JP5251149B2 - Laminated body for oxide semiconductor electrode, oxide semiconductor electrode, and dye-sensitized solar cell module - Google Patents

Description

  The present invention uses an oxide semiconductor electrode suitably used for a dye-sensitized solar cell and the like, a laminate for an oxide semiconductor electrode suitably used for producing the oxide semiconductor electrode, and an oxide semiconductor electrode The present invention relates to a dye-sensitized solar cell module and the like.

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

  An example of a general configuration of the dye-sensitized solar cell is shown in FIG. As illustrated in FIG. 5, a general dye-sensitized solar cell 100 includes a porous layer including metal oxide semiconductor fine particles carrying a first electrode layer 112 and a dye sensitizer on a substrate 111. An electrolyte layer 101 having a redox pair is a sealing material between the oxide semiconductor electrode 110 in which the layers 113 are stacked in this order and the counter electrode substrate 120 in which the second electrode layer 122 is formed on the counter substrate 121. 102 has a configuration formed inside 102. Then, the dye sensitizer adsorbed on the surface of the metal oxide semiconductor fine particles is excited by receiving sunlight from the substrate 111 side, and the excited electrons are conducted to the first electrode layer, and are then passed through the external circuit. Conducted to two electrode layers. Thereafter, electricity is generated by returning the electrons to the ground level of the dye sensitizer through the redox pair. A typical example of such a dye-sensitized solar cell is a Gretcher cell in which the porous layer is made of porous titanium dioxide and the content of the dye sensitizer is increased. It has been widely studied as a sensitized solar cell. In recent years, a dye-sensitized solar cell module having a high electromotive force has been known by connecting a plurality of dye-sensitized solar cells in parallel or in series (for example, Patent Document 1). .

  Here, in order to form the porous layer that is characteristic of the above-described Gretchel cell, it is generally necessary to perform a baking treatment at 300 ° C. to 700 ° C. on the porous layer forming composition. It is. 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 such problems, Patent Document 2 discloses that after a porous layer containing metal oxide semiconductor fine particles is formed on a heat-resistant substrate, an electrode layer made of a metal oxide is formed on the porous layer. Forming the oxide semiconductor electrode laminate, and then bonding the base material onto the electrode layer of the oxide semiconductor electrode laminate, and further peeling the heat-resistant substrate to form the oxide semiconductor electrode (Transfer method) is disclosed. According to such a transfer method, it is possible to form a porous layer on an arbitrary base material by transferring the porous layer baked on the heat-resistant substrate. Therefore, such a transfer method is useful in that an appropriate base material can be selected according to the use of the oxide semiconductor electrode. Particularly in recent years, there has been a demand for flexibility in dye-sensitized solar cells, which is useful in that a flexible oxide semiconductor electrode can be easily produced using a flexible substrate according to the above transfer method. It is.

  By the way, in the dye-sensitized solar cell using the oxide semiconductor electrode as described above, a transparent material is used as the first electrode layer so as not to prevent incident light from the substrate side. Is common. As such materials, metal oxides such as ITO (indium tin oxide) and FTO (fluorine-doped tin oxide) have been mainly used. However, since such a metal oxide does not have a sufficiently low electric resistance, the photoelectric conversion efficiency of the dye-sensitized solar cell is reduced due to the electric resistance of the first electrode layer. Problems were pointed out.

  For such a problem, Patent Document 3 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 such a method, although the photoelectric conversion efficiency can be improved by providing a conductive layer made of a metal or alloy having a lower resistance value than the electrode layer, the conductive layer is formed by iodine or the like contained in the electrolyte layer. The problem of being corroded has been pointed out. Furthermore, Patent Document 1 described above discloses that the conductive layer is prevented from being corroded by covering the conductive layer with a sealant that separates a plurality of dye-sensitized solar cells. However, even in such a method, it is still impossible to sufficiently prevent corrosion of the conductive layer. Further, as in Patent Document 1 and Patent Document 2, when a conductive layer is disposed between the electrode layer and the electrolyte layer, the thickness of the conductive layer is greater than the cell gap of the dye-sensitized solar cell. There is a restriction that it cannot be thickened. Accordingly, it has been pointed out that even if the conductive layer is formed, the thickness is insufficient, so that it cannot contribute to the improvement of photoelectric conversion efficiency.

WO 97/16838 pamphlet JP 2002-184475 A JP 2003-203681 A

  The present invention has been made in view of such problems, and is provided with a conductive layer having a thickness larger than that of a conventional transfer method, whereby a dye-sensitized type having high photoelectric conversion efficiency and excellent durability. The main object is to provide a laminated body for an oxide semiconductor electrode capable of producing a solar cell module.

  In order to solve the above-described problems, the present invention provides a heat-resistant substrate having heat resistance, a release layer formed in a pattern on the heat-resistant substrate, containing metal oxide semiconductor fine particles, and formed to cover the release layer An oxide semiconductor layer containing metal oxide semiconductor fine particles and having a lower porosity than the release layer, a first electrode layer formed on the oxide semiconductor layer and made of a metal oxide, and the first There is provided a stacked body for an oxide semiconductor electrode, characterized by having a conductive layer formed in a pattern on a region where one electrode layer is formed and the release layer is not formed.

According to the present invention, when the conductive layer is formed on the first electrode layer, when the dye-sensitized solar cell module is manufactured using the oxide semiconductor electrode laminate of the present invention, The conductive layer is not restricted by thickness. For this reason, according to this invention, as a result of being able to form a conductive layer with arbitrary thickness, a dye-sensitized solar cell module with high photoelectric conversion efficiency is produced by having a conductive layer thicker than before. An oxide semiconductor electrode stack that can be obtained can be obtained.
In addition, the oxide semiconductor electrode laminate according to the present invention includes the conductive layer on the first electrode layer and the region where the release layer is not formed. In the dye-sensitized solar cell module manufactured using the laminated body for an oxide semiconductor electrode, the conductive layer can be prevented from being corroded by the action of the redox couple. For this reason, according to this invention, a highly durable dye-sensitized solar cell module can be obtained.
Furthermore, the oxide semiconductor electrode laminate of the present invention uses a transfer method by bonding the surface on the first electrode side on which the conductive layer is formed to an arbitrary base material and peeling off the heat-resistant substrate. An oxide semiconductor electrode can be manufactured. Here, in the present invention, since the release layer is formed in a pattern, only the portion where the release layer is formed is selectively transferred onto an arbitrary base material when the heat-resistant substrate is peeled off. can do. For this reason, according to the present invention, the oxide semiconductor electrode in which the oxide semiconductor layer is patterned can be manufactured in a simple process. As a result, a dye-sensitized solar cell module can be manufactured with high productivity. it can.
Therefore, according to the present invention, a dye-sensitized solar cell module having high photoelectric conversion efficiency and excellent durability is prepared by a transfer method by providing a conductive layer having a thickness larger than that of the conventional one. The laminated body for oxide semiconductor electrodes which can be provided can be provided.

  In the laminated body for oxide semiconductor electrodes of this invention, it is preferable that the thickness of the said conductive layer exists in the range of 1 micrometer-500 micrometers. When the thickness of the conductive layer is within such a range, the oxide semiconductor electrode laminate of the present invention can be used to produce a dye-sensitized solar cell module with higher photoelectric conversion efficiency. Because it can.

  The present invention also includes a base material, an adhesive layer formed on the base material and made of a thermoplastic resin, a first electrode layer formed on the adhesive layer and made of a metal oxide, and the first electrode layer. A porous layer including a metal oxide semiconductor fine particle formed in a pattern on the first electrode layer and a sealing layer formed in a region where the porous layer is not formed; A conductive layer formed on the surface of the first electrode layer on the adhesive layer side and in a position facing the region where the sealing layer is formed so as to be accommodated in the adhesive layer. An oxide semiconductor electrode is provided.

According to the present invention, the conductive layer is formed on the surface of the first electrode layer on the adhesive layer side so as to be housed in the adhesive layer. There are no restrictions. For this reason, according to the present invention, the conductive layer can be formed with an arbitrary thickness. As a result, an oxide semiconductor electrode with high photoelectric conversion efficiency can be obtained by having a conductive layer with a thickness larger than that of the conventional one.
Moreover, the oxide semiconductor electrode of the present invention is such that the conductive layer is on the surface of the first electrode layer on the side of the adhesive layer, and is located at a position facing the region where the sealing layer is formed. In the dye-sensitized solar cell module produced using the oxide semiconductor electrode of the present invention, the conductive layer is prevented from being corroded by the action of the redox couple. it can. For this reason, according to this invention, a highly durable dye-sensitized solar cell module can be obtained.

  In the oxide semiconductor electrode of the present invention, the conductive layer preferably has a thickness in the range of 1 μm to 500 μm. This is because when the thickness of the conductive layer is within such a range, a dye-sensitized solar cell module with higher photoelectric conversion efficiency can be manufactured using the oxide semiconductor electrode of the present invention.

  Furthermore, the present invention provides the above-described oxide semiconductor electrode according to the present invention, a counter substrate, and a counter electrode substrate having a second electrode layer formed on the counter substrate and made of a metal oxide. An electrolyte layer that is bonded via the sealing layer so that the porous layer and the second electrode layer face each other, and further includes a redox pair between the oxide semiconductor electrode and the counter electrode substrate The present invention provides a dye-sensitized solar cell module characterized by having a structure in which is formed.

  According to the present invention, a plurality of colored paper-sensitized solar cells are connected in parallel, and the oxide semiconductor electrode according to the present invention is used, so that excellent photoelectric conversion efficiency is achieved. It is possible to obtain a dye-sensitized solar cell module that is excellent in durability.

  The present invention provides an oxide semiconductor capable of producing a dye-sensitized solar cell module having high photoelectric conversion efficiency and excellent durability by including a conductive layer having a thickness larger than that of a conventional method by a transfer method. There exists an effect that the laminated body for electrodes can be provided.

The present invention relates to an oxide semiconductor electrode laminate, an oxide semiconductor electrode, and a dye-sensitized solar cell module.
Hereinafter, these will be described in order.

A. First, the laminated body for oxide semiconductor electrodes of this invention is demonstrated. As described above, the oxide semiconductor electrode laminate of the present invention includes a heat-resistant substrate having heat resistance, a release layer formed in a pattern on the heat-resistant substrate and containing metal oxide semiconductor fine particles, and the release layer. And an oxide semiconductor layer containing metal oxide semiconductor fine particles and having a lower porosity than the release layer, and a first electrode formed on the oxide semiconductor layer and made of a metal oxide And a conductive layer formed in a pattern on a region on the first electrode layer and on which the release layer is not formed.

  Such a laminated body for oxide semiconductor electrodes of the present invention will be described. FIG. 1 is a schematic cross-sectional view showing an example of the oxide semiconductor electrode laminate of the present invention. As illustrated in FIG. 1, an oxide semiconductor electrode 10 of the present invention includes a heat-resistant substrate 1 having heat resistance, a release layer 2 formed in a pattern on the heat-resistant substrate 1 and containing metal oxide semiconductor fine particles. The oxide semiconductor layer 3 is formed on the oxide semiconductor layer 3 so as to cover the release layer 2 and contains metal oxide semiconductor fine particles and has a lower porosity than the release layer 2. The first electrode layer 4 is made of a metal oxide, and the conductive layer 5 is formed on the first electrode layer 4. In the oxide semiconductor electrode laminate 10 according to the present invention, the conductive layer 5 is formed in a pattern on the first electrode layer 4 and on the region where the release layer 2 is not formed. Is.

  The laminate for an oxide semiconductor electrode of the present invention is suitably used for producing an oxide semiconductor electrode suitable mainly for producing a dye-sensitized solar cell module. Here, a typical method for manufacturing an oxide semiconductor electrode using the stacked body for oxide semiconductor electrodes of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view illustrating an example of a method for manufacturing an oxide semiconductor electrode using the stacked body for oxide semiconductor electrodes of the present invention. As illustrated in FIG. 2, the oxide semiconductor electrode stacked body 10 of the present invention uses the oxide semiconductor electrode stacked body 10 (FIG. 2A), and the oxide semiconductor electrode stacked body 10. A base material bonding step (FIG. 2B) for bonding the base material 21 on the first electrode layer 4 via the adhesive layer 22, and a heat resistant substrate peeling step for peeling the heat resistant substrate 1 (FIG. 2C). Thus, the oxide semiconductor electrode 20 ′ is preferably used for manufacturing the oxide semiconductor electrode 20 ′ (FIG. 2D). Here, the oxide semiconductor electrode laminate 10 according to the present invention has the release layer 2 formed in the pattern, so that only the region where the release layer is formed in the heat-resistant substrate release step is selectively used. The heat-resistant substrate 1 can be peeled off. For this reason, the oxide semiconductor electrode 20 ′ manufactured using the oxide semiconductor electrode stack 10 of the present invention has the oxide semiconductor layer 3 formed in a pattern. Therefore, it can be said that the oxide semiconductor electrode stacked body 10 of the present invention can easily produce 20 'of an oxide semiconductor electrode suitably used for producing a module element.

According to the oxide semiconductor electrode laminate of the present invention, a dye-sensitized solar cell module is produced using the oxide semiconductor electrode laminate of the present invention by being formed on the first electrode layer. In this case, the conductive layer is not restricted by the thickness. For this reason, according to this invention, as a result of being able to form a conductive layer with arbitrary thickness, a dye-sensitized solar cell module with high photoelectric conversion efficiency is produced by having a conductive layer thicker than before. An oxide semiconductor electrode stack that can be obtained can be obtained.
In addition, the oxide semiconductor electrode laminate according to the present invention includes the conductive layer on the first electrode layer and the region where the release layer is not formed. In the dye-sensitized solar cell module manufactured using the laminated body for an oxide semiconductor electrode, the conductive layer can be prevented from being corroded by the action of the redox couple. For this reason, according to this invention, a highly durable dye-sensitized solar cell module can be obtained.
Furthermore, the oxide semiconductor electrode laminate of the present invention uses a transfer method by bonding the surface on the first electrode side on which the conductive layer is formed to an arbitrary base material and peeling off the heat-resistant substrate. An oxide semiconductor electrode can be manufactured. In the present invention, since the release layer is formed in a pattern, the release layer is formed when the heat-resistant substrate is peeled off. Only can be selectively transferred onto any substrate. For this reason, according to the present invention, the oxide semiconductor electrode in which the oxide semiconductor layer is patterned can be manufactured in a simple process. As a result, a dye-sensitized solar cell module can be manufactured with high productivity. it can.
For this reason, according to the present invention, a dye-sensitized solar cell module having high photoelectric conversion efficiency and excellent durability can be produced by a transfer method by providing a conductive layer having a larger thickness than the conventional one. The laminated body for oxide semiconductor electrodes which can be provided can be provided.

The oxide semiconductor electrode of the present invention has at least a heat-resistant substrate, a release layer, an oxide semiconductor layer, a conductive layer, and a first electrode layer, and may have any other configuration as necessary. It is.
Hereafter, each structure used for the oxide semiconductor electrode of this invention is demonstrated in order.

1. Conductive layer First, the conductive layer used in the present invention will be described. The conductive layer used in the present invention is formed on the first electrode layer described later and in a pattern on the region where the release layer is not formed. An oxide semiconductor electrode manufactured using a body has a function of collecting current generated by photoelectric conversion in an oxide semiconductor layer or the like.
Hereinafter, such a conductive layer will be described.

  The conductive layer used in the present invention is formed in a pattern on a first electrode layer described later and on a region where the release layer is not formed. And since a conductive layer is formed in such an aspect, a conductive layer can be formed with arbitrary thickness, without receiving restrictions in particular in thickness. Here, “on the region where the release layer is not formed” means that the conductive layer is formed when the oxide semiconductor electrode laminate of the present invention is viewed from the direction perpendicular to the surface of the first electrode layer. This means that the position where the release layer is formed and the position where the release layer is formed do not overlap.

  Since the conductive layer used in the present invention has the above-described current collecting function, it is preferable that the thickness is large in order to reduce the electric resistance. In particular, the thickness of the conductive layer used in the present invention is preferably in the range of 1 μm to 500 μm, more preferably in the range of 3 μm to 200 μm, and still more preferably in the range of 5 μm to 80 μm. . This is because when the thickness of the conductive layer is larger than the above range, it may be difficult to manufacture the oxide semiconductor electrode using the oxide semiconductor electrode laminate of the present invention. Moreover, it is because the electroconductivity of a conductive layer may become inadequate when it is thinner than the said range.

  The material constituting the conductive layer used in the present invention is not particularly limited as long as it is conductive and can be formed in a desired pattern. In particular, the conductive material used in the present invention is more conductive than transparent metal oxides such as ITO (indium tin oxide) and FTO (fluorine-doped tin oxide), which are typical constituent materials of the first electrode layer described later. Is preferably high.

Examples of the conductive material include metals, alloys, and carbon. Among them, in the present invention, one or more of Ti, Pt, Al, Ag, Ag alloy (Ag / Pd, Ag / Nd, Ag / Au), Cu, Cu alloy, etc. are used. This is because these alloys have a particularly high conductivity among the conductive materials, and thus a conductive layer having a higher current collection efficiency can be obtained.
In the present invention, since the conductive layer is formed on the surface of the first electrode layer opposite to the heat-resistant substrate, for example, an oxide produced using the oxide semiconductor electrode laminate of the present invention. Even when the semiconductor electrode is used in a dye-sensitized solar cell module, the conductive layer is less likely to be corroded by a redox couple or the like. Therefore, in the present invention, when selecting the conductive material, there is an advantage that any conductive material can be selected without particularly considering corrosion resistance.

  In addition, the conductive layer used in the present invention is formed in a pattern on a first electrode layer to be described later, but the pattern for forming the conductive layer includes the laminate for oxide semiconductor electrodes of the present invention. Depending on the application of the oxide semiconductor electrode manufactured using the electrode, the pattern is particularly limited as long as the pattern allows the light irradiated to the oxide semiconductor layer from the conductive layer side through the first electrode layer to be transmitted more than a certain amount. It is not something. Especially in this invention, it is preferable to employ | adopt the thing which exhibits the shape which combined many thin lines as said pattern, and has a high aperture ratio. According to such a pattern, for example, even in the case where a material that does not transmit light is used as the conductive material, the light beam irradiated to the oxide semiconductor layer from the conductive layer side through the first electrode layer. This is because the transmittance can be made extremely high.

  When the pattern has the shape as described above, the line width of the fine line is such that the transmittance of light irradiated on the oxide semiconductor layer from the conductive layer side through the first electrode layer can be within a desired range. If it is, it will not specifically limit. Especially in this invention, it is preferable that the line | wire width of the said fine wire is the range of 10 micrometers-3000 micrometers, and it is especially preferable that it is the range of 100 micrometers-1000 micrometers. This is because if the line width is narrower than the above range, it may not be possible to improve the conductivity due to the formation of the conductive layer. Further, if the thickness is larger than the above range, the transmittance of light irradiated from the conductive layer side to the oxide semiconductor layer through the first electrode layer may be lowered.

  Moreover, when the said pattern is made into the shape as mentioned above, it is preferable that the aperture ratio of the said conductive layer is in the range of 60% to 99%, particularly preferably in the range of 80% to 99%. Here, the aperture ratio is defined by the ratio of the area not shielded by the conductive layer in the unit area when the conductive layer used in the present invention is viewed from the direction perpendicular to the surface.

The pattern of the conductive layer used in the present invention is preferably such that the area shielded by the conductive layer per unit area is constant when the conductive layer is viewed from the direction perpendicular to the surface. This is because the conductivity of the conductive layer can be made excellent.
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 particularly preferable. This is because it becomes easy to uniformly dispose the conductive layer.

2. Oxide Semiconductor Layer Next, the porous layer used in the present invention will be described. The porous layer used in the present invention is formed on a heat resistant substrate described later and so as to cover a release layer described later. The porous layer used in the present invention contains metal oxide semiconductor fine particles, and imparts semiconductor properties to the oxide semiconductor electrode produced using the oxide semiconductor electrode laminate of the present invention. It is what has.
Hereinafter, such a porous layer will be described in detail.

(1) Metal Oxide Semiconductor Fine Particle The metal oxide semiconductor fine particle used in the present invention is not particularly limited as long as it is made of a metal oxide having semiconductor characteristics, and for the oxide semiconductor electrode of the present invention. The oxide semiconductor electrode manufactured using the stacked body can be appropriately selected and used depending on the application or the like of the oxide semiconductor electrode. Examples of the metal oxide constituting 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 , and Mn. ₃ O ₄ , Y ₂ O ₃ , WO ₃ , Ta ₂ O ₅ , Nb ₂ O ₅ , La ₂ O _{3 and the} like can be mentioned. These metal oxide semiconductor fine particles are suitable for forming a porous oxide semiconductor layer, and can be preferably used in the present invention because energy conversion efficiency can be improved and costs can be reduced.

The metal oxide semiconductor fine particles used in the present invention may be all made of the same metal oxide, or two or more kinds of those made of different metal oxides may be used. In addition, the metal oxide semiconductor fine particles used in the present invention may have a core-shell structure in which one type is a core fine particle and the other metal oxide semiconductor fine particles include the core fine particle to form a shell.
In particular, in the present invention, it is most preferable to use TiO ₂ as the semiconductor oxide fine particles. This is because TiO ₂ is particularly excellent in semiconductor characteristics.

  The particle diameter of the metal oxide semiconductor fine particles used in the present invention is not particularly limited as long as the surface area of the oxide semiconductor layer can be within a desired range, but is usually within the range of 1 nm to 10 μm. Is preferable, and it is particularly preferably in the range of 10 nm to 1000 nm. If the particle size is smaller than the above range, each metal oxide semiconductor fine particle may aggregate to form secondary particles, and if the particle size is larger than the above range, the oxide semiconductor layer becomes thicker. This is because the porosity of the oxide semiconductor layer, that is, the specific surface area may decrease. Here, when the surface area of the oxide semiconductor layer is reduced, for example, when the dye-sensitized solar cell module is used to fabricate the oxide semiconductor electrode laminate of the present invention, it is sufficient for photoelectric conversion. In some cases, it is difficult to support a dye sensitizer on the porous layer.

In the present invention, all the metal oxide semiconductor fine particles may have the same particle diameter, or two or more kinds of metal oxide semiconductor fine particles having different particle diameters may be used.
In addition, since the light scattering effect in the oxide semiconductor layer can be enhanced by using the metal oxide semiconductor fine particles having different particle diameters together, for example, dye sensitization using the oxide semiconductor electrode laminate of the present invention. When the solar cell module is manufactured, there is an advantage that light absorption by the dye sensitizer can be efficiently performed.

  In the present invention, when two or more kinds of metal oxide semiconductor fine particles having different particle diameters are used, as a combination of different particle diameters, for example, metal oxide semiconductor fine particles in a range of 10 nm to 50 nm and a range of 50 nm to 800 nm are used. The combination with the metal oxide semiconductor fine particle in the inside can be illustrated.

(2) Arbitrary component The oxide semiconductor layer used in the present invention may contain an optional component in addition to the metal oxide semiconductor fine particles. The optional component used in the present invention is not particularly limited as long as a desired function can be imparted to the oxide semiconductor electrode laminate of the present invention. In particular, the oxide semiconductor layer used in the present invention preferably contains a dye sensitizer as an optional component. That is, it is preferable that the dye sensitizer is attached to the surface of the metal oxide semiconductor fine particles contained in the oxide semiconductor layer in the present invention. When the oxide semiconductor layer is used for producing the dye-sensitized solar cell module by including the dye-sensitizer in the oxide semiconductor layer, the dye-sensitized solar cell module is used. This is because the manufacturing process 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. Examples of the organic dye include acridine, azo, indigo, quinone, coumarin, merocyanine, and phenylxanthene dyes. In the present invention, among these organic dyes, a coumarin dye is preferably used. The metal complex dye is preferably a ruthenium dye, and particularly preferably a ruthenium bipyridine dye and a ruthenium terpyridine dye, which are ruthenium complexes. This is because such a ruthenium complex has a wide wavelength range of light to be absorbed, so that the wavelength range of light that can be photoelectrically converted can be greatly expanded.

(3) Oxide Semiconductor Layer The thickness of the oxide semiconductor layer used in the present invention can be appropriately determined according to the use of the oxide semiconductor electrode laminate of the present invention, and is not particularly limited. In particular, the thickness of the oxide semiconductor layer in the present invention is usually preferably in the range of 1 μm to 100 μm, and particularly preferably in the range of 5 μm to 30 μm. This is because when the thickness of the oxide semiconductor layer is larger than the above range, the oxide semiconductor layer itself tends to cause cohesive failure, which tends to cause film resistance. If the thickness is smaller than the above range, it is difficult to form an oxide semiconductor layer having a uniform thickness. For example, a dye-sensitized solar cell is manufactured using the oxide semiconductor electrode laminate of the present invention. This is because, in some cases, the oxide semiconductor layer containing the dye sensitizer cannot sufficiently absorb sunlight or the like, which may cause poor performance.

  The oxide semiconductor layer in the present invention has a lower porosity than a peeling layer described later, and the adhesion between the heat resistant substrate and the oxide semiconductor layer may be higher than the adhesion between the peeling layer described later and the heat resistant substrate. There is no particular limitation as long as it is within a possible range. Therefore, the porosity of the oxide semiconductor layer used in the present invention can be appropriately determined according to the use of the oxide semiconductor electrode manufactured using the oxide semiconductor electrode stack of the present invention. However, in the present invention, it is preferably in the range of 10% to 60%, and more preferably in the range of 20% to 50%. When the porosity of the oxide semiconductor layer is smaller than the above range, for example, when a dye-sensitized solar cell module is manufactured using the oxide semiconductor electrode of the present invention, This is because light may not be absorbed effectively. Moreover, it is because it may become impossible to make the oxide semiconductor layer contain a desired amount of the dye sensitizer when the range is larger than the above range.

  In addition, the porosity in this invention shows the nonoccupancy rate of the metal oxide 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 a peeling 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.

3. Release Layer Next, the release layer used in the present invention will be described. The release layer used in the present invention contains metal oxide semiconductor fine particles and is formed in a pattern on the heat-resistant substrate. In addition, the release layer used in the present invention reduces the adhesion between the above-described oxide semiconductor layer and a heat-resistant substrate described later, and the oxide semiconductor electrode can be transferred by using the oxide semiconductor electrode laminate of the present invention. An oxide semiconductor in which only an oxide semiconductor layer formed so as to overlap with a peeling layer is selectively peeled from a heat-resistant substrate when an electrode is manufactured, and an oxide semiconductor layer (porous layer) is formed in a pattern It is possible to produce an electrode.
Hereinafter, such a release layer will be described.

  The release layer used in the present invention is formed to be porous by containing metal oxide semiconductor fine particles, but the release layer used in the present invention is more porous than the above-described oxide semiconductor layer. Is expensive. Here, the porosity of the release layer used in the present invention is higher than the porosity of the oxide semiconductor layer described above, and the oxide layer is formed by a transfer method using the oxide semiconductor electrode laminate of the present invention. When the semiconductor electrode is manufactured, there is no particular limitation as long as it is within a range in which only the portion where the release layer is formed can be selectively peeled from the heat-resistant substrate. In particular, the porosity of the release layer used in the present invention is preferably in the range of 25% to 65%, particularly preferably in the range of 30% to 60%. This is because if the porosity of the release layer is smaller than the above range, the adhesion to the heat-resistant substrate is increased, and it may be difficult to selectively peel only the portion where the release layer is formed. . Moreover, it is because it may become difficult to form a peeling layer in desired pattern shape when larger than the said range.

  Here, the metal oxide semiconductor fine particles and arbitrary compounds contained in the release layer used in the present invention are the same as those used in the porous layer, and thus the description thereof is omitted here.

4). First Electrode Layer Next, the first electrode layer used in the present invention will be described. The 1st electrode layer used for this invention consists of a metal oxide, and is formed on the said oxide semiconductor layer.
Hereinafter, such a first electrode layer will be described.

  As a metal oxide which comprises the 1st electrode layer used for this invention, if it has desired electroconductivity, it will not specifically limit. Especially, it is preferable that the metal oxide used for this invention has a transmittance | permeability with respect to sunlight. Thereby, when a dye-sensitized solar cell module is produced using the oxide semiconductor electrode laminate of the present invention, it is possible to prevent power generation efficiency from being impaired.

Examples of such a metal oxide having sunlight permeability include SnO ₂ , ITO, IZO, and ZnO. In the present invention, any of these metal oxides can be suitably used. Among these, 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 first electrode layer used in the present invention may be composed of a single layer or may be composed of a plurality of layers laminated. Examples of the configuration in which a plurality of layers are stacked include a mode in which layers having different work functions are stacked and a mode in which layers made of different metal oxides are stacked.

The thickness of the 1st electrode layer used for this invention will not be specifically limited if it exists in the range which can implement | achieve desired electroconductivity according to the use etc. of the laminated body for oxide semiconductor electrodes of this invention. In particular, the thickness of the first electrode layer in the present invention is usually preferably in the range of 5 nm to 2000 nm, and particularly preferably in the range of 10 nm to 1000 nm. If the thickness is larger than the above range, it may be difficult to form a homogeneous first electrode layer. If the thickness is smaller than the above range, the oxide semiconductor electrode laminate of the present invention is used. This is because there is a possibility that the conductivity of the first electrode layer may be insufficient.
In addition, the said thickness shall point out the total thickness which added the thickness of all the layers, when the 1st electrode layer is comprised by the laminated | stacked several layer.

5. Next, the heat resistant substrate used in the present invention will be described. The heat-resistant substrate used in the present invention is not particularly limited as long as it has desired heat resistance. In particular, the electrode laminate of the present invention is used in the present invention because it is generally subjected to a high-temperature firing process in the process of forming the oxide semiconductor layer and the release layer on a heat-resistant substrate. The heat-resistant substrate to be used preferably has heat resistance that can withstand the heating temperature during the baking treatment performed when the oxide semiconductor layer and the release layer are formed. By using such a heat-resistant substrate having sufficient heat resistance, a sufficient baking treatment is performed when forming the oxide semiconductor layer and the release layer in the process of manufacturing the oxide semiconductor electrode laminate of the present invention. Therefore, there is an advantage that the binding property between the oxide semiconductor layer and the metal oxide semiconductor fine particles constituting the release layer can be increased.

  It is preferable that the heat resistant substrate used in the present invention has acid resistance among the above heat resistant materials. Here, “acid resistance” in the present invention means that the coating liquid used for forming the oxide semiconductor layer and the release layer in the process of producing the oxide semiconductor electrode laminate of the present invention is acidic. In the case where the heat-resistant substrate is not corroded by the coating solution, or even when the substrate is slightly corroded, the acid decomposition product is denatured such as multiple oxide semiconductor layers and release layers, Acid resistance that does not cause peeling.

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

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

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

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

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

  As a combination in which the material of the heat resistant layer and the acid resistant layer is a metal, for example, the material of the heat resistant layer is a simple metal, a metal alloy, or a metal oxide, and the material of the acid resistant layer is the heat resistant layer. The combination which is a metal simple substance other than the metal used for (1), a metal alloy, or a metal oxide can be mentioned. Specifically, as a combination of the material of the heat resistant layer / the material of the acid resistant layer, Ti simple substance / Ti oxide, SUS / Cr simple substance, SUS / Si oxide, SUS / Ti oxide, SUS / Al oxide, Examples thereof include SUS / Cr oxide.

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

5. Use of oxide semiconductor electrode laminate The use of the oxide semiconductor electrode laminate of the present invention is not particularly limited, but in particular, an oxide semiconductor electrode used for the production of a dye-sensitized solar cell module is produced. Used to do. That is, the oxide semiconductor electrode used in the dye-sensitized solar cell module has a configuration in which an oxide semiconductor layer (porous layer) is formed in a pattern, but for the oxide semiconductor electrode of the present invention. If a laminate is used, an oxide semiconductor layer can be easily formed in a pattern by selectively transferring the oxide semiconductor layer formed at the site where the release layer is formed onto an arbitrary substrate. Since a semiconductor electrode can be produced, it is suitably used for such applications. In addition, since the conductive layer is formed in the above-described manner in the stacked body for an oxide semiconductor electrode of the present invention, an oxide semiconductor electrode having excellent photoelectric conversion efficiency and excellent durability is manufactured. be able to.

6). Method for Producing Oxide Semiconductor Electrode Laminate The oxide semiconductor electrode laminate of the present invention can be generally produced using a known method. As such a method, for example, a heat-resistant substrate is used, and a release layer-forming coating solution containing metal oxide semiconductor fine particles is applied in a pattern on the heat-resistant substrate, thereby forming a patterned release layer. A layer forming step for forming a release layer, and a coating solution for forming an oxide semiconductor layer containing metal oxide semiconductor fine particles on the heat-resistant substrate so as to cover the release layer forming layer The oxide semiconductor layer forming layer forming step for forming the oxide semiconductor layer forming layer, and the release layer and the oxide semiconductor layer are formed by firing the release layer forming layer and the oxide semiconductor layer forming layer. A firing step to form, a first electrode layer forming step to form a first electrode layer made of a metal oxide on the oxide semiconductor layer, and the release layer on the first electrode layer. Conductive layer in areas that are not A conductive layer forming step of forming, there may be employed a method having.
Hereinafter, such a method will be described in detail as an example of a method for producing the oxide semiconductor electrode laminate of the present invention.

(1) Release layer forming layer forming step First, the release layer forming step will be described. As described above, this step uses a heat resistant substrate, and a release layer forming coating liquid containing metal oxide semiconductor fine particles is applied in a pattern on the heat resistant substrate, thereby forming a patterned release layer forming layer. Is a step of forming.

a. Peeling layer forming coating liquid The peeling layer forming coating liquid used in this step is usually composed of metal oxide semiconductor fine particles, an organic substance, and a solvent, and contains other compounds as necessary. Used. Here, the metal oxide semiconductor fine particles used in the coating solution for forming the release layer are the same as those described in the above section “2. Oxide semiconductor layer”, and thus the description thereof is omitted here. .

  The content of metal oxide semiconductor fine particles in the solid content of the release layer forming coating liquid is less than the content of metal oxide semiconductor fine particles in the solid content of the oxide semiconductor layer forming coating liquid described later. There is no particular limitation as long as it is within the range. Among these, in this step, the content of the metal oxide semiconductor fine particles is preferably in the range of 20% by mass to 80% by mass, particularly 30% by mass to 70% by mass in the solid content of the release layer forming coating liquid. It is preferable to be within the range. When the content of the metal oxide semiconductor fine particles is larger than the above range, the adhesion with the heat resistant substrate is increased, and the peelability between the release layer and the heat resistant substrate may be impaired, and the content is lower than the above range. This is because it may be difficult to form a uniform oxide semiconductor layer forming layer on the formed release layer forming layer.

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

  Next, the organic substance used for the said peeling layer forming coating liquid is demonstrated. The organic material used for the release layer forming coating solution is not particularly limited as long as it is easily decomposed in the baking step described later. Among these, in this step, it is preferable to use a synthetic resin as the organic substance. This is because the synthetic resin can obtain a compound having a desired thermal decomposability by arbitrarily selecting the molecular weight and material, and thus has advantages such as less restrictions on the processing conditions of the baking treatment described later.

  The synthetic resin is preferably one that is difficult to dissolve in a solvent used in a coating liquid for forming an oxide semiconductor layer described later. Further, the rigid resin used in this step preferably has a synthetic resin weight average molecular weight in the range of 2000 to 600000, particularly preferably in the range of 5000 to 300000, and more preferably in the range of 10000 to 200000. Preferably there is. If the molecular weight of the synthetic resin is larger than the above range, thermal decomposition in the baking step described later may be insufficient, and if the molecular weight is smaller than the above range, the viscosity of the coating solution for forming the release layer is low. This is because the metal oxide semiconductor fine particles may be aggregated.

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

  The content of the organic substance in the release layer-forming coating solution is not particularly limited as long as it is within a range in which the release layer can be provided with a porous property that can peel the heat-resistant substrate with a desired release force. Among them, the content of the organic matter in the release layer forming coating liquid in this step is preferably within a range of 0.01% by mass to 30% by mass with respect to the release layer forming coating liquid, and particularly 0.1%. It is preferable to be within the range of mass% to 15 mass%. This is because if the content of the organic substance is less than the above range, the peel load of the heat-resistant substrate becomes high, which may be disadvantageous in terms of productivity. Moreover, when there is more content than the said range, it is because a peeling layer may self-peel from a heat-resistant board | substrate after heat-firing.

  Next, the solvent used for the coating solution for forming the release layer will be described. The solvent used for the release layer-forming coating solution is not particularly limited as long as it can dissolve the organic substance in a desired amount. Such solvents include ketones, hydrocarbons, esters, alcohols, halogenated hydrocarbons, glycol derivatives, ethers, ether esters, amides, acetates, ketone esters, glycol ethers, Examples include sulfones and sulfoxides. These solvents may be used alone or as a mixed solvent in which two or more kinds are mixed. Among these, in this step, it is preferable to use an organic solvent such as acetone, methyl ethyl ketone, toluene, methanol, isopropyl alcohol, normal propyl alcohol, normal butanol, isobutanol, terpineol, ethyl cellosolve, butyl cellosolve, or butyl carbitol. This is because such an organic solvent has excellent wettability with respect to the heat-resistant substrate, and thus can improve the coating property of the coating solution for forming the release layer on the heat-resistant substrate.

  Various additives may be used in the release layer forming coating solution in order to improve the coating suitability of the release layer forming coating solution with respect to the heat-resistant substrate. For example, as the additive, a surfactant, a viscosity modifier, a dispersion aid, a pH adjuster, or the like can be used. For example, examples of the pH adjuster include nitric acid, hydrochloric acid, acetic acid, dimethylformamide, ammonia and the like. Examples of the dispersion aid include polymers such as polyethylene glycol, hydroxyethyl cellulose, and carboxymethyl cellulose, surfactants, acids, and chelating agents.

b. Next, a method for applying the release layer forming coating solution in a pattern on a heat resistant substrate will be described. The method for applying the release layer forming coating solution in this step is not particularly limited as long as it can be applied in a desired pattern. Examples of such a method include a screen printing method, a die coating method, a gravure coating method, and an offset coating method.

(2) Oxide Semiconductor Layer Formation Layer Formation Step First, the oxide semiconductor layer formation layer formation step will be described. In this step, the oxide semiconductor layer forming layer is formed by applying an oxide semiconductor layer forming coating solution containing metal oxide semiconductor fine particles on the heat-resistant substrate so as to cover the release layer forming layer. Is a step of forming.

a. Oxide Semiconductor Layer-Forming Coating Solution As the oxide semiconductor layer-forming coating solution used in this step, one containing a resin in addition to the metal oxide semiconductor fine particles is usually used. Here, since the metal oxide semiconductor fine particles are the same as those described in the section “2. Oxide semiconductor layer”, the description thereof is omitted here.

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

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

  Next, a method for applying the oxide semiconductor layer forming coating solution onto the heat resistant substrate will be described. The coating method used in this step is not particularly limited as long as it is a method capable of uniformly coating a coating liquid for forming an oxide semiconductor layer with a desired thickness. Examples of such methods include die coating, gravure coating, gravure reverse coating, roll coating, reverse roll coating, bar coating, blade coating, knife coating, air knife coating, slot die coating, slide die coating, dip coating, micro bar coating, Microbar reverse coating, offset coating, screen printing (rotary method) and the like can be mentioned.

(3) Firing step Next, the firing step will be described. This step is performed by baking the release layer forming layer formed by the release layer forming layer forming step and the oxide semiconductor layer forming layer formed by the oxide semiconductor layer forming layer. This is a step of forming a release layer and an oxide semiconductor layer.

  The method for firing the release layer forming layer and the oxide semiconductor layer forming layer in this step is not particularly limited as long as it can be uniformly fired without uneven heating, and a known heating method can be used. .

  The firing temperature in this step is not particularly limited as long as it is within a range in which the resin contained in the porous layer forming coating solution and the organic matter contained in the release layer forming coating solution can be thermally decomposed. The temperature is preferably in the range of 300 ° C to 700 ° C, and more preferably in the range of 350 ° C to 600 ° C.

(4) First electrode layer forming step Next, the first electrode layer forming step will be described. This step is a step of forming a first electrode layer made of a metal oxide on the oxide semiconductor layer.

  In this step, the method for forming the first electrode layer on the oxide semiconductor layer is not particularly limited as long as the method can form the first electrode layer having a uniform thickness and excellent planarity. A known method can be used as a method of forming the oxide film. As a specific example of the method for forming the first electrode layer, a method described in JP-A-2005-166648 can be suitably used.

(5) Conductive layer forming step Next, the conductive layer forming step will be described. This step is a step of forming a conductive layer on the first electrode layer and in a region where the release layer is not formed.

  The method for forming the conductive layer in this step is not particularly limited as long as it is a method that can form a conductive layer on the first electrode layer and in a region where the release layer is not formed. The method specifically used to form the conductive layer in this step is appropriately selected according to the type of the conductive material. For example, a vacuum deposition method (resistance heating, dielectric heating, EB heating) Chemical vapor deposition method, thermal chemical vapor deposition method, chemical vapor deposition method such as photochemical vapor deposition method (Chemical Vapor Deposition method, CVD method), physical vapor phase such as sputtering method, ion plating method, etc. Examples include a growth method (Physical Vapor Deposition method, PVD method).

B. Next, the oxide semiconductor electrode of the present invention will be described. As described above, the oxide semiconductor electrode of the present invention includes a base material, an adhesive layer formed on the base material and made of a thermoplastic resin, and formed on the adhesive layer and made of a metal oxide. An electrode layer, a porous layer formed in a pattern on the first electrode layer and containing metal oxide semiconductor fine particles, and a region on the first electrode layer where the porous layer is not formed So as to be accommodated in the adhesive layer at a position on the surface of the first electrode layer on the adhesive layer side and facing the region where the sealing layer is formed. And a conductive layer formed.

  Such an oxide semiconductor electrode of the present invention will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of the oxide semiconductor electrode of the present invention. As illustrated in FIG. 3, the oxide semiconductor electrode 20 of the present invention is formed on a base material 21, an adhesive layer 22 formed on the base material 21 and made of a thermoplastic resin, and on the adhesive layer 22. A first electrode layer 4 made of a metal oxide, a porous layer 23 formed in a pattern on the first electrode layer 4 and containing metal oxide semiconductor fine particles, and the first electrode layer 4. In addition, the sealing layer 24 formed in a region where the porous layer 23 is not formed, and the surface of the first electrode layer 4 on the adhesive layer 22 side, and the sealing layer 24 is formed. And a conductive layer 5 formed so as to be accommodated in the adhesive layer 22 at a position opposite to the region.

According to the present invention, the conductive layer is formed on the surface of the first electrode layer on the adhesive layer side so as to be housed in the adhesive layer. There are no restrictions. For this reason, according to the present invention, the conductive layer can be formed with an arbitrary thickness. As a result, an oxide semiconductor electrode with high photoelectric conversion efficiency can be obtained by having a conductive layer with a thickness larger than that of the conventional one.
Moreover, the oxide semiconductor electrode of the present invention is such that the conductive layer is on the surface of the first electrode layer on the side of the adhesive layer, and is located at a position facing the region where the sealing layer is formed. In the dye-sensitized solar cell module produced using the oxide semiconductor electrode of the present invention, the conductive layer is prevented from being corroded by the action of the redox couple. it can. For this reason, according to this invention, a highly durable dye-sensitized solar cell module can be obtained.

The oxide semiconductor electrode of the present invention has at least a base material, an adhesive layer, a first electrode layer, a porous layer, a sealing layer, and a conductive layer, and has any other configuration as necessary. Is also good.
Hereafter, each structure used for the oxide semiconductor electrode of this invention is demonstrated in order.

  Note that the first electrode layer used in the oxide semiconductor electrode of the present invention is the same as that described in the section “A. Stack for oxide semiconductor electrode”, and therefore, the description thereof is omitted here.

1. Base material First, the base material used for this invention is demonstrated. The substrate used in the present invention has a self-supporting property capable of supporting the first electrode layer, the adhesive layer, the conductive layer, the sealing layer, and the porous layer used in the present invention. There is no particular limitation. Therefore, the base material used in the present invention may be a flexible material having flexibility, or may be a rigid material having no flexibility, such as quartz glass, Pyrex (registered trademark), and synthetic quartz plate. May be. In particular, the base material used in the present invention is preferably a flexible material, and among the flexible materials, a film base material is preferable. This is because the film substrate is excellent in processability and can reduce the manufacturing cost.

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

  Further, the thickness of the base material used in the present invention can be appropriately selected according to the use of the oxide semiconductor electrode of the present invention, but is usually preferably in the range of 50 μm to 2000 μm. In particular, it is preferably in the range of 75 μm to 1800 μm, and more preferably in the range of 100 μm to 1500 μm. This is because if the thickness of the substrate is thinner than the above range, sufficient mechanical strength may not be imparted to the oxide semiconductor electrode of the present invention. Moreover, it is because the processability of the oxide semiconductor electrode of this invention may be impaired when the thickness of a base material is too large.

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. Because the base material has gas barrier properties, for example, when the oxide semiconductor electrode of the present invention is used in a dye-sensitized solar cell module, the temporal stability of the dye-sensitized solar cell module can be improved. is there. In particular, in the present invention, the oxygen transmission rate is 1 cc / m ² / day · atm or less under conditions of a temperature of 23 ° C. and a humidity of 90%, and the water vapor transmission rate is 1 g under the conditions of a temperature of 37.8 ° C. and a humidity of 100%. It is preferable to use a 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.

2. Next, the adhesive layer used in the present invention will be described. The adhesive layer used in the present invention is formed on the above-described substrate and is made of a thermoplastic resin. The adhesive layer used in the present invention serves to facilitate the transfer by bonding the first electrode layer and the substrate mainly when the oxide semiconductor electrode of the present invention is produced by a transfer method.

  The adhesive resin used for the adhesive layer is not particularly limited as long as it is a resin that melts at a desired temperature. Among them, the adhesive resin 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, and more preferably in the range of 65 ° C to 150 ° C. It is preferable to be within. When the melting point is lower than the above range, for example, when the dye-sensitized solar cell module produced using the oxide semiconductor electrode of the present invention is used outdoors, it is between the substrate and the first electrode layer. This is because the adhesion may not be sufficiently maintained. Further, when the melting point is higher than the above range, for example, when the oxide semiconductor electrode of the present invention is produced by a transfer method, a heating step higher than the melting point is required in the transfer step. This is because the base material itself may be damaged by heat depending on the type of.

  Examples of the adhesive resin used in the present invention include polyethylene, polypropylene, polyisobutylene, polystyrene, polyolefin such as ethylene-propylene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, triacetic acid. Cellulose derivatives such as cellulose, copolymers of poly (meth) acrylic acid and its esters, polyvinyl acetals such as polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral, polyacetals, polyamides, polyimides, nylons, polyester resins, urethane resins, epoxies Examples thereof include a resin, a silicone resin, and a fluororesin. Moreover, as adhesive resin used for this invention, what was described in Unexamined-Japanese-Patent No. 2006-310256 can be mentioned, for example. In the present invention, any of these adhesive resins can be suitably used. Among them, polyolefin, ethylene-vinyl acetate are preferred from the viewpoints of adhesion, resistance to electrolyte, light transmission and transferability. A copolymer, urethane resin, epoxy resin, silane-modified resin, and acid-modified resin are preferred.

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

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

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

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

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

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

  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 exemplified.

  The thickness of the adhesive layer used in the present invention is not particularly limited as long as it can express a necessary adhesive force and can accommodate a conductive layer described later, depending on the type of adhesive resin constituting the adhesive layer. . In particular, the thickness of the adhesive layer used in the present invention is usually preferably in the range of 5 μm to 300 μm, and particularly preferably in the range of 10 μm to 200 μm. 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.

3. Next, the porous layer used in the present invention will be described. The porous layer used in the present invention is formed in a pattern on the first electrode layer, includes metal oxide semiconductor fine particles, and has a function of imparting characteristics as a semiconductor to the oxide semiconductor electrode of the present invention. It is what has.

  The porous layer used in the present invention is formed in a pattern on the first electrode layer, but the pattern in which the porous layer is formed in the present invention is not particularly limited. It is appropriately determined according to the use of the oxide semiconductor electrode. For example, when the oxide semiconductor electrode of the present invention is used in a dye-sensitized solar cell module, it is most preferable to use a stripe pattern.

  The porous layer used in the present invention is the oxide described in the section “A. Stack for oxide semiconductor electrode” except that the porous layer is formed in a pattern on the first electrode layer as described above. Since it is the same as that of a semiconductor layer, detailed description here is abbreviate | omitted.

  The porous layer used in the present invention is usually composed of a single layer, but may have a configuration in which two or more layers are laminated. The porous layer used in the present invention has a structure in which two or more layers are laminated. An oxide semiconductor layer and a release layer are laminated in this order on the first electrode layer. It can be illustrated. Here, the oxide semiconductor layer and the release layer are the same as those described in the section of “A. Stack for oxide semiconductor electrode”, and thus the description thereof is omitted here.

4). Next, the sealing layer used in the present invention will be described. The sealing layer used in the present invention is formed on the first electrode layer and in a region where the porous layer is not formed. In addition, the sealing layer used in the present invention seals each porous layer when, for example, a dye-sensitized solar cell module is produced using the oxide semiconductor electrode of the present invention, and the dye-sensitized layer here It has the function which insulates between solar cells.

  The material used for the sealing layer used for this invention is suitably selected according to the use etc. of the oxide semiconductor electrode of this invention. For example, when the oxide semiconductor electrode of the present invention is used for a dye-sensitized solar cell module, the material used for the encapsulant is particularly suitable if it has durability against the redox couple contained in the electrolyte layer. It is not limited. Examples of such materials include polyethylene, polypropylene, polyisobutylene, polystyrene, polyolefin such as ethylene-propylene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, cellulose triacetate, and the like. Derivatives, copolymers of poly (meth) acrylic acid and its esters, polyvinyl acetals such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyacetals, polyamides, polyimides, nylons, polyester resins, urethane resins, epoxy resins, silicone resins And fluororesin.

  In addition, the sealing layer used for this invention may be formed so that it may become integral with the contact bonding layer mentioned above.

5. Next, the conductive layer used in the present invention will be described. The sealing layer used in the present invention is accommodated in the adhesive layer on the surface of the first electrode layer on the adhesive layer side and in a position facing the region where the sealing layer is formed. Is formed. The conductive layer used in the present invention has a function of reducing the electrical resistance of the oxide semiconductor electrode of the present invention and improving the photoelectric conversion efficiency.

  As described above, the conductive layer used in the present invention is housed in the adhesive layer on the surface of the first electrode layer on the adhesive layer side and in a position facing the region where the sealing layer is formed. It is formed as described. And since a conductive layer is formed in such an aspect, a conductive layer can be formed with arbitrary thickness, without receiving restrictions in particular in thickness. Here, the “position facing the region where the sealing layer is formed” means that the conductive layer is formed when the oxide semiconductor electrode of the present invention is viewed from the direction perpendicular to the surface of the first electrode layer. This means that the existing position overlaps the position where the sealing layer is formed. In addition, the phrase “so as to be accommodated in the adhesive layer” means that the conductive layer is covered with the adhesive layer, and the uneven shape resulting from the formation of the conductive layer by the adhesive layer is flattened. This means that a conductive layer is formed.

  Here, the conductive layer used in the present invention is the same as that described in the above section “A. Stack for oxide semiconductor electrode” except that the conductive layer is formed in the above-described manner. The description here is omitted.

6). Arbitrary Configuration The oxide semiconductor electrode of the present invention has at least the above-described base material, adhesive layer, first electrode layer, conductive layer and porous layer, but has other optional configurations as necessary. It may be. The arbitrary structure used in the present invention is not particularly limited, and a structure having an arbitrary function is used depending on the use of the oxide semiconductor electrode of the present invention and the method for manufacturing the oxide semiconductor electrode of the present invention. Can do.

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

6). Production Method of Oxide Semiconductor Electrode The oxide semiconductor electrode of the present invention can be produced using a generally known method. As a manufacturing method of the oxide semiconductor electrode of the present invention, for example, the above-described stacked body for an oxide semiconductor electrode according to the present invention is used, and an adhesive layer is formed on the first electrode layer of the stacked body for an oxide semiconductor electrode. On the surface of the first electrode layer facing the region where the conductive layer is formed, and a base material adhesion step for adhering the base material via the heat-resistant substrate, a heat-resistant substrate peeling step for peeling the heat-resistant substrate from the porous layer, And a sealing layer forming step of forming a sealing layer. According to such a method, since only the oxide semiconductor layer formed so as to be laminated on the release layer can be transferred onto the base material, the oxide having the porous layer formed in a pattern shape. A semiconductor electrode can be easily produced.
Hereinafter, such a method will be described in detail as an example of the method for producing an oxide semiconductor electrode of the present invention.

(1) Base material adhesion process First, the said base material adhesion process is demonstrated. This step is a step of bonding the base material via the adhesive layer on the first electrode layer of the oxide semiconductor electrode laminate using the oxide semiconductor electrode laminate according to the present invention.

  In this step, as a method of bonding the first electrode layer and the base material via the adhesive layer, the adhesive layer is formed on the base material in advance, and the base material having the adhesive layer is used as the adhesive layer and the first layer. A method in which the electrode layer is disposed so as to adhere, and then heat-sealed; a film made of an adhesive resin; and a method in which the first electrode layer and the substrate are laminated through the film, etc. Can be mentioned.

  The method for forming an adhesive layer made of an adhesive resin on the substrate is not particularly limited. For example, an adhesive layer forming coating solution containing an adhesive resin is applied on the substrate. Can be formed.

(2) Heat-resistant substrate peeling process Next, the said heat-resistant board | substrate peeling process is demonstrated. This step is a step of peeling the heat-resistant substrate bonded on the porous layer from the porous layer after the base material bonding step.

  In the heat-resistant substrate peeling 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.

(3) Sealing layer formation process In the said sealing layer formation process, as a method of forming a sealing layer, a sealing layer is formed on the surface facing the area | region in which the said conductive layer of the said 1st electrode layer was formed. There is no particular limitation as long as it can be formed. Examples of such a method include a method of bonding a sealing layer formed in a pattern on the first electrode layer in accordance with the pattern of the porous layer.

C. Next, the dye-sensitized solar cell module of the present invention will be described. As described above, the dye-sensitized solar cell module of the present invention includes the oxide semiconductor electrode according to the present invention, a counter substrate, and the second formed of the metal oxide formed on the counter substrate. A counter electrode base material having an electrode layer is bonded via the sealing layer so that the porous layer and the second electrode layer face each other, and further the oxide semiconductor electrode and the counter electrode group It has a structure in which an electrolyte layer including a redox pair is formed between the material and the material.

  Such a dye-sensitized solar cell module of the present invention will be described with reference to the drawings. FIG. 4 is a schematic sectional view showing an example of the dye-sensitized solar cell module of the present invention. As illustrated in FIG. 4, the dye-sensitized solar cell module 30 of the present invention is formed on the oxide semiconductor electrode 20 according to the present invention, the counter substrate 41, and the counter substrate 41, In the counter electrode base material 40 having the second electrode layer 42 made of a metal oxide, the sealing layer 24 so that the porous layer 23 provided in the oxide semiconductor electrode 20 and the second electrode layer 42 face each other. And an electrolyte layer 31 including an oxidation-reduction pair is formed between the oxide semiconductor electrode 20 and the counter electrode base material 40. In such an example, the dye-sensitized solar cell module 30 of the present invention has a plurality of dye-sensitized solar cells C separated by the sealing layer 24 connected in parallel. In addition, in the example shown in FIG. 4, it has the structure by which the four cells C were connected in parallel.

  According to the present invention, a plurality of colored paper-sensitized solar cells are connected in parallel, and the oxide semiconductor electrode according to the present invention is used, so that excellent photoelectric conversion efficiency is achieved. It is possible to obtain a dye-sensitized solar cell module that is excellent in durability.

The dye-sensitized solar cell module of the present invention has at least the oxide semiconductor electrode, a counter electrode base material, and an electrolyte layer, and may have any other configuration as necessary. .
Hereafter, each structure used for the dye-sensitized solar cell module of this invention is demonstrated in order.

1. Oxide Semiconductor Electrode First, the oxide semiconductor electrode used in the present invention will be described. The oxide semiconductor electrode used in the present invention is the oxide semiconductor electrode according to the present invention, and the porous layer contains a dye sensitizer.
Such an oxide semiconductor electrode is the same as that described in the above section “B. Oxide Semiconductor Electrode”, and thus a detailed description thereof is omitted here.

2. Electrolyte Layer Next, the electrolyte layer used in the present invention will be described. The electrolyte layer in the present invention includes a 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 of a dye-sensitized solar cell. Among them, the redox couple used in the present invention is preferably a combination of iodine and iodide and a combination of bromine and bromide.

Examples of the combination of iodine and iodide used in the present invention as the redox couple, for example, can be cited LiI, NaI, KI, and metal iodide such as CaI _2, a combination of I _2.
Further, examples of the combination of bromine and bromide include a combination of a metal bromide such as LiBr, NaBr, KBr, and CaBr ₂ and Br ₂ .

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

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

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

(1) Second electrode layer The second electrode layer used in the present invention is not particularly limited as long as it is made of a metal oxide having desired conductivity. As described above, the first electrode layer included in the oxide semiconductor electrode used in the present invention is also made of a metal oxide, and is formed on the porous layer by spray pyrolysis. However, the second electrode layer used in the present invention is different from the first electrode layer in that it is not limited to the one formed by spray pyrolysis.

  In the present invention, the metal oxide used for the second electrode layer is not particularly limited as long as it has desired conductivity. As such a metal oxide, the same thing as what was demonstrated as a metal oxide used for a 1st electrode layer in the above-mentioned "A. Oxide semiconductor electrode laminated body" section can be used.

  The second electrode layer used in the present invention may be composed of a single layer or may be composed of a plurality of layers laminated. Examples of the configuration in which a plurality of layers are laminated include an invention in which layers having different work functions are laminated, and an invention in which layers made of different metal oxides are laminated.

  The thickness of the second electrode layer used in the present invention is usually preferably in the range of 5 nm to 2000 nm, and particularly preferably in the range of 10 nm to 1000 nm.

(2) Opposite base material The counter base material in the present invention can be the same as that described in the section of the base material of “B. Oxide semiconductor electrode”, and the description thereof is omitted here. To do.

(3) Other layers The counter electrode base material used in the present invention may have other configurations than the second electrode layer and the counter base material, if necessary. Examples of other configurations used in the present invention include a catalyst layer. In the present invention, since the catalyst layer is formed 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). Method for Producing Dye-Sensitized Solar Cell Module Next, an example of a method for producing the dye-sensitized solar cell module of the present invention will be described. The dye-sensitized solar cell module of the present invention is formed by forming an electrolyte layer between the porous layer of the oxide semiconductor electrode of the present invention and the second electrode substrate of the counter electrode substrate. Can be manufactured.

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

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

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

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

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

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

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

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

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

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

1. Example 1
(1) Release layer forming step As a release layer forming coating solution, TiO ² fine particles (Nippon Aerosil) with a primary particle size of 20 nm, 9.1% by mass, ethyl cellulose (Nisshin Kasei Co., Ltd.) 9.1% by mass, and terpineol A coating solution containing 81.8% by mass was prepared. This release layer-forming coating solution is applied on a glass substrate (thickness: 1 mm) by screen printing to apply a 1 cm × 1 cm area at 5 mm intervals to four squares and dried at 120 ° C. for 10 minutes to form a release layer. A layer was formed.

(2) Oxide Semiconductor Layer Formation Step Next, Solar Nanox Ti Nanoxide T / SP is prepared as an oxide semiconductor layer formation coating solution, and screen printing is performed on the glass substrate on which the release layer formation layer is formed. The oxide semiconductor layer forming layer was stacked in a 5 cm × 5 cm region so as to cover the release layer forming layer by the method.

(3) Firing step Next, firing was performed at 500 ° C. for 30 minutes in an atmospheric pressure atmosphere using an electric muffle furnace (P90 manufactured by Denken). Thereby, a release layer and an oxide semiconductor layer formed as a porous body were obtained.

(4) 1st electrode layer formation process Then, the coating liquid for 1st electrode layer formation which melt | dissolved 0.1 mol / L of indium chloride and 0.005 mol / L of tin chloride in ethanol was prepared, and the glass which performed the said baking is prepared. The substrate was placed on a hot plate (400 ° C.) with the oxide semiconductor layer facing upward, and the above coating liquid was sprayed on the heated oxide semiconductor layer with an ultrasonic sprayer. A certain ITO film was formed to 500 nm.

(5) Conductive layer formation process Next, the conductive layer was formed with the silver paste with the line | wire width of 1 mm in the space | interval width of 5 mm in the area | region which is on the ITO film | membrane and the peeling layer is not formed. This obtained the laminated body for oxide semiconductor electrodes of this invention.
In addition, it was 50 micrometers when the film thickness of the formed conductive layer was measured with the stylus type film thickness meter (Dektak).

2. Example 2
A heat sealant (Binell: DuPont) was placed as an adhesive layer on a PET film (E5100 thickness 125 μm, manufactured by Toyobo Co., Ltd.) as a base material, and the ITO film surface of the oxide semiconductor electrode laminate produced in Example 1 and 135 ° C. We pasted together.

  Next, after the glass substrate is peeled from the oxide semiconductor electrode laminate, the above-mentioned Surlyn openings are made to coincide with the porous layer by Surlyn having a thickness of 50 μm obtained by punching four 1 cm × 1 cm regions. The oxide semiconductor layer was attached. Thereby, the oxide semiconductor electrode of the present invention was obtained. In the obtained oxide semiconductor electrode, a 1 cm × 1 cm porous layer was formed on the ITO film, and a conductive layer having a width of 1 mm was formed in 5 mm intervals between the oxide semiconductor layers.

3. Example 3
As a dye sensitizer, a ruthenium complex (Kojima Chemical Co., Ltd. RuL ₂ (NCS) ₂ ) was dissolved in an absolute ethanol solution to a concentration of 3 × 10 −4 mol / L to prepare an adsorption dye solution. Example 2 A sensitizing dye was supported on the porous layer by immersing the oxide semiconductor electrode prepared in (1).

  Next, using methoxyacetonitrile as a solvent, lithium iodide at a concentration of 0.1 mol / L, iodine at a concentration of 0.05 mol / L, dimethylpropylimidazolium iodide at a concentration of 0.3 mol / L, a concentration of 0.5 mol / L Tertiary butyl pyridine was dissolved to obtain a coating solution for forming an electrolyte layer. Next, the opposing base material was cut into 5 cm × 5 cm, and the surlyn was released and bonded to the oxide semiconductor layer. Next, an electrolyte layer forming coating solution was impregnated between the opposing base material and the oxide semiconductor electrode to prepare a dye-sensitized solar cell module. Here, as the above-mentioned counter substrate, a film having a thickness of 150 nm and a surface resistance of 7 Ω / □, a platinum film having a film thickness of 50 nm applied by sputtering on the counter film substrate having an ITO sputtered layer. Using.

Evaluation of the produced dye-sensitized solar cell module was performed by using AM1.5, pseudo-sunlight (incident light intensity of 100 mW / cm ² ) as a light source, and entering from the substrate side having the oxide semiconductor layer adsorbed with the dye, Current-voltage characteristics were measured by applying voltage with a source measure unit (Caseley 2400 type). As a result, the short circuit current was 15, ² mA / cm ² , the open circuit voltage was 710 mV, the fill factor was 0.65, and the conversion efficiency was 7.0%.

4). Comparative Example A dye-sensitized solar cell module was produced in the same manner as in the example except that the conductive layer was not formed. Evaluation of the produced dye-sensitized solar cell module was performed by using AM1.5, pseudo-sunlight (incident light intensity of 100 mW / cm ² ) as a light source, and entering from the substrate side having the oxide semiconductor layer adsorbed with the dye, Current-voltage characteristics were measured by applying voltage with a source measure unit (Caseley 2400 type). As a result, the short-circuit current was 15, 0 mA / cm ² , the open-circuit voltage 712 mV, the fill factor 0.36, and the conversion efficiency 3.7%.

It is a schematic sectional drawing which shows an example of the laminated body for oxide semiconductor electrodes of this invention. It is the schematic which shows an example of the method of producing an oxide semiconductor electrode using 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 an example of the dye-sensitized solar cell module of this invention. It is the schematic which shows the example of a general dye-sensitized solar cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Heat-resistant substrate 2 ... Release layer 3 ... Oxide semiconductor layer 4 ... 1st electrode layer 5 ... Conductive layer 10 ... Oxide semiconductor electrode laminated body 20, 20 '... Oxide semiconductor electrode 21 ... Base material 22 ... Adhesive layer DESCRIPTION OF SYMBOLS 23 ... Porous layer 24 ... Sealing layer 30 ... Dye-sensitized solar cell module 31 ... Electrolyte layer 40 ... Counter electrode base material 41 ... Opposite base material 42 ... Second electrode layer

Claims (5)

A heat-resistant substrate having heat resistance;
A release layer formed in a pattern on the heat-resistant substrate and containing metal oxide semiconductor fine particles,
An oxide semiconductor layer formed so as to cover the release layer, containing metal oxide semiconductor fine particles, and having a lower porosity than the release layer;
A first electrode layer formed on the oxide semiconductor layer and made of a metal oxide;
A laminate for an oxide semiconductor electrode, comprising: a conductive layer formed in a pattern on a region on the first electrode layer and on which the release layer is not formed.   2. The oxide semiconductor electrode laminate according to claim 1, wherein a thickness of the conductive layer is in a range of 1 μm to 500 μm. A substrate;
An adhesive layer formed on the substrate and made of a thermoplastic resin;
A first electrode layer formed on the adhesive layer and made of a metal oxide;
A porous layer formed in a pattern on the first electrode layer and containing metal oxide semiconductor fine particles;
A sealing layer formed on the first electrode layer and in a region where the porous layer is not formed;
A conductive layer formed on the surface of the first electrode layer on the side of the adhesive layer and facing the region where the sealing layer is formed so as to be accommodated in the adhesive layer. And
The oxide semiconductor characterized in that the porous layer has a higher porosity in a region located farther from the first electrode layer than in a region located on the first electrode layer side. electrode.   The oxide semiconductor electrode according to claim 3, wherein the conductive layer has a thickness in the range of 1 μm to 500 μm.   A counter electrode substrate comprising the oxide semiconductor electrode according to claim 3 or 4, and a counter substrate, and a second electrode layer formed on the counter substrate and made of a metal oxide, An electrolyte in which a porous layer and the second electrode layer are bonded via the sealing layer so as to face each other, and further includes an oxidation-reduction pair between the oxide semiconductor electrode and the counter electrode substrate A dye-sensitized solar cell module having a structure in which a layer is formed.

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