JP4894133B2 - Method for producing metal oxide semiconductor fine particle layer laminate - Google Patents

Description

  The present invention relates to a method and an apparatus for producing a metal oxide semiconductor fine particle layer laminate used for, for example, a dye-sensitized solar cell, and further uses them to produce a dye-sensitized solar cell at low cost. The present invention relates to a method and an apparatus for manufacturing a dye-sensitized solar cell that can be used.

  In recent years, global warming caused by carbon dioxide has become a global problem. In recent years, solar cells that use solar energy have attracted attention as environmentally friendly and clean energy sources, and active research and development has been promoted. It has been. As such a solar cell, a single crystal silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon solar cell and the like have already been put into practical use. However, the solar cell has a low environmental load and may be reduced in cost. As a result, dye-sensitized solar cells are attracting attention and research and development are underway.

  The dye-sensitized solar cell is, for example, from the light incident side, a transparent substrate, a transparent electrode formed on the transparent substrate, an oxide semiconductor layer carrying a dye sensitizer, an electrolyte layer having an electrolyte, And a counter electrode board | substrate is laminated | stacked in order, and a cell is formed.

  A feature of a dye-sensitized solar cell, in particular, a Gretcher cell, is that a porous oxide semiconductor layer obtained by firing titanium oxide that is a nanoparticle is used. By making the oxide semiconductor layer porous, the adsorption amount of the sensitizing dye can be increased and the light absorption ability can be improved.

  Such a porous oxide semiconductor layer is formed by applying a coating liquid containing metal oxide semiconductor fine particles on a transparent electrode on a transparent substrate and baking it. In this oxide semiconductor layer forming step, for example, when a glass substrate is used as a transparent substrate, it is possible to perform baking at 400 to 600 ° C. to form a porous oxide semiconductor layer. When using a film substrate that is inferior in heat resistance to the substrate, the film must be baked at a temperature lower than the heat resistant temperature of the film, and the bonding force between the metal oxide semiconductor fine particles becomes insufficient. In some cases, a sufficient transmission path from the sensitizing dye to the oxide semiconductor layer and the transparent electrode cannot be secured. Further, the adhesion between the film substrate and the oxide semiconductor layer is not sufficient, and there is a problem that the film cannot follow the flexibility of the film and the film is peeled off or cracked. Furthermore, as described above, the above baking treatment not only limits the type of the transparent substrate, but also has a problem that the cost increases.

  Therefore, in Patent Document 1, an oxide semiconductor fine particle layer is formed by depositing oxide semiconductor fine particles on a transparent electrode on a transparent substrate by electrophoresis, and a dye is supported on the oxide semiconductor fine particle layer. A method for forming an oxide semiconductor layer is disclosed. According to this method, since the oxide semiconductor layer can be formed without performing the baking treatment as described above, the glass substrate can be used as the transparent substrate, and the cost performance is excellent. A dye-sensitized solar cell can be obtained. However, this method only shows a method for forming an oxide semiconductor layer on a single wafer.

JP 2002-100416 A

  The present invention has been made in view of the above problems, and for example, a metal oxide semiconductor capable of efficiently producing a metal oxide semiconductor fine particle layer laminate for use in a dye-sensitized solar cell at low cost. Provided are a method for producing a fine particle layered product, a production apparatus therefor, and a production method for a dye-sensitized solar cell capable of producing a dye-sensitized solar cell at low cost using the same, and a production apparatus therefor The main purpose is to do.

  In order to achieve the above object, the present invention provides a conductive film substrate having a long film substrate that can be moved continuously and an electrode layer formed on the long film substrate. The conductive film substrate is immersed in a bath solution in which semiconductor fine particles are dispersed, and a voltage is applied to the electrode layer and an electrode plate disposed in the bath solution so as to face the electrode layer. A method for producing a metal oxide semiconductor fine particle layer laminate comprising electrodepositing the metal oxide semiconductor fine particles on an electrode layer and continuously forming the metal oxide semiconductor fine particle layer on the electrode layer. provide.

  According to the present invention, since a metal oxide semiconductor fine particle layer can be continuously formed using a long film substrate, there is an advantage that productivity is improved. In addition, since the metal oxide semiconductor fine particle layer can be formed without performing a baking treatment, a film substrate having a heat resistance lower than that of a glass substrate can be suitably used. Further, such a film substrate is processed. Since it is excellent in properties, it can be easily combined with other devices, and the range of applications of the metal oxide semiconductor fine particle layer laminate produced according to the present invention can be expanded. Moreover, when manufacturing a dye-sensitized solar cell, for example using the metal oxide semiconductor fine particle layer laminated body manufactured by this invention, it is useful for weight reduction, reduction of manufacturing cost, and improvement of productivity.

  Moreover, in the said invention, it is preferable that the application of the voltage to the said electrode layer is performed before the said electroconductive film board | substrate is immersed in the bath liquid which disperse | distributed the said metal oxide semiconductor fine particle.

  Furthermore, in the said invention, it is preferable that the application of the voltage to the said electrode layer is based on the conveyance roll which conveys the said conductive film board | substrate. As a result, it is possible to apply a voltage to the electrode layer while conveying the conductive film substrate, and thus it is possible to shorten the manufacturing process when manufacturing the metal oxide semiconductor fine particle layer laminate. is there.

The present invention also includes a substrate, a first electrode layer formed on the substrate, a metal oxide semiconductor fine particle formed on the first electrode layer, and carrying a dye sensitizer. An oxide semiconductor layer that conducts charges generated from the dye sensitizer by light irradiation, a counter substrate facing the substrate, and an electrode formed on the counter substrate and facing the first electrode layer A charge that is located between the second electrode layer, the oxide semiconductor layer, and the second electrode layer and is conducted by the oxide semiconductor layer is oxidized through the first electrode layer and the second electrode layer. A method for producing a dye-sensitized solar cell having an electrolyte layer that transports when transported to a physical semiconductor layer,
The oxide semiconductor layer is formed by forming a metal oxide semiconductor fine particle layer on the first electrode layer on the substrate using the method for producing a metal oxide semiconductor fine particle laminate according to the invention. Provided is a method for producing a dye-sensitized solar cell, wherein the dye-sensitized solar cell is formed by supporting the dye-sensitizer on a fine particle layer.

  In the present invention, since the metal oxide semiconductor fine particle layer can be formed without performing the firing treatment by using the above method for producing a metal oxide semiconductor fine particle layer laminate, the dye enhancement can be performed efficiently at a low cost. It becomes possible to manufacture a sensitive solar cell. In addition, since a film substrate having a heat resistance lower than that of a glass substrate can be suitably used, it is useful in terms of processing, and the weight of the dye-sensitized solar cell can be reduced.

  The present invention also provides a continuous roll film substrate and an unwinding roll on which a conductive film substrate having an electrode layer formed on the long film substrate is wound; A voltage application unit that applies a voltage to the electrode layer of the conductive film substrate that is fed from a roll, and a bath liquid that is disposed after the voltage application unit and in which metal oxide semiconductor fine particles are dispersed are housed, and A bath provided so that the conductive film substrate is immersed in the bath solution, an electrode plate disposed in the bath so as to face the electrode layer of the conductive film substrate, the electrode layer, and the electrode A metal oxide having a power source for applying a voltage to the electrode plate and a metal oxide semiconductor fine particle layer formed by electrodepositing the metal oxide semiconductor fine particles on the electrode layer in the bath Providing an apparatus for manufacturing a metal oxide semiconductor fine particle layer laminated body and having a winding portion for winding the conductor particle layer laminate.

  According to the present invention, since a metal oxide semiconductor fine particle layer can be continuously formed by performing a roll-to-roll process using a long film substrate, there is an advantage that productivity is improved. In addition, since the metal oxide semiconductor fine particle layer can be formed without performing a baking treatment, a film substrate that is inferior in heat resistance to a glass substrate can be suitably used, which is useful for reducing weight and reducing manufacturing costs. It is. Furthermore, since the film substrate is excellent in processability, it can be easily combined with other devices, and the range of applications of the metal oxide semiconductor fine particle layer laminate produced according to the present invention can be expanded.

  In the said invention, it is preferable that the said voltage application part is a conveyance roll which conveys the said conductive film board | substrate. As a result, it is possible to apply a voltage to the electrode layer while conveying the conductive film substrate, and thus it is possible to shorten the manufacturing process when manufacturing the metal oxide semiconductor fine particle layer laminate. is there.

  Moreover, in the said invention, it is preferable to have a drying part which is arrange | positioned between the said bathtub and the said winding-up part, and dries the said metal oxide semiconductor fine particle electrodeposited on the said electrode layer. This is because the metal oxide semiconductor fine particle layer is formed by electrodepositing and drying the metal oxide semiconductor fine particles on the electrode layer. In addition, the bonding force between the metal oxide semiconductor fine particles is increased, and the adhesion between the conductive film substrate and the metal oxide semiconductor fine particle layer is improved.

Furthermore, the present invention provides a substrate, a first electrode layer formed on the substrate, a metal oxide semiconductor fine particle formed on the first electrode layer, and carrying a dye sensitizer. An oxide semiconductor layer that conducts charges generated from the dye sensitizer by light irradiation, a counter substrate facing the substrate, and an electrode formed on the counter substrate and facing the first electrode layer A charge that is located between the second electrode layer, the oxide semiconductor layer, and the second electrode layer and is conducted by the oxide semiconductor layer is oxidized through the first electrode layer and the second electrode layer. An apparatus for producing a dye-sensitized solar cell having an electrolyte layer that performs transport when transported to a physical semiconductor layer,
An apparatus for producing a dye-sensitized solar cell, comprising the apparatus for producing a metal oxide semiconductor fine particle layer laminate according to the above invention as the oxide semiconductor layer forming portion is provided.

  According to the present invention, since the metal oxide semiconductor fine particle layer stack can be formed without performing the firing treatment by having the metal oxide semiconductor fine particle layer laminate manufacturing apparatus, the color can be efficiently produced at low cost. A sensitized solar cell can be manufactured. Moreover, the film board | substrate which is inferior to a glass substrate in heat resistance can be used suitably, and it is useful in a processing surface and weight reduction.

  In the method for producing a metal oxide semiconductor fine particle layer laminate according to the present invention, a metal oxide semiconductor fine particle layer can be formed by a roll-to-roll process without performing a firing step, thereby reducing weight, reducing production costs, and productivity. It is useful for improvement. Therefore, the metal oxide semiconductor fine particle layer laminate produced by the present invention can be suitably used for various devices such as a dye-sensitized solar cell.

  Hereinafter, the manufacturing method and manufacturing apparatus of the metal oxide semiconductor fine particle layer laminate of the present invention, and the manufacturing method and manufacturing apparatus of the dye-sensitized solar cell using these will be described.

A. First, a method for producing a metal oxide semiconductor fine particle layer laminate of the present invention will be described.

  The method for producing a metal oxide semiconductor fine particle layer laminate according to the present invention comprises a conductive film substrate having a continuously movable long film substrate and an electrode layer formed on the long film substrate. The conductive material is immersed in a bath solution in which metal oxide semiconductor fine particles are dispersed and a voltage is applied to the electrode layer and an electrode plate disposed in the bath solution so as to face the electrode layer. The metal oxide semiconductor fine particles are electrodeposited on the electrode layer of the film substrate to continuously form metal oxide semiconductor fine particle layers on the electrode layer.

  The manufacturing method of the metal oxide semiconductor fine particle layer laminated body of this invention is demonstrated using drawing. FIG. 1 shows an example of an apparatus for producing a metal oxide semiconductor fine particle layer laminate used in the method for producing a metal oxide semiconductor fine particle layer laminate of the present invention. As shown in FIG. 1, first, an unwinding roll 1 around which a conductive film substrate 10 is wound is prepared (conductive film substrate preparation step). The conductive film substrate 10 has a film substrate 11 and an electrode layer 12 as shown in FIG. Next, as shown in FIG. 1, it arrange | positions so that the electrode layer of the electroconductive film board | substrate 10 drawn | fed out from the unwinding roll 1 and the voltage application part 2 may contact | connect. Further, the conductive film substrate 10 is immersed in the bath liquid 3 in which metal oxide semiconductor fine particles are dispersed (immersion step). In the bath liquid 3, an electrode plate 5 is disposed so as to face the electrode layer of the conductive film substrate 10. Further, the voltage application unit 2 and the electrode plate 5 are applied with a DC voltage by the power supply unit 6, and when the voltage application unit 2 is applied as a negative electrode and the electrode plate 5 is applied as a positive electrode, for example, The metal oxide semiconductor fine particles having a positive surface charge in the bath liquid 3 migrate and adhere to the surface of the electrode layer of the conductive film substrate 10 applied to the negative electrode by the voltage application unit 2 by electrophoresis. Thereby, a metal oxide semiconductor fine particle layer is formed (metal oxide semiconductor fine particle layer forming step). Further, the metal oxide semiconductor fine particles attached on the electrode layer of the conductive film substrate 10 are dried by the drying unit 8 (drying process). Finally, the metal oxide semiconductor fine particle layer stack having the metal oxide semiconductor fine particle layer is wound around the winding portion 9 (winding step). The metal oxide semiconductor fine particle layer laminate produced by the above series of steps includes, for example, as shown in FIG. 3, a film substrate 11, an electrode layer 12 formed on the film substrate 11, and the electrode layer 12 And the metal oxide semiconductor fine particle layer 13 formed on the substrate.

According to the present invention, since the metal oxide semiconductor fine particle layer can be continuously formed through the roll-to-roll process, there is an advantage that productivity is improved. In addition, conventionally, a baking treatment is performed to form a porous metal oxide semiconductor fine particle layer. When a film substrate having a heat resistance lower than that of a glass substrate is used, the metal oxide semiconductor fine particle layer is formed. However, in the present invention, a metal oxide semiconductor fine particle layer can be formed without performing a baking treatment, and therefore a film substrate having poor heat resistance is preferably used. Can do. Furthermore, since the film substrate is excellent in processability, it can be easily combined with other devices, and the range of applications of the metal oxide semiconductor fine particle layer laminate produced according to the present invention can be expanded. Moreover, when manufacturing a dye-sensitized solar cell, for example using the metal oxide semiconductor fine particle layer laminated body manufactured by this invention, it is useful for weight reduction, reduction of manufacturing cost, and improvement of productivity.
Hereafter, each process in the manufacturing method of such a metal oxide semiconductor fine particle layer laminated body is demonstrated.

1. Conductive film substrate preparation step In the method for producing a metal oxide semiconductor fine particle layer laminate of the present invention, a conductive film substrate having a long film substrate and an electrode layer formed on the film substrate is prepared. A conductive film substrate preparation step is performed.

The conductive film substrate used in this step has, for example, a long film substrate 11 and an electrode layer 12 formed on the film substrate, as shown in FIG.
Hereinafter, each configuration of such a conductive film substrate will be described.

(1) Long film substrate In this invention, since a metal oxide semiconductor fine particle layer laminated body is manufactured continuously by a roll-to-roll process, the long film substrate used for this invention is flexible. It is preferable that there is. In addition, the film substrate is not particularly limited regardless of whether it is transparent or opaque. For example, the film substrate is a pigment using the metal oxide semiconductor fine particle layer laminate produced according to the present invention. When the sensitized solar cell is manufactured, when the film substrate is located on the light receiving surface side, it is preferably a transparent film substrate having transparency excellent in light transmittance. Furthermore, it is preferable that it is excellent in heat resistance, weather resistance, water vapor, and other gas barrier properties. Specifically, ethylene / tetrafluoroethylene copolymer film, biaxially stretched polyethylene terephthalate film, polyethersulfone (PES) film, polyetheretherketone (PEEK) film, polyetherimide (PEI) film, polyimide ( PI) film and plastic film such as polyester naphthalate (PEN). Since these film substrates are excellent in processability and easy to combine with other devices, the range of applications of the metal oxide semiconductor fine particle layer laminate produced according to the present invention can be expanded. It is also effective in improving productivity and reducing manufacturing costs.

  Such a film may be used alone or may be a composite film in which two or more kinds of films are laminated.

(2) Electrode layer The material for forming the electrode layer used in the present invention is not particularly limited as long as it is excellent in conductivity. Moreover, when manufacturing a dye-sensitized solar cell using the metal oxide semiconductor fine particle layer laminated body of this invention, the said electrode layer does not have corrosivity with respect to the electrolyte contained in a dye-sensitized solar cell. Furthermore, in the dye-sensitized solar cell, when the electrode layer is located on the light receiving surface side, it is preferably a transparent electrode layer excellent in light transmittance. For example, a material having excellent light _{permeability,} may be mentioned SnO 2, ITO, IZO, ZnO or the like. Among these, fluorine-doped SnO ₂ and ITO are preferable. This is because these materials are excellent in both conductivity and permeability.

  The electrode layer may be a single layer or may be a laminated layer. As the film thickness of such an electrode layer, the film thickness is in the case of a single electrode layer, and the total film thickness is in the range of 0.1 to 2000 nm in the case of a plurality of layers. It is preferable to be in the range of 500 nm.

  Further, an electrode used in the present invention can be formed by disposing a metal mesh having a sufficient aperture and light transmission on the film substrate, or by integrating or laminating the metal mesh and the material for forming the electrode layer described above. It can also be a layer.

(3) Method for Forming Conductive Film Substrate In the present invention, as a method for forming an electrode layer on the film substrate, a generally used method can be used. Specifically, wet coating, vapor deposition , Sputtering method, CVD method and the like. Of these, vapor deposition, sputtering, and CVD are preferred.

  In order to improve the adhesion between the electrode layer and the film substrate, an adhesive layer may be provided on the film substrate. The material for forming such an adhesive layer is not particularly limited as long as it improves the adhesion between the film substrate and the electrode layer. Specifically, a heat sealant, an adhesive, an adhesive, a heat Examples thereof include a curable resin and an ultraviolet curable resin.

2. Immersion step In the method for producing a metal oxide semiconductor fine particle layer laminate of the present invention, an immersion step is performed in which the conductive film substrate is immersed in a bath solution in which metal oxide semiconductor fine particles are dispersed.

  In the present invention, since the metal oxide semiconductor fine particles are electrodeposited on the electrode layer of the conductive film substrate in the bath liquid in which the metal oxide semiconductor fine particles are dispersed, the electrode layer of the conductive film substrate is What is necessary is just to fully immerse in the bath liquid which disperse | distributed the metal oxide semiconductor fine particle. Therefore, when the electrode layer of the conductive film substrate passes through the surface of the bath liquid in which the metal oxide semiconductor fine particles are dispersed, the entire conductive film substrate does not need to be immersed in the bath liquid. 2, the electrode layer 12 needs to be immersed in the bath solution, but the film substrate 11 may or may not be immersed in the bath solution.

  In the present invention, for example, as shown in FIG. 1, an electrode plate 5 is disposed in a bath liquid 3 in which the metal oxide semiconductor fine particles are dispersed, and the conductive film is placed in the bath liquid 3. When the substrate 10 is immersed, it is necessary to immerse the electrode plate 5 and the electrode layer of the conductive film substrate 10 so as to face each other. According to the present invention, when a DC voltage is applied to the voltage application unit 2 and the electrode plate 5 by the power supply unit 6, the metal oxide semiconductor fine particles in the bath liquid 3 in which the metal oxide semiconductor fine particles are dispersed are converted into the voltage application unit 2. The metal oxide semiconductor fine particle layer is formed by migrating to the electrode layer surface of the conductive film substrate 10 fed by the electrode and electrodepositing. Therefore, it is preferable that the electrode plate and the electrode layer of the conductive film substrate are arranged at a predetermined distance.

  The distance between the electrode layer of the conductive film substrate and the electrode plate in the bath liquid in which the metal oxide semiconductor fine particles are dispersed is greatly different depending on the apparatus, but generally within a range of 0.1 mm to 10 mm, Especially, it is preferable to be in the range of 0.2 mm to 8 mm. When the distance between the electrode layer and the electrode plate is within the above range, the metal oxide semiconductor fine particles can be uniformly electrodeposited on the electrode layer. It is because it can form.

The metal oxide semiconductor fine particles used in the bath liquid in which the metal oxide semiconductor fine particles are dispersed are not particularly limited as long as they can conduct charges to the electrode layer. For example, when a dye-sensitized solar cell is produced using the metal oxide semiconductor fine particle layer laminate produced according to the present invention, the charge generated from the dye-sensitized agent contained in the dye-sensitized solar cell is Any material that can be conducted to the electrode layer may be used. _{Specifically, TiO 2, ZnO, SnO 2} , ITO, ZrO 2, SiO X, MgO, Al 2 O 3, CeO 2, Bi 2 O 3, Mn 3 O 4, Y 2 O 3, WO 3, Ta ₂ O ₅ , Nb ₂ O ₅ , La ₂ O _{3 and the} like can be mentioned. These metal oxide semiconductor fine particles are suitable for forming a porous oxide semiconductor layer, and are preferable because energy conversion efficiency can be improved and costs can be reduced. In addition, any one of the metal oxide semiconductor fine particles may be used, or two or more kinds may be mixed and used. Among these, TiO ₂ can be preferably used. Furthermore, it is good also as a core-shell structure which makes one type | mold core fine particle, and includes a core fine particle and forms a shell with another metal oxide semiconductor fine particle.

  Such a surface charge of the metal oxide semiconductor fine particles may be a positive electrode or a negative electrode. In the present invention, the conductive film substrate is immersed in a bath solution in which metal oxide semiconductor fine particles are dispersed so that the electrode layer of the conductive film substrate and the electrode layer face the electrode layer. By applying a voltage to the arranged electrode plate, the metal oxide semiconductor fine particles are electrodeposited on the electrode layer of the conductive film substrate to form a metal oxide semiconductor fine particle layer on the electrode layer. Is. Therefore, it is necessary to set the charges of the electrode layer and the electrode plate of the conductive film substrate in consideration of the surface charge of the metal oxide semiconductor fine particles. That is, when the surface charge of the metal oxide semiconductor fine particles is a positive electrode, the electrode layer on which the metal oxide semiconductor fine particles are electrodeposited is a negative electrode, and the electrode plate in the bath liquid is set to be a positive electrode. On the other hand, when the surface charge of the metal oxide semiconductor fine particles is a negative electrode, the electrode layer on which the metal oxide semiconductor fine particles are electrodeposited is set as a positive electrode, and the electrode plate in the bath liquid is set as a negative electrode.

  The particle diameter of the metal oxide semiconductor fine particles is not particularly limited, but specifically, it is preferably in the range of 1 nm to 10 μm, and more preferably in the range of 10 nm to 500 nm. When the particle size is smaller than the above range, it is difficult to produce such fine particles themselves, and the respective particles may aggregate to form secondary particles. On the other hand, when the particle diameter is larger than the above range, the metal oxide semiconductor fine particle layer may be thickened, which may increase the resistance.

  Furthermore, the same kind or different kind of metal oxide semiconductor fine particles having a particle diameter within the above range and different particle diameters may be mixed and used. As a result, the light scattering effect can be enhanced, and for example, when a dye-sensitized solar cell is produced using the metal oxide semiconductor fine particle layer laminate produced according to the present invention, the metal oxide semiconductor fine particle layer is sensitized. This is because more light can be confined in the oxide semiconductor layer formed by supporting the dye, and thus light absorption in the dye sensitizer can be efficiently performed. For example, the metal oxide semiconductor fine particles in the range of 10 to 50 nm and the metal oxide semiconductor fine particles in the range of 50 to 200 nm can be mixed and used.

  Here, the oxide semiconductor layer means a layer in which a dye sensitizer is supported in the pores of a metal oxide semiconductor fine particle layer that is a porous body. In addition, the oxide semiconductor layer is formed from a dye sensitizer carried in the pores of, for example, a dye-sensitized solar cell using the metal oxide semiconductor fine particle layer laminate produced according to the present invention. It functions as a member that conducts charges generated by light irradiation to the electrode layer.

  The bath liquid in which the metal oxide semiconductor fine particles used in the present invention are dispersed is one in which the metal oxide semiconductor fine particles are uniformly dispersed in an appropriate solvent so as not to aggregate.

  The solvent for dispersing the metal oxide semiconductor fine particles is preferably one having low conductivity. This is because when the conductivity of the solvent is high, the formation of the metal oxide semiconductor fine particle layer may be adversely affected. Specific examples of such a solvent include water or methanol, ethanol, isopropyl alcohol, tert-butanol, propylene glycol monomethyl ether, terpineol, dichloromethane, acetone, acetonitrile, ethyl acetate and the like.

  In addition, the concentration of the metal oxide semiconductor fine particles in the bath liquid in which the metal oxide semiconductor fine particles are dispersed is in the range of 0.5 wt% to 20 wt%, particularly in the range of 1 wt% to 15 wt%. Preferably there is. When the concentration of the metal oxide semiconductor fine particles is lower than the above range, the electrodeposition amount of the metal oxide semiconductor fine particles on the electrode layer may be insufficient, while when the concentration is higher than the above range, This is because the metal oxide semiconductor fine particles may be aggregated.

  Further, the temperature of the bath liquid in which the metal oxide semiconductor fine particles are dispersed may be room temperature and need not be controlled. This is because the influence of temperature is relatively small when electrodepositing the metal oxide semiconductor fine particles on the electrode layer.

3. Metal oxide semiconductor fine particle layer forming step In the method for producing a metal oxide semiconductor fine particle layer laminate of the present invention, a DC voltage is applied to the voltage application part and the electrode plate by a power supply part to disperse the metal oxide semiconductor fine particles. The metal oxide semiconductor fine particles in the bath solution are migrated to the electrode layer surface of the conductive film substrate to which a voltage is applied by the voltage application unit and attached to form a metal oxide semiconductor fine particle layer on the electrode layer A metal oxide semiconductor fine particle layer forming step is performed.

  In the present invention, for example, as shown in FIG. 1, the voltage application unit 2 and the electrode plate 5 are applied with a DC voltage by the power supply unit 6, and the voltage application unit 2 is an electrode of the conductive film substrate 10. Since it is in contact with the layer, the electrode layer of the conductive film substrate 10 is powered by the voltage application unit 2.

  In the present invention, the voltage application unit is not particularly limited as long as the voltage application unit is arranged so as to be in contact with the electrode layer of the conductive film substrate. It is preferable to arrange a voltage application unit so that a voltage is applied to the electrode layer of the conductive film substrate before the substrate is immersed in a bath solution in which the metal oxide semiconductor fine particles are dispersed.

  Furthermore, in this invention, as shown, for example in FIG. 1, it is preferable that the voltage application part 2 is a conveyance roll which conveys the said conductive film board | substrate 10. As shown in FIG. As a result, it is possible to apply a voltage to the electrode layer while conveying the conductive film substrate, and thus it is possible to shorten the manufacturing process when manufacturing the metal oxide semiconductor fine particle layer laminate. is there.

  In this invention, when applying a voltage to a voltage application part and an electrode plate, a negative electrode and a positive electrode are set with the surface charge which the said metal oxide semiconductor fine particle has. That is, as described above, when the surface charge of the metal oxide semiconductor fine particles is a positive electrode, the electrode layer for electrodepositing the metal oxide semiconductor fine particles is a negative electrode, that is, the voltage application part is a negative electrode, The electrode plate is set to be a positive electrode. On the other hand, when the surface charge of the metal oxide semiconductor fine particles is a negative electrode, the electrode layer on which the metal oxide semiconductor fine particles are electrodeposited is the positive electrode, that is, the voltage application part is the positive electrode, and the electrode plate in the bath liquid is the negative electrode Set to be.

  The voltage applied to the voltage application section and the electrode plate is preferably set to have an electric field strength in the range of 50 V / cm to 5000 V / cm, particularly in the range of 80 V / cm to 3000 V / cm. .

  Furthermore, if there is a potential difference between the voltage application unit and the electrode plate, the positive electrode and the negative electrode can be set, so the voltage applied to the voltage application unit may be zero, for example. In this case, the voltage applied to the electrode plate is preferably within the above range.

  In the present invention, the thickness of the metal oxide semiconductor fine particle layer is not particularly limited as long as it can sufficiently obtain a function of conducting charge to the electrode layer. For example, when a metal oxide semiconductor fine particle layer laminate manufactured according to the present invention is used to form a dye-sensitized solar cell, the oxide semiconductor layer is formed using the metal oxide semiconductor fine particle layer. It is sufficient that a function of conducting charges generated from the dye sensitizer by light irradiation on the physical semiconductor layer can be sufficiently obtained. Specifically, it is preferably in the range of 1 μm to 50 μm, and more preferably in the range of 3 μm to 30 μm.

5). Drying step In the method for producing a metal oxide semiconductor fine particle layer laminate of the present invention, it is preferable to perform a drying step of drying the metal oxide semiconductor fine particles attached on the electrode layer of the conductive film substrate by the drying unit. This is because by performing this drying step, the bonding force between the metal oxide semiconductor fine particles can be increased, and the adhesion between the conductive film substrate and the metal oxide semiconductor fine particle layer can be improved.

  The method for drying the metal oxide semiconductor fine particles is not particularly limited as long as it is a drying method capable of removing the solvent adhering to the metal oxide semiconductor fine particles. For example, the entire specific space such as an oven is heated. For example, a method of passing through an apparatus, a method of irradiating infrared rays, a method of applying hot air, and the like can be used.

  Moreover, it is preferable that a drying process is performed between the said metal oxide semiconductor fine particle layer formation process and the winding-up process mentioned later.

  The drying temperature in this step varies depending on the type of the film substrate to be used, and may be appropriately set so as to be lower than the melting point and softening point of the film substrate. For example, the drying temperature is set within a range of 60 ° C to 450 ° C. Among these, it is preferable that the temperature be in the range of 100 ° C to 250 ° C. When the drying temperature is higher than the above range, the film substrate may be deformed or altered, and when the temperature is lower than the above range, the electrodeposited metal oxide semiconductor fine particles may be sufficiently dried. This is because it may not be possible.

  The drying time is usually within a range of 5 seconds to 30 minutes, preferably within a range of 10 seconds to 10 minutes.

6). Winding step In the method for producing a metal oxide semiconductor fine particle layer laminate of the present invention, after forming the metal oxide semiconductor fine particle layer, the metal oxide semiconductor fine particle layer laminate usually having this metal oxide semiconductor fine particle layer The winding-up process which winds up to a winding-up part is performed.

  In the present invention, the metal oxide semiconductor fine particle layer can be continuously formed through the roll-to-roll process, so that the productivity is improved.

B. Next, a method for producing the dye-sensitized solar cell of the present invention will be described.
The method for producing a dye-sensitized solar cell of the present invention includes a substrate, a first electrode layer formed on the substrate, a metal oxide semiconductor fine particle formed on the first electrode layer, and a dye. A sensitizer is supported, and is formed on the counter substrate, the oxide semiconductor layer that conducts charges generated from the dye sensitizer by light irradiation, the counter substrate facing the substrate, and the first substrate. The second electrode layer, which is an electrode facing the electrode layer, and the electric charges located between the oxide semiconductor layer and the second electrode layer and conducted by the oxide semiconductor layer are the first electrode layer and the second electrode layer. A method for producing a dye-sensitized solar cell having an electrolyte layer for transporting when transported to the oxide semiconductor layer via an electrode layer,
The oxide semiconductor layer is formed by forming a metal oxide semiconductor fine particle layer on the first electrode layer on the substrate using the method for producing the metal oxide semiconductor fine particle laminate, and the metal oxide semiconductor fine particle layer. It is formed by supporting the above dye sensitizer.

  Conventionally, since a baking process is performed when forming a porous oxide semiconductor layer, it has been difficult to use a film substrate having somewhat inferior heat resistance. By using the method for producing a layered laminate, a metal oxide semiconductor fine particle layer can be formed without performing a firing treatment, and thus it is possible to produce a dye-sensitized solar cell efficiently at low cost. Become. In addition, since a film substrate that is somewhat inferior in heat resistance can be suitably used, it is useful in terms of processing, and the dye-sensitized solar cell can be reduced in weight.

  Such a dye-sensitized solar cell manufactured according to the present invention will be specifically described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing an example of a dye-sensitized solar cell manufactured according to the present invention. As shown in FIG. 4, the dye-sensitized solar cell manufactured according to the present invention includes a substrate 21, a first electrode layer 22, an oxide semiconductor layer 23, an electrolyte layer 24, a second electrode layer 25, and a counter substrate 26. Are sequentially stacked. The oxide semiconductor layer 23 is porous, and a dye sensitizer is supported on the surface thereof. Furthermore, the first electrode layer 22 and the second electrode layer 25 are opposed electrodes.

In such a dye-sensitized solar cell, the photocurrent is obtained by utilizing the charge generated from the dye sensitizer. Generally, the charge generated from the dye sensitizer includes electrons. it can. Hereinafter, the principle of the dye-sensitized solar cell will be described using the charges generated from the dye-sensitizer as electrons. First, when light enters from the direction of the arrow shown in FIG. 4, the dye sensitizer carried on the oxide semiconductor layer 23 absorbs light and shifts to an excited state. The dye sensitizer in the excited state generates electrons, and the generated electrons are passed to the oxide semiconductor layer 23. Further, it is carried to the second electrode layer 25 through the lead wire 27 connected to the first electrode layer 22. Thereby, a photocurrent can be obtained. The dye sensitizer is oxidized by passing generated electrons to the oxide semiconductor layer 23. Further, the resulting electrons, after moving to the second electrode layer 25, a redox couple present in the electrolyte layer 24 I ^- / I ₃ ^- Reduction of I ^{- -} that I ₃ of the. Furthermore, I ⁻ can be returned to the ground state by reducing the oxidized dye sensitizer.

  In the method for producing a dye-sensitized solar cell of the present invention, a dye-sensitized solar cell having the above-described configuration can be produced, and the method for producing a metal oxide semiconductor fine particle laminate described above is used. There is no particular limitation as long as it forms an oxide semiconductor layer, and a general method can be used.

Moreover, in the method for producing a dye-sensitized solar cell of the present invention, for example, as shown in FIG. 5, first, the first electrode layer 22 is first formed on the substrate 21 (FIG. 5A, first electrode layer formation). Process). Next, the oxide semiconductor layer 23 which has metal oxide semiconductor fine particles on the first electrode layer 22 and carries a dye sensitizer and conducts charges generated from the dye sensitizer by light irradiation. (FIG. 5B, oxide semiconductor layer forming step). Further, an electrolyte layer 24 is formed on the oxide semiconductor layer 23 (FIG. 5C, electrolyte layer forming step). Finally, a second electrode layer 25 and a counter substrate 26 that face the first electrode layer 22 and the substrate 21 are provided (FIG. 5D, counter electrode substrate forming step).
Hereinafter, each process of the manufacturing method of such a dye-sensitized solar cell is demonstrated.

1. First electrode layer forming step In the present invention, a first electrode layer forming step of forming the first electrode layer on the substrate is performed.
Since this step is the same as that described in the column of the conductive film substrate preparation step in “A. Method for producing metal oxide semiconductor fine particle laminate” described above, description thereof is omitted here.

2. Oxide semiconductor layer forming step In the present invention, the first electrode layer has metal oxide semiconductor fine particles, a dye sensitizer is supported, and a charge generated from the dye sensitizer by light irradiation. An oxide semiconductor layer forming step is performed in which an oxide semiconductor layer that conducts heat is formed.

  The oxide semiconductor layer is formed by forming a metal oxide semiconductor fine particle layer on the first electrode layer using the method for producing a metal oxide semiconductor fine particle laminate of the invention, and forming the dye on the metal oxide semiconductor fine particle layer. It is formed by carrying a sensitizer.

  The method for forming the metal oxide semiconductor fine particle layer is the same as that described in the column of “A. Method for producing metal oxide semiconductor fine particle laminate” described above, and thus the description thereof is omitted here.

  The method for supporting the dye sensitizer on the metal oxide semiconductor fine particle layer is not particularly limited, but the metal oxide semiconductor fine particle layer is preferably porous having communication holes. A method capable of adsorbing the dye sensitizer to the pores of the layer is preferable. For example, the metal oxide semiconductor fine particle layer is immersed in the dye sensitizer solution and allowed to penetrate and then dried, or the dye sensitizer solution is applied onto the metal oxide semiconductor fine particle layer and allowed to penetrate. Thereafter, a drying method and the like can be mentioned.

  The dye sensitizer used in the present invention is not particularly limited as long as it can absorb light and generate an electromotive force. Specifically, an organic dye or a metal complex dye can be used. Examples of organic dyes include acridine, azo, indigo, quinone, coumarin, merocyanine, and phenylxanthene dyes. Among these, a coumarin type is preferable. Further, as the metal complex dye, a ruthenium dye is preferable, and a ruthenium bipyridine dye and a ruthenium terpyridine dye, which are ruthenium complexes, are particularly preferable. The metal oxide semiconductor fine particle layer can hardly absorb visible light (light having a wavelength of about 400 to 800 nm). However, for example, when a ruthenium complex is supported on the metal oxide semiconductor fine particle layer, the visible light is greatly increased. Can be photoelectrically converted, and the wavelength region of light that can be photoelectrically converted can be greatly expanded.

  The solvent used in the dye sensitizer solution is selected from an aqueous solvent and an organic solvent according to the dye sensitizer used.

3. Next, the counter electrode substrate forming step will be described. The counter electrode substrate forming step is a step of providing a second electrode layer and a counter substrate that face the first electrode layer and the substrate.

  This step is performed either before or after the electrolyte layer forming step, depending on the method of forming the electrolyte layer in the electrolyte layer forming step described later. That is, as described later, an electrolyte layer is formed by applying an electrolyte layer forming coating solution used for forming an electrolyte layer on the oxide semiconductor layer and drying (hereinafter, such an electrolyte layer). In some cases, the method of forming a dye-sensitized solar cell can be produced by performing the electrolyte layer forming step described later first and then performing this step. Alternatively, the oxide semiconductor layer and the second electrode layer are disposed with a predetermined gap so that the oxide semiconductor layer and the second electrode layer face each other, and an electrolyte layer forming coating is formed in the gap. When an electrolyte layer is formed by injecting a liquid (hereinafter, a method for forming such an electrolyte layer may be referred to as an injection method), this step is first performed, and then an electrolyte layer described later. By performing the forming step, a dye-sensitized solar cell can be produced.

  For example, when it is formed by a coating method in the electrolyte layer forming step to be described later, the method for forming the second electrode layer and the counter substrate in this step is not particularly limited, but specifically, the second electrode layer is The counter substrate thus formed is prepared, and such a counter substrate can be bonded to the electrolyte layer.

  In addition, in the case where the second electrode layer and the counter substrate are formed in this step when the electrolyte layer is formed by an injection method in the later-described electrolyte layer forming step, a counter substrate on which the second electrode layer is formed in advance is prepared and oxidized. The physical semiconductor layer and the second electrode layer can be formed so as to face each other with a predetermined gap.

  In this case, the gap between the oxide semiconductor layer and the second electrode layer is not particularly limited as long as an electrolyte layer can be formed in the gap, but generally within a range of 0.01 μm to 100 μm, Especially, it is preferable that it exists in the range of 0.1 micrometer-50 micrometers. If the gap is narrower than the above range, it is not preferable because it may take a long time to inject the electrolyte layer forming coating solution. If the gap is wider than the above range, the electrolyte formed in such a gap is not preferable. This is not preferable because the thickness of the layer may increase.

  In the case where the oxide semiconductor layer and the second electrode layer are arranged with a predetermined gap, either a substrate or a counter substrate facing the substrate is used to accurately adjust the gap to a desired gap. A spacer may be formed on either side. Examples of such spacers include those commonly used, such as glass spacers, resin spacers, and olefinic porous membranes.

(1) Counter substrate The counter substrate in this invention opposes the board | substrate which comprises a dye-sensitized solar cell. Such a counter substrate in the present invention is not particularly limited as long as it is transparent or opaque. However, when the counter substrate is located on the light receiving surface side, it transmits light. It is preferable to have excellent transparency. Furthermore, it is preferable that it is excellent in heat resistance, weather resistance, water vapor, and other gas barrier properties. Specifically, transparent flexible materials such as quartz glass, Pyrex (registered trademark), synthetic quartz plate, etc. that are not flexible, ethylene / tetrafluoroethylene copolymer film, biaxially stretched polyethylene terephthalate film, polyethersulfone (PES) film, polyetheretherketone (PEEK) film, polyetherimide (PEI) film, polyimide (PI) film, polyester naphthalate (PEN) and other plastic films. In the present invention, among these, a film substrate using a plastic film is preferable. This is because the processability is excellent, so it is easy to combine with other devices, and the range of applications can be expanded. It is also effective in improving productivity and reducing manufacturing costs.

  Such a film may be used alone or may be a composite film in which two or more kinds of films are laminated.

(2) Second electrode layer The second electrode layer in the present invention is formed on the counter substrate and is an electrode facing the first electrode layer.

  The material for forming the second electrode layer is not particularly limited as long as it is excellent in conductivity and does not corrode with respect to the electrolyte. However, when the material is located on the light receiving surface side. Is preferably excellent in light transmittance. In addition, it is preferable to select a material in consideration of a work function or the like of the material forming the first electrode layer which is an electrode facing the second electrode layer.

  In addition, regarding the material and the forming method that can be specifically used when forming the second electrode layer, the electrode layer of the conductive film substrate in “A. Method for producing metal oxide semiconductor fine particle layer laminate” described above is used. Since it is the same as what was described in the column, description here is abbreviate | omitted.

  Such a second electrode layer may be composed of a single layer or may be laminated using materials having different work functions. For example, as shown in FIG. 3, when light enters from the direction of the arrow, a transparent electrode is used as the first electrode layer 12, and further, as the second electrode layer 15 that is an electrode facing the first electrode layer 12. As an example, a case where a layer in which a layer in which Pt is vapor-deposited and a layer made of ITO are stacked is used can be given.

  Furthermore, the film thickness of the second electrode layer is within the range of 0.1 to 500 nm in the case of a single electrode layer, and the total film thickness within the range of 1 to 500 nm. It is preferable to be within a range of ˜300 nm.

4). Electrolyte layer forming step The electrolyte layer forming step in the present invention is a step of forming an electrolyte layer between the oxide semiconductor layer and the second electrode layer.

  The electrolyte layer formed in this step is located between the oxide semiconductor layer and the second electrode layer, and the charge conducted by the oxide semiconductor layer is oxidized through the first electrode layer and the second electrode layer. Transporting when transported to the physical semiconductor layer is performed. Therefore, the electrolyte layer formed by this step is not particularly limited as long as it has such a function, and may be an electrolyte layer in any form of solid, gel, or liquid.

  In such an electrolyte layer, for example, when it is in a gel form, there is no particular limitation whether it is a physical gel or a chemical gel. A physical gel is gelled near room temperature due to physical interaction, and a chemical gel is a gel formed by chemical bonding by a crosslinking reaction or the like.

  Further, when the electrolyte layer is formed by this step, the thickness thereof is not particularly limited, but since the electrolyte layer is formed by filling the oxide semiconductor layer, the thickness of the oxide semiconductor layer is also reduced. It is preferable that it is in the range of 2 μm to 100 μm including the range of 2 μm to 50 μm. If the film thickness is thinner than the above range, the oxide semiconductor layer and the second electrode layer are likely to come into contact with each other, causing a short circuit. If the film thickness is thicker than the above range, the internal resistance increases and the performance is deteriorated. It is.

  As described above, as a method for forming the electrolyte layer, a coating method for forming the electrolyte layer used for forming the electrolyte layer is applied on the oxide semiconductor layer and dried to form the electrolyte layer, or in this step, Before, the electrolyte layer is formed by placing the oxide semiconductor layer and the second electrode layer with a predetermined gap so as to face each other and injecting an electrolyte layer forming coating solution into the gap. Examples thereof include an injection method. Hereinafter, the method for forming the electrolyte layer will be described separately in both cases.

(1) Application Method First, an application method for forming an electrolyte layer by applying an electrolyte layer forming coating solution for forming an electrolyte layer on the oxide semiconductor layer and solidifying it will be described. By such a forming method, a solid electrolyte layer can be mainly formed.

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

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

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

  Furthermore, as the polymer for holding the redox counter electrolyte, it is preferable to use a conductive polymer having a high hole transporting property such as CuI, polypyrrole, or polythiophene.

  In addition, a crosslinking agent, a photopolymerization initiator, or the like may be contained as an additive. In the case of an electrolyte layer forming coating solution containing such an additive, after applying the electrolyte layer forming coating solution, an actinic ray is irradiated and cured to form a solid electrolyte layer. be able to.

(2) Injection Method Next, an injection method for forming an electrolyte layer by injecting a coating solution for forming an electrolyte layer used for forming an electrolyte layer between the oxide semiconductor layer and the second electrode layer will be described.

  By using such an injection method, liquid, gel and solid electrolyte layers can be formed. For example, in the case of forming a gel, there is no particular limitation on either a physical gel or a chemical gel. A physical gel is gelled near room temperature due to physical interaction, and a chemical gel is a gel formed by chemical bonding by a crosslinking reaction or the like.

  An example of a method for producing the dye-sensitized solar cell of the present invention when forming an electrolyte layer by an injection method will be described with reference to FIG. First, the substrate 21 on which the first electrode layer 22 and the oxide semiconductor layer 23 are formed and the counter substrate 26 on which the second electrode layer 25 is formed are prepared. As shown in FIG. The substrate 21 and the counter substrate 26 are arranged so that the semiconductor layer 23 and the second electrode layer 25 face each other with a predetermined gap.

  Next, an electrolyte layer forming coating solution used for forming the electrolyte layer is injected into a gap formed between the oxide semiconductor layer 23 and the second electrode layer 25 as shown in FIG. Thereby, as shown in FIG. 6C, the electrolyte layer 24 can be formed between the oxide semiconductor layer 23 and the second electrode layer 25. Further, when the electrolyte layer formed by such an injection method is in a liquid or gel state, in order to prevent solvent volatilization, electrolyte layer loss, etc., as shown in FIG. In addition, a dye-sensitized solar cell can be manufactured by sealing with an organic polymer 31 or the like.

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

  The oxidation-reduction counter electrolyte is the same as that described in the above-described coating method, and therefore description thereof is omitted here.

  When an electrolyte layer is formed by such an injection method, as a method for injecting an electrolyte forming coating solution into the gap formed between the oxide semiconductor layer and the second electrode layer, the coating solution can be easily used. Although it will not specifically limit if it is a method which can be inject | poured, For example, the method of inject | pouring using a capillary phenomenon can be used.

  In addition, after injecting the electrolyte layer forming coating solution by an injection method, for example, temperature adjustment, ultraviolet irradiation, electron beam irradiation, etc. are performed to generate a two-dimensional or three-dimensional cross-linking reaction. A solid electrolyte layer can be formed.

5). Dye-sensitized solar cell The dye-sensitized solar cell manufactured according to the present invention includes a substrate, a first electrode layer formed on the substrate, and a metal oxide semiconductor formed on the first electrode layer. An oxide semiconductor layer having fine particles and carrying a dye sensitizer and conducting charges generated from the dye sensitizer by light irradiation, a counter substrate facing the substrate, and the counter substrate The second electrode layer, which is formed and is opposed to the first electrode layer, is located between the oxide semiconductor layer and the second electrode layer, and the electric charge conducted by the oxide semiconductor layer is the first electrode layer. And an electrolyte layer that performs transport when transported to the oxide semiconductor layer via the electrode layer and the second electrode layer. Further, the oxide semiconductor layer is formed by forming a metal oxide semiconductor fine particle layer on the first electrode layer on the substrate using the method for manufacturing a metal oxide semiconductor fine particle laminate described above. It is formed by supporting the dye sensitizer on the semiconductor fine particle layer.

  Conventionally, since a baking process is performed when forming a porous oxide semiconductor layer, it has been difficult to use a film substrate having somewhat inferior heat resistance. By using the method for producing a layered laminate, a metal oxide semiconductor fine particle layer can be formed without performing a baking treatment, so that a dye-sensitized solar cell can be produced efficiently at low cost. In addition, since a film substrate having somewhat inferior heat resistance can be suitably used, the dye-sensitized solar cell can be reduced in weight.

C. Next, the manufacturing apparatus of the metal oxide semiconductor fine particle layer laminated body of this invention is demonstrated.
The apparatus for producing a metal oxide semiconductor fine particle layer laminate of the present invention comprises a long film substrate that can be moved continuously and a conductive film substrate having an electrode layer formed on the long film substrate. An unwinding roll, a voltage applying unit for applying a voltage to the electrode layer of the conductive film substrate unwound from the unwinding roll, and a metal oxide semiconductor fine particle disposed after the voltage applying unit. A bath provided so that the conductive film substrate is immersed in the bath solution, and disposed in the bathtub so as to face the electrode layer of the conductive film substrate. An electrode plate, a power source for applying a voltage to the electrode layer and the electrode plate, and a metal acid formed by electrodepositing the metal oxide semiconductor fine particles on the electrode layer in the bath It is characterized in that it has a winding portion for winding the metal oxide semiconductor fine particle layer laminate having an object layer of fine semiconductor particles.

  An apparatus for producing a metal oxide semiconductor fine particle layer laminate of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory view showing an example of a production apparatus for a metal oxide semiconductor fine particle layer laminate of the present invention. As shown in FIG. 1, in the apparatus for manufacturing a metal oxide semiconductor fine particle layer laminate according to the present invention, first, a conductive film substrate 10 is unwound from an unwinding roll 1. The conductive film substrate 10 has a film substrate 11 and an electrode layer 12 as shown in FIG. Next, when the voltage is applied from the power supply unit 6 to the voltage application unit 2 by arranging the electrode layer of the conductive film substrate 10 to be in contact with the voltage application unit 2, the electrode layer of the conductive film substrate 10. Is applied to the negative electrode. Also, a bath 4 disposed after the voltage application unit 2 and containing a bath solution 3 in which metal oxide semiconductor fine particles are dispersed is provided, and the conductive film substrate 10 is soaked in the bath solution 3. Inside, an electrode plate 5 is provided so as to face the electrode layer of the conductive film substrate 10. Since the DC voltage is applied to the voltage application unit 2 and the electrode plate 5 by the power supply unit 6, the electrode plate 5 is applied to the positive electrode and has a positive surface charge in the bath liquid 3. The metal oxide semiconductor fine particles migrate and adhere to the electrode layer surface of the conductive film substrate 10 applied to the negative electrode by electrophoresis. Further, the conductive fill substrate to which the metal oxide semiconductor fine particles are adhered is conveyed by the guide rolls 7a, 7b and 7c, and the metal oxide semiconductor fine particles adhered on the electrode layer of the conductive film substrate 10 is dried by the drying unit 8. As a result, a metal oxide semiconductor fine particle layer is formed, and the metal oxide semiconductor fine particle layer stack having the metal oxide semiconductor fine particles is wound around the winding portion 9.

According to the present invention, since a metal oxide semiconductor fine particle layer can be continuously formed by performing a roll-to-roll process using a long film substrate, there is an advantage that productivity is improved. In addition, since the metal oxide semiconductor fine particle layer can be formed without performing a baking treatment, a film substrate that is inferior in heat resistance to a glass substrate can be suitably used, which is useful for reducing weight and reducing manufacturing costs. It is. Furthermore, since the film substrate is excellent in processability, it can be easily combined with other devices, and the range of applications of the metal oxide semiconductor fine particle layer laminate produced according to the present invention can be expanded.
Hereafter, each structure of the manufacturing apparatus of such a metal oxide semiconductor fine particle layer laminated body is demonstrated.

1. Voltage application part The voltage application part used for this invention applies a voltage to the electrode layer of an electroconductive film board | substrate. Further, a DC voltage is applied to the voltage application unit and an electrode plate described later by a power supply unit.

  In this invention, the voltage application part is arrange | positioned so that the electrode layer of an electroconductive film board | substrate may be touched, and if it has arrange | positioned before the bathtub mentioned later, the arrangement | positioning will not be specifically limited.

  Moreover, as a shape of a voltage application part, if it is a shape which touches the electrode layer of a conductive film board | substrate, it will not specifically limit, For example, a brush, a roll, etc. can be mentioned. In this invention, it is preferable that a voltage application part is a roll among the above, and is a conveyance roll which conveys a conductive film board | substrate further. As a result, it is possible to apply a voltage to the electrode layer while conveying the conductive film substrate, and thus it is possible to shorten the manufacturing process when manufacturing the metal oxide semiconductor fine particle layer laminate. is there.

  The material used for the voltage application unit is not particularly limited as long as it can feed power to the electrode layer of the conductive film substrate. Usually, a material that can be used as the voltage application unit is used. To do.

  In addition, the voltage application unit is applied with a voltage by the power supply unit. If there is a potential difference between the voltage application unit and an electrode plate described later, a positive electrode and a negative electrode can be set. Since the oxide semiconductor fine particles can be electrodeposited, for example, the voltage applied to the voltage application unit may be zero. In this case, the voltage application unit may be grounded without being connected to the power supply unit.

2. Bathtub In the present invention, the bathtub is disposed after the voltage application unit, the bath liquid in which the metal oxide semiconductor fine particles are dispersed is stored, and the conductive film substrate is provided so as to be immersed in the bath liquid. Is. An electrode plate is disposed in the bathtub so as to face the electrode layer of the conductive film substrate.
Hereinafter, each structure of such a bathtub is demonstrated.

(1) Bath liquid in which metal oxide semiconductor fine particles are dispersed The bath liquid in which metal oxide semiconductor fine particles used in the present invention are dispersed is contained in a bathtub, and metal oxide semiconductor fine particles are suitable. The solvent is uniformly dispersed so as not to aggregate.

  In addition, since the metal oxide semiconductor fine particles and the solvent used in such a bath liquid are the same as those described in the column of “A. Method for producing metal oxide semiconductor fine particle layer laminate” described above, The description here is omitted.

  Further, in the present invention, when the conductive film substrate passes through the surface of the bath solution, the metal oxide semiconductor fine particles migrate to the electrode plate to which a voltage is applied, and on the electrode layer of the conductive film substrate. It is electrodeposited. Therefore, it is preferable that the liquid level of the bath liquid is maintained at a constant height so that the conductive film substrate is sufficiently immersed.

(2) Electrode plate The electrode plate used for this invention is provided in the said bathtub, and is arrange | positioned so as to oppose the electrode layer of an electroconductive film board | substrate. Further, a direct current voltage is applied to the electrode plate and the voltage application unit by a power supply unit.

  In the present invention, when the electrode plate is applied to, for example, the positive electrode, the metal oxide semiconductor fine particles in the bath liquid migrate to the electrode plate by electrophoresis, and then the electrode layer of the conductive film substrate applied to the negative electrode Metal oxide semiconductor fine particles are electrodeposited thereon.

  The arrangement of the electrode plate is not particularly limited as long as it is provided in a bath solution in which metal oxide semiconductor fine particles are dispersed and arranged to face the electrode layer of the conductive film substrate. Is not to be done. In addition, about arrangement | positioning of an electrode plate, since it described in the column of the immersion process of "A. manufacturing method of a metal oxide semiconductor fine particle layer laminated body" mentioned above, description here is abbreviate | omitted.

  The shape of such an electrode plate is not particularly limited as long as the metal oxide semiconductor fine particles are electrodeposited on the electrode layer of the conductive film substrate so that there is no unevenness. For example, a flat plate shape as shown in FIG. Or a roll-shaped one as shown in FIG. When the electrode plate is in a roll shape, it is possible to install the electrode plate along the shape of the guide roll that conveys the conductive film substrate.

  Moreover, as a material used for an electrode plate, normally, what can be used for an electrode plate shall be used.

3. Power supply part The power supply part used for this invention applies a voltage to the said voltage application part and the said electrode plate. The electrode layer of the conductive film substrate is supplied with power through the voltage application unit.

  Such a power supply unit is not particularly limited as long as a voltage can be applied, and a commonly used one is used.

  Moreover, when applying a voltage to a voltage application part and an electrode plate, a negative electrode and a positive electrode are set with the surface charge which the said metal oxide semiconductor fine particle has. That is, when the surface charge of the metal oxide semiconductor fine particles is a positive electrode, the voltage application part is set to the negative electrode and the electrode plate is set to the positive electrode so that the electrode layer on which the metal oxide semiconductor fine particles are electrodeposited becomes the negative electrode. . On the other hand, when the surface charge of the metal oxide semiconductor fine particles is a negative electrode, the voltage application part is set to the positive electrode and the electrode plate is set to the negative electrode so that the electrode layer on which the metal oxide semiconductor fine particles are electrodeposited becomes the positive electrode. .

  The voltage applied to the voltage application section and the electrode plate is described in the column of the metal oxide semiconductor fine particle layer forming step in “A. Method for producing metal oxide semiconductor fine particle layer laminate” described above. Description of is omitted.

4). Drying unit In the present invention, for example, as shown in FIG. 1, the metal oxide semiconductor fine particles disposed between the bathtub 4 and the winding unit 9 and electrodeposited on the electrode layer of the conductive film substrate 10 are dried. It is preferable to have a drying unit 8. This is because the metal oxide semiconductor fine particle layer is formed by electrodepositing and drying the metal oxide semiconductor fine particles on the electrode layer. In addition, the bonding force between the metal oxide semiconductor fine particles is increased, and the adhesion between the conductive film substrate and the metal oxide semiconductor fine particle layer is improved.

  The method for drying the metal oxide semiconductor fine particles is not particularly limited as long as it is a drying method capable of removing the solvent adhering to the metal oxide semiconductor fine particles. For example, the entire specific space such as an oven is heated. For example, a method of passing through an apparatus, a method of irradiating infrared rays, a method of applying hot air, and the like can be used.

  In addition, since it described in the column of the drying process of "A. manufacturing method of a metal oxide semiconductor fine particle layer laminated body" regarding the drying temperature, drying time, etc., description here is abbreviate | omitted.

5). Guide Roll The metal oxide semiconductor fine particle layer laminate manufacturing apparatus of the present invention may have guide rolls 7a, 7b, 7b for transporting the conductive film substrate 10 as shown in FIG. In the case of having such a guide roll, the guide roll disposed so as to be in contact with the electrode layer of the conductive film substrate has the same potential as the voltage application unit so as not to affect the electrode layer fed by the voltage application unit. Controlled. For example, in FIG. 1, the guide roll 7 a is controlled to the same potential as the voltage application unit 2. At this time, since the guide roll 7 b is disposed so as to be in contact with the film substrate of the conductive film substrate 10, it is not necessary to control the guide roll 7 b to the same potential as the voltage application unit 2.

D. Next, the manufacturing apparatus of the dye-sensitized solar cell used for this invention is demonstrated.
The dye-sensitized solar cell manufacturing apparatus of the present invention includes a substrate, a first electrode layer formed on the substrate, a metal oxide semiconductor fine particle formed on the first electrode layer, and a dye. A sensitizer is supported, and is formed on the counter substrate, the oxide semiconductor layer that conducts charges generated from the dye sensitizer by light irradiation, the counter substrate facing the substrate, and the first substrate. The second electrode layer, which is an electrode facing the electrode layer, and the electric charges located between the oxide semiconductor layer and the second electrode layer and conducted by the oxide semiconductor layer are the first electrode layer and the second electrode layer. An apparatus for producing a dye-sensitized solar cell having an electrolyte layer for transporting when transported to the oxide semiconductor layer through an electrode layer,
It has the manufacturing apparatus of the said metal oxide semiconductor fine particle layer laminated body as said oxide semiconductor layer formation part, It is characterized by the above-mentioned.

  According to the present invention, since the metal oxide semiconductor fine particle layer stack can be formed without performing the firing treatment by having the metal oxide semiconductor fine particle layer laminate manufacturing apparatus, the color can be efficiently produced at low cost. A sensitized solar cell can be manufactured. Moreover, the film board | substrate which is inferior to a glass substrate in heat resistance can be used suitably, and it is useful in a processing surface and weight reduction.

  In the present invention, a dye sensitizer is supported on the metal oxide semiconductor fine particle layer of the metal oxide semiconductor fine particle layer laminate produced by the metal oxide semiconductor fine particle layer laminate production apparatus, thereby providing an oxide semiconductor. A layer can be formed.

  The metal oxide semiconductor fine particle layer laminate manufacturing apparatus is the same as that described in the above-mentioned “C. Metal oxide semiconductor fine particle layer laminate manufacturing apparatus”, and a description thereof will be omitted here. . Further, each member of the dye-sensitized solar cell and a method for forming these members are the same as those described in “B. Manufacturing method of dye-sensitized solar cell” described above, and thus description thereof is omitted here. To do.

  In the present invention, the dye-sensitized solar cell manufacturing apparatus is not particularly limited as long as it has the metal oxide semiconductor fine particle layer laminate manufacturing apparatus as the oxide semiconductor layer forming part. As a device for forming each member of the dye-sensitized solar cell, a commonly used device is used.

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
[Example]
The apparatus for producing a metal oxide semiconductor fine particle layer laminate shown in FIG. 1 was used. The metal oxide semiconductor fine particle layer laminate manufacturing apparatus includes an unwinding roll 1, a winding unit 9, a voltage applying unit 2, a bath 4 in which a bath liquid 3 in which metal oxide semiconductor fine particles are dispersed is disposed, and voltage application. The power supply unit 6 connected to the unit 2 and the electrode plate 5 and the drying unit 8 are included. Further, as the conductive film substrate, a PET film substrate on which an ITO electrode was formed (Tobe, OTEC-110, thickness 188 μm, surface resistance 10Ω / □) (hereinafter referred to as ITO-PET film) was used.

  In the metal oxide semiconductor fine particle layer laminate manufacturing apparatus shown in FIG. 1, first, the ITO-PET film 10 is unwound from the unwinding roll 1 attached to the unwinding portion. Moreover, the ITO electrode surface of the drawn ITO-PET film 10 is disposed so as to be in contact with the voltage application unit 2 that also serves as a transport roll. As a result, a voltage is applied from the power supply unit 6 to the ITO electrode surface. Further, the fed ITO-PET film 10 is conveyed so as to be at a constant interval from the electrode plate 5 disposed in the bathtub 4 through a guide roll 7 a controlled to the same potential as the voltage application unit 2. Further, two guide rolls 7b and 7c are arranged on the upper part of the electrode plate 5 so as to be parallel to the electrode plate 5. The two guide rolls 7b and 7c have a movable mechanism. It has a mechanism that is controlled so that the distance from the electrode plate 5 is constant.

  The bath 4 is filled with a bath liquid 3 in which metal oxide semiconductor fine particles are dispersed to a level that coincides with the back surface of the ITO-PET film 10 to be conveyed. As the bath liquid in which the metal oxide semiconductor fine particles are dispersed, titanium oxide fine particles having a primary particle diameter of about 30 nm (F-4, manufactured by Showa Denko KK) are used, and acetonitrile: tert-butanol = 1: 1 (weight) Ratio) was mixed with the titanium oxide fine particles and dispersed with an ultrasonic disperser for 30 minutes to prepare a 5.3 wt% solution.

  Since the ζ potential of the titanium oxide was positively charged, the electrode plate 5 disposed in the bathtub 4 was used as the positive electrode and the voltage application unit 2 serving also as the guide roll was used as the negative electrode in order to perform the electrodeposition process. A voltage was applied to The conveyance speed is controlled to 0.5 m / min, and the distance between the electrode plate 5 and the ITO electrode surface of the ITO-PET film 10 is controlled to 5 mm, and a titanium oxide film is formed on the ITO electrode surface with an applied voltage of 800 V / cm. A film was formed. After the film formation, the ITO-PET film 10 exiting from the bath 4 passed through the guide roll 7 and passed through the drying unit 8 to remove acetonitrile and tert-butanol. Then, the metal oxide semiconductor fine particle layer laminated body in which the titanium oxide film was formed on the ITO-PET film by the winding unit 9 was wound up. After winding, it was confirmed that the total amount of residual solvent in the titanium oxide film was 26 mg. Moreover, the thickness of the titanium oxide film after winding was 12 μm, and there were no cracks and no peeling from the ITO electrode surface.

  Next, a dye-sensitized solar cell was manufactured using the obtained metal oxide semiconductor fine particle layer laminate.

As a sensitizing dye, a ruthenium complex (manufactured by Kojima Chemical Co., Ltd.) was used, and a sensitizing dye solution dissolved in ethyl alcohol was prepared so that its concentration was 3 × 10 ⁻⁴ mol / l. Next, the obtained metal oxide semiconductor fine particle layer laminate was immersed in this sensitizing dye solution, left to stand at a liquid temperature of 40 ° C. for 1 hour, then pulled up and air-dried. As a result, the sensitizing dye was supported on the titanium oxide film.

  Thereafter, the metal oxide semiconductor fine particle layer stack was trimmed so as to be a square of 1 cm × 1 cm when viewed in plan to obtain a metal oxide semiconductor electrode.

  On the other hand, the counter electrode used was a film of platinum having a thickness of 100 nm formed on the ITO-PET film substrate by sputtering. In order to keep the gap between the metal oxide semiconductor electrode and the counter electrode at 50 μm, a 50 μm thick heat-sealing film (DuPont, Surlyn) made in a rectangular frame shape with a width of 3 mm was thermally bonded outside the trimming frame region. . Thereafter, an electrolytic solution was injected from an injection hole previously formed in the counter electrode. In the electrolyte, methoxyacetonitrile is used as a solvent, and in this solvent, lithium iodide is 0.1 mol / l, iodine is 0.05 mol / l, dimethylpropylimidazolium iodide is 0.3 mol / l, and tert-butylpyridine is used. Those dissolved at a rate of 0.5 mol / l were used.

In measuring the performance of the obtained dye-sensitized solar cell, the current-voltage characteristics when using pseudo-sunlight (AM1.5, irradiation intensity 100 mW / cm ² ) as a light source are shown as a source measure unit (Keutley 2400 type). ). As a result, the battery characteristics were a short-circuit current of 6.7 mA / cm ² , an open-circuit voltage of 0.62 V, a fill factor of 0.53, and a conversion efficiency of 2.2%.

It is explanatory drawing which shows an example of the manufacturing apparatus of the metal oxide semiconductor fine particle layer laminated body of this invention. It is a schematic sectional drawing which shows an example of the electroconductive film board | substrate used for this invention. It is a schematic sectional drawing which shows an example of the metal oxide semiconductor fine particle layer laminated body manufactured by the manufacturing method of the metal oxide semiconductor fine particle layer laminated body of this invention. It is a schematic sectional drawing which shows an example of the dye-sensitized solar cell manufactured by the manufacturing method of the dye-sensitized solar cell of this invention. It is process drawing which shows an example of the manufacturing method of the dye-sensitized solar cell of this invention. It is process drawing which shows the other example of the manufacturing method of the dye-sensitized solar cell of this invention. It is explanatory drawing which shows an example of the manufacturing apparatus of the metal oxide semiconductor fine particle layer laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Unwinding roll 2 ... Voltage application part 3 ... Bath liquid which disperse | distributed metal oxide semiconductor fine particles 4 ... Bath 5 ... Electrode plate 6 ... Power supply part 7a, 7b, 7c ... Guide roll 8 ... Drying part 9 ... Winding up Part 10: Conductive film substrate

Claims (7)

A conductive film substrate having a continuously movable long film substrate and an electrode layer formed on the long film substrate is immersed in a bath solution in which metal oxide semiconductor fine particles are dispersed. By applying a voltage to the electrode layer and an electrode plate disposed in the bath solution so as to face the electrode layer, the metal oxide semiconductor fine particles are electrically charged on the electrode layer of the conductive film substrate. A method for producing a metal oxide semiconductor fine particle layer laminate, wherein a metal oxide semiconductor fine particle layer is continuously formed on the electrode layer by applying
Application of voltage to the electrode layer is performed before immersing the conductive film substrate in a bath solution in which the metal oxide semiconductor fine particles are dispersed. Manufacturing method. 2. The method for producing a metal oxide semiconductor fine particle layer laminate according to claim 1 , wherein the application of a voltage to the electrode layer is by a transport roll for transporting the conductive film substrate. A substrate; a first electrode layer formed on the substrate; and a metal oxide semiconductor fine particle formed on the first electrode layer and carrying a dye sensitizer; An oxide semiconductor layer that conducts charges generated from a sensitizer, a counter substrate facing the substrate, a second electrode layer formed on the counter substrate and facing the first electrode layer, Charges located between the oxide semiconductor layer and the second electrode layer and conducted by the oxide semiconductor layer are transported to the oxide semiconductor layer through the first electrode layer and the second electrode layer. A method for producing a dye-sensitized solar cell having an electrolyte layer for transporting when
The metal oxide semiconductor fine particle layer is formed on the first electrode layer on the substrate using the metal oxide semiconductor fine particle laminate manufacturing method according to claim 1, A method for producing a dye-sensitized solar cell, which is formed by supporting the dye-sensitizer on an oxide semiconductor fine particle layer. An unwinding roll on which a conductive film substrate having an electrode layer formed on the long film substrate and the long film substrate which can be continuously moved is wound;
A voltage application unit for applying a voltage to the electrode layer of the conductive film substrate fed from the unwinding roll;
A bath disposed after the voltage application unit, in which a bath liquid in which metal oxide semiconductor fine particles are dispersed is stored, and the conductive film substrate is immersed in the bath liquid; and
In the bathtub, an electrode plate arranged to face the electrode layer of the conductive film substrate,
A power supply for applying a voltage to the electrode layer and the electrode plate;
Metal and a winding section for winding the metal oxide semiconductor fine particle layer laminate having a metal oxide semiconductor fine particle layer formed by electrodeposition of the metal oxide semiconductor fine particles on the electrode layer in said bath An apparatus for manufacturing an oxide semiconductor fine particle layer laminate,
The said voltage application part is arrange | positioned in the position before the said conductive film board | substrate is immersed in the said bath liquid in the said bathtub, The manufacturing apparatus of the metal oxide semiconductor fine particle layer laminated body characterized by the above-mentioned . The said voltage application part is a conveyance roll which conveys the said electroconductive film board | substrate, The manufacturing apparatus of the metal oxide semiconductor fine particle layer laminated body of Claim 4 characterized by the above-mentioned. 6. The drying device according to claim 4, further comprising a drying unit that is disposed between the bathtub and the winding unit and that dries the metal oxide semiconductor fine particles electrodeposited on the electrode layer. An apparatus for producing a metal oxide semiconductor fine particle layer laminate. A substrate; a first electrode layer formed on the substrate; and a metal oxide semiconductor fine particle formed on the first electrode layer and carrying a dye sensitizer; An oxide semiconductor layer that conducts charges generated from a sensitizer, a counter substrate facing the substrate, a second electrode layer formed on the counter substrate and facing the first electrode layer, Charges located between the oxide semiconductor layer and the second electrode layer and conducted by the oxide semiconductor layer are transported to the oxide semiconductor layer through the first electrode layer and the second electrode layer. An apparatus for producing a dye-sensitized solar cell having an electrolyte layer for transporting when
A dye-sensitized solar cell comprising the apparatus for producing a metal oxide semiconductor fine particle layer laminate according to any one of claims 4 to 6 as the oxide semiconductor layer forming unit. Manufacturing equipment.

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