WO2013094653A1

WO2013094653A1 - Dye-sensitized solar cell element, dye-sensitized solar cell module, method for manufacturing dye-sensitized solar cell element, and oxide semiconductor electrode substrate

Info

Publication number: WO2013094653A1
Application number: PCT/JP2012/082963
Authority: WO
Inventors: 美帆佐々木
Original assignee: 大日本印刷株式会社
Priority date: 2011-12-19
Filing date: 2012-12-19
Publication date: 2013-06-27
Also published as: JP2013127923A; JP5327306B2

Abstract

The main aim of this invention is to provide a dye-sensitized solar cell element that has superior design properties, has a simple manufacturing process, and has high power generation efficiency. The present invention solves the problem described above by providing a dye-sensitized solar cell element in which an oxide semiconductor electrode substrate that has a first electrode substrate providing the function of an electrode and an oxide semiconductor layer that holds a dye-sensitizing agent on the surface of the oxide semiconductor film that is formed on the first electrode substrate and includes metal oxide semiconductor particles, and a counter electrode substrate having a second electrode substrate providing at least the function of an electrode are arranged so that the oxide semiconductor layer is opposite the second electrode substrate; and an electrolytic layer including an oxidation-reduction pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, wherein the oxide semiconductor layer has at least two regions having different film thicknesses and different transmittances; at least two of these regions are formed into one body; in the oxide semiconductor layer, the color tone in the region having a thick film is darker; and the color tone in the region having a thin film is lighter compared to the color tone of the region having the thick film.

Description

Dye-sensitized solar cell element, dye-sensitized solar cell module, method for producing dye-sensitized solar cell element, and oxide semiconductor electrode substrate

The present invention can provide a dye-sensitized solar cell element excellent in design and the dye-sensitized solar cell element, and a method for producing a dye-sensitized solar cell element capable of simplifying the production process. The present invention also relates to a dye-sensitized solar cell module and an oxide semiconductor electrode substrate.

In recent years, environmental problems such as global warming caused by an increase in carbon dioxide have become serious, and countermeasures are being promoted worldwide. In particular, active research and development on solar cells using solar energy as a clean energy source with a low environmental impact is underway. As such solar cells, single crystal silicon solar cells, polycrystalline silicon solar cells, amorphous silicon solar cells, compound semiconductor solar cells and the like have already been put into practical use, but these solar cells have high production costs, etc. There is a problem. Therefore, 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 addition to low production costs and low environmental impact, dye-sensitized solar cells have added values that are difficult to realize with existing silicon solar cells such as colorfulness, lightweight flexibility, and see-through performance. Is also excellent.

Dye-sensitized solar cells are being considered for application to electronic devices where there is a strong demand for miniaturization and low power consumption. By using the dye-sensitized solar cell as a main power source or auxiliary power source for an electronic device, it is expected to eliminate the need for charging the electronic device or lengthen the charge cycle. Since such an electronic device is for personal use, the design is an important factor. Accordingly, development of products using dye-sensitized solar cells having excellent design properties for these needs is also being studied.

Here, a dye-sensitized solar cell excellent in design is examined.
In Patent Document 1, a transparent electrode layer is formed on a transparent substrate, and a pattern of a dye-carrying semiconductor is formed by carrying a dye on the porous oxide semiconductor following the pattern formation of the porous oxide semiconductor on the transparent electrode layer. The method of manufacturing the dye-sensitized solar cell excellent in the design property provided with the 2 or more types of pigment | dye carrying | support semiconductor which has a mutually different color by performing 2 times or more is disclosed. This method makes it possible to express a pattern such as a specific character, symbol, or figure, but it is necessary to form a pattern of the dye-carrying semiconductor at least twice, and the manufacturing process is complicated. There was a problem.
In Patent Document 2, the photoelectric conversion layer is screen-printed a plurality of times using a plurality of masks having different patterns, and the pigment is adsorbed by changing the thickness of the photoelectric conversion layer for each region, thereby transmitting incident light. There is disclosed a dye-sensitized solar cell excellent in design with different shades of color for each region based on the difference in rate. With the above method, a pattern using color shading can be expressed, but there is a problem that the screen printing needs to be performed a plurality of times and the manufacturing process is complicated.
Furthermore, in Patent Document 3, a porous titanium oxide layer made of titanium oxide fine particles and carrying a dye sensitizer is classified into the type, thickness, laminated structure of the dye sensitizer, the particle diameter of the titanium oxide fine particles, or the above A method for producing the porous titanium oxide layer exhibiting a predetermined color by adjusting the blending ratio and the like in the case where the titanium oxide fine particles are composed of two or more types of titanium oxide fine particles having different particle sizes. It is disclosed. By this method, it is possible to express a predetermined pattern using the porous titanium oxide layer and obtain a dye-sensitized solar cell excellent in design, but the porous oxidation exhibiting a predetermined color. In order to form a titanium layer, the kind of dye sensitizer, the thickness, the laminated structure, the particle size of the titanium oxide fine particles, or the case where the titanium oxide fine particles are composed of two or more types of titanium oxide fine particles having different particle sizes. It is necessary to appropriately adjust the blending ratio and the like, and development of a method for producing a dye-sensitized solar cell that is simpler and excellent in design is demanded. Further, in the above method, since a plurality of types of titanium oxide fine particles are used, further improvement in cost is required.

In addition, to date, there has been a demand for further improvement in power generation efficiency as well as excellent design for dye-sensitized solar cell elements.

Japanese Unexamined Patent Publication No. 2011-124053 JP 2009-170239 A JP 2010-113905 A

The present invention has been made in view of the above problems, a dye-sensitized solar cell element having excellent design properties, a simple manufacturing process, and high power generation efficiency, and a dye-sensitized dye using the same. The main object of the present invention is to provide an oxide semiconductor electrode substrate used in a dye-sensitized solar cell element, a method for producing the dye-sensitized solar cell element, and a dye-sensitized solar cell element.

In order to solve the above problems, the present invention provides a first electrode base material having a function as an electrode, and a surface of an oxide semiconductor film formed on the first electrode base material and containing metal oxide semiconductor fine particles. In addition, an oxide semiconductor electrode substrate having an oxide semiconductor layer carrying a dye sensitizer and a counter electrode substrate having at least a second electrode base material having a function as an electrode are the oxide semiconductor layer and The dye-sensitized solar cell element, wherein the second electrode base material is disposed so as to face each other, and an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate. The dye-sensitized solar cell element, wherein the oxide semiconductor layer has at least two regions having different thicknesses and different transmittances, and the at least two regions are integrally formed. I will provide a.

In the present invention, the oxide semiconductor layer has at least two regions having different film thicknesses and transmittances, thereby expressing color shading corresponding to the difference between the film thicknesses and transmittances of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, a dye-sensitized solar cell element excellent in design can be obtained.

The present invention provides a first electrode substrate having a function as an electrode, and a dye sensitizer on the surface of an oxide semiconductor film formed on the first electrode substrate and containing metal oxide semiconductor fine particles. An oxide semiconductor electrode substrate having a held oxide semiconductor layer and a counter electrode substrate having a second electrode base material having at least a function as an electrode are opposed to the oxide semiconductor layer and the second electrode base material. A dye-sensitized solar cell element in which an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, wherein the oxide semiconductor layer is The present invention provides a dye-sensitized solar cell element characterized by having at least two regions having different film thicknesses and different pore diameters, and wherein the at least two regions are composed of particle groups having the same composition.

In the present invention, the oxide semiconductor layer has at least two regions having different film thicknesses and pore diameters, thereby expressing the color shading corresponding to the difference between the film thicknesses and the pore diameters of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, a dye-sensitized solar cell element excellent in design can be obtained.
Moreover, in order to obtain the dye-sensitized solar cell element which has the outstanding design property because the particle | grains which comprise the said at least 2 area | region in the said oxide semiconductor layer have the same composition, several types of particle | grains from which a composition differs Since it is not necessary to use different for each area, the cost can be reduced as compared with the conventional case.

The present invention provides a first electrode substrate having a function as an electrode, and a dye sensitizer on the surface of an oxide semiconductor film formed on the first electrode substrate and containing metal oxide semiconductor fine particles. An oxide semiconductor electrode substrate having a held oxide semiconductor layer and a counter electrode substrate having a second electrode base material having at least a function as an electrode are opposed to the oxide semiconductor layer and the second electrode base material. And an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, and the oxide semiconductor layer has a different thickness and a different transmittance. Provided is a dye-sensitized solar cell module comprising a plurality of dye-sensitized solar cell elements, each having at least two regions, which are integrally formed with at least two regions. .

In the present invention, the oxide semiconductor layer has at least two regions having different film thicknesses and transmittances, thereby expressing color shading corresponding to the difference between the film thicknesses and transmittances of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, a dye-sensitized solar cell module excellent in design can be obtained.

The present invention provides a first electrode substrate having a function as an electrode, and a dye sensitizer on the surface of an oxide semiconductor film formed on the first electrode substrate and containing metal oxide semiconductor fine particles. An oxide semiconductor electrode substrate having a held oxide semiconductor layer and a counter electrode substrate having a second electrode base material having at least a function as an electrode are opposed to the oxide semiconductor layer and the second electrode base material. And an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, and the oxide semiconductor layer has at least two different thicknesses and different pore diameters. A dye-sensitized solar cell module comprising a plurality of dye-sensitized solar cell elements each having two regions, wherein the at least two regions are composed of a group of particles having the same composition. Offer To.

In the present invention, the oxide semiconductor layer has at least two regions having different film thicknesses and pore diameters, thereby expressing the color shading corresponding to the difference between the film thicknesses and the pore diameters of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, a dye-sensitized solar cell module excellent in design can be obtained.
Further, in order to obtain a dye-sensitized solar cell module having an excellent design property because the particles constituting the at least two regions in the oxide semiconductor layer have the same composition, a plurality of types of particles having different compositions Since it is not necessary to use different for each area, the cost can be reduced as compared with the conventional case.

This invention is a manufacturing method of the dye-sensitized solar cell element which manufactures the dye-sensitized solar cell element mentioned above, Comprising: The said oxide containing the said metal oxide semiconductor fine particle on the said 1st electrode base material An oxide semiconductor electrode substrate forming step of forming the oxide semiconductor electrode substrate by forming a semiconductor film and forming the oxide semiconductor layer having the dye sensitizer carried on the surface of the oxide semiconductor film. A counter electrode substrate preparation step for preparing the counter electrode substrate having the second electrode base material, and the oxide semiconductor electrode substrate and the counter electrode substrate so as to face each other with the electrolyte layer therebetween. A dye-sensitized solar cell element assembling step for assembling a sensitized solar cell element, wherein the oxide semiconductor electrode substrate forming step partially pressurizes the oxide semiconductor film or the oxide semiconductor film To provide a method of manufacturing a dye-sensitized solar cell characterized by having either a pressurization step of step of pressing with partially different pressures.

In the present invention, the oxide semiconductor electrode substrate forming step includes either a step of partially pressing the oxide semiconductor film or a step of partially pressing the oxide semiconductor film with a different pressure. In the oxide semiconductor film, a pressurized region and a non-pressed region, or a region pressurized with one pressure and a region pressurized with a pressure different from the one pressure can be formed, respectively. . When the oxide semiconductor film is pressurized, the pore diameter of the oxide semiconductor film is reduced. Therefore, each region in the oxide semiconductor film can produce a difference in pore diameter of the oxide semiconductor film by an amount corresponding to the presence or absence of pressurization or the magnitude of the pressure to be applied. By supporting the dye sensitizer on the film, it is possible to make a difference in the transmittance of each region.
Thus, in this invention, it becomes possible to manufacture the dye-sensitized solar cell element excellent in the designability by having the process of pressurizing the said oxide semiconductor film.
In addition, the step of pressurizing the oxide semiconductor film improves the adhesion between the oxide semiconductor electrode substrate and the first electrode base material, and makes it possible to manufacture a dye-sensitized solar cell element having high power generation efficiency.

The present invention provides a first electrode substrate having a function as an electrode, and a dye sensitizer on the surface of an oxide semiconductor film formed on the first electrode substrate and containing metal oxide semiconductor fine particles. The oxide semiconductor layer includes at least two regions having different thicknesses and different transmittances, and the at least two regions are integrally formed. An oxide semiconductor electrode substrate is provided.

In the present invention, the oxide semiconductor layer has at least two regions having different film thicknesses and transmittances, thereby expressing color shading corresponding to the difference between the film thicknesses and transmittances of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, an oxide semiconductor electrode substrate with excellent design can be obtained.

The present invention provides a first electrode base material having a function as an electrode, and an oxide semiconductor film including metal oxide semiconductor fine particles formed on the first electrode base material and carrying a dye sensitizer. An oxide semiconductor electrode substrate, wherein the oxide semiconductor layer has at least two regions having different thicknesses and different pore diameters, and the at least two regions are composed of a particle group having the same composition I will provide a.

In the present invention, the oxide semiconductor layer has at least two regions having different film thicknesses and pore diameters, thereby expressing the color shading corresponding to the difference between the film thicknesses and the pore diameters of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, an oxide semiconductor electrode substrate with excellent design can be obtained.
Further, in the oxide semiconductor layer, the particles constituting the at least two regions have the same composition, whereby a dye-sensitized solar cell element having excellent design properties is obtained using the oxide semiconductor electrode substrate. For this reason, since it is not necessary to use different types of particles having different compositions for each region, the cost can be reduced as compared with the prior art.

In the present invention, the dye-sensitized solar cell element having excellent design and high power generation efficiency, the dye-sensitized solar cell module using the same, and the dye-sensitized solar cell element are used. An oxide semiconductor electrode substrate that can be provided can be provided. Moreover, the manufacturing method of the dye-sensitized solar cell element which can manufacture the said dye-sensitized solar cell element simply can be provided.

It is the schematic which shows an example of the dye-sensitized solar cell element of this invention. It is a schematic sectional drawing which shows the other example of the dye-sensitized solar cell element of this invention. It is a schematic sectional drawing which shows the other example of the dye-sensitized solar cell element of this invention. It is a schematic process drawing which shows an example of the manufacturing method of the dye-sensitized solar cell element of this invention. It is a schematic process drawing which shows the other example of the manufacturing method of the dye-sensitized solar cell element of this invention. It is the schematic which shows an example of the roll press process in this invention.

Hereinafter, the dye-sensitized solar cell element, the dye-sensitized solar cell module, the method for producing the dye-sensitized solar cell element, and the oxide acid conductor electrode substrate of the present invention will be described in detail.

I. Dye-sensitized solar cell element The dye-sensitized solar cell element of the present invention has two aspects.
Hereinafter, the first aspect and the second aspect will be described separately.

A. 1st aspect The dye-sensitized solar cell element of this aspect is a 1st electrode base material provided with the function as an electrode, and the oxide semiconductor formed on the said 1st electrode base material and containing a metal oxide semiconductor fine particle An oxide semiconductor electrode substrate having an oxide semiconductor layer carrying a dye sensitizer on the surface of the film, and a counter electrode substrate having at least a second electrode base material having a function as an electrode, The semiconductor layer and the second electrode base material are disposed so as to face each other, and an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, The oxide semiconductor layer has at least two regions having different thicknesses and different transmittances, and the at least two regions are integrally formed.
Hereinafter, description will be given with reference to the drawings.

FIG. 1A is a schematic plan view showing an example of the dye-sensitized solar cell element of this embodiment, and FIG. 1B is a cross-sectional view taken along the line AA in FIG. 1 (c) is an enlarged view of a region D in FIG. 1 (b).
As shown in FIG. 1 (a) and FIG. 1 (b), the dye-sensitized solar cell element 100 of this embodiment is formed on the first electrode base material 10 and the first electrode base material 10, and is made of metal. An oxide semiconductor electrode substrate 1 having an oxide semiconductor layer 13 in which a dye sensitizer is supported on the surface of an oxide semiconductor film containing oxide semiconductor fine particles, and the oxide semiconductor layer 13 are formed so as to cover the oxide semiconductor layer 13 and are oxidized and reduced. It has an electrolyte layer 2 including a pair, and a counter electrode substrate 3 formed so as to face the oxide semiconductor electrode substrate 1 with the electrolyte layer 2 interposed therebetween and having a second electrode base material.
The oxide semiconductor layer 13 has at least two regions having different thicknesses and different transmittances. Therefore, in the dye-sensitized solar cell element 100 shown in FIG. 1, the oxide semiconductor layer 13 includes a region having a film thickness of 13a and a region having a film thickness of 13b as shown in FIG. It has. In addition, the area | region whose film thickness is 13a is equivalent to the area | regions other than the character part of Fig.1 (a), and the area | region whose film thickness is 13b is equivalent to the character part of "DNP" shown in Fig.1 (a). To do.
Further, in the oxide semiconductor layer 13, the two regions, ie, the region having a film thickness of 13 a and the region having a film thickness of 13 b are formed integrally, and an interface exists between the two regions. do not do.

According to this aspect, since the oxide semiconductor layer constituting the dye-sensitized solar cell element has at least two regions having different thicknesses and transmittances, the thicknesses and transmittances of the at least two regions are increased. It is possible to express the shade of the color corresponding to the difference. That is, in the oxide semiconductor layer, the transmittance of a region with a small thickness is high, while the transmittance of a region with a large thickness is low.
As described above, the transmittance of the oxide semiconductor layer varies depending on the film thickness, and the color tone of a region having a high haze rate becomes thin due to white turbidity, while the color tone of a region having a low haze rate becomes dark. Therefore, a dye-sensitized solar cell element excellent in design can be obtained by using the oxide semiconductor layer.
Hereinafter, the oxide semiconductor electrode substrate, the electrolyte layer, and the counter electrode substrate that constitute the dye-sensitized solar cell element of this embodiment will be described.

1. Oxide Semiconductor Electrode Substrate An oxide semiconductor electrode substrate constituting the dye-sensitized solar cell element of the present embodiment is formed on a first electrode base material having a function as an electrode, and the first electrode base material, It has an oxide semiconductor layer in which a dye sensitizer is supported on the surface of an oxide semiconductor film containing metal oxide semiconductor fine particles.

Since the oxide semiconductor layer used for such an oxide semiconductor electrode substrate has at least two regions with different film thicknesses and different transmittances, it is possible to express color shading. In addition, by using the oxide semiconductor electrode substrate, it is possible to obtain a dye-sensitized solar cell element excellent in design.
Hereinafter, constituent members of the oxide semiconductor electrode substrate will be described.

(1) Oxide Semiconductor Layer The oxide semiconductor layer in this embodiment is formed on the first electrode substrate described later, and is dye-sensitized on the surface of the oxide semiconductor film containing metal oxide semiconductor fine particles. The drug is carried. The oxide semiconductor layer has at least two regions with different thicknesses and different transmittances.
Hereinafter, the fact that the oxide semiconductor layer has at least two regions having different thicknesses will be described with reference to the drawings.

FIG. 2 is a schematic cross-sectional view showing an example of the dye-sensitized solar cell element of this embodiment.
In the dye-sensitized solar cell element 100 shown in FIG. 2, the oxide semiconductor layer 13 has three regions having

film thicknesses

13c, 13d, and 13e.
The three regions are thicker in the order of 13c <13d <13e, and the transmittances differ from each other due to the difference in film thickness.

In this embodiment, a method for forming the oxide semiconductor layer having at least two regions having different thicknesses and transmittances is not particularly limited. For example, the oxide semiconductor film is applied with different pressures. And then supporting the dye sensitizer to form the oxide semiconductor layer having at least two regions having different film thicknesses and transmittances, and supporting the dye sensitizer on the oxide semiconductor film. The oxide semiconductor layer is formed by forming the oxide semiconductor layer, and then the oxide semiconductor layer is pressurized with a different pressure. By using the above method, the thickness of the region where the oxide semiconductor film or the oxide semiconductor layer is pressed is reduced, and the pore diameter is reduced by an amount corresponding to the reduced thickness. Therefore, in the oxide semiconductor layer, the transmittance of a region where the oxide semiconductor film or the oxide semiconductor layer is pressurized is increased. That is, when the oxide semiconductor layer having at least two regions having different thicknesses and transmittances is formed by pressurization, the pore diameter in the region where the oxide semiconductor layer is thin is reduced. The transmittance will be higher than before pressurization.
Therefore, in the dye-sensitized solar cell element 100 of FIG. 2, the haze ratio in the region where the film thickness is 13c is high, the color tone is cloudy and looks the thinnest, while the haze in the region where the film thickness is 13e. The rate will be low and the color will appear darkest.
2 that are not described in FIG. 2 can be the same as those in FIG.

The oxide semiconductor layer used in this embodiment includes at least two regions having different thicknesses, and includes one region having one thickness and another thickness different from the one thickness. The film thickness difference with the region is not particularly limited as long as the desired design or the like can be expressed using color shading, but for example, within a range of 0.01 μm to 10 μm. Preferably, it is preferably within the range of 0.1 μm to 5 μm, and particularly preferably within the range of 0.5 μm to 3 μm.
Note that the film thickness difference here refers to a difference in film thickness between two regions which are adjacent to each other and have different film thicknesses in the oxide semiconductor layer. Note that “adjacent to each other” refers to a state in which two target areas are in contact with each other without interposing other areas. That is, in the case of the oxide semiconductor layer 13 in the dye-sensitized solar cell 100 of FIG. 2, it indicates the difference between the film thickness 13c and the film thickness 13d, or the difference between the film thickness 13d and the film thickness 13e. For example, it does not indicate the difference in film thickness in regions that are not adjacent to each other, such as the difference between the film thickness 13c and the film thickness 13e.

The thickness of the oxide semiconductor layer used in this embodiment can be appropriately determined according to the use of the dye-sensitized solar cell element of this embodiment, and is not particularly limited. In the sensitized solar cell element, the thickness of the thinnest region of the oxide semiconductor layer is preferably, for example, in the range of 0.1 μm to 50 μm, and more preferably in the range of 0.3 μm to 30 μm. In particular, it is preferably in the range of 1 μm to 20 μm.
If the thickness of the oxide semiconductor layer is thinner than the above range, it may not be a highly efficient dye-sensitized solar cell element, whereas if it is thicker than the above range, This is because the transmittance of the oxide semiconductor layer is lowered, the color itself cannot be seen, and an excellent design property may not be obtained.
Note that in the case where the oxide semiconductor layer includes a plurality of layers, the above thickness refers to the total thickness of all the layers.

As described above, the oxide semiconductor layer in this embodiment includes at least two regions having different thicknesses. That is, the oxide semiconductor layer has an uneven shape on the surface.
In this embodiment, the uneven shape is appropriately adjusted according to the design of characters, patterns, and the like represented by the difference in film thickness of the oxide semiconductor layer. Examples of the cross-sectional shape of the concave portion of the oxide semiconductor layer include a polygonal shape, a circular shape, and a tapered shape.

In addition, the oxide semiconductor layer used in this embodiment includes at least two regions having different transmittances, one region having one transmittance, and another region having another transmittance different from one. The transmittance difference with the region is not particularly limited as long as a desired design or the like can be expressed by using the color shade due to the transmittance difference, but is preferably 2% or more, for example. Of these, 3% or more is preferable, and 5% or more is particularly preferable.
When the transmittance difference is within the above range, the color density can be sufficiently expressed at the interface of the regions having different transmittances, and excellent design properties can be obtained.
Note that the transmittance difference here refers to a difference in transmittance between regions adjacent to each other in the oxide semiconductor layer including at least two regions having different transmittances. Note that “adjacent to each other” refers to a state in which two target areas are in contact with each other without interposing other areas. That is, in the case of the oxide semiconductor layer 13 in the dye-sensitized solar cell 100 of FIG. 2, the transmittance difference between the region having the film thickness 13c and the region having the film thickness 13d, or the region having the film thickness 13d This refers to the difference in transmittance with the region having the film thickness 13e. For example, the transmittance of the regions that are not adjacent to each other, such as the difference in transmittance between the region with the film thickness 13c and the region with the film thickness 13e. It does not indicate a difference.

The transmittance of the oxide semiconductor layer used in this embodiment is appropriately adjusted according to the use of the dye-sensitized solar cell element of this embodiment, the size of the particles used, the dispersion method, and the like, and is particularly limited. However, in the dye-sensitized solar cell element of this embodiment, the transmittance of the thinnest region of the oxide semiconductor layer is preferably in the range of 5% to 99%, for example. In particular, it is preferably in the range of 10% to 90%, and particularly preferably in the range of 20% to 80%.
Note that the transmittance here refers to the transmittance with respect to light incident on the oxide semiconductor layer.

The transmittance of the oxide semiconductor layer is a value measured using a haze meter (HGM-2K) manufactured by Suga Test Instruments Co., Ltd. in the visible light region.
The transmittance difference of the oxide semiconductor layer is a value obtained by subtracting the value measured by the above method.

Furthermore, the oxide semiconductor layer used in this embodiment is formed by integrally forming at least two regions having different film thicknesses and transmittances as described above.

Here, “integrally formed” means a state where a thick film region and a thin film region are formed without having an interface, and in the thick film region, the thickness direction In other words, this indicates a state in which no interface exists.
Hereinafter, it will be described in detail with reference to the drawings.

2, in the dye-sensitized solar cell element 100 of FIG. 2, the oxide semiconductor layer 13 has regions having film thicknesses of 13c, 13d, and 13e, respectively, as described above. These adjacent regions on the first electrode substrate 10 do not have an interface in the surface direction of the dye-sensitized solar cell element 100, and are formed integrally.

In addition, the oxide semiconductor layer in this embodiment may be a single layer as shown in FIG. 2, or a plurality of oxide semiconductor layers in the thickness direction of the dye-sensitized solar cell element as shown in FIG. Layers may be laminated.
As shown in FIG. 3, the oxide semiconductor layer 13 used in this embodiment is integrally formed even when the oxide semiconductor layer 13 includes two layers, an oxide semiconductor layer 13A and an oxide semiconductor layer 13B. It has been done. In other words, the oxide semiconductor layer 13A and the oxide semiconductor layer 13B themselves do not have an interface in the thickness direction of the dye-sensitized solar cell element 100 of this embodiment.

As described above, the oxide semiconductor layer used in this embodiment has at least two regions with different film thicknesses and different transmittances, and is particularly limited as long as each layer is integrally formed. For example, at least two regions having different thicknesses and transmittances in the oxide semiconductor layer may have different pore diameters, and each region may be composed of a particle group having the same composition.

Here, “the particles have the same composition” means that when the oxide semiconductor layer is composed of one kind of particle group, the average particle diameter of each particle group in at least two regions in the oxide semiconductor layer is equal to one. In the case where the oxide semiconductor layer is composed of two or more types of particle groups, the average particle size of each particle group and the mixing ratio thereof are the same.
For example, when the oxide semiconductor layer is composed of one kind of particle group, the average particle diameter of the particle group constituting the oxide semiconductor layer is at least 2 different in film thickness and transmittance in the oxide semiconductor layer. Match in two areas.
Examples of the method for measuring the average particle diameter of the particle group include laser analysis and three-dimensional image analysis. The laser analysis method is effective when the measurement target is in an ink state, and the three-dimensional image analysis method is effective when the measurement target is in a film state. In addition to the particle size distribution measurement, these measurement methods can also measure the mixing ratio of each particle.

In the case where the oxide semiconductor layer includes two or more types of particle groups, the average particle size of the two or more types of particle groups in at least two regions having different film thicknesses and transmittances in the oxide semiconductor layer. The diameters match and the mixing ratios of the particle groups match.
Here, “the mixing ratio of each particle group is the same” means that at least two regions having different thicknesses and transmittances in the oxide semiconductor layer have the same ratio in the two or more types of particle groups. It refers to being composed.

In addition, the oxide semiconductor layer used in this embodiment includes at least two regions having different transmittances, and the at least two regions may have different pore diameters. When the pore diameters of the at least two regions are different, the difference in pore diameter between one region having one pore diameter and another region having another pore diameter different from one pore diameter is as described above. There is no particular limitation as long as the transmittance can be varied depending on the difference in pore diameter, and as a result, a desired design or the like can be expressed using color shading in at least two regions having different pore diameters. In this embodiment, for example, it is preferably in the range of 1 nm to 20 nm, more preferably in the range of 2 nm to 15 nm, and particularly preferably in the range of 3 nm to 10 nm.
Note that the difference in pore diameter here refers to the difference in pore diameter between adjacent areas in the oxide semiconductor layer having at least two areas having different pore diameters. Note that “adjacent to each other” refers to a state in which two target areas are in contact with each other without interposing other areas. That is, in the case of the oxide semiconductor layer 13 in the dye-sensitized solar cell 100 of FIG. 2, the difference between the pore diameter in the region having the film thickness 13c and the pore diameter in the region having the film thickness 13d, or the film thickness 13d. Is the difference between the pore diameter of the region that is and the pore diameter of the region that is the film thickness 13e. For example, the difference between the pore diameter of the region that is the film thickness 13c and the pore diameter of the region that is the film thickness 13e is As such, it does not indicate a difference in pore diameter between regions that are not adjacent to each other.
By making the difference in pore diameter within the above range, it is possible to have a difference in transmittance due to the difference in pore diameter, and as a result, it is possible to sufficiently represent the color shade at the interface of the regions having different pore diameters, Excellent design properties can be obtained.
In addition, a difference in the haze ratio of the oxide semiconductor layer can be given due to a difference in pore diameter of the oxide semiconductor layer. That is, in the oxide semiconductor layer, the haze ratio can be increased in a region where the pore diameter is relatively large, and the haze ratio can be decreased in a region where the pore diameter is relatively small. For this reason, the color tone of the region having a relatively large pore diameter and a high haze ratio is thin by being clouded, while the color tone of the region having a relatively small pore diameter and a low haze ratio is dark. Here, the haze ratio is a ratio between the parallel light transmittance and the diffuse light transmittance in the incident light. The difference in haze ratio in this embodiment varies depending on the above-described difference in pore diameter, the material of the oxide semiconductor layer, and the like. For example, it is preferably in the range of 0.05 to 99. It is preferably in the range of 1 to 50, particularly preferably in the range of 0.3 to 30.
The haze ratio is a value measured using a haze meter (HGM-2K) manufactured by Suga Test Instruments Co., Ltd.

Further, the pore diameter of the oxide semiconductor layer used in this embodiment is appropriately adjusted according to the use of the dye-sensitized solar cell element of this embodiment, and is not particularly limited. In the dye-sensitized solar cell element of this embodiment, the pore diameter of the thinnest region of the oxide semiconductor layer is preferably in the range of, for example, 1 nm to 80 nm, and more preferably in the range of 3 nm to 50 nm. It is particularly preferable that the thickness is in the range of 5 nm to 30 nm.
In the present invention, the pore diameter refers to the maximum peak of the pore diameter.

The pore diameter of the oxide semiconductor layer can be measured using a highly accurate fully automatic gas adsorption device (BELSORP 28SA manufactured by Nippon Bell Co., Ltd.). Note that nitrogen gas can be used as the adsorption gas.

Hereinafter, the oxide semiconductor film and the dye sensitizer constituting the oxide semiconductor layer will be described.

(A) Oxide Semiconductor Film The oxide semiconductor film used in this embodiment is formed on the first electrode substrate and contains metal oxide semiconductor fine particles.
Hereinafter, the metal oxide semiconductor fine particles contained in the oxide semiconductor film will be described.

(I) Metal oxide semiconductor fine particles The metal oxide semiconductor fine particles used in this embodiment are not particularly limited as long as they are made of a metal oxide having semiconductor characteristics. Examples of the metal oxide constituting the metal oxide semiconductor fine particles used in this embodiment 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. Among these, in this embodiment, it is most preferable to use metal oxide semiconductor fine particles made of TiO ₂ . This is because TiO ₂ is particularly excellent in semiconductor characteristics.

The average particle diameter of the metal oxide semiconductor particles used in this embodiment is usually preferably in the range of 1 nm to 10 μm, particularly preferably in the range of 10 nm to 1000 nm.

(Ii) Other components The oxide semiconductor film used in this embodiment may contain an optional component in addition to the metal oxide semiconductor fine particles. As another component contained in the oxide semiconductor film, for example, a resin can be given. This is because when the resin is contained in the oxide semiconductor film, the brittleness of the oxide semiconductor film used in this embodiment can be improved.

Examples of the resin that can be used for the oxide semiconductor film in this embodiment include polyvinyl pyrrolidone, ethyl cellulose, caprolactan, and the like.

(B) Dye sensitizer The oxide semiconductor layer used in this embodiment is one in which a dye sensitizer is supported on the surface of the oxide semiconductor film described above.
Hereinafter, the dye sensitizer used in this embodiment will be described.

The dye sensitizer used in this embodiment 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 dyes include acridine, azo, indigo, quinone, coumarin, merocyanine, phenylxanthene, indoline, and carbazole dyes. In this embodiment, among these organic dyes, a coumarin dye is preferably used. Further, as the metal complex dye, it is preferable to use a ruthenium dye, and it is particularly preferable to use a ruthenium bipyridine dye and a ruthenium terpyridine dye which are ruthenium complexes. This is because such a ruthenium complex has a wide wavelength range of light to be absorbed, so that the wavelength range of light that can be photoelectrically converted can be greatly expanded.

Examples of the dye sensitizer used in this embodiment include any hue such as a ruthenium complex having a yellow to green hue, a coumarin organic dye having a red hue, and a merocyanine organic dye having a blue hue. Therefore, it is possible to obtain an oxide semiconductor layer having a vivid color tone by supporting these dye sensitizers on the metal oxide semiconductor fine particles.

(2) First Electrode Base Material The first electrode base material used in this embodiment is not particularly limited as long as it has at least a function as an electrode. Moreover, at least any one of the 1st electrode base material used for this aspect and the 2nd electrode base material used for the counter-electrode board | substrate mentioned later is an electrode base material which has transparency. For example, when the first electrode base material does not have transparency, a metal substrate having a metal layer can be exemplified. When the first electrode base material has transparency, the base material is transparent on the base material. A transparent conductive substrate having a conductive film can be given. In this aspect, it is preferable to use a metal substrate for the first electrode base material used for the oxide semiconductor electrode substrate. This is because power generation efficiency can be increased by using a metal substrate with low electrical resistance.
Hereinafter, each of the metal substrate and the transparent conductive substrate will be described.

(A) Metal substrate The metal substrate used in this embodiment is not particularly limited as long as it has a metal layer. Specifically, there are a case where only a metal layer is provided and a case where a base material and a metal layer disposed on the base material are provided.
Hereinafter, each case will be described.

(I) In the case of having only a metal layer The metal layer is not particularly limited as long as it can be used as a metal substrate, may have flexibility, or does not have flexibility. It may be a thing. Examples of the metal layer having flexibility include metal foil.
In addition, the presence or absence of the said flexibility can be judged by performing the metal material bending test method of JISZ2248, and determining whether it bends when a force of 5 × 10 ³ N is applied.

Specific examples of the metal material used for the metal foil include Cu, Al, Ti, Cr, W, Mo, Pt, Ta, Nb, Zr, Zn, and a simple substance such as Fe, and SUS or the like. An alloy etc. are mentioned, Among these, it is preferable to use Ti etc. with high heat resistance.

The thickness of such a metal foil is preferably in the range of 5 μm to 1000 μm, more preferably in the range of 10 μm to 500 μm, and still more preferably in the range of 20 μm to 200 μm.

In addition, a metal substrate can be mentioned as a metal layer which does not have flexibility. Since the metal material used for such a metal substrate can be the same as the metal material used for the metal foil described above, the description thereof is omitted here.

(Ii) When it has a base material and the metal layer arrange | positioned on a base material The metal layer mentioned above and a base material are each demonstrated.

Examples of the metal layer include a metal thin film and a metal plate. In this case, a metal thin film is more preferable. In the metal layer here, the metal layer disposed on the base material can be etched and formed into a pattern, etc., so that by using a metal thin film as the metal layer, etching can be performed. The metal layer can be easily patterned.

The thickness of such a metal thin film is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.010 μm to 0.5 μm, and particularly preferably in the range of 0.020 μm to 0.3 μm.

The metal material used for the metal thin film can be the same as the metal material used for the metal foil described in the section “(i) In the case of having only a metal layer”. .

Next, the base material will be described.
As a base material used here, what has transparency may be sufficient and what does not have transparency may be sufficient. Specifically, a transparent inorganic substrate or a transparent resin substrate can be used. As the transparent resin base material, a base material composed of a resin having general transparency can be used, for example, a base material composed of a resin such as polyethylene terephthalate, polyester naphthalate, or polycarbonate. it can. Examples of the transparent inorganic substrate include a synthetic quartz substrate and a glass substrate. The thickness of the transparent substrate is preferably in the range of 5 μm to 2000 μm.

(B) Transparent conductive substrate The transparent conductive substrate used for this aspect has a base material and a transparent conductive film.
Hereinafter, the base material and the transparent conductive film used in this embodiment will be described.

As a base material used for the transparent conductive substrate, since the dye-sensitized solar cell element of this embodiment is disposed on a light receiving surface that receives sunlight, it is necessary to have transparency to sunlight. It is what is done. The detailed description of the base material can be the same as that described in the section “(a) Metal substrate (ii) When having a base material and a metal layer disposed on the base material”. The description here is omitted.

The transparent conductive film is formed on the substrate. The transparent conductive film is not particularly limited as long as it has desired transparency and has desired conductivity. Examples of the material used for the transparent conductive film include metal oxides and conductive polymer materials. Examples of the metal oxide include SnO ₂ , ZnO, a compound in which tin is added to indium oxide (ITO), a compound in which zinc oxide is added to indium oxide (IZO), and the like. Examples of the conductive polymer material include polythiophene, polyaniline, polypyrrole, polyethylenedioxythiophene, and derivatives thereof. Moreover, these can also be used in mixture of 2 or more types.

The total light transmittance of the transparent conductive film is preferably 85% or more, and more preferably 90% or more.
The method for measuring the total light transmittance of the transparent conductive film here is the same as the method for measuring the transmittance described in the above section “1. Oxide Semiconductor Electrode Substrate (1) Oxide Semiconductor Layer”. it can.

The sheet resistance of the transparent conductive film is preferably 500Ω / □ or less, and more preferably 300Ω / □ or less. The transparent conductive film may be composed of a single layer or may be composed of a plurality of layers.

The film thickness of the transparent conductive film is usually preferably in the range of 5 nm to 2000 nm, particularly preferably in the range of 10 nm to 1000 nm.

Since a general forming method can be used as a method for forming the transparent conductive film, description thereof is omitted here. The detailed formation method will be described later in the section “III. Method for producing dye-sensitized solar cell element, A. Oxide semiconductor electrode substrate formation step, 2. First electrode substrate preparation step”.

2. Electrolyte Layer The electrolyte layer used in this embodiment is formed between the above-described oxide semiconductor electrode substrate and a counter electrode substrate described later, and includes a redox pair.
Hereinafter, the electrolyte layer used in this embodiment will be described.

The redox couple used in the electrolyte layer in this embodiment is not particularly limited as long as it is used in a dye-sensitized solar cell element. For example, a combination of iodine and iodide can be mentioned. As the content of the redox couple, the ratio of the redox couple in the electrolyte layer is preferably in the range of 1% by mass to 50% by mass, and more preferably in the range of 5% by mass to 35% by mass.

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.

The thickness of such an electrolyte layer is not particularly limited, but it is preferable that the oxide semiconductor layer is porous having communication holes. In the case where a layer is formed, it is preferably in the range of 2 μm to 100 μm including the thickness of the oxide semiconductor layer, and more preferably in the range of 2 μm to 50 μm. When the film thickness is smaller than the above range, the oxide semiconductor layer and the counter electrode substrate are likely to come into contact with each other, causing a short circuit. On the other hand, when the film thickness is thicker than the above range, the internal resistance is increased. This is because it leads to performance degradation.

3. Counter Electrode Substrate The counter electrode substrate used in this embodiment has a second electrode base material having at least a function as an electrode, and is arranged so that the above-described oxide semiconductor layer and the second electrode base material face each other. Is.
Hereinafter, the counter electrode substrate used in this embodiment will be described.

(1) Second electrode base material
The second electrode substrate used in this embodiment is not particularly limited as long as it has at least a function as an electrode. Moreover, at least any one of the 2nd electrode base material used for this aspect and the 1st electrode base material used for the oxide semiconductor layer side board | substrate mentioned above is an electrode base material which has transparency. For example, when the second electrode substrate does not have transparency, a metal substrate having a metal layer can be cited. When the second electrode substrate has transparency, a transparent conductive film is formed on the substrate and the substrate. And a transparent conductive substrate. In this aspect, it is preferable to use a transparent conductive substrate for the conductive substrate used for the counter electrode substrate. The detailed description of the metal substrate and the transparent conductive substrate can be the same as that described in the section of “1. Oxide semiconductor layer side substrate (3) First electrode base material”. Description of is omitted.

(2) Others The counter electrode substrate used in this embodiment has a catalyst layer formed as necessary.
Hereinafter, the catalyst layer used in this embodiment will be described.

By forming a catalyst layer on the counter electrode substrate, the dye-sensitized solar cell element of this embodiment can be made more excellent in power generation efficiency. Examples of such a catalyst layer include, for example, an embodiment in which Pt is vapor-deposited on the counter electrode substrate, polyethylene dioxythiophene (PEDOT), polystyrene sulfonic acid (PSS), polyaniline (PA), paratoluene sulfonic acid (PTS). ) And a mixture thereof, an embodiment of forming a catalyst layer can be mentioned, but is not limited thereto.

The film thickness of such a catalyst layer is preferably in the range of 5 nm to 500 nm, more preferably in the range of 10 nm to 300 nm, and particularly preferably in the range of 15 nm to 100 nm.

B. Second Aspect A dye-sensitized solar cell element according to the present aspect includes a first electrode base material having a function as an electrode, and an oxide semiconductor formed on the first electrode base material and including metal oxide semiconductor fine particles. An oxide semiconductor electrode substrate having an oxide semiconductor layer carrying a dye sensitizer on the surface of the film, and a counter electrode substrate having at least a second electrode base material having a function as an electrode, The semiconductor layer and the second electrode base material are disposed so as to face each other, and an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, The oxide semiconductor layer has at least two regions having different film thicknesses and different pore diameters, and the at least two regions are composed of particle groups having the same composition.

In this embodiment, the oxide semiconductor layer has at least two regions having different film thicknesses and pore diameters, thereby expressing the color shading corresponding to the difference between the film thicknesses and the pore diameters of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, a dye-sensitized solar cell element excellent in design can be obtained.
Moreover, according to this aspect, since the particles constituting at least two regions having different film thicknesses and pore diameters in the oxide semiconductor layer have the same composition, the dye-sensitized solar cell element having excellent design properties Therefore, since it is not necessary to use a plurality of types of particles having different compositions, the cost can be reduced as compared with the conventional case.
Furthermore, since the particles constituting at least two regions of the oxide semiconductor layer have the same composition, it is not necessary to provide the coating process of the oxide semiconductor film forming coating solution a plurality of times in the manufacturing process. There is no need to use different types of particles for each region, and a dye-sensitized solar cell element having excellent design properties can be easily produced. The method for producing the dye-sensitized solar cell element of the present invention will be described in detail in the section “III. Method for producing dye-sensitized solar cell element” described later.
Hereinafter, the oxide semiconductor electrode substrate, the electrolyte layer, and the counter electrode substrate that constitute the dye-sensitized solar cell element of this embodiment will be described.

Such an oxide semiconductor electrode substrate has different pore diameters depending on the film thickness of the oxide semiconductor layer. As a result, a difference in transmittance can be provided, and color shading can be expressed. Therefore, by using the oxide semiconductor electrode substrate, there is an effect that a dye-sensitized solar cell element excellent in design can be obtained.
Hereinafter, constituent members of the oxide semiconductor electrode substrate will be described.

(1) Oxide semiconductor layer The oxide semiconductor film in this aspect is formed on the 1st electrode base material mentioned later, and contains metal oxide semiconductor fine particles. The oxide semiconductor layer has at least two regions having different film thicknesses and different pore diameters, and the at least two regions are composed of particle groups having the same composition.

The oxide semiconductor layer in this embodiment is particularly limited as long as it has at least two regions having different film thicknesses and different pore sizes, and the at least two regions are composed of particle groups having the same composition. It is not a thing.
Note that the oxide semiconductor layer has at least two regions having different thicknesses and pore diameters, and the detailed description about the fact that the at least two regions are composed of a particle group having the same composition, etc. First Embodiment 1. Oxide Semiconductor Electrode Substrate (1) Since it can be the same as that described in the section of “Oxide Semiconductor Layer”, description thereof is omitted here.

(2) First Electrode Base Material The first electrode base material used in this embodiment is not particularly limited as long as it has at least a function as an electrode. Moreover, at least any one of the 1st electrode base material used for this aspect and the 2nd electrode base material used for the counter-electrode board | substrate mentioned later is an electrode base material which has transparency.
In addition, about the 1st electrode base material used for this aspect, it may be the same as that of the above-mentioned item of "A. 1st aspect 1. Oxide semiconductor electrode substrate (3) 1st electrode base material". Since it is possible, description here is abbreviate | omitted.

2. Electrolyte Layer The electrolyte layer used in this embodiment is formed between the above-described oxide semiconductor electrode substrate and a counter electrode substrate described later, and includes a redox pair.
In addition, about the electrolyte layer used for this aspect, since it can be made to be the same as that of the description of the said "A. 1st aspect 2. Electrolyte layer", description here is abbreviate | omitted.

3. Counter Electrode Substrate The counter electrode substrate used in this embodiment has a second electrode base material having at least a function as an electrode, and is arranged so that the above-described oxide semiconductor layer and the second electrode base material face each other. Is.
In addition, about the counter electrode board | substrate used for this aspect, since it can be made to be the same as that of what was described in the term of the said "A. 1st aspect 3. Counter electrode board | substrate", description here is abbreviate | omitted.

II. Dye-sensitized solar cell module The dye-sensitized solar cell module of the present invention has two aspects.
Hereinafter, the third mode and the fourth mode will be described separately.

A. Third Aspect A dye-sensitized solar cell module according to the present aspect includes a first electrode base material having a function as an electrode, and an oxide semiconductor formed on the first electrode base material and including metal oxide semiconductor fine particles. An oxide semiconductor electrode substrate having an oxide semiconductor layer carrying a dye sensitizer on the surface of the film, and a counter electrode substrate having at least a second electrode base material having a function as an electrode, The semiconductor layer and the second electrode base material are disposed so as to face each other, and an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate. A plurality of dye-sensitized solar cell elements each having at least two regions having different film thicknesses and different transmittances and having the at least two regions formed integrally are connected in series or in parallel.

According to this aspect, since the oxide semiconductor layer constituting the dye-sensitized solar cell element has at least two regions having different thicknesses and transmittances, the thicknesses and transmittances of the at least two regions are increased. It is possible to express the shade of the color corresponding to the difference. That is, in the oxide semiconductor layer, the transmittance of a region with a small thickness is high, while the transmittance of a region with a large thickness is low.
As described above, the oxide semiconductor layer has a difference in transmittance depending on the film thickness, and the color tone of a region having a high haze rate becomes thin due to white turbidity, while the color tone of a region having a low haze rate becomes dark. Therefore, by using the oxide semiconductor layer, a dye-sensitized solar cell element excellent in design can be obtained, and a dye excellent in design can be obtained by connecting the dye-sensitized solar cell elements. A sensitized solar cell module can be obtained.

In addition, about the dye-sensitized solar cell element used for the dye-sensitized solar cell module of this aspect, it is the same as that described in the above-mentioned section of “I. Dye-sensitized solar cell element A. First aspect”. Therefore, the description here is omitted.

The aspect in which a plurality of dye-sensitized solar cell elements are connected in this aspect is particularly limited as long as desired design and electromotive force can be obtained by the dye-sensitized solar cell module of this aspect. It is not something. Such an embodiment may be an embodiment in which the dye-sensitized solar cell elements are connected in series, or an embodiment in which the dye-sensitized solar cell elements are connected in parallel.

In addition, the aspect in which a plurality of the dye-sensitized solar cell elements are connected may be an aspect in which a plurality of the dye-sensitized solar cell elements are formed between a pair of substrates. The said dye-sensitized solar cell element formed independently may be the aspect connected with external wiring etc.

B. 4th aspect The dye-sensitized solar cell module of this aspect is a 1st electrode base material provided with the function as an electrode, and the oxide semiconductor formed on the said 1st electrode base material and containing a metal oxide semiconductor fine particle An oxide semiconductor electrode substrate having an oxide semiconductor layer carrying a dye sensitizer on the surface of the film, and a counter electrode substrate having at least a second electrode base material having a function as an electrode, The semiconductor layer and the second electrode base material are disposed so as to face each other, and an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate. A plurality of dye-sensitized solar cell elements each having at least two regions having different film thicknesses and different pore diameters, wherein the at least two regions are composed of particles having the same composition are connected in series or in parallel. is there.

In this embodiment, the oxide semiconductor layer has at least two regions having different film thicknesses and pore diameters, thereby expressing the color shading corresponding to the difference between the film thicknesses and the pore diameters of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, a dye-sensitized solar cell module excellent in design can be obtained.
In addition, since the particles constituting at least two regions having different film thicknesses and pore diameters in the oxide semiconductor layer have the same composition, in order to obtain a dye-sensitized solar cell module having excellent design properties Since it is not necessary to use a plurality of types of particles having different values, the cost can be reduced as compared with the prior art.
Further, since the particles constituting at least two regions of the oxide semiconductor layer have the same composition, it is not necessary to provide the coating process of the coating solution for forming the oxide semiconductor film multiple times in the manufacturing process. It is not necessary to use different types of particles for each, and a dye-sensitized solar cell module having excellent design can be easily manufactured.

In addition, about the dye-sensitized solar cell element used for the dye-sensitized solar cell module of this aspect, it is the same as what was demonstrated in the above-mentioned item of "I. Dye-sensitized solar cell element B. 2nd aspect". Therefore, the description here is omitted.

In addition, the dye-sensitized solar cell module of this embodiment can be the same as that described in the above section “A. Third Embodiment”, so description thereof is omitted here.

III. Method for Producing Dye-Sensitized Solar Cell Element The method for producing the dye-sensitized solar cell element of the present invention is a dye-sensitized method for producing the dye-sensitized solar cell element according to the first and second aspects described above. Type solar cell element manufacturing method, wherein an oxide semiconductor film containing metal oxide semiconductor fine particles is formed on a first electrode substrate, and a dye sensitizer is carried on the surface of the oxide semiconductor film By forming the oxide semiconductor layer, an oxide semiconductor electrode substrate forming step for forming the oxide semiconductor electrode substrate, a counter electrode substrate preparing step for preparing the counter electrode substrate having the second electrode base material, A dye-sensitized solar cell element assembly step for assembling a dye-sensitized solar cell element by disposing the oxide semiconductor electrode substrate and the counter electrode substrate so as to face each other with the electrolyte layer interposed therebetween, Oxide semiconductor electrode group In the manufacturing method, the plate forming step includes a pressing step of either partially pressing the oxide semiconductor film or partially pressing the oxide semiconductor film with a different pressure. is there.
Hereinafter, description will be given with reference to the drawings.

FIG. 4 is a schematic process diagram showing an example of a method for producing a dye-sensitized solar cell element of the present invention.
As shown in FIG. 4, in the method for manufacturing a dye-sensitized solar cell element of the present invention, an oxide semiconductor film is formed by forming an oxide semiconductor film 11 containing metal oxide semiconductor fine particles on a first electrode substrate 10. Step (FIG. 4A), pressurizing step of applying pressure to the oxide semiconductor film 11 using the mold 4 (FIG. 4B), and the surface of the pressurized oxide semiconductor film 11 An oxide semiconductor electrode substrate forming step having an oxide semiconductor layer forming step (FIG. 4C) for supporting the dye sensitizer 12 and forming an oxide semiconductor layer, and a dye sensitization of the oxide semiconductor electrode substrate 1 The electrolyte layer 2 is formed on the surface side on which the agent 12 is supported (electrolyte layer forming step (FIG. 4D)), and the oxide semiconductor electrode substrate 1 and the counter electrode substrate 3 face each other with the electrolyte layer 2 interposed therebetween. A dye-sensitized solar cell assembly process (FIG. 4 (e)) Is shall.
Note that in the pressurizing step in FIG. 4 (FIG. 4B), in the oxide semiconductor film 11, a region pressurized with one pressure and a region pressurized with another pressure different from the one pressure However, the oxide semiconductor film may be partially pressurized to form a pressurized region and a non-pressurized region in the oxide semiconductor film.

In the present invention, the oxide semiconductor electrode substrate forming step includes either a step of partially pressing the oxide semiconductor film or a step of partially pressing the oxide semiconductor film with a different pressure. In the oxide semiconductor film, a pressurized region and a non-pressed region, or a region pressurized with one pressure and a region pressurized with a pressure different from the one pressure can be formed, respectively. . The oxide semiconductor film has a small pore size when pressurized. Accordingly, each region in the oxide semiconductor film can have a difference in pore diameter corresponding to the presence or absence of pressurization or the magnitude of the pressure to be pressed, and thus the transmittance in each region is different. It becomes possible. That is, since it is possible to represent the shade of the color corresponding to the difference in the transmittance of each region, it is possible to manufacture a dye-sensitized solar cell element excellent in design.

Conventionally, in order to produce a dye-sensitized solar cell element having excellent design properties, a plurality of production steps were used.In the present invention, by having a step of pressurizing the oxide semiconductor film, It is possible to impart excellent design properties to the dye-sensitized solar cell element. That is, a dye-sensitized solar cell element excellent in design can be manufactured by a simpler method.

As shown in FIG. 5, the oxide semiconductor film 11 is formed even when the oxide semiconductor film 11 formed on the first electrode substrate 10 is composed of a plurality of layers (here, two

layers

11A and 11B). Can give a difference in the pore diameter of the particles corresponding to the presence or absence of pressurization or the magnitude of the pressurization pressure, thereby making it possible to make a difference in the transmittance of each region. That is, by supporting the dye sensitizer 12 on the oxide semiconductor film 11 having regions where the pore diameter and transmittance of the particles are different, colors corresponding to the difference in the pore diameter and transmittance of the particles in each region. This makes it possible to manufacture the dye-sensitized solar cell element 100 having excellent design properties.
Moreover, this invention can integrate each layer by a pressurization process (FIG.5 (b)). That is, as shown in FIGS. 5A to 5C, generation of a gap or the like at the interface between the

oxide semiconductor films

11A and 11B is prevented, and the adhesion between the oxide semiconductor film 11 and the first electrode substrate 10 is prevented. Can be improved.
Furthermore, since the surface of the oxide semiconductor film 11 can be smoothed by the pressurizing step (FIG. 5B), the oxide semiconductor layer carrying the dye sensitizer 12 on the oxide semiconductor film 11 The adhesion between the electrolyte layer 13 and the electrolyte layer 2 can be improved. As a result, the charge mobility is increased, and a dye-sensitized solar cell element having high power generation efficiency can be manufactured.
Note that reference numerals not described in FIG. 5 can be the same as those in FIG.
Hereinafter, each process of the manufacturing method of the dye-sensitized solar cell element of this invention is each demonstrated.

A. Oxide Semiconductor Electrode Substrate Formation Step In the oxide semiconductor electrode substrate formation step of the present invention, an oxide semiconductor film containing metal oxide semiconductor fine particles is formed on a first electrode base material, and a dye is formed on the surface of the oxide semiconductor film. A step of forming an oxide semiconductor electrode substrate by forming an oxide semiconductor layer carrying a sensitizer, wherein the oxide semiconductor film is partially pressurized or the oxide semiconductor film is partially formed It is a process which has one of the pressurization processes of the process of pressurizing with a different pressure.
Hereinafter, a pressurizing step included in the oxide semiconductor electrode substrate forming step, a step of preparing a first electrode base material (hereinafter referred to as a first electrode base material preparing step), and forming an oxide semiconductor film. The description will be divided into a step (hereinafter referred to as an oxide semiconductor film formation step) and a step of forming an oxide semiconductor layer (hereinafter referred to as an oxide semiconductor layer formation step).

1. Pressurization Step The pressurization step in the present invention is a step of partially pressurizing the oxide semiconductor film or a step of partially pressing the oxide semiconductor film with a different pressure.

The pressurizing method in this step is not particularly limited as long as it can apply a desired pressure to the oxide semiconductor film. For example, a press process can be mentioned. Specific examples of the press treatment include roll press work or flat plate press work, and roll press work is particularly preferable.

The roll press process is a rolling process that forms a desired concavo-convex structure on the surface by pressing a rotating roller having a concavo-convex pattern. Further, in the roll press process, a concavo-convex structure is formed on the surface of the molding object by passing a rotating roller in the roll press machine a plurality of times.

FIG. 6 is a schematic view showing an example of roll press processing. As shown in FIG. 6, the roll press machine 200 includes a molding target side rotation roller 6 and a concave / convex pattern mold 4 arranged so as to contact the molding target arranged on the molding target side rotation roller 6. I have it. In FIG. 6, the first electrode base material 10 having the oxide semiconductor film 11 on the surface is disposed as the object to be molded, and the rotating roller 5 having the concavo-convex pattern mold 4 so as to be in contact with the oxide semiconductor film 11. Is provided. When the rotating roller 5 provided so as to be in contact with the oxide semiconductor film 11 rotates, the mold 4 having an uneven pattern provided on the rotating roller 5 is pressed against the oxide semiconductor film 11.

By carrying out such roll press processing, it becomes possible to perform orientation / constant pressure pressing, and the thickness of the molded body can be made uniform.

The cross-sectional shape, height, width, and period of the concavo-convex pattern mold provided on the surface of the rotating roller depend on the thickness of the oxide semiconductor film described above and the pattern and design represented in the dye-sensitized solar cell element. Are appropriately prepared.

The difference between the one pressure and the other pressure when the oxide semiconductor film has a region pressurized with one pressure and a region pressurized with another pressure different from the one pressure. Are appropriately adjusted depending on the selection of the density of the color that appears when the oxide semiconductor film material or the dye sensitizer is supported, and is not particularly limited. In this embodiment, for example, it is preferably in the range of 0.001 t / cm to 5 t / cm, more preferably in the range of 0.005 t / cm to 1 t / cm, particularly 0.01 t / cm. It is preferably in the range of ˜0.1 t / cm.

Further, when the oxide semiconductor film has a pressurized region and a non-pressurized region, the pressure applied to the pressurized region may be a material supporting the oxide semiconductor film or a dye sensitizer. The color is appropriately adjusted depending on the selection of the shade of the color that appears, and is not particularly limited. In this embodiment, for example, it is preferably in the range of 0.001 t / cm to 5 t / cm, more preferably in the range of 0.005 t / cm to 1 t / cm, and particularly 0.03 t / cm. It is preferably in the range of ˜0.1 t / cm.

In addition, it is preferable to perform a baking process after the said pressurization process. In general, the firing treatment is known to be a treatment that can sinter metal oxide semiconductor fine particles contained in an oxide semiconductor film to form a conduction path and improve photoelectric conversion efficiency. However, compared with the case where the baking treatment is performed before the pressurization step, the above-described effect that the photoelectric conversion efficiency is improved when the baking treatment is performed after the pressurization step.
A preferable firing temperature for the firing treatment is not particularly limited as long as it does not exceed the heat resistance temperature of the first electrode substrate, but it is preferably in the range of 200 ° C. to 600 ° C., for example.

2. 1st electrode base material preparation process The 1st electrode base material preparation process in the manufacturing method of the dye-sensitized solar cell element of this invention is a process of preparing a 1st electrode layer on a base material.

As a method for forming the first electrode layer on the substrate, a general method can be used, and examples thereof include a vapor deposition method, a sputtering method, and a CVD method. In the present invention, the sputtering method is particularly preferable.

Although it does not specifically limit as a base material used in this process, A film base material is preferable especially. This is because, in the pressurizing step described later, a pressurizing process can be easily performed as long as the film substrate has excellent workability.
In addition, about the material of the 1st electrode base material used for this process, said "I. Dye-sensitized solar cell element A. 1st aspect 1. Oxide semiconductor electrode substrate (2) 1st electrode base material" Since it can be the same as that described in the section, the explanation here is omitted.

3. Oxide semiconductor film formation process The oxide semiconductor film formation process in the manufacturing method of the dye-sensitized solar cell element of the present invention forms an oxide semiconductor film containing metal oxide semiconductor fine particles on the first electrode substrate. It is a process to do.

In this step, the method for forming the oxide semiconductor film is not particularly limited. For example, a coating liquid for forming an oxide semiconductor film in which metal oxide semiconductor fine particles are dispersed or dissolved in an appropriate solvent is used as the first method. A method of forming an oxide semiconductor film by coating on an electrode substrate and drying is exemplified.

In such a forming method, the method for applying the coating liquid for forming an oxide semiconductor film is not particularly limited as long as it is a general application method. Specifically, a die coating method, a gravure coating method, a gravure method, and the like. Reverse coating method, roll coating method, reverse roll coating method, bar coating method, blade coating method, knife coating method, air knife coating method, slot die coating method, slide die coating method, dip coating method, micro bar coating method, micro bar reverse coating And screen printing (rotary method).
An oxide semiconductor film can be formed by applying and drying a coating liquid for forming an oxide semiconductor film using such a coating method.

For the detailed description of the metal oxide semiconductor fine particles used in the oxide semiconductor film forming step, refer to “I. Dye-sensitized solar cell element A. First aspect 1. Oxide semiconductor electrode substrate (1) Oxide semiconductor film” The description is omitted here since it can be the same as that in the section "."

4). Oxide Semiconductor Layer Forming Step The oxide semiconductor layer forming step in the method for producing a dye-sensitized solar cell element of the present invention includes the oxide semiconductor layer in which a dye sensitizer is supported on the surface of the oxide semiconductor film described above. Is a step of forming.

The method for supporting the dye sensitizer after forming the oxide semiconductor film by applying the coating liquid for forming the oxide semiconductor film by the above coating method and drying it is not particularly limited. In the present invention, for example, a method of immersing an oxide semiconductor film in a dye sensitizer solution and allowing it to penetrate, and then drying, or applying a dye sensitizer solution on the oxide semiconductor film and allowing it to penetrate. Thereafter, a drying method and the like can be mentioned.

In such a method, the solvent used in the dye sensitizer solution is appropriately prepared according to the type of the dye sensitizer used, and examples thereof include an aqueous solvent and an organic solvent. .

For the detailed description of the dye sensitizer used in the oxide semiconductor layer forming step, see "I. Dye-sensitized solar cell element A. First aspect 1. Oxide semiconductor electrode substrate (2) Oxide semiconductor layer" Since it can be the same as that of the term, the explanation here is omitted.

B. Counter electrode substrate preparation step The counter electrode substrate preparation step in the method for producing the dye-sensitized solar cell element of the present invention is a step of preparing a second electrode substrate which is an electrode facing the first electrode substrate described above on the electrolyte. is there.

The method for forming the second electrode substrate is described in the above-mentioned section “III. Method for producing dye-sensitized solar cell element, A. Oxide semiconductor electrode substrate forming step, 2. First electrode substrate preparing step”. Since it can be the same as that described above, the description thereof is omitted here.

In such a process, as a method for forming the second electrode substrate on the electrolyte layer, for example, a second electrode substrate is prepared in advance so that the second electrode substrate and the electrolyte layer are in contact with each other. The method of forming by bonding to can be mentioned.

The detailed contents of the material used for the second electrode substrate may be the same as those described in the section “I. Dye-sensitized solar cell element A. First aspect 3. Counter electrode substrate”. Since it is possible, description here is abbreviate | omitted.

C. Step of Forming Electrolyte Layer The step of forming the electrolyte layer in the method for producing the dye-sensitized solar cell element of the present invention (hereinafter referred to as the electrolyte layer forming step) is generated by received sunlight. In this step, an electrolyte layer having a function of moving the charged charges toward the first electrode base in the oxide semiconductor electrode substrate is formed on the oxide semiconductor layer.

In this step, the method for forming the electrolyte layer is not particularly limited as long as it can be formed with high thickness accuracy. The electrolyte layer is solid, gel, or liquid. It is appropriately adjusted depending on whether or not. As such a method, after forming an electrolyte layer on the oxide semiconductor electrode substrate of the dye-sensitized solar cell element, a method of arranging a counter electrode substrate on the electrolyte layer (first method), and A method (second method) of disposing an oxide semiconductor electrode substrate on the electrolyte layer after forming an electrolyte layer on the counter electrode substrate of the dye-sensitized solar cell element, and the oxide semiconductor electrode substrate and the counter electrode substrate And a method of forming an electrolyte layer between the oxide semiconductor electrode substrate and the counter electrode substrate (third method).

As the first method, for example, a coating method for forming an electrolyte layer by coating a coating solution for forming an electrolyte layer on the oxide semiconductor electrode substrate and drying it can be used. The second method also includes a method of forming an electrolyte layer by a coating method as described above. Further, as the third method, the oxide semiconductor electrode substrate of the dye-sensitized solar cell element and the counter electrode substrate are disposed with a predetermined gap so as to face each other, and an electrolyte layer is disposed in the gap. An injection method for forming an electrolyte layer can be used by injecting a forming coating solution.

The electrolyte layer forming coating solution can be prepared by dispersing or dissolving the material used for the electrolyte layer in a suitable solvent.

The coating method for the electrolyte layer forming coating solution is not particularly limited as long as it is a general coating method. For example, a die coating method, a gravure coating method, a gravure reverse coating method, a roll coating method, a reverse roll List coating method, bar coating method, blade coating method, knife coating method, air knife coating method, slot die coating method, slide die coating method, dip coating method, micro bar coating method, micro bar reverse coating method, screen printing method, etc. Can do.
In addition, as a method for injecting the coating liquid for forming the electrolyte layer, since a general injection method can be used, description thereof is omitted here.

The detailed contents of the electrolyte layer can be the same as those described in the section “I. Dye-sensitized solar cell element A. First aspect 2. Electrolyte layer”. Omitted.

D. Dye-sensitized solar cell element assembling step The dye-sensitized solar cell element assembling step in the method for producing a dye-sensitized solar cell element of the present invention includes the oxide semiconductor electrode substrate and the counter electrode substrate, and the electrolyte layer. It is the process of combining via.

In addition, about the dye-sensitized solar cell element obtained by the manufacturing method of the dye-sensitized solar cell element of this invention, it is the same as that described in the above-mentioned item of "I. Dye-sensitized solar cell element". It can be.

IV. Oxide Semiconductor Electrode Substrate The oxide semiconductor electrode substrate of the present invention has two aspects.
Hereinafter, the fifth aspect and the sixth aspect will be described separately.

A. Fifth Aspect The oxide semiconductor electrode substrate according to the present aspect includes a first electrode base material having a function as an electrode, and an oxide semiconductor film formed on the first electrode base material and including metal oxide semiconductor fine particles. It has an oxide semiconductor layer carrying a dye sensitizer on the surface, the oxide semiconductor layer has at least two regions having different thicknesses and different transmittances, and the at least two regions are It is formed integrally.

In this embodiment, the oxide semiconductor layer has at least two regions having different film thicknesses and transmittances, thereby expressing color shading corresponding to the difference between the film thicknesses and transmittances of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, an oxide semiconductor electrode substrate with excellent design can be obtained.

The oxide semiconductor electrode substrate of this embodiment may be the same as that described in the above-mentioned section “I. Dye-sensitized solar cell element A. First embodiment 1. Oxide semiconductor electrode substrate”. Since it is possible, description here is abbreviate | omitted.

B. Sixth Aspect The oxide semiconductor electrode substrate according to the present aspect includes a first electrode base material having a function as an electrode, and an oxide semiconductor film formed on the first electrode base material and including metal oxide semiconductor fine particles. It has an oxide semiconductor layer carrying a dye sensitizer on its surface, the oxide semiconductor layer has at least two regions with different thicknesses and different pore sizes, and the at least two regions are the same It consists of a group of particles having a composition.

In this embodiment, the oxide semiconductor layer has at least two regions having different film thicknesses and pore diameters, thereby expressing the color shading corresponding to the difference between the film thicknesses and the pore diameters of the at least two regions. It becomes possible. That is, by using the oxide semiconductor layer, a dye-sensitized solar cell element excellent in design can be obtained.
In addition, since the particles constituting the at least two regions in the oxide semiconductor film have the same composition, in order to obtain a dye-sensitized solar cell element having excellent design properties using the oxide semiconductor electrode substrate In addition, it is not necessary to use a plurality of types of particles having different compositions for each region, and the cost can be reduced as compared with the prior art.

The oxide semiconductor electrode substrate of this embodiment may be the same as that described in the section of “I. Dye-sensitized solar cell element B. Second embodiment 1. Oxide semiconductor electrode substrate” described above. Since it is possible, description here is abbreviate | omitted.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

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

[Example 1]
(Oxide semiconductor electrode substrate formation process)
-Preparation of 1st electrode base material First, 50-micrometer-thick Ti foil (Takeuchi Metal Foil Industry Co., Ltd.) was prepared.

-Preparation of coating solution for forming oxide semiconductor film Next, metal oxide semiconductor fine particles P25 (manufactured by Nippon Aerosil Co., Ltd., trade name: P25) were added to ethanol, and 0.5% ethylcellulose STD-100 (Nisshin) Kasei Kogyo Co., Ltd.) was mixed to prepare a coating liquid for forming an oxide semiconductor film.

-Formation of oxide semiconductor film By applying the prepared coating liquid for forming an oxide semiconductor layer on the Ti foil as the first electrode base material by a bar coating method, and then drying at 120 ° C. An oxide semiconductor film containing metal oxide semiconductor fine particles was formed on the first electrode substrate.
At this time, the thickness of the oxide semiconductor film was 11 μm.
Further, the transmittance was 57.8%, and the pore diameter (maximum peak of pore diameter) was 19 nm.
Furthermore, the specific surface area was 52.7 m ² / g.

-Pressure process Then, the pressure was applied to the said metal oxide semiconductor film with the pressure of 0.05 t / cm, and the speed | rate of 1 m / min using the roll press machine. The press roll of the roll press machine has a character “DNP” cut and arranged at a depth of 1 mm in width and 500 μm in depth.
After pressing, it was baked at 500 ° C. for 30 minutes.
At this time, the film thickness of the pressurized oxide semiconductor film (a region other than the letters “DNP”) was 7 μm.
Further, the transmittance of the pressurized oxide semiconductor film was 65%, and the pore diameter (maximum peak of pore diameter) was 12 nm.
Furthermore, the specific surface area after pressing was 47.7 m ² / g.

-Oxide semiconductor layer formation step Next, an organic dye (trade name: N719, manufactured by Diesol Co., Ltd.) as a dye sensitizer and a volume ratio of acetonitrile and tert-butyl alcohol to a concentration of 0.3 mM is 1: A dye-supporting coating solution was prepared by dissolving in 1 solution. The first electrode substrate on which the oxide semiconductor film containing the metal oxide semiconductor fine particles described above was formed was immersed in the dye-supporting coating solution for 20 hours. Thereafter, the pigment-carrying coating solution was pulled up from the pigment-carrying coating solution, washed with acetonitrile, and then air-dried. Thus, a dye sensitizer was supported on the pore surfaces of the metal oxide semiconductor fine particles to form an oxide semiconductor layer, which was used as an oxide semiconductor electrode substrate.

(Counter electrode substrate formation process)
A transparent conductive film with an ITO film (sheet resistance: 30Ω / □) formed on a PEN film is prepared, and a counter electrode substrate is formed by laminating platinum with a thickness of 13 mm (transmittance 80%) on the ITO film. did.

(Dye-sensitized solar cell assembly process)
-Preparation of electrolyte layer forming coating solution 6 mol / l hexyl methyl imidazolide (manufactured by Toyama Pharmaceutical Co., Ltd.), 0.6 mol / l I ₂ (manufactured by Merck), and 0.45 mol / l n- Methyl benzimidazol (manufactured by Sigma-Aldrich) was dissolved in hexyl methyl imidazolium tetraciano borate (manufactured by Merck) to obtain an electrolytic solution.
Next, 10 wt% of STD-100 (Nisshin Kasei Co., Ltd.) was dissolved in ethanol to obtain a resin solution.
Then, the said electrolyte solution and resin solution were mixed by electrolyte solution: resin solution = 1: 6 (weight ratio), and it was set as the coating liquid for electrolyte layer formation.

-Formation of electrolyte layer On the oxide semiconductor electrode substrate mentioned above, the electrolyte formation coating liquid was apply | coated by the Miyabar method, and it heated at 120 degreeC for 10 minute (s), and formed the electrolyte layer.

-Bonding of oxide semiconductor electrode substrate, electrolyte layer and counter electrode substrate The oxide semiconductor electrode substrate on which the electrolyte layer is formed and the counter electrode substrate are bonded together and thermally laminated to obtain a dye-sensitized solar cell element. It was.

[Example 2]
(Oxide semiconductor electrode substrate formation process)
-Preparation of 1st electrode base material The base material was set as the PEN film (made by Teijin DuPont) with a thickness of 125 micrometers. An ITO film having a sheet resistance of 30Ω / □ was formed on the PEN film by a sputtering method to obtain a first electrode substrate.

-Formation of Oxide Semiconductor Film The first electrode is prepared by applying the prepared coating liquid for forming an oxide semiconductor film onto the first electrode substrate by a bar coating method and then drying at 120 ° C. An oxide semiconductor film including metal oxide semiconductor fine particles was formed over the base material.
At this time, the thickness of the oxide semiconductor film was 11 μm.
Further, the transmittance was 57.8%, and the pore diameter (maximum peak of pore diameter) was 19 nm.
Furthermore, the specific surface area after pressing was 52.7 m ² / g.

A dye-sensitized solar cell element was produced in the same manner as in Example 1 except that the oxide semiconductor electrode substrate was formed as described above.

[Comparative Example 1]
(Oxide semiconductor electrode substrate formation process)
-Preparation of 1st electrode base material First, 50-micrometer-thick Ti foil (Takeuchi Metal Foil Industry Co., Ltd.) was prepared.

-Formation of oxide semiconductor film The prepared coating liquid for forming an oxide semiconductor film is applied onto the Ti foil as the first electrode substrate by a bar coating method, and then dried at 120 ° C. An oxide semiconductor film containing metal oxide semiconductor fine particles was formed on the first electrode substrate.
At this time, the thickness of the oxide semiconductor film was 11 μm.
Further, the transmittance was 57.8%, and the pore diameter (maximum peak of pore diameter) was 19 nm.

-Pressurization process Subsequently, the metal oxide semiconductor film was roll-pressed at a pressure of 0.05 t / cm and a speed of 1 m / min using a roll press machine, and the film thickness was set to 7 μm by applying pressure.
Further, the transmittance of the pressurized oxide semiconductor film was 65%, and the pore diameter (maximum peak of the pore diameter) was 12 nm.
In addition, the thing of the mirror surface was used for the press roll of the said roll press machine.

A dye-sensitized solar cell element was produced in the same manner as in Example 1 and Example 2 except that the oxide semiconductor electrode substrate was formed as described above.

[Comparative Example 2]
(Oxide semiconductor electrode substrate formation process)
-Preparation of 1st electrode base material The base material was set as the PEN film (made by Teijin DuPont) with a thickness of 125 micrometers. An ITO film having a sheet resistance of 30Ω / □ was formed on the PEN film by a sputtering method to obtain a first electrode substrate.

-Formation of Oxide Semiconductor Film The first electrode is prepared by applying the prepared coating liquid for forming an oxide semiconductor film onto the first electrode substrate by a bar coating method and then drying at 120 ° C. An oxide semiconductor film including metal oxide semiconductor fine particles was formed over the base material.
At this time, the thickness of the oxide semiconductor film was 11 μm.
Further, the transmittance was 57.8%.
Furthermore, the pore diameter (maximum peak of the pore diameter) was 19 nm.

-Pressurization process Subsequently, the metal oxide semiconductor film was roll-pressed at a pressure of 0.05 t / cm and a speed of 1 m / min using a roll press machine, and the film thickness was set to 7 μm by applying pressure.
Further, the transmittance of the pressurized oxide semiconductor film was 65%.
Furthermore, the pore diameter (maximum peak of pore diameter) of the pressurized oxide semiconductor film was 12 nm.
In addition, the thing of the mirror surface was used for the press roll of the said roll press machine.

-Oxide semiconductor layer formation step Next, an organic dye (trade name: N719, manufactured by Diesol Co., Ltd.) as a dye sensitizer and a volume ratio of acetonitrile and tert-butyl alcohol to a concentration of 0.3 mM is 1: A dye-supporting coating solution was prepared by dissolving in 1 solution. The first electrode substrate on which the oxide semiconductor layer containing the metal oxide semiconductor fine particles described above was formed was immersed in the dye-supporting coating solution for 20 hours. Thereafter, the pigment-carrying coating solution was pulled up from the pigment-carrying coating solution, washed with acetonitrile, and then air-dried. Thus, a dye sensitizer was supported on the pore surfaces of the metal oxide semiconductor fine particles to form an oxide conductor layer, which was used as an oxide semiconductor electrode substrate.

A dye-sensitized solar cell element was produced in the same manner as in Example 1, Example 2, and Comparative Example 1 except that the oxide semiconductor electrode substrate was formed as described above.

[Evaluation results]
The photoelectric conversion characteristics of the dye-sensitized solar cell elements in Examples 1 and 2 and Comparative Examples 1 and 2 were measured using a spectral sensitivity characteristic apparatus CP-2000 (manufactured by Spectrometer Co., Ltd.).
Moreover, the design property of each said dye-sensitized solar cell element was evaluated visually.
The results are shown in Table 1.

[Experiment 1] to [Experiment 6]
In the pressing step, the pressure applied to the oxide semiconductor film is set to 0 t / cm, 0.03 t / cm, 0.05 t / cm, 0.07 t / cm, 0.1 t / cm, and 0.3 t / cm. Except for this, a dye-sensitized solar cell element was produced in the same manner as in Example 1.

[Evaluation results]
Transmittance difference, pore diameter difference (maximum peak diameter difference of pore diameter), film thickness difference between the pressed area and the unpressed area of the dye-sensitized solar cell element in Experimental Examples 1 to 6 It measured about the haze rate difference.
The results are shown in Table 2.
The haze ratio is a ratio of parallel light transmittance and diffuse light transmittance in incident light,
It measured using the haze meter (Suga test machine model number: HGM-2K).

DESCRIPTION OF SYMBOLS 1 ... Oxide semiconductor electrode substrate 10 ... 1st electrode base material 11 ... Oxide semiconductor film 12 ... Dye sensitizer 13 ... Oxide semiconductor layer 2 ... Electrolyte layer 3 ... 2nd electrode base material 4 ... Mold 5 ... Rotation Roller 6 ... Molded object side rotating roller 100 ... Dye-sensitized solar cell element 200 ... Roll press machine

Claims

A first electrode base material having a function as an electrode, and an oxidation in which a dye sensitizer is carried on the surface of an oxide semiconductor film formed on the first electrode base material and containing metal oxide semiconductor fine particles An oxide semiconductor electrode substrate having an oxide semiconductor layer and a counter electrode substrate having a second electrode base material having at least a function as an electrode are disposed so that the oxide semiconductor layer and the second electrode base material face each other. A dye-sensitized solar cell element in which an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate,
The oxide semiconductor layer has at least two regions having different thicknesses and different transmittances, and the at least two regions are integrally formed,
A dye-sensitized solar cell element characterized in that, in the oxide semiconductor layer, the color tone of the thick film region is dark and the color tone of the thin film region is thinner than the color tone of the thick film region .
A first electrode base material having a function as an electrode, and an oxidation in which a dye sensitizer is carried on the surface of an oxide semiconductor film formed on the first electrode base material and containing metal oxide semiconductor fine particles An oxide semiconductor electrode substrate having an oxide semiconductor layer and a counter electrode substrate having a second electrode base material having at least a function as an electrode are disposed so that the oxide semiconductor layer and the second electrode base material face each other. A dye-sensitized solar cell element in which an electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate,
The oxide semiconductor layer has at least two regions having different thicknesses and different pore diameters, and the at least two regions are composed of particle groups having the same composition,
A dye-sensitized solar cell element characterized in that, in the oxide semiconductor layer, the color tone of the thick film region is dark and the color tone of the thin film region is thinner than the color tone of the thick film region .
A first electrode base material having a function as an electrode, and an oxidation in which a dye sensitizer is carried on the surface of an oxide semiconductor film formed on the first electrode base material and containing metal oxide semiconductor fine particles An oxide semiconductor electrode substrate having an oxide semiconductor layer and a counter electrode substrate having a second electrode base material having at least a function as an electrode are disposed so that the oxide semiconductor layer and the second electrode base material face each other. An electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, and the oxide semiconductor layer has at least two regions having different thicknesses and different transmittances. The at least two regions are integrally formed, and in the oxide semiconductor layer, the color tone of the thick film region is dark and the color tone of the thin film region is the color tone of the thick film region. Compared to thin pigment Dye-sensitized solar cell module, wherein the sensitive solar cells which are connected to a plurality series or in parallel.
A first electrode base material having a function as an electrode, and an oxidation in which a dye sensitizer is carried on the surface of an oxide semiconductor film formed on the first electrode base material and containing metal oxide semiconductor fine particles An oxide semiconductor electrode substrate having an oxide semiconductor layer and a counter electrode substrate having a second electrode base material having at least a function as an electrode are disposed so that the oxide semiconductor layer and the second electrode base material face each other. An electrolyte layer including a redox pair is formed between the oxide semiconductor electrode substrate and the counter electrode substrate, and the oxide semiconductor layer has at least two regions having different thicknesses and different pore diameters. In the oxide semiconductor layer, the color tone of the thick region is dark and the color tone of the thin region is the color tone of the thick region. Thin compared to Dye-sensitized solar cell module, wherein the Motozo sensitized solar cell elements are connected to each other in series or in parallel.
A method for producing a dye-sensitized solar cell element for producing the dye-sensitized solar cell element according to claim 1 or 2,
The oxide semiconductor film containing the metal oxide semiconductor fine particles is formed on the first electrode substrate, and the oxide semiconductor layer in which the dye sensitizer is supported on the surface of the oxide semiconductor film is formed. The oxide semiconductor electrode substrate forming step of forming the oxide semiconductor electrode substrate, the counter electrode substrate preparing step of preparing the counter electrode substrate having the second electrode base material, the oxide semiconductor electrode substrate and the A dye-sensitized solar cell element assembling step for assembling a dye-sensitized solar cell element by arranging a counter electrode substrate so as to face each other through the electrolyte layer,
The oxide semiconductor electrode substrate forming step includes a pressurizing step of either partially pressing the oxide semiconductor film or partially pressing the oxide semiconductor film with a different pressure. A method for producing a dye-sensitized solar cell element.
A first electrode base material having a function as an electrode, and an oxidation in which a dye sensitizer is carried on the surface of an oxide semiconductor film formed on the first electrode base material and containing metal oxide semiconductor fine particles A semiconductor layer,
The oxide semiconductor layer has at least two regions having different thicknesses and different transmittances, and the at least two regions are integrally formed,
In the oxide semiconductor layer, an oxide semiconductor electrode substrate characterized in that a color tone of a thick region is dark and a color tone of a thin region is thinner than a color tone of the thick region.
A first electrode base material having a function as an electrode, and an oxide formed on the first electrode base material and having a dye sensitizer supported on the surface of an oxide semiconductor film containing metal oxide semiconductor fine particles Having a semiconductor layer,
The oxide semiconductor layer has at least two regions having different thicknesses and different pore diameters, and the at least two regions are composed of particle groups having the same composition,
In the oxide semiconductor layer, an oxide semiconductor electrode substrate characterized in that a color tone of a thick region is dark and a color tone of a thin region is thinner than a color tone of the thick region.