is less than the above range, it may not be possible to contribute to the improvement of productivity of the oxide semiconductor electrode using the oxide semiconductor electrode laminate of the present invention.

  The porosity of the oxide semiconductor layer is preferably in the range of 10% to 60%, and more preferably in the range of 20% to 50%. For example, when the oxide semiconductor electrode laminate of the present invention is used as an oxide semiconductor electrode and used in a dye-sensitized solar cell, the porosity of the oxide semiconductor layer is smaller than the above range, Since the specific surface area becomes small, there is a possibility that the porous layer containing the dye sensitizer cannot effectively absorb sunlight or the like, and when it is larger than the above range, a desired amount of dye is added to the oxide semiconductor layer. This is because there is a possibility that a sensitizer cannot be contained.

  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 will be high, so productivity may be lost, and if it is larger than the above range, a homogeneous intervening layer will be formed. It may be difficult to do.

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

4). Oxide Semiconductor Electrode Laminate The oxide semiconductor electrode laminate of the present invention is used for manufacturing an oxide semiconductor electrode by forming the oxide semiconductor electrode with a heat resistant substrate by a transfer method and then peeling the heat resistant substrate. Can be used.

5. Method for Producing Oxide Semiconductor Electrode Laminate The method for producing the oxide semiconductor electrode laminate of the present invention is particularly limited as long as each structure of the oxide semiconductor electrode laminate described above can be laminated with good adhesion. Is not to be done. As such a method, for example, it can be formed by the method described in the section of “E. Method for Manufacturing Oxide Semiconductor Electrode”, which will be described later.

B. Next, the oxide semiconductor electrode of the present invention will be described. The oxide semiconductor electrode of the present invention is formed in a pattern on one side of a base material, an adhesive layer made of a thermoplastic resin, a transparent electrode layer made of a metal oxide, and the transparent electrode layer. An oxide semiconductor electrode comprising: a first electrode layer made of a conductive layer formed on the first electrode layer; and a porous layer formed on the first electrode layer and containing metal oxide semiconductor fine particles. The conductive layer and the adhesive layer are formed in contact with each other.

  Next, the oxide semiconductor electrode of the present invention will be described with reference to FIG. FIG. 3 is a schematic sectional view showing an example of the oxide semiconductor electrode of the present invention. As shown in FIG. 3, the oxide semiconductor electrode 20 of the present invention is formed on the base material 7, the adhesive layer 6 formed on the base material 7 and made of a thermoplastic resin, and the adhesive layer 6. A first electrode layer 5 comprising a transparent electrode layer 3 made of a metal oxide and a conductive layer 4 formed in a pattern on the surface of the transparent electrode layer 3, and a metal oxide formed on the first electrode layer 5; It consists of a porous layer 2 containing semiconductor fine particles, and is formed so that the conductive layer 4 of the first electrode layer 5 and the adhesive layer 6 are in contact with each other.

  According to the present invention, the first electrode layer can be made excellent in conductivity by including the conductive layer. Therefore, when the oxide semiconductor electrode of the present invention is used for a dye-sensitized solar cell, high photoelectric conversion efficiency can be obtained. In addition, since the conductive layer is between the adhesive layer and the transparent electrode layer of the first electrode layer, it is not subject to corrosion due to redox pairs such as iodine contained in the electrolyte layer, so that it is stable over time. It can be. Furthermore, since the conductive layer is formed in a pattern, blocking of incident light can be suppressed.

  The oxide semiconductor electrode of the present invention comprises a first electrode layer comprising a base material, an adhesive layer, a transparent electrode layer and a conductive layer, and a porous layer. Hereinafter, each structure of such an oxide semiconductor electrode will be described in detail.

1. First Electrode Layer First, the first electrode layer used in the present invention will be described. The first electrode layer used in the present invention is the same as the contents described in the section “1. First electrode layer” of “A. Oxide semiconductor electrode laminate” above. Description is omitted.

2. Next, the porous layer used in the present invention will be described. The porous layer used in the present invention is the same as the contents described in the section “3. Porous layer” of the above “A. Stack for oxide semiconductor electrode”. Omitted.

3. Next, the adhesive layer used for the oxide semiconductor electrode of the present invention will be described. The adhesive layer used in the present invention is made of a thermoplastic resin having a function of adhering the base material and the conductive layer. When the oxide semiconductor electrode of the present invention is manufactured using a transfer method, It has a function of improving the transferability of the porous layer described later. Hereinafter, such an adhesive layer will be described.

(1) Thermoplastic resin The thermoplastic resin in the adhesive layer used in the present invention preferably has a melting point in the range of 50 ° C to 200 ° C, particularly preferably in the range of 60 ° C to 180 ° C. In particular, it is preferably in the range of 65 ° C to 150 ° C. When the oxide semiconductor electrode of the present invention is prepared by a transfer method, the base material described later and the conductive layer are thermally fused with the thermoplastic resin, but the melting point of the thermoplastic resin is more than the above range. If it is too high, the heating temperature at the time of heat-sealing becomes high, and the base material described later may be damaged by heat. Also, if the melting point is lower than the above range, when the dye-sensitized solar cell using the oxide semiconductor electrode of the present invention is used outdoors, the adhesive layer melts depending on the environment, resulting in this This is because, for example, the function of the first electrode layer formed on the adhesive layer may be impaired.
The “melting point” in the present invention means the peak top temperature of the endothermic peak of the DSC curve obtained by a differential scanning calorimetry (DSC (Differential Scanning Calorimetry)) at a rate of temperature increase of 10 ° C./min. Shall.

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

  In addition, as another example of the thermoplastic resin, for example, homopolymers of α-olefins having about 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, the α-olefins and ethylene, propylene, 1 Other α-olefins having about 2 to 20 carbon atoms such as -butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, Mention may be made of copolymers with vinyl acetate, (meth) acrylic acid, (meth) acrylic acid esters, and the like, (anhydrous) maleic acid-modified resins, silane-modified resins, olefin elastomers and other polyolefin compounds.

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

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

  These polyolefin compounds can be used alone or in combination of two or more. In the present invention, among these polyolefin compounds, from the viewpoint of adhesion, modified polyolefins, particularly modified ethylene resins (for example, silane-modified resins composed of a copolymer of an ethylenically unsaturated silane compound and a polyolefin compound, ethylene-acetic acid). Vinyl copolymers, ethylene copolymers such as ethylene-ethyl acrylate copolymer, etc.) are preferred. Of these, the case where a silane-modified resin is used as the adhesive layer is most preferable. This is because the adhesive force exhibited by the adhesive layer can be further strengthened by using the silane-modified resin.

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

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

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

  Further, 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 the silane-modified resin obtained by the polymerization reaction It is preferable that the residual amount in the range is 0.001% by mass or less. Especially in this invention, it is preferable that 0.001 weight part or more is contained with respect to 100 weight part of polyolefin compounds in the said silane modified resin composition, and 0.01 weight part-5 weight part are contained especially. It is preferable.

  Furthermore, the content of the ethylenically unsaturated silane compound in the silane-modified resin composition is preferably in the range of 0.001 to 4 parts by weight, particularly 0.01 to 100 parts by weight of the polyethylene for polymerization. Within the range of parts by weight 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.

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

  Furthermore, the adhesive layer used in the present invention preferably contains at least one additive selected from the group consisting of a light stabilizer, an ultraviolet absorber, a heat stabilizer and an antioxidant. By including these additives, it is possible to obtain a long-term stable mechanical strength, yellowing prevention effect, cracking prevention effect, and workability.

  The light stabilizer supplements the active species that initiate photodegradation in the thermoplastic resin used in the adhesive layer and prevents photooxidation. Examples of such light stabilizers include hindered amine compounds and hindered piperidine compounds.

  The UV absorber absorbs harmful UV rays in sunlight and converts 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. This is to prevent this. Examples of such ultraviolet absorbers include benzophenone, benzotriazole, salicylate, acrylonitrile, metal complex, hindered amine, and ultrafine titanium oxide (particle diameter: 0.01 μm to 0.06 μm) or superfine Examples thereof include inorganic ultraviolet absorbers such as fine particle zinc oxide (particle diameter: 0.01 μm to 0.04 μm).

  Examples of the heat stabilizer include tris (2,4-di-t-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorus Acids, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, and bis (2,4-di-t-butylphenyl) pentaerythritol Examples include phosphorous heat stabilizers such as diphosphite; lactone heat stabilizers such as the reaction product of 8-hydroxy-5,7-di-t-butyl-furan-2-one and o-xylene. Can do. In particular, when a heat stabilizer is used in the present invention, it is preferable to use a phosphorus heat stabilizer and a lactone heat stabilizer in combination.

  Furthermore, the antioxidant prevents oxidative degradation of the thermoplastic resin used for the adhesive layer. Examples of such antioxidants include phenol-based, amine-based, sulfur-based, phosphorus-based, and lactone-based antioxidants.

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

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

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

(3) 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 thermoplastic resin constituting the adhesive layer, but usually 5 μm. Within the range of -300 micrometers is preferable, and the inside of the range of 10 micrometers-200 micrometers is especially 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.

4). Next, the substrate used in the present invention will be described. Although the base material used for this invention will not be specifically limited if it has desired transparency according to the use etc. of the oxide semiconductor electrode of this invention, Usually, the transmittance | permeability with respect to the light of wavelength 400nm-1000nm is sufficient. 78% or more, more preferably 80% or more. If the transmittance of the substrate is lower than the above range, for example, when a dye-sensitized solar cell is produced using the oxide semiconductor electrode of the present invention, the power generation efficiency may be impaired. It is.

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. This is because, when the base material has gas barrier properties, for example, when the oxide semiconductor electrode of the present invention is used for a dye-sensitized solar cell, stability over time can be improved. 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 base material used in the present invention is not particularly limited as long as it has a desired self-supporting property, depending on the use of the oxide semiconductor electrode of the present invention. In the present invention, usually, it is preferably in the range of 50 μm to 2000 μm, particularly preferably in the range of 75 μm to 1800 μm, and particularly preferably in the range of 100 μm to 1500 μm. This is because if the thickness of the base material is smaller than the above range, the necessary self-supporting property may not be ensured, and if the thickness is thicker than the above range, workability may be impaired.

5. Oxide Semiconductor Electrode The oxide semiconductor electrode of the present invention is formed on one side of a base material, an adhesive layer formed on the base material and made of a thermoplastic resin, a transparent electrode layer made of a metal oxide, and the transparent electrode layer. An oxide semiconductor electrode comprising: a first electrode layer made of a conductive layer formed in a pattern; and a porous layer formed on the first electrode layer and containing metal oxide semiconductor fine particles. There is no particular limitation as long as the conductive layer of one electrode layer and the adhesive layer are formed so as to contact each other.

The porous layer in the oxide semiconductor electrode of the present invention may be patterned. This is because the oxide semiconductor electrode of the present invention can be made suitable for producing a dye-sensitized solar cell having a high module electromotive force by patterning the porous layer. The 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 2 is patterned as shown in FIG. In addition, as shown in FIG. 4B, when the porous layer 2 includes the oxide semiconductor layer 2a and the intervening layer 2b, it is preferable that both layers are patterned in the same shape.
Furthermore, as a patterning aspect of the porous layer in the present invention, it is preferable that the porous layer and the first electrode layer are patterned. When the porous layer and the first electrode layer are patterned, for example, the pattern shape of the porous layer and the first electrode layer is such that the pattern shape of the porous layer is more than the pattern shape of the first electrode layer. It is preferable that the pattern shapes are different from each other due to a small aspect.

  In the present invention, when the porous layer is patterned, the pattern can be arbitrarily determined according to the application of the oxide semiconductor electrode of the present invention. preferable.

  Moreover, in this invention, it is preferable that the conductive layer opening part of the conductive layer formed in the pattern shape is filled with the said adhesive layer. This is because the adhesiveness between the first electrode layer and the adhesive layer can be increased by filling the conductive layer opening of the first electrode layer with the adhesive layer. In addition, since the adhesive layer is made of a thermoplastic resin and the conductive layer opening is filled with the adhesive layer, it is necessary to process the adhesive layer in an uneven shape corresponding to the pattern of the conductive layer in advance. This is because the productivity of the oxide semiconductor electrode of the present invention can be improved.

  The oxide semiconductor electrode of the present invention is a substrate for a dye-sensitized photocharge capacitor used for a dye-sensitized photocharge capacitor, an electrochromic display substrate used for an electrochromic display, and a photocatalytic reaction in the atmosphere. It can be used as a pollutant-decomposing substrate capable of decomposing the pollutants of the present invention, and a dye-sensitized solar cell base material used for dye-sensitized solar cells, among others, used for dye-sensitized solar cells. It is suitably used for a dye-sensitized solar cell substrate.

6). Method for Manufacturing Oxide Semiconductor Electrode The method for manufacturing an oxide semiconductor electrode of the present invention is not particularly limited as long as each of the above-described oxide semiconductor structures can be stacked with good adhesion. As such a method, for example, it can be formed by the method described in the section “E. Manufacturing Method of Oxide Semiconductor Electrode”, which will be described later.

C. Oxide semiconductor electrode with heat-resistant substrate The oxide semiconductor electrode with heat-resistant substrate of the present invention is characterized by having a heat-resistant substrate on the porous layer of the oxide semiconductor electrode described above.

  Next, the oxide semiconductor electrode with a heat-resistant substrate of the present invention will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view showing an example of an oxide semiconductor electrode with a heat-resistant substrate of the present invention. As shown in FIG. 5, the oxide semiconductor electrode 30 with a heat-resistant substrate of the present invention has the heat-resistant substrate 1 on the porous layer 2 of the oxide semiconductor electrode 20.

  According to the present invention, by having a heat-resistant substrate on the porous layer of the oxide semiconductor electrode, the heat-resistant substrate can be easily peeled off to easily produce an oxide semiconductor electrode having excellent adhesion between the layers. An oxide semiconductor electrode with a substrate can be obtained.

  The oxide semiconductor electrode with a heat resistant substrate of the present invention comprises a heat resistant substrate and an oxide semiconductor electrode. Hereinafter, each structure of the oxide semiconductor electrode with a heat-resistant board | substrate of this invention is demonstrated.

1. Heat-resistant substrate The heat-resistant substrate used in the present invention has the same contents as those described in the section “2. Heat-resistant substrate” in “A. Oxide semiconductor electrode laminate”. Omitted.

2. Oxide Semiconductor Electrode The oxide semiconductor electrode used in the present invention has the same contents as those described in the above section “B. Oxide Semiconductor Electrode”, and thus the description thereof is omitted here.

3. Oxide Semiconductor Electrode with Heat Resistant Substrate The oxide semiconductor electrode with a heat resistant substrate of the present invention is a dye-sensitized photocharging capacitor electrode, an electrochromic display electrode, a pollutant decomposition substrate, and a dye-sensitized electrode. It can be used for the production of a base material for a type solar cell, and among others, it can be suitably used for the production of a base material for a dye-sensitized solar cell.

4). Method for Producing Oxide Semiconductor Electrode with Heat-Resistant Substrate The method for producing an oxide semiconductor electrode with a heat-resistant substrate of the present invention is particularly limited as long as each of the components of the oxide semiconductor electrode with a heat-resistant substrate can be stacked with good adhesion. Is not to be done. As such a method, for example, it can be formed by a method similar to the method described in the section “E. Method for Manufacturing Oxide Semiconductor Electrode”, which will be described later.

D. Dye-sensitized solar cell The dye-sensitized solar cell of the present invention is a porous oxide oxide electrode described above in which a dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. And the second electrode layer of the counter electrode base material composed of the second electrode layer and the counter base material are arranged to face each other via an electrolyte layer containing a redox pair. .

  Next, the dye-sensitized solar cell of the present invention will be described with reference to the drawings. FIG. 6 is a schematic cross-sectional view showing an example of the dye-sensitized solar cell of the present invention. As shown in FIG. 6, in the dye-sensitized solar cell 40 of the present invention, the oxide semiconductor electrode 20 having the porous layer 2 containing the metal oxide semiconductor fine particles carrying the dye sensitizer has an oxidation-reduction pair. The counter electrode base material 43 including the second electrode layer 41 and the counter base material 42 is disposed so as to face the electrolyte layer 31.

  According to the present invention, by having the above-described oxide semiconductor electrode, a dye-sensitized solar cell excellent in photoelectric conversion efficiency can be obtained. Hereafter, each structure of the dye-sensitized solar cell of this invention is demonstrated in detail.

1. Oxide Semiconductor Electrode First, the oxide semiconductor electrode used in the present invention will be described. Since the oxide semiconductor electrode used in the present invention is the above-described oxide semiconductor electrode, the photoelectric conversion efficiency of the dye-sensitized solar cell of the present invention can be improved. The oxide semiconductor electrode is the same as that described in the above section “B. Oxide Semiconductor Electrode”, and the description thereof is omitted here.

2. Electrolyte Layer Next, 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 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. good.

(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 an oxidation-reduction pair or an imidazolium salt as a cation is used as a solvent. can do.
Furthermore, when the electrolyte layer is in a solid state, it may be any material that does not include a redox pair and functions as a hole transporting agent. For example, a hole transporting agent including CuI, polypyrrole, polythiophene, etc. There may be.

3. 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) Second electrode layer Generally, the second electrode layer in the present invention is made of a metal oxide. Examples of such a transparent electrode layer described in the section “(2) Transparent electrode layer” of “1. First electrode layer” of “A. Stack for oxide semiconductor electrode” described above. The same can be used. Moreover, as a 2nd electrode layer used for this invention, the conductive layer may be formed similarly to the 1st electrode layer mentioned above. This is because the photoelectric conversion efficiency of the dye-sensitized solar cell of the present invention can be made excellent. As such a second electrode layer, the one described in the section “1. First electrode layer” of “A. Stack for oxide semiconductor electrode” can be used. The description in is omitted.

(2) Opposing base material The opposing base material in the present invention is the same as that described in the section “4. Base material” of “B. .

(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.

4). Dye-sensitized solar cell The dye-sensitized solar cell of the present invention is a porous oxide oxide electrode described above in which a dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. And the second electrode layer of the counter electrode base material composed of the second electrode layer and the counter base material are arranged to face each other via an electrolyte layer containing a redox pair. . According to the present invention, by having the above-described oxide semiconductor electrode, a dye-sensitized solar cell excellent in photoelectric conversion efficiency can be obtained.

5. Next, a method for producing the dye-sensitized solar cell of the present invention will be described. The dye-sensitized solar cell of the present invention is produced by forming an electrolyte layer between the porous layer of the oxide semiconductor electrode described above and the second electrode substrate of the counter electrode substrate. be able to.

  In the present invention, as a method of forming an electrolyte layer between the porous layer of the oxide semiconductor electrode described above and the second electrode substrate of the counter electrode substrate, each layer can be formed with high thickness accuracy. If it is, it will not specifically limit. As such a method, after forming an electrolyte layer on the porous layer, a method of forming a second electrode layer on the electrolyte layer (first method), and a second method facing the porous layer A method (second method) of forming an electrolyte layer between the porous layer and the second electrode layer after forming the electrode layer can be mentioned.

In the present invention, the first method is preferably a coating method in which a composition for forming an electrolyte layer is applied on the porous layer and dried to form an electrolyte layer, and then a counter electrode substrate is applied. .
Further, as a second method, the porous layer and the second electrode layer of the counter electrode base material are arranged with a predetermined gap so as to face each other, and the electrolyte layer forming composition is placed in the gap. An injection method for forming an electrolyte layer by injecting is preferable. Hereinafter, such a coating method and an injection method will be described.

(1) Coating method First, the composition for forming an electrolyte layer is applied on the porous layer of the above-described oxide semiconductor electrode and dried to form an electrolyte layer, followed by coating to provide a counter electrode base material. Explain the law. By such a method, a solid electrolyte layer can be mainly formed.

  In such a coating method, a known coating method can be used as a coating method of the composition for forming a porous layer, and specifically, die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating. , Bar coating, blade coating, knife coating, air knife coating, slot die coating, slide die coating, dip coating, micro bar coating, micro bar reverse coating, screen printing (rotary method), and the like.

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

(2) Injection method Next, the porous layer included in the above-described oxide semiconductor electrode and the second electrode layer included in the counter electrode base material are arranged with a predetermined gap so as to face each other. An injection method for forming an electrolyte layer by injecting a composition for forming an electrolyte layer will be described.

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

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

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

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

E. TECHNICAL FIELD The present invention relates to a porous layer forming step of forming a porous layer on a heat resistant substrate, a transparent electrode layer forming step of forming a transparent electrode layer on the porous layer, and the transparent electrode. A conductive layer forming step of forming a conductive layer on the layer, an adhesive layer and a base material applying step of laminating an adhesive layer and a base material on the conductive layer in this order, and a heat resistant substrate peeling step of peeling the heat resistant substrate; , Has.

  A method for manufacturing such an oxide semiconductor electrode will be described with reference to the drawings. FIG. 7 shows an example of a method for manufacturing an oxide semiconductor electrode of the present invention. As illustrated in FIG. 7, in the method for manufacturing an oxide semiconductor electrode of the present invention, a heat resistant substrate 1 is prepared (FIG. 7A), and a porous layer is formed on the heat resistant substrate 1. A forming step (FIG. 7B), a transparent electrode layer forming step for forming the transparent electrode layer 3 on the porous layer 2 (FIG. 7C), and a conductive layer 4 on the transparent electrode layer 3. A conductive layer forming step (FIG. 7 (d)) to be formed, and an adhesive layer and base material applying step (FIG. 7 (e)) in which the adhesive layer 6 and the base material 7 are laminated in this order on the conductive layer 4. Then, as shown in FIG. 8, the oxide semiconductor 30 with a heat resistant substrate is prepared (FIG. 8A), and the oxide semiconductor with heat resistant substrate is prepared. By performing a heat-resistant substrate peeling step (FIG. 8B) for peeling the heat-resistant substrate 1 of 30 from the porous layer 2 It is intended to prepare a compound semiconductor electrode 20.

According to the present invention, by forming the base material after the porous layer forming step of forming the porous layer, the base is not affected by the temperature conditions required in the porous layer forming step. The material of the material can be selected. In addition, after the conductive layer is formed on the transparent electrode layer to form the first electrode layer, the adhesive layer is formed on the first electrode layer, and the adhesive layer is made of a thermoplastic resin. It is possible that the adhesive layer does not need to be processed in a concavo-convex shape corresponding to the pattern of the conductive layer. Therefore, the productivity of the oxide semiconductor electrode can be improved.
Hereafter, the manufacturing method of such an oxide semiconductor electrode of this invention is demonstrated.

1. Porous layer forming step The porous layer forming step is a step of forming a porous layer on a heat resistant substrate. In such a porous layer forming step, for example, a porous layer forming coating solution containing metal oxide semiconductor fine particles, a resin, and a solvent is applied on a heat resistant substrate, and then fired. Thus, a porous layer can be formed on the heat resistant substrate.
Also, an intermediate layer forming layer forming step for forming an intermediate layer forming layer on the heat-resistant substrate in this step, and an oxide semiconductor layer forming layer for forming the oxide semiconductor layer forming layer on the intermediate layer forming layer. Using a layer forming step and a firing step of firing the intervening layer forming layer and the oxide semiconductor layer forming layer to form a porous intervening layer and a porous layer made of an oxide semiconductor layer Thus, the porous layer formed by this step can have a configuration including two layers of an oxide semiconductor layer and an intervening layer.

  The heat-resistant substrate used in this step is the same as that described in the section “2. Heat-resistant substrate” of “A. Oxide semiconductor electrode laminate”, and thus the description thereof is omitted here.

  The metal oxide semiconductor fine particles used in the coating liquid for forming a porous layer are the “(1) metal oxide semiconductor” in “3. Porous layer” of “A. Oxide semiconductor electrode laminate”. Since it is the same as that described in the section “Fine Particles”, the description is omitted here. Moreover, what is necessary is just to adjust suitably content in the metal oxide semiconductor fine particle in the said coating liquid for porous layer formation according to the porosity provided to the said porous layer.

  The resin used in the porous layer forming coating solution is not particularly limited as long as it is easily decomposed in the firing step. As such a resin, for example, those described in JP-A No. 2005-166648 can be suitably used.

  The solvent used in the porous layer forming coating solution is not particularly limited as long as it can dissolve the resin in a desired amount, but water or an alcohol solvent is preferably used.

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

2. Transparent electrode layer forming step Next, the transparent electrode layer forming step will be described. In the transparent electrode layer forming step, a transparent electrode layer made of a metal oxide is formed on the porous layer.

  The metal oxide used in this step is the same as the contents described in “(2) Transparent electrode layer” of “1. First electrode layer” of “A. Stack for oxide semiconductor electrode”. Therefore, the description here is omitted.

  In this step, the method for forming the transparent electrode layer on the porous layer is not particularly limited as long as it can form a transparent electrode layer having a uniform thickness and excellent planarity. A transparent electrode is formed in two steps by a solution treatment step in which a base electrode layer is provided inside or on the surface of the porous layer using a coating liquid and an upper electrode layer formation step in which a main transparent electrode layer is provided on the base electrode layer. A method of forming a layer can be used. According to such a method, the metal element which the metal oxide which comprises a transparent electrode layer can be easily included in the said porous layer, and a dense transparent electrode layer can be formed. Moreover, the reverse electron transfer from the porous layer into the electrolyte can be suppressed by coating the surface of the metal oxide semiconductor fine particles forming the porous layer with the metal oxide constituting the transparent electrode layer. As a specific example of the method for forming such a transparent electrode layer, the method for forming the first electrode layer described in JP-A-2005-166648 can be suitably used.

3. Next, the conductive layer forming step will be described. This step is a step of forming a conductive layer made of a conductive material on the transparent electrode layer.

  The conductive material used in this step is the same as that described in “(1) Conductive layer” of “1. First electrode layer” in “A. Stack for oxide semiconductor electrode”. Therefore, the description here is omitted.

  In this step, the method for forming the conductive layer is not particularly limited as long as the conductive material is formed on the transparent electrode layer with good adhesion. Examples of such a method include chemical vapor deposition methods such as vacuum vapor deposition (resistance heating, dielectric heating, EB heating), chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition ( Examples thereof include a method of forming using thin film forming means such as a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a Chemical Vapor Deposition method (CVD method), a sputtering method, an ion plating method or the like. The method for forming the conductive layer can be appropriately selected depending on the conductive material for forming the conductive layer.

  In this step, the conductive layer is formed in a pattern on the transparent electrode layer. The method for forming the conductive layer in a pattern is not particularly limited as long as it can form a desired pattern, but after forming a thin film on the entire surface of the transparent electrode layer using the thin film forming means, etching, etc. A conductive layer having a desired pattern shape is formed in one step using a two-step method of forming a desired pattern shape by the pattern forming means, or a mask on which the desired pattern shape is drawn and the thin film forming means. A method is mentioned. In the present invention, a method of forming a conductive layer having a pattern shape in one step using the mask and the thin film forming means is preferable. This is because the production process can be simplified, and waste generated during etching or the like can be suppressed.

4). Next, the adhesive layer and the base material application step will be described. In the adhesive layer and base material application step, an adhesive layer and a base material are provided on the conductive layer to form an oxide semiconductor electrode with a heat resistant substrate. Hereinafter, such an adhesive layer and a base material provision process are demonstrated.

The adhesive layer used in this step is made of a thermoplastic resin, and as such a thermoplastic resin, those described in the section “3. Adhesive layer” of “B. Oxide semiconductor electrode” above. It is the same.
In addition, the base material used in this step is the same as that described in the section “4. Base material” of “B. Oxide semiconductor electrode”, and therefore the description thereof is omitted here.

  In this step, the method for applying the adhesive layer and the substrate is not particularly limited as long as it can provide the adhesive layer and the substrate with good adhesion on the conductive layer. As such a method, after previously forming an adhesive layer made of a thermoplastic resin on a base material, and arranging the base material having the adhesive layer so that the adhesive layer and the conductive layer are bonded, A method of heat-sealing (first method) and a method of producing a heat-meltable film made of a thermoplastic resin and laminating a conductive layer and a substrate through the heat-meltable film (second method) Method) and an extrusion lamination method (third method) in which a thermoplastic resin is directly poured between the conductive layer and the base material and thermally welded.

  In addition, in this step, for example, an opening filling assisting step may be included in order to more reliably fill the conductive layer opening of the first electrode layer with the adhesive layer. The adhesive layer is made of a thermoplastic resin, so that the conductive layer opening can be filled with the adhesive layer without processing the concave / convex shape corresponding to the pattern of the conductive layer on the adhesive layer in advance. By including the opening filling auxiliary step, the conductive layer opening is more reliably filled with the adhesive layer.

In this step, as the opening filling auxiliary step, for example, a filler injection step for injecting a filler made of the same component as the thermoplastic resin constituting the adhesive layer into the conductive layer opening, and the conductive layer An air removal step of reducing the pressure when laminating the adhesive layer and the base material and removing the air enclosed in the opening of the conductive layer can be exemplified.
The filling material injection step is performed before the conductive layer, the adhesive layer, and the base material are laminated, so that the filling of the conductive layer opening by the adhesive layer can be made more reliable.
The air removing step is effective when the thermoplastic resin constituting the adhesive layer is prevented from flowing into the conductive layer opening because air is accumulated in the conductive layer opening. The air removal step may be performed when the conductive layer, the adhesive layer, and the substrate are laminated, or may be performed simultaneously with the filler injection step. Moreover, you may implement in both the time of laminating | stacking the said conductive layer, an adhesive layer, and a base material, and the said filler injection process.

5. Next, the heat-resistant substrate peeling process used for this invention is demonstrated. This process is a process for producing the oxide semiconductor electrode 20 by peeling the heat-resistant substrate 1 from the porous layer 2 of the oxide semiconductor electrode 30 with the heat-resistant substrate, as already described with reference to FIG.

  In this step, a method for peeling the heat-resistant substrate from the oxide semiconductor electrode with a heat-resistant substrate is not particularly limited, and a general peeling method can be used. In this step, the heat-resistant substrate can be peeled off by mechanical polishing or chemical removal such as etching.

  In the heat-resistant substrate peeling step, the heat-resistant substrate is peeled off from the porous layer, and the peeled state may be peeled off from the boundary between the heat-resistant substrate and the porous layer. Alternatively, the porous layer may be peeled off by cohesive failure. In addition, when the porous layer is composed of two layers of an oxide semiconductor layer and an intervening layer, the heat-resistant substrate is peeled off from the intervening layer. In this case as well, the heat-resistant substrate is similarly separated from the heat-resistant substrate and the intervening layer. The interlayer may be peeled off from the boundary, or the intervening layer may be peeled off by cohesive failure.

6). Other Steps The oxide semiconductor electrode manufacturing method of the present invention may include other steps in addition to the above steps. Examples of other steps used in the present invention include a patterning step for patterning a porous layer and a dye sensitizer carrying step for containing a dye sensitizer in the porous layer. In addition, the oxide semiconductor electrode of this invention can be made into the base material for dye-sensitized solar cells used for a dye-sensitized solar cell by a dye-sensitizer carrying | support process. Hereinafter, these steps will be described.

(Patterning process)
First, the patterning process used for this invention is demonstrated. The patterning step in the present invention is a step of patterning the porous layer.

  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.

  As a patterning method other than the above, as illustrated in FIG. 9, a patterning substrate 50 having a heat-meltable resin layer 52 patterned on an arbitrary substrate 51 and the oxide semiconductor electrode 20 of the present invention are prepared. (FIG. 9 (a)), after heat-sealing so that the heat-meltable resin layer 52 and the porous layer 2 are in contact with each other, the patterning substrate 50 is peeled off (FIG. 9 (b)). The oxide semiconductor electrode 20 in which the layer is patterned can be obtained. The method for forming the patterned hot-melt resin layer on the substrate is not particularly limited, and a known method such as a printing method can be used.

  When producing a dye-sensitized solar cell using the oxide semiconductor electrode of the present invention, the patterning step may be performed in a state where the porous layer does not contain a dye sensitizer, and will be described later. After the dye sensitizer carrying step, patterning may be performed in a state where the porous layer contains the dye sensitizer.

(Dye sensitizer carrying step)
Next, the dye sensitizer carrying step used in the present invention will be described. The dye sensitizer carrying step in the present invention is a step of carrying the dye sensitizer on the porous layer. The oxide semiconductor electrode of this invention can be made into the base material for dye-sensitized solar cells used for a dye-sensitized solar cell by a dye sensitizer carrying | support process. The dye sensitizer used in this step is the same as that described in the section “3. Porous layer” of the “A. Oxide semiconductor electrode laminate”, and is therefore described here. Is omitted.

  In the present invention, the timing of loading the dye sensitizer on the porous layer in the dye sensitizer supporting step is not particularly limited as long as it is after the porous layer forming step. After the step, it may be carried out before the first electrode layer forming step, or after the first electrode layer forming step, and before the adhesive layer and base material applying step, and the adhesive layer and base material applying. You may implement after a process and before the said heat-resistant board | substrate peeling process. Further, it may be performed after the heat-resistant substrate peeling step and before the patterning step, or after the patterning step.

  In the dye sensitizer supporting step, the method of supporting the dye sensitizer on the porous layer is a method capable of adsorbing the dye sensitizer on the surface of the metal oxide semiconductor fine particles contained in the porous layer. There is no particular limitation. For example, a method in which a porous layer is infiltrated into a dye sensitizer solution and then dried, a method in which a solution of a dye sensitizer is applied and infiltrated into a porous layer, and then dried can be exemplified. .

  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]
1. Formation of porous layer Titanium oxide paste Ti-Nanoxide D (manufactured by Solaronix) having a particle size of about 13 nm is applied as a coating liquid for forming an oxide semiconductor layer onto a non-alkali glass substrate, which is a heat-resistant substrate, by a doctor blade method. Then, it was dried at room temperature for 20 minutes and at about 100 ° C. for 30 minutes. Thus, an oxide semiconductor layer forming layer was formed on the heat resistant substrate.

  Next, the layer for forming an oxide semiconductor layer was baked at 500 ° C. for 30 minutes in an atmospheric pressure atmosphere using an electric muffle furnace (P90 manufactured by Denken). Thereby, the porous layer was formed.

2. Formation of transparent electrode layer Indium chloride 0.1 mol / L and tin chloride 0.005 mol / L were dissolved in ethanol to prepare a coating solution for forming a transparent electrode layer. Next, the porous layer is heated by placing the heat-resistant substrate on which the porous layer is formed on a hot plate (400 ° C.) so that the porous layer faces upward, and the heated porous A transparent electrode layer made of an ITO film having a thickness of 500 nm was formed on the layer by spraying the transparent electrode layer forming coating solution with an ultrasonic sprayer.

3. Formation of Conductive Layer Silver was used as a conductive material for forming the conductive layer, and a conductive layer having a thickness of 5 μm was formed on the transparent electrode layer by a mask vapor deposition method. The obtained conductive layer had a lattice shape with a line width of 30 μm and an opening of 300 μm. The aperture ratio at this time was 83%.

4). Application of adhesive layer and base material 2 parts by weight of vinyl methoxysilane and 0.1 part by weight of radical generator are mixed with 98 parts by weight of linear low density polyethylene (LLDPE) having a density of 0.898 g / cm ^3. A silane-modified polyethylene resin was obtained by polymerization. The resin was mixed with weathering agent pellets comprising an antioxidant, an ultraviolet absorber, and a light stabilizer, and an adhesive layer comprising a 50 μm thermoplastic resin film was obtained by melt extrusion using a T-die.

  Next, the corona-treated surface of the base material made of PET film (Toyobo E5100, thickness 125 μm), the adhesive layer and the first electrode layer were laminated in this order, and then heat laminated at 130 ° C. with a heat resistant substrate. An oxide semiconductor electrode was produced.

5. Peeling of heat-resistant substrate Next, the heat-resistant substrate of the oxide semiconductor electrode with a heat-resistant substrate was peeled off to produce an oxide semiconductor electrode.

6). Preparation of Dye-Sensitized Solar Cell Substrate The porous layer was trimmed to 10 cm × 10 cm, and the first electrode layer was exposed in regions other than the porous electrode layer. Then, as a dye sensitizer, ruthenium complex RuL ₂ (NCS) ₂ -2TBA (Peccell Technologies, Inc. PECC07), acetonitrile / tert-butanol in which volume ratio was mixed with acetonitrile 1 at a ratio of 1 to tert-butanol A dye solution for adsorption is prepared by dissolving in a solution at 3 × 10 −4 mol / L, and the oxide semiconductor electrode is immersed in the dye solution for adsorption, thereby sensitizing the porous layer with the dye. A dye-sensitized solar cell substrate was prepared by supporting the agent.

7). Preparation of dye-sensitized solar cell Using methoxyacetonitrile as a solvent, 0.1 mol / L lithium iodide, 0.05 mol / L iodine, 0.3 mol / L dimethylpropylimidazolium iodide, 0.5 mol / L An electrolyte layer forming composition for forming an electrolyte layer was prepared by dissolving L tertiary butylpyridine.

  The dye-sensitized solar cell substrate and the opposing substrate were bonded to each other with a 20 μm thick Surlyn film, and an electrolyte layer forming coating solution was impregnated between them to produce a dye-sensitized solar cell. . As the counter substrate, a platinum film having a film thickness of 150 nm and a surface resistance of 7 Ω / □ and a platinum film having a film thickness of 50 nm provided on the counter film substrate having an ITO sputter layer was used.

[Comparative Example 1]
A dye-sensitized solar cell was produced in the same manner as in Example 1 except that the conductive layer was not provided in Example 1.

[Evaluation]
The dye-sensitized solar cell is evaluated using dye-sensitized solar cells having a porous layer in which a dye-sensitizer is adsorbed using AM1.5 and simulated sunlight (incident light intensity of 100 mW / cm ² ) as a light source. Incidence was made from the battery substrate side, and current-voltage characteristics were measured by applying voltage with a source measure unit (Caseley 2400 type). As a result, for the comparative example, the short-circuit current value was 4.8 mA / cm ² , the open circuit voltage was 0.685 V, the fill factor was 0.28, and the photoelectric conversion efficiency was 0.92%. The value was 13.8 mA / cm ² , the open circuit voltage was 0.696 V, the fill factor was 0.62, and the photoelectric conversion efficiency was 6.0%, confirming improvement in the characteristics of the solar cell.

It is a schematic sectional drawing which shows an example of the laminated body for oxide semiconductor electrodes of this invention. It is a schematic sectional drawing which shows the other example of the laminated body for oxide semiconductor electrodes of this invention. It is a schematic sectional drawing which shows an example of the oxide semiconductor electrode of this invention. It is a schematic sectional drawing which shows the other example of the oxide semiconductor electrode of this invention. It is a schematic sectional drawing which shows an example of the oxide semiconductor electrode with a heat-resistant board | substrate 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 method of the oxide semiconductor electrode of this invention. It is process drawing which shows an example of the heat-resistant board | substrate peeling process in this invention. It is process drawing which shows an example of the patterning process in this invention. It is a schematic sectional drawing which shows an example of the general structure of a dye-sensitized solar cell. It is a schematic sectional drawing which shows an example of the dye-sensitized solar cell which has an contact bonding layer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Heat-resistant board | substrate 2 ... Porous layer 2a ... Oxide semiconductor layer 2b ... Interposition layer 3 ... Transparent electrode layer 4 ... Conductive layer 5 ... 1st electrode layer 6 ... Adhesive layer 7 ... Base material 10 ... Lamination | stacking for oxide semiconductor electrodes Body 20 ... Oxide semiconductor electrode 30 ... Oxide semiconductor electrode with heat-resistant substrate 31 ... Electrolyte layer 40 ... Dye-sensitized solar cell 41 ... Second electrode layer 42 ... Opposite substrate 43 ... Counter electrode substrate 50 ... Patterning group Material 51 ... Base material 52 ... Hot-melt resin layer

Claims (6)

  A heat-resistant substrate having heat resistance, a porous layer formed on the heat-resistant substrate and containing metal oxide semiconductor fine particles, a transparent electrode layer formed on the porous layer and made of a metal oxide, and the transparent electrode And a first electrode layer made of a conductive layer formed in a pattern on the surface of the layer.   A first electrode comprising a base material, an adhesive layer formed on the base material and made of a thermoplastic resin, a transparent electrode layer made of a metal oxide, and a conductive layer formed in a pattern on one side of the transparent electrode layer An oxide semiconductor electrode having a layer and a porous layer formed on the first electrode layer and including metal oxide semiconductor fine particles, wherein the conductive layer of the first electrode layer and the adhesive layer are An oxide semiconductor electrode formed so as to be in contact with each other.   The oxide semiconductor electrode according to claim 2, wherein the conductive layer opening of the first electrode layer is filled with the adhesive layer.   An oxide semiconductor electrode with a heat-resistant substrate, comprising a heat-resistant substrate on the porous layer of the oxide semiconductor electrode according to claim 2.   The porous layer, the second electrode layer, and the opposing group of the oxide semiconductor electrode according to claim 2 or 3, wherein a dye sensitizer is adsorbed on the surface of the metal oxide semiconductor fine particles contained in the porous layer. A dye-sensitized solar cell, characterized in that a second electrode layer of a counter electrode substrate made of a material is disposed so as to face each other via an electrolyte layer containing a redox pair.   A porous layer forming step of forming a porous layer on a heat resistant substrate, a transparent electrode layer forming step of forming a transparent electrode layer on the porous layer, and a conductive layer forming of forming a conductive layer on the transparent electrode layer An oxide semiconductor comprising: a step, an adhesive layer and a base material applying step for laminating an adhesive layer and a base material on the conductive layer in this order; and a heat resistant substrate peeling step for peeling the heat resistant substrate Electrode manufacturing method.

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