JP2005142089A - Forming method of porous semiconductor electrode, manufacturing method of electrode board for dye-sensitized solar cell, electrode board for dye-sensitized solar cell, and the dye-sensitized solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a forming method of a porous semiconductor electrode, capable of forming a porous semiconductor electrode of a required shape under comparatively high productivity. <P>SOLUTION: By an electric field jet method that is a method of discharging coating liquid by impressing voltage on an electrode fitted at a discharge outlet of the coating liquid or its vicinity, the coating liquid containing a large number of semiconductor fine particles is coated on a matter to be coated to form a coating film, and by fixing the semiconductor fine particles in the coating film on the matter to be coated, the porous semiconductor electrode is formed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for forming a porous semiconductor electrode, a method for producing an electrode substrate for a dye-sensitized solar cell using this forming method, an electrode substrate for a dye-sensitized solar cell, and a dye-sensitized solar cell.

  The use of solar power generation systems is increasing today because the load on the surrounding environment is small compared to power generation systems using fossil fuels and nuclear fuel, and it is easy to save resources.

  The solar cell used in the photovoltaic power generation system is a photoelectric conversion element that can directly convert light energy into electrical energy. This solar cell includes a silicon solar cell, a compound semiconductor solar cell (gallium arsenide solar cell, Indium phosphide solar cells, CIS (copper indium selenium) solar cells, etc.), dye-sensitized solar cells, and the like. Among these solar cells, silicon solar cells are already widely used as consumer solar cells. In recent years, attention has been focused on dye-sensitized solar cells that can be easily reduced in cost and weight as compared with silicon solar cells.

FIG. 8 is a schematic view showing a cross-sectional structure of a typical dye-sensitized solar cell (Gretzel cell). Dye-sensitized solar cell 250 ^shown, _I ^- / I ₃ - is a wet solar cell with an electrolyte solution 205 was sandwiched between a pair of electrode substrates 220 and 230 structure containing a redox couple.

  The electrode substrate 220 includes a transparent glass substrate 211, a transparent electrode (fluorine-doped tin oxide film) 213 formed on one surface thereof, and a semiconductor electrode (porous titanium oxide thin film) 215 formed thereon. And functions as a photoelectrode. The semiconductor electrode 215 is formed by a sol-gel method, and is a sintered body of a large number of anatase-type titanium oxide fine particles. The surface of the semiconductor electrode 215 is adsorbed with a dye 217 made of one of ruthenium (Ru) complexes. The absorption wavelength range of the dye 217 extends to a longer wavelength side than the absorption wavelength range of titanium oxide. Yes. The energy level of electrons when the dye 217 is photoexcited is higher than the position of the conduction band edge of titanium oxide. In FIG. 8, the dye 217 is drawn as one layer for convenience. On the other hand, the electrode substrate 230 has a transparent glass substrate 221, a transparent conductive film (fluorine-doped tin oxide film) 223 formed on one surface thereof, and a platinum thin film 225 formed thereon, Function. The transparent electrode 213 in the electrode substrate 220 and the transparent conductive film 223 in the electrode substrate 230 are connected to the load 240 by lead wires 235a and 235b.

When the dye-sensitized solar cell 250 is irradiated with light within the absorption wavelength range of the dye 217, the dye 217 is excited, and photoexcited electrons (e ⁻ ) are injected into the semiconductor electrode 215. Electronic (e ^-) dye 217 lost in, ^I in the electrolyte solution 205 - / _{I 3} ^- from redox pairs deprive electrons (I ^- reacts with _{I 3} ^- to occur), return to the original state . On the other hand, the electrons (e ⁻ ) injected into the semiconductor electrode 215 move to the transparent electrode 213 and further reach the electrode substrate 230 via the lead wire 235a, the load 240, and the lead wire 235b and react with I ₃ ^−. , I ⁻ . Therefore, a closed circuit is formed in the dye-sensitized solar cell 250 by the light irradiation. When this closed circuit is formed, the dye-sensitized solar cell 250 generates power constantly. By using the dye 217, it is possible to generate power using light having a longer wavelength than the light in the absorption wavelength region of the semiconductor electrode 215, so that the photoelectric conversion efficiency can be increased. Incidentally, the platinum thin film 225, the serving other to increase the conductivity of the electrode substrate _{^{230, I - / I 3 -}} I 3 of the redox pair ^- is I ^- also serves as a catalyst as it is reduced to.

  Because the sheet resistance of the transparent electrode is relatively high, in order to obtain a dye-sensitized solar cell with a large operating current, the structure is a structure in which a plurality of relatively small cells are electrically connected in parallel. It is preferable to make it. Further, in order to obtain a dye-sensitized solar cell having a high operating voltage, it is preferable that the structure is a structure in which a plurality of relatively small cells are electrically connected in series. The term “cell” as used herein means that an electrolyte layer is interposed between a pair of electrodes composed of at least one photoelectrode and at least one counter electrode, and this cell alone can be used as a dye-sensitized solar cell. Function.

  From the viewpoint of obtaining a dye-sensitized solar cell having a structure in which a plurality of cells are electrically connected in parallel or in series at low cost, a porous semiconductor electrode functioning as a photoelectrode is formed on one transparent substrate. It is preferable to form a plurality on one side.

  For example, Patent Document 1 discloses a photoelectric device in which a plurality of porous semiconductor electrodes are formed by applying a suspension containing a particulate inorganic semiconductor material to a desired portion by screen printing, drying, solidifying, and firing. A conversion element (solar cell) is described.

Patent Document 2 discloses that after applying a dispersion of a semiconductor fine particle, a colloidal solution, etc., the coating film is selectively irradiated with electromagnetic waves to sinter the semiconductor fine particles, and then the unsintered portion is washed. A method of manufacturing a semiconductor electrode is described in which a porous semiconductor electrode patterned into a desired shape is obtained by removal.
JP 2002-319689 (No. 0025-0051, especially No. 0032-0033) JP 2002-134435 (Nos. 0005 to 0030, especially No. 0021 and No. 0029)

  However, in the formation of the porous semiconductor electrode using screen printing as described in Patent Document 1, it is necessary to increase the viscosity of the suspension as a material. Along with this, the semiconductor fine particles in the suspension are easily aggregated, and there is a problem that productivity is relatively low.

  In addition, when forming the porous semiconductor electrode by the method described in Patent Document 2, it is necessary to perform a process of removing the unsintered portion after performing the sintering of the semiconductor fine particles by irradiation with electromagnetic waves. There is a problem that productivity is relatively low.

  The present invention has been made to solve the above problems, and a first object of the present invention is to provide a porous semiconductor electrode having a desired shape and capable of forming a porous semiconductor electrode with relatively high productivity. It is to provide a method for forming a porous semiconductor electrode.

  In addition, a second object of the present invention is to provide a dye-sensitized solar that can easily manufacture an electrode substrate for a dye-sensitized solar cell including a porous semiconductor electrode having a desired shape with relatively high productivity. It is providing the manufacturing method of the electrode substrate for batteries.

  A third object of the present invention is to provide an electrode substrate for a dye-sensitized solar cell that can be easily manufactured with a relatively high productivity with a porous semiconductor electrode having a desired shape. .

  A fourth object of the present invention is to provide a dye-sensitized solar cell that can be easily manufactured with a relatively high productivity and having a porous semiconductor electrode of a desired shape.

  The method for forming a porous semiconductor electrode of the present invention that achieves the first object described above is an electric field jet method that is a method of discharging a coating liquid by applying a voltage to an electrode provided at or near the discharge port of the coating liquid. A first step of applying a coating liquid containing a large number of semiconductor fine particles to a coated object to form a coating film; and a second step of fixing the semiconductor fine particles in the coated film to the coated object. It is characterized by including these.

  In the electric field jet method, typically, an electrode is disposed in the vicinity of a discharge hole of a discharge head such as a nozzle-shaped discharge head or a discharge head having a slit-shaped discharge hole, and an AC or DC voltage is applied to the electrode. In this way, a coating liquid having a desired pattern is formed by continuously or intermittently discharging the coating liquid from the discharge holes onto the object to be coated.

  According to this electric field jet method, a coating film having a desired pattern and a desired film thickness can be formed in a relatively short time even when the viscosity of the coating solution is relatively high. In addition, when it is necessary to dry the coating film at a relatively low temperature, such as when the heat resistance of the object to be coated is relatively low, it may be desired to lower the viscosity of the coating solution to some extent. However, even in such a case, according to the electric field jet method, a coating film having a desired pattern and a desired film thickness can be formed in a relatively short time.

  Therefore, according to the method for forming a porous semiconductor electrode of the present invention, it is possible to form a porous semiconductor electrode having a desired shape with relatively high productivity.

  The method for producing the electrode substrate for a dye-sensitized solar cell of the present invention that achieves the second object described above includes a preparation step of preparing a transparent substrate having a transparent electrode formed on one side, and the transparent electrode, A semiconductor electrode forming step of forming a porous semiconductor electrode by a method for forming a porous semiconductor electrode of the present invention using a large number of semiconductor fine particles, and a dye supporting step of supporting a dye on the surface of the porous semiconductor electrode. (Hereinafter, this manufacturing method may be referred to as “manufacturing method I”).

  According to the production method I of the present invention, since the porous semiconductor electrode is formed by the above-described method for forming a porous semiconductor electrode of the present invention, a dye-sensitized solar cell electrode having a porous semiconductor electrode of a desired shape It becomes easy to manufacture the substrate with relatively high productivity.

  In the manufacturing method I of the present invention, (1) in the preparation step, a transparent substrate having one transparent electrode formed on one side is prepared, and in the semiconductor electrode formation step, a plurality of the transparent electrodes are formed on the one transparent electrode. Forming a porous semiconductor electrode (hereinafter, this manufacturing method may be referred to as “manufacturing method II”); (2) preparing a transparent substrate having a plurality of transparent electrodes formed on one side in the preparation step; In the semiconductor electrode forming step, one porous semiconductor electrode is formed on each of the plurality of transparent electrodes (hereinafter, this manufacturing method may be referred to as “manufacturing method III”), or (3) In the preparation step, preparing a transparent substrate on which a transparent electrode is formed on one side and a patterning layer whose surface wettability is changed by light irradiation is formed on the transparent electrode (hereinafter, this production method) Is called "Production Method IV" There.), It is preferable.

  According to the above production method II, it is possible to obtain a dye-sensitized solar cell electrode substrate suitable for obtaining a dye-sensitized solar cell having a structure in which a plurality of cells are electrically connected in parallel. Easy to manufacture under.

  According to the above production method III, it is possible to obtain a dye-sensitized solar cell electrode substrate suitable for obtaining a dye-sensitized solar cell having a structure in which a plurality of cells are electrically connected in series. Easy to manufacture under.

  According to the above manufacturing method IV, the wettability of a desired region can be relatively increased by selectively exposing the surface of the patterning layer, and therefore, a coating film is formed substantially only on the desired region. It becomes easy.

  The electrode substrate for a dye-sensitized solar cell of the present invention that achieves the third object described above is manufactured by any one of the above-described manufacturing methods I to IV of the present invention.

  According to the electrode substrate for a dye-sensitized solar cell of the present invention, the porous semiconductor electrode is formed by the above-described method for forming a porous semiconductor electrode of the present invention. Can be easily manufactured under relatively high productivity.

  The dye-sensitized solar cell of the present invention that achieves the fourth object described above is disposed so as to face a first electrode substrate having a semiconductor electrode having a dye supported on the surface, and the first electrode substrate. A dye-sensitized solar cell comprising a second electrode substrate and an electrolyte layer interposed between the first electrode substrate and the second electrode substrate, wherein the first electrode substrate comprises: It is the electrode substrate for the dye-sensitized solar cell of the present invention described above.

  According to the dye-sensitized solar cell of the present invention, the electrode substrate for the dye-sensitized solar cell of the present invention described above is used as the first electrode substrate, so that the porous semiconductor electrode having a desired shape is provided. Can be easily manufactured under relatively high productivity.

  According to the method for forming a porous semiconductor electrode of the present invention, a porous semiconductor electrode having a desired shape can be formed with relatively high productivity. For example, a dye-sensitized solar cell with a large operating current is used. Alternatively, it becomes easy to provide a dye-sensitized solar cell with a high operating voltage at a low cost.

  Further, according to the method for forming the electrode substrate for dye-sensitized solar cell of the present invention and the electrode substrate for dye-sensitized solar cell of the present invention, the dye-sensitized solar cell having a porous semiconductor electrode of a desired shape Since the battery electrode substrate can be manufactured with relatively high productivity, it is possible to provide a dye-sensitized solar cell with a large operating current or a dye-sensitized solar cell with a high operating voltage at a low cost. It becomes easy.

  According to the dye-sensitized solar cell of the present invention, it is possible to manufacture a solar cell having a desired shape of a porous semiconductor electrode with relatively high productivity. It becomes easy to provide a sensitive solar cell or a dye-sensitized solar cell having a high operating voltage at low cost.

  Hereinafter, a method for forming a porous semiconductor electrode of the present invention, a method for producing a dye-sensitized solar cell electrode substrate, a dye-sensitized solar cell electrode substrate, and a dye-sensitized solar cell, respectively, are illustrated in the drawings. The description will be made sequentially with appropriate reference.

<Method for producing porous semiconductor electrode>
As described above, the method for forming a porous semiconductor electrode according to the present invention uses a field jet method in which a coating liquid is discharged by applying a voltage to an electrode provided at or near the discharge port of the coating liquid. A first step of applying a coating liquid containing semiconductor fine particles to an object to be coated to form a coating film; and a second step of fixing the semiconductor fine particles in the coating film to the object to be coated. . Hereinafter, it explains in full detail for every process.

(First step)
The coating solution used in the first step contains a large number of semiconductor fine particles. Various semiconductor fine particles can be used as the semiconductor fine particles. For example, when forming a porous semiconductor electrode used in a dye-sensitized solar cell, titanium oxide, zinc oxide, tin oxide, indium tin oxide, zirconium oxide, silicon oxide, magnesium oxide, aluminum oxide, oxidation Fine particles of a metal oxide semiconductor such as cesium, bismuth oxide, manganese oxide, yttrium oxide, tungsten oxide, tantalum oxide, niobium oxide, and lanthanum oxide can be used, and the conductivity type is usually N-type. Among these metal oxide semiconductor fine particles, titanium oxide fine particles, particularly anatase-type titanium oxide fine particles are preferable from the viewpoint of excellent light resistance, safety, and economy. The “semiconductor fine particles” referred to in the present invention include not only fine-particle-shaped semiconductors but also amorphous micro-semiconductors and fine-powder semiconductors.

  The average particle diameter of the metal oxide semiconductor fine particles is preferably about 250 nm or less, and particularly preferably has a size that allows the quantum size effect to be exhibited. By using such metal oxide semiconductor fine particles, it becomes possible to easily form a mesoscopic porous semiconductor electrode exhibiting a quantum size effect, so that a dye-sensitized solar cell with high photoelectric conversion efficiency is obtained. It becomes easy.

  Moreover, when it is going to form the porous semiconductor electrode used with a dye-sensitized solar cell, as needed, the microparticles | fine-particles (for example, titanium oxide microparticles | fine-particles) with an average particle diameter of about 50-200 nm which function as a light-scattering center ) Can be used in combination. By incorporating a light scattering center into a porous semiconductor electrode using metal oxide semiconductor fine particles having a relatively small average particle size, the photoelectric conversion efficiency of the dye-sensitized solar cell can be improved.

  Since the coating solution used in the first step needs to be liquid (has fluidity) at the discharge temperature, an organic liquid or an inorganic liquid is used as a dispersion medium, and desired semiconductor fine particles are dispersed in the dispersion medium. It is preferable to use the same. Usually, the coating liquid is composed of a composition containing at least a dispersion medium and semiconductor fine particles, but various additives such as a dispersant, an antifoaming agent and a thixotropic agent can be appropriately mixed as necessary.

  For example, (i) a method in which semiconductor fine particles are precipitated as crystallized fine particles in a predetermined solvent to form a sol solution, or (ii) the semiconductor fine particles are mixed with a suitable dispersion medium using a ball mill, a sand mill, a roll mill, or the like. The mixture can be prepared by a method of mixing and dispersing in a dispersion medium using a known dispersing machine such as a kneader, a homogenizer, or a planetary mixer. When preparing the coating liquid by the method (ii) above, if the semiconductor fine particles to be used are agglomerated, an appropriate time in the process until obtaining the dispersion liquid, for example, before mixing with the dispersion medium, It is preferable to loosen the agglomerated semiconductor fine particles in the process of mixing with or after mixing with the dispersion medium. The coating solution can also be prepared by mixing the sol solution (i) and the dispersion (ii).

  When an inorganic liquid is used as a dispersion medium for the coating liquid, specific examples thereof include water, nitric acid, hydrochloric acid and the like. When an organic liquid is used as a dispersion medium, specific examples thereof include, for example, (a) chlorinated organic liquids such as chloroform, methylene chloride, dichloroethane, (b) ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, methyl cellosolve. , Ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, butyl carbitol acetate, ether organic liquids such as tetrahydrofuran, (c) aromatic hydrocarbon organic liquids such as toluene and xylene, (d) acetone , Ketone organic liquids such as methyl ethyl ketone, (e) ester organic liquids such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, (f) isopropyl alcohol (IPA), ethyl alcohol, methyl alcohol, butyl alcohol, Over tertiary butyl alcohol, alpha-terpineol, alcoholic organic liquid such as ethylene glycol, and the like can be used. When the dispersion liquid contains a binder described later, a dispersion medium capable of dissolving the binder is used.

  In order to improve the adhesion between the porous semiconductor electrode and the object to be coated, and the mechanical strength of the porous semiconductor electrode itself, when the semiconductor fine particles are not baked in fixing the coating film to the object to be coated, In the above coating solution, a resin component made of a polymer material can be dissolved as a binder. Further, even when the semiconductor fine particles are baked when the coating film is fixed to an object to be coated, the above resin component can be used. In this case, the resin component is removed by baking. As a result, a more porous semiconductor electrode can be formed.

  Examples of such resin components include cellulose resins, polyester resins, polyamide resins, polyacrylate resins, polycarbonate resins, polyurethane resins, polyolefin resins, polyvinyl acetal resins, fluorine resins, polyimide resins, etc. Resins and polyhydric alcohols such as polyethylene glycol can be used.

  In the case where the semiconductor fine particles are not baked in fixing the coating film to the object to be coated, it is preferable that the amount of the binder added to the coating solution is as small as possible. Specifically, the ratio with respect to the total solid content in the coating powder is preferably 0.5% by mass or less, and more preferably 0.2% by mass or less. On the other hand, when the semiconductor fine particles are baked when fixing the coating film to the object to be coated, it is preferable that the content of the resin component in the coating solution is approximately in the range of 0.5 to 20% by mass.

In addition to the binder, the above coating solution may contain various additives for improving the coating suitability. Examples of the additive include a surfactant, a viscosity modifier, a dispersion aid, and a pH adjuster. For example, nitric acid, hydrochloric acid, acetic acid, dimethylformamide, ammonia or the like can be used as a pH adjuster. In addition, since the electric conductivity of the coating liquid is preferably in the range of about 1 × 10 ⁻⁸ to 1 × 10 ⁻² / Ωm from the viewpoint of coating the coating liquid by the electric field jet method, It is preferable to select and use one or more types of dispersion media as appropriate so that a coating solution having conductivity can be obtained.

From the viewpoint of obtaining a coating solution having high coating suitability, the viscosity measured by a viscosity measuring device such as a coaxial double cylinder described in JISZ8803 is generally 0.001 to 1000 N · s / m ² (0. It is preferable to adjust the viscosity so as to be in the range of about 0.01 to 500 N · s / m ² , more preferably in the range of 1 cP to 100,000 cP).

  The coating of the coating liquid by the electric field jet method is arranged at least in the vicinity of the discharge port of the coating machine, as described in, for example, Japanese Patent Application Laid-Open No. 2000-246887 and Japanese Patent Application Laid-Open No. 2001-88306. It is performed continuously or intermittently while applying an AC or DC voltage to the electrodes. At this time, an electric field is formed by applying a voltage to the above electrode, and the semiconductor fine particles in the coating liquid are dielectrically polarized by this electric field and exert a repulsive force on each other. Therefore, even if the viscosity of the coating liquid is high, the semiconductor fine particles Aggregation can be prevented.

  The above-mentioned electrode can also be disposed on a part or the whole of the container part that stores the coating liquid in the coating machine, if necessary. Moreover, it can also apply | coat, pressurizing the coating liquid accommodated in the container part. Furthermore, it is possible to apply a voltage while applying a voltage between the electrode and the article to be coated.

  In the case of continuously discharging the coating liquid, it is possible to apply both an AC voltage and a DC voltage, but preferably an AC voltage is applied. The voltage intensity is preferably in the range of about 100 V to 10 kV, and more preferably in the range of about 1 to 7 kV from the viewpoint of voltage control and ejection stability. The applied voltage is preferably a rectangular wave. Although it depends on the viscosity of the coating solution and the material composition, the optimum frequency of the applied voltage varies when the electrical conductivity of the coating solution is different. In many cases, the optimum frequency of the applied voltage increases as the electrical conductivity increases. If the frequency is low, deposition on the electrode tends to occur, which is not preferable. Further, when the frequency is high, there is a problem that control becomes difficult due to the performance of the power source. A preferred frequency range is approximately 1 Hz to 10 kHz. From the viewpoint of maintaining continuity of discharge and voltage control, the frequency is more preferably about 100 Hz to 4 kHz. In the case of a direct current voltage, the voltage strength is preferably in the range of approximately 100 V to 10 kV, or approximately in the range of −100 V to −10 kV. The coating film can be formed in a line shape or a surface shape by continuous discharge. When there is a difference in wettability on the surface on which the coating film is to be formed, the coating film can be formed discontinuously (for example, in the form of dots) even if it is continuously discharged.

On the other hand, when the intermittent discharge (ON · OFF discharge) the coating liquid, changes in the pressure applied to the coating liquid, depending on whether the absolute value of the applied voltage exceeds the threshold value V _1, it is possible to control the discharge. By controlling the intensity of the applied voltage, the discharge amount can be controlled. The size of the threshold value V ₁ was, depending on the composition and the electrode arrangement of the coating solution, generally it is preferably in the range of 100V～3kV. The voltage for discharging the coating solution is preferably in the range of about 100 V to 10 kV, more preferably in the range of about 1 to 7 kV, as in the case of continuous discharge. By setting it as intermittent discharge, the coating film arrange | positioned at dot shape, for example can be formed.

  The distance from the discharge port to the surface to be coated can be appropriately set, but is preferably set in the range of about 50 to 10000 μm, more preferably in the range of about 100 to 1000 μm. If this distance is too short, it is difficult to stably form a meniscus, and if it is too long, the discharge linearity is impaired, which is not preferable.

  What is used as the object to be coated is appropriately selected according to the use of the porous semiconductor electrode. For example, when a porous semiconductor electrode used in a dye-sensitized solar cell is to be formed, a transparent substrate having a transparent electrode formed on one side with indium tin oxide or fluorine-doped tin oxide is coated. The above-mentioned coating solution is applied onto the transparent electrode in the transparent substrate to form a coating film. Moreover, the film thickness of the coating film and the shape in plan view are also appropriately selected according to the use of the porous semiconductor electrode. When the porous semiconductor electrode used in the dye-sensitized solar cell is to be formed, it is preferable to select the film thickness of the coating film within a range of about 5 to 30 μm.

(Second step)
In the second step, the semiconductor fine particles in the above-mentioned coating film are fixed to the object to be coated. This fixing can be performed by various methods depending on the type of coating liquid and the heat resistance of the object to be coated.

  For example, when the heat resistance of the coated object is relatively high, the semiconductor fine particles in the coated film can be fixed to the coated object by baking or sintering the coated film. On the other hand, when the heat resistance of the object to be coated is relatively low, the coating film is dried by atmosphere heating, heating by irradiation with infrared rays (including far infrared rays), heating by irradiation with light having an absorption wavelength of semiconductor fine particles, or the like. As a result, the semiconductor fine particles in the coating film can be fixed to the object to be coated. When the heat resistance of the object to be coated is relatively low, from the viewpoint of obtaining a porous semiconductor electrode having high adhesion to the object to be coated, the infrared ray irradiation does not include light of the absorption wavelength of the semiconductor fine particles. It is preferable that the liquid phase component is volatilized by heating uniformly, and then, if necessary, the semiconductor fine particles are activated by irradiating light with the absorption wavelength of the semiconductor fine particles, whereby the impurities adsorbed on the semiconductor fine particles It is preferable to remove the liquid phase component. Even when the coating film is dried by any method, this drying is preferably performed at a temperature lower than the heat resistant temperature of the article to be coated.

  By performing the first step and the second step described above in this order, a porous semiconductor electrode having a desired shape can be formed on the object to be coated with relatively high productivity.

<Dye-sensitized solar cell electrode substrate and manufacturing method thereof (first embodiment)>
FIG. 1 is a schematic view showing the basic cross-sectional structure of the electrode substrate for a dye-sensitized solar cell of the present invention. The illustrated dye-sensitized solar cell electrode substrate 20 (hereinafter referred to as “electrode substrate 20”) is used to obtain a dye-sensitized solar cell in which a plurality of cells are electrically connected in parallel. Is.

  In this electrode substrate 20, one transparent electrode 3 is formed on one side of the transparent base material 1, and a plurality of porous semiconductor electrodes 5 are formed in parallel on the transparent electrode 3. Each porous semiconductor electrode 5 is formed of a large number of semiconductor fine particles 5a. Each porous semiconductor electrode 5 carries a dye 7. Further, a plurality of lead wires 9 are formed on the transparent electrode 3 so as to correspond to one porous semiconductor electrode 5 one by one, and the outer surface of each lead wire 9 is protected as necessary. Layer 11 is provided. In FIG. 1, for convenience, the dye 7 supported on the porous semiconductor electrode 5 is drawn as one layer. Hereinafter, the electrode substrate 20 and the manufacturing method thereof will be described in detail.

(1) Transparent base material The transparent base material 1 transmits light of a desired wavelength region in the wavelength region ranging from the ultraviolet region to the infrared region in an average value of approximately 85% or more, and has desired light resistance and weather resistance. It is preferable to use an inorganic material or an organic material, and if necessary, various additives can be used in combination to form the film by various methods. The “desired wavelength range” can be appropriately selected in consideration of the absorption wavelength ranges of the porous semiconductor electrode 5 and the dye 7.

  As the transparent substrate 1, for example, a rigid material such as a quartz glass plate, a Pyrex (registered trademark) glass plate, or synthetic quartz can be used, but from the viewpoint of increasing the flexibility of the electrode substrate 20. Is more preferable to use a transparent glass sheet or a transparent resin film than the rigid material as the transparent substrate 1, and it is particularly preferable to use a transparent resin film.

  Examples of the transparent resin film include biaxially stretched polyethylene terephthalate (PET) film, ethylene / tetrafluoroethylene copolymer film, polyethersulfone (PES) film, polyetheretherketone (PEEK) film, and polyether. An imide (PEI) film, a polyimide (PI) film, a polyester naphthalate (PEN) film, a polycarbonate (PC) film, a cyclic polyolefin film, or the like can be used. From the viewpoint of reducing the manufacturing cost of the electrode substrate 20, a transparent resin film formed of a relatively inexpensive resin material is used rather than a transparent resin film formed of a relatively expensive resin material such as engineering plastic. It is preferable to use it. When a transparent resin film is used as the transparent substrate 1, the film thickness can be appropriately selected within a range of about 15 to 500 μm depending on the use of the dye-sensitized solar cell produced using the electrode substrate 20. It is.

  In addition, since the temperature of the transparent substrate 1 is also increased when forming the porous semiconductor electrode 5, it is preferable to consider the heat resistance when selecting the material and thickness of the transparent substrate 1.

(2) Transparent electrode The transparent electrode 3 receives carriers (electrons) from each porous semiconductor electrode 5 formed thereon when the dye-sensitized solar cell is irradiated with light of a desired wavelength range. Alternatively, carriers (holes) are transmitted to each porous semiconductor electrode 5 formed thereon, and can be formed using various conductive materials.

  In consideration of light transmittance and conductivity, the transparent electrode 3 is preferably formed of indium tin oxide (ITO), fluorine-doped tin oxide, indium zinc oxide (IZO), zinc oxide (ZnO) or the like, and particularly fluorine-doped. It is preferable to form with tin oxide or ITO. The film thickness of the transparent electrode 3 can be appropriately selected within a range of about 0.1 nm to 500 nm, and the sheet resistance is preferably as low as possible, generally about 15Ω / □ or less.

  In manufacturing the electrode substrate 20, first, a preparation process for preparing the transparent base material 1 on which the transparent electrode 3 is formed on one side is performed. Such a transparent base material 1 may be produced by itself, or may be purchased by others.

  When the transparent electrode 3 is formed on one side of the transparent substrate 1 itself, the transparent electrode 3 can be formed by a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method. From the viewpoint of suppressing the manufacturing cost, it is preferable to form the transparent electrode 3 by an ion plating method or a sputtering method.

(3) Porous semiconductor electrode Each porous semiconductor electrode 5 receives a carrier (electron) from the dye 7 when the dye 7 is photoexcited, or carriers to the dye 7 when the dye 7 is photoexcited. It conveys (holes). The film thickness of each porous semiconductor electrode 5 is appropriately selected within a range of approximately 5 to 30 μm.

  In manufacturing the electrode substrate 20, a semiconductor electrode forming process for forming each porous semiconductor electrode 5 is performed following the above-described preparation process. This step is performed by forming a predetermined number of porous semiconductor electrodes 5 each having a desired shape (for example, a rectangular shape) in accordance with the porous semiconductor electrode forming method of the present invention described above. Here, in order to avoid duplication, description about the material and formation method of the porous semiconductor electrode 5 is abbreviate | omitted.

  If the porous semiconductor electrode 5 having a desired film thickness cannot be formed only by performing the first step and the second step in the method for forming a porous semiconductor electrode of the present invention described above once, The second process is performed after the process is repeated as many times as necessary, or the first process and the second process performed thereafter are set as one set and this set is repeated as many times as necessary.

(4) Dye Dye 7 is for sensitizing porous semiconductor electrode 5. As the dye 7, (A) the absorption wavelength range extends to a longer wavelength side than the absorption wavelength range of the porous semiconductor electrode 5, and (B) the porous semiconductor electrode 5 is an N-type semiconductor. In the case where the energy level of electrons when photoexcited is higher than the position of the conduction band edge of the porous semiconductor electrode 5, (C) when the porous semiconductor electrode 5 is an N-type semiconductor, The time required to inject carriers into the semiconductor electrode 5 is preferably shorter than the time required to recapture carriers from the porous semiconductor electrode 5.

  For example, when the porous semiconductor electrode 5 is formed of anatase-type titanium oxide, it is preferable to use a ruthenium complex represented by the following formula (I) as the dye 7.

  From the viewpoint of obtaining a dye-sensitized solar cell with high photoelectric conversion efficiency using the electrode substrate 20, among the ruthenium complexes represented by the above formula (I), X is NCS (thiocyanate) (cis-di). It is particularly preferred to use (thiocyanate) -N, N′-bis (2,2′-bipyridyl-4,4′-dicarboxylic acid) ruthenium (II).

  Of course, metal complex dyes other than the ruthenium complex described above and organic dyes can also be used. Specific examples of the organic dye include acridine dyes, azo dyes, indigo dyes, quinone dyes, coumarin dyes, merocyanine dyes, and phenylxanthene dyes. Of these organic dyes, coumarin dyes are preferable.

  In manufacturing the electrode substrate 20, subsequent to the above-described semiconductor electrode forming step, a dye carrying step for carrying the above dye 7 on the semiconductor fine particles 5 a forming the porous semiconductor electrode 5 is performed. From the viewpoint of obtaining a dye-sensitized solar cell with high photoelectric conversion efficiency, it is preferable to support the dye 7 on as many semiconductor fine particles 5a as possible, and in particular, each of the semiconductor fine particles 5a forming the porous semiconductor electrode 5. It is preferable to support the dye 7 on the surface.

  For this purpose, it is preferable to support the dye 7 on the porous semiconductor electrode 5 by a method capable of adsorbing the dye 7 up to the inner surface of the pores of each porous semiconductor electrode 5. For example, (A) a dye solution (hereinafter referred to as “dye-supporting coating solution”) is prepared, and the transparent substrate 1 formed up to each porous semiconductor electrode 5 is immersed in the dye-supporting coating solution. Then, a method of drying, or (B) a method of contacting and infiltrating each porous semiconductor electrode 5 by a method such as coating, spraying or spraying of a dye-supporting coating solution, followed by drying. Therefore, the dye 7 can be adsorbed to the surface in the pores of the individual porous semiconductor electrodes 5, and the dye 7 can be supported on the surface of each of the semiconductor fine particles 5a.

  The dye-supporting coating liquid is prepared by appropriately selecting either an aqueous solvent or an organic solvent according to the type of the dye used. If necessary, the transparent substrate 1 formed up to each porous semiconductor electrode 5 is immersed in the dye-supporting coating liquid, or the dye-supporting coating liquid is applied to each porous semiconductor electrode 5, sprayed, Or spraying etc. can be performed in multiple times. When the above immersion, coating, spraying, or spraying is performed in a plurality of times, drying of the coating liquid that has adhered to and penetrated each porous semiconductor electrode 5 is completed by the required number of times of immersion, coating, spraying, or spraying. It is preferable to do it at the end without doing it until. Moreover, when performing the said immersion, application | coating, spraying, or spraying in multiple steps, the pigment | dye density | concentration in the pigment | dye supporting coating liquid, the liquid temperature of a coating liquid, etc. can be changed suitably in the middle. .

  In order to obtain a dye-sensitized solar cell having a high photoelectric conversion efficiency, it is preferable to support the dye 7 on each porous semiconductor electrode 5 in the form of a monomolecular film. It is preferable to wash and remove the excess dye 7 supported on the substrate with a solvent that can be used for the preparation of the dye-supporting coating solution. When the immersion, coating, spraying, or spraying is performed in a plurality of times, the extra dye 7 can be washed and removed at a desired time, but it is preferably performed every time.

  By subjecting each porous semiconductor electrode 5 to surface treatment in advance, it is possible to increase the moving speed of carriers (electrons) from the dye 7 to the porous semiconductor electrode 5. After supporting the dye 7 on each porous semiconductor electrode 5, the porous semiconductor electrode 5 and the dye 7 are subjected to a predetermined treatment, for example, the porous semiconductor electrode 5 is formed of titanium oxide, and the dye 7 is made of the ruthenium complex described above. In some cases, it is possible to improve the photoelectric conversion efficiency of the dye-sensitized solar cell using the electrode substrate 20 by performing a treatment with a base such as t-butylpyridine.

(5) Lead wire and protective layer Each lead wire 9 is for collecting the electrons moved from each porous semiconductor electrode 5 to the transparent electrode 3 and outputting them in parallel electrically. The semiconductor electrodes 5 are arranged in the vicinity of the corresponding porous semiconductor electrodes 5 so as to correspond one by one. Each lead wire 9 extends in a direction substantially parallel to the extending direction of the corresponding porous semiconductor electrode 5.

  These lead wires 9 are made of a single metal or alloy having higher conductivity than the transparent electrode 3, such as copper (Cu), iron (Fe), nickel (Ni), chromium (Cr), aluminum (Al), gold (Au ), Silver (Ag), stainless steel, titanium (Ti) or the like, and among these metals or alloys, it is preferable to use copper, nickel, stainless steel, titanium, or the like having high conductivity. From the viewpoint of reducing the manufacturing cost of the electrode substrate 20, it is preferable to use copper, nickel, and stainless steel, which are inexpensive conductive materials.

  Each lead wire 9 is formed, for example, by forming a large vapor-deposited film (meaning a film formed by a physical vapor deposition method or a chemical vapor deposition method; the same shall apply hereinafter) on the transparent electrode 3. For example, by etching into a desired shape using an etching mask formed by photolithography, or by depositing a deposited film by physical vapor deposition or chemical vapor deposition using a mask having the desired shape Can be formed. The formation of each lead wire 9 can be performed at any time before and after the semiconductor electrode formation step described above, but the desired lead wire 9 is formed before the semiconductor electrode formation step. easy.

  On the other hand, the protective layer 11 is for protecting the lead wire 9 from the electrolyte when a dye-sensitized solar cell is produced using the electrode substrate 20. For this reason, the protective layer 11 includes, for example, (i) nitrides such as silicon nitride and aluminum nitride, (ii) nickel (Ni), zinc (Zn), gold (Au), platinum (Pt), chromium (Cr), Simple metals such as aluminum (Al), cadmium (Cd), tungsten (W), tin (Sn), cobalt (Co), iron (Fe), titanium (Ti), manganese (Mn), zirconium (Zr), ( iii) It is formed of a material having corrosion resistance to the electrolyte, such as an alloy composed of two or more of the above-mentioned single metals.

  The protective layer 11 is formed by, for example, forming a large vapor-deposited film isotropically so as to cover each lead wire 9 and forming the vapor-deposited film into a desired shape using an etching mask formed by, for example, a photolithography method. A vapor deposition film of a desired material is formed on the outer surface (upper surface and each side surface) of each lead wire 9 by etching or physical vapor deposition or chemical vapor deposition using a mask having a predetermined shape. Can be formed. Furthermore, it can be formed by electroplating, electroless plating, or chemical conversion treatment. If necessary, the protective layer 11 can be subjected to a surface treatment such as a chromate treatment. When the protective layer 11 is formed by electroless plating, the plating layer is also formed at a place other than the outer surface of the lead wire 9, so that the plating layer formed at an unnecessary place by a method such as etching or lift-off Remove.

  In order to protect the lead wire 9 from the above-described electrolyte, it is preferable to make the protective layer 11 as dense as possible. When the heat resistance of the transparent substrate 1 is relatively low, a relatively dense protective layer 11 can be obtained by forming the protective layer 11 by electroplating, electroless plating, or chemical conversion treatment.

  The formation of the protective layer 11 can be performed before or after the semiconductor electrode forming step described above, but it is easier to form the desired protective layer 11 if performed before the semiconductor electrode forming step. .

(6) Arbitrary member A gas barrier layer, an auxiliary electrode, a corrosion prevention layer, a patterning layer, etc. can be formed in the electrode substrate 20 as needed. Hereinafter, these optional members will be described.

(A) Gas barrier layer The gas barrier layer is formed by allowing oxygen or moisture to enter the dye-sensitized solar cell through the electrode substrate 20 when the dye-sensitized solar cell is manufactured using the electrode substrate 20, and the dye This is for preventing the electrolyte used in the sensitized solar cell from evaporating to the outside through the electrode substrate 20, and is provided between the transparent substrate 1 and the transparent electrode 3 or the back surface of the transparent substrate 1 (transparent It means a surface opposite to the surface on which the electrode 3 is formed.

The oxygen permeability of the gas barrier layer is preferably about 1 cc / m ² / day · atm (about 10 ml / m ² / day / MPa) or less, and the water vapor permeability is about 1 g / m ² / day or less. It is preferable. Such a gas barrier layer can be formed by a deposited film or film of a desired organic material, or by a deposited film of a desired inorganic material.

  By preventing oxygen from entering the dye-sensitized solar cell, deterioration of the dye 7 and the electrolyte is suppressed, so that a decrease in the performance of the dye-sensitized solar cell over time can be suppressed. In addition, by suppressing the intrusion of moisture, for example, even when the transparent electrode 3 is formed of a material that is relatively easily deteriorated by moisture, such as ITO, the deterioration of its performance over time is suppressed. A decrease in battery performance over time can be suppressed.

(B) Auxiliary electrode The auxiliary electrode is for increasing the conductivity of the electrode substrate 20 and is provided between the transparent substrate 1 and the transparent electrode 3 so as to be in contact with the transparent electrode 3. As a material for the auxiliary electrode, various metals or alloys having higher conductivity than the transparent electrode 3 can be used. The shape of the auxiliary electrode in plan view is preferably a shape in which a large number of fine lines are combined, such as a lattice shape, a mesh shape, or a parallel stripe shape, from the viewpoint of suppressing a decrease in the amount of light incident on the dye 7 as much as possible. .

  Such an auxiliary electrode is formed by, for example, providing a large vapor-deposited film on the transparent substrate 1 or the gas barrier layer, and etching the vapor-deposited film into a desired shape using an etching mask formed by, for example, a photolithography method. Or by forming a vapor deposition film of a desired material on the transparent substrate 1 or the above gas barrier layer by physical vapor deposition or chemical vapor deposition using a mask having a desired shape. Can do. Furthermore, a desired metal foil is bonded onto the transparent substrate 1 or the above gas barrier layer using an adhesive, and the metal foil is etched into a desired shape using an etching mask formed by, for example, a photolithography method. Can also be formed.

(C) Corrosion prevention layer The corrosion prevention layer is for preventing the auxiliary electrode from being corroded by the electrolyte of the dye-sensitized solar cell when the above-mentioned auxiliary electrode is provided. Similarly to the layer 11, it is formed so as to cover at least the outer surface of the auxiliary electrode. If necessary, a corrosion prevention layer can also be formed on a region of the surface of the layer serving as the base of the auxiliary electrode that is not covered by the auxiliary electrode.

(D) Patterning layer The “patterning layer” in the present specification means a layer capable of changing the wettability of the surface by light irradiation. Specific examples of this patterning layer include: (i) a photocatalyst-containing layer having a structure in which a photocatalyst (fine particles of photo semiconductor) is dispersed in a hydrophobic binder, and (ii) hydrolysis and polycondensation of chlorosilane, alkoxysilane, or the like. The resulting organopolysiloxane layer, (iii) a reactive silicone-crosslinked organopolysiloxane layer with excellent water repellency and oil repellency, and (iv) a self-assembled film exhibiting water repellency using fluoroalkylsilane, etc. , Etc.

  The photocatalyst-containing layer (i) above changes the wettability of the exposed region by selectively exposing the surface with light in a wavelength region including the absorption wavelength of the photocatalyst contained in the photocatalyst-containing layer. This can be made hydrophilic. Such a photocatalyst-containing layer is prepared by, for example, preparing a coating liquid in which a photocatalyst is dispersed in a hydrophobic binder, applying the coating liquid to a desired location to form a coating film, and then drying the coating film. Can be formed.

  Moreover, each layer of said (ii)-(iv) can change the wettability of the exposed area | region by selectively exposing the surface, for example by ultraviolet light, and can hydrophilize here. In selectively exposing the surface of each layer of (ii) to (iv) above, a photocatalyst-containing layer can be provided on the surface of the photomask (ultraviolet mask) on the exposed object side, if necessary. By providing this photocatalyst-containing layer on the photomask, it is possible to perform a desired hydrophilization treatment with longer wavelength ultraviolet light.

  As shown in FIG. 2, the patterning layer 13 is provided on the transparent electrode 3 and used as an underlayer for the porous semiconductor electrode 5. A region where the porous semiconductor electrode 5 is to be formed in the surface of the patterning layer 13 is hydrophilized as described above. When the above-mentioned coating liquid that is the material of the porous semiconductor electrode 5 is applied on the patterning layer 13 in this state by the electric field jet method, a coating film is easily formed substantially only on the above-mentioned hydrophilic region. can do. In addition, since each member except the patterning layer 13 among the members shown in FIG. 2 has already been described with reference to FIG. 1, the same reference numerals as those used in FIG. 1 are used for these members. The description is omitted.

  Since the electrode substrate 20 described above is one of the electrode substrates for dye-sensitized solar cells of the present invention described above, it has been described in the description of the electrode substrate for dye-sensitized solar cells of the present invention. Has a technical effect.

<Dye-sensitized solar cell electrode substrate and manufacturing method thereof (second embodiment)>
FIG. 3 is a schematic view showing another basic cross-sectional structure of the electrode substrate for a dye-sensitized solar cell of the present invention. The illustrated dye-sensitized solar cell electrode substrate 30 (hereinafter referred to as "electrode substrate 30") is used to obtain a dye-sensitized solar cell in which a plurality of cells are electrically connected in series. Is.

  This electrode substrate 30 has (1) a point in which a plurality of transparent electrodes 23 are formed on one side of the transparent substrate 21, and (2) a porous semiconductor electrode 25 is formed on each transparent electrode 23 one by one. In addition, a region 23a where the porous semiconductor electrode 25 is not formed is present at a predetermined edge of the upper surface of each transparent electrode 23, and (3) the lead wire 9 and the protective layer 11 are formed. This is different from the electrode substrate 20 described above in that it does not.

  Since the other configuration except for the differences (1) to (3) is the same as the configuration of the electrode substrate 20, the members shown in FIG. 3 are functionally common to the members shown in FIG. For those that do, a reference numeral obtained by adding 20 to the numerical value of the reference numeral used in FIG.

  The electrode substrate 30 can be manufactured in the same manner as the electrode substrate 10 except that the plurality of transparent electrodes 23 are formed on the transparent base material 21 and the lead wires 9 and the protective layer 11 are not formed.

  The plurality of transparent electrodes 23 are formed, for example, by forming a large vapor-deposited film with a desired material on one surface of the transparent substrate 21, and etching the vapor-deposited film into a desired shape using an etching mask formed by, for example, a photolithography method. Or by forming a vapor deposition film of a desired material on one surface of the transparent substrate 21 by physical vapor deposition or chemical vapor deposition using a mask having a desired shape.

  Since the electrode substrate 30 is a kind of the electrode substrate for the dye-sensitized solar cell of the present invention described above, similarly to the electrode substrate 20 described above, the electrode substrate 30 for the electrode substrate for the dye-sensitized solar cell of the present invention is described. There are technical effects described in the explanation.

<Dye-sensitized solar cell (first embodiment)>
FIG. 4 is a schematic view showing the basic principle of the dye-sensitized solar cell of the present invention. In the illustrated dye-sensitized solar cell 100, the electrode substrate 20 of the first form described above is used as the first electrode substrate, and one first conductive film 44 and a plurality of second conductive materials are provided on one side of the transparent base material 42. A dye-sensitized solar cell electrode substrate 50 (hereinafter referred to as “electrode substrate 50”) on which the film 46 is formed is used as the second electrode substrate.

  Since the configuration of the electrode substrate 20 has already been described, the description thereof is omitted here. Moreover, as the transparent base material 42 and the 1st electrically conductive film 44 in the electrode substrate 50, since the same thing as the transparent base material 1 or the transparent electrode 3 in the electrode substrate 20 mentioned above can be used, respectively, these transparent base materials are used. The description of the material 42 and the first conductive film 44 is also omitted here.

  Each second conductive film 46 formed on the first conductive film 44 is for improving the conductivity of the electrode substrate 50, and one second conductive material is provided for one porous semiconductor electrode 5 in the electrode substrate 20. The films 46 are arranged in parallel on the first conductive film 44 so as to correspond. One porous semiconductor electrode 5 and the second conductive film 46 corresponding to the porous semiconductor electrode 5 substantially overlap each other in plan view.

  The second conductive film 46 is formed by appropriately selecting a conductive material having corrosion resistance to the electrolyte according to the type of electrolyte used in the dye-sensitized solar cell using the electrode substrate 50. The material of the second conductive film 46 is most preferably platinum (Pt), but the second conductive film 46 can also be formed of carbon, a conductive polymer, or the like. From the viewpoint of obtaining a dye-sensitized solar cell with high photoelectric conversion efficiency using the electrode substrate 50, one ionic species constituting a redox pair in the electrolyte of the dye-sensitized solar cell reacts with a carrier during light irradiation. The second conductive film 46 is preferably formed of a metal (for example, platinum (Pt)) that can function as a catalyst when generating the other ionic species.

  Each of the second conductive films 46 is formed by, for example, providing a large deposited film on the first conductive film 44 and etching the deposited film into a desired shape using an etching mask formed by, for example, a photolithography method, or A vapor deposition film of a desired material can be formed on the first conductive film 44 by physical vapor deposition or chemical vapor deposition using a mask having a desired shape. The film thickness of the second conductive film 46 can be appropriately selected within a range of approximately 1 to 500 nm. From the viewpoint of suppressing the manufacturing cost of the electrode substrate 50, it is preferable to form each second conductive film 46 by a sputtering method using a mask having a desired shape.

  The electrode substrate 20 and the electrode substrate 50 are disposed so that the porous semiconductor electrode 5 in the electrode substrate 20 and the second conductive film 46 in the electrode substrate 50 face each other. A plurality of spacers 48 are arranged between the adjacent porous semiconductor electrodes 5 and between the adjacent second conductive films 46 between them. The lead wire 9 and the protective layer 11 are covered with a spacer 48. An electrolyte layer 90 is interposed between each porous semiconductor electrode 5 and the second conductive film 46 corresponding to the porous semiconductor electrode 5. Although not shown, in the dye-sensitized solar cell 100, the periphery of the electrode substrates 20 and 50 is sealed with a sealing agent in order to prevent the electrolyte forming the electrolyte layer 90 from leaking out. Sealed.

  Each spacer 48 is formed of a material having corrosion resistance with respect to the electrolyte, such as glass or resin, for example, and maintains a distance between the electrode substrates 20 and 50 at a predetermined distance to prevent a short circuit. The individual spacers 48 can be formed in advance on one of the electrode substrates 20 and 50, or are used by being fixed to at least one of the electrode substrates 20 and 50 when the dye-sensitized solar cell 100 is assembled. You can also. The spacer 48 can also serve as a sealant.

  The electrolyte layer 90 is located between the electrode substrate 10 and the electrode substrate 20 and is reduced by the photoexcited dye 7, while being oxidized by carriers (electrons) supplied through the electrode substrate 20. A closed circuit including the substrate 10 and the electrode substrate 20 can be formed.

  As the material of the electrolyte layer 90, various electrolytes used in a dye-sensitized solar cell containing at least a redox pair contributing to carrier transport can be used, and the form thereof is liquid, solid, and It may be any gel. From the viewpoint of improving the durability and stability of the dye-sensitized solar cell 100, it is preferable to use a room temperature molten salt electrolyte or a gel electrolyte.

The redox couple is not particularly limited as long as it is used for an electrolyte. Examples of the combination of raw materials include a combination of iodine and iodide, or a combination of bromine and bromide. It is done. For example, specific examples of combinations of iodine and iodide include metal iodides such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI ₂ ), and iodine. A combination with (I ₂ ) can be mentioned. Specific examples of combinations of bromine and bromide include lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), calcium bromide (CaBr ₂ ), and the like, and bromide (Br). ₂ ) and a combination thereof.

  When a gel electrolyte is used as the material of the electrolyte layer 90, the electrolyte may be 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 a chemical bond such as a crosslinking reaction. The physical gel can be prepared by using a gelling agent such as polyacrylonitrile or polymethacrylate, and as the chemical gel, an acrylic ester-based or methacrylic ester-based one can be used.

  When a solid electrolyte is used as the material of the electrolyte layer 90, it is preferable to use a conductive polymer having a high hole transporting property such as copper iodide (CuI), polypyrrole, or polythiophene as the electrolyte.

  Although the thickness of the electrolyte layer 90 can be selected as appropriate, the total thickness of the electrolyte layer 90 and the porous semiconductor electrode 5 corresponding to the electrolyte layer 90 is within a range of approximately 2 μm to 100 μm, and of these, approximately 2 μm. It is preferable to select the thickness of the electrolyte layer 90 so as to be in the range of ˜50 μm. If the thickness of the electrolyte layer 90 is thinner than the above range, the porous semiconductor electrode 5 and the second conductive film 46 are likely to come into contact with each other, causing a short circuit. Moreover, when the thickness of the electrolyte layer 90 is thicker than the above range, the internal resistance of the dye-sensitized solar cell 100 increases, and the performance of the dye-sensitized solar cell 100 decreases.

  The electrolyte layer 90 described above can be formed by various methods depending on the material. As a specific example of the method of forming the electrolyte layer 90, a method of forming the electrolyte layer 90 by applying an electrolyte layer forming coating solution so as to cover the porous semiconductor electrode 5 and drying it (hereinafter referred to as “coating method”). Or the electrode substrates 20 and 50 are arranged so that the porous semiconductor electrode 5 and the second conductive film 46 have a predetermined interval, and the electrode substrate 20 and the electrode substrate 50 are separated from each other. Examples thereof include a method of forming the electrolyte layer 90 by injecting a coating solution for forming an electrolyte layer into the gap (hereinafter sometimes referred to as “injection method”). Hereinafter, these “coating method” and “injection method” will be described.

(I) Coating Method The coating method is a method mainly used for forming the solid electrolyte layer 90, and at least a redox pair and this redox pair are used as the coating liquid for forming the electrolyte layer used in this coating method. It is preferable to contain a polymer that holds Moreover, it is preferable that a crosslinking agent, a photopolymerization initiator, and the like are added to the electrolyte layer forming coating solution.

  The coating solution for forming the electrolyte layer can be applied by 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, and micro bar. It can be performed by various methods such as coating, microbar reverse coating, and screen printing (rotary method).

  When the above-mentioned photopolymerization initiator is contained in the electrolyte layer forming coating solution, the electrolyte layer 90 is formed by exposing the photopolymerization initiator to light after applying this electrolyte layer forming coating solution. Can do.

(II) Injection Method The injection method is a method used for forming a liquid, gel, or solid electrolyte layer. When the electrolyte layer 90 is formed by this method, the spacer 48 described above is used. It is preferable to hold the electrode substrate 20 and the electrode substrate 50 at a desired interval in advance. Injection | pouring of the coating liquid for electrolyte layer formation can be performed using a capillary phenomenon, for example. In the case of forming a gel-like or solid electrolyte layer 90, a two-dimensional or three-dimensional crosslinking reaction is performed by, for example, performing temperature adjustment, ultraviolet irradiation, electron beam irradiation, etc. after injecting the electrolyte layer forming coating solution. Give rise to

  In the dye-sensitized solar cell 100 having the above-described configuration, one porous semiconductor electrode 5, one dye 7 corresponding to the porous semiconductor electrode 5, the electrolyte layer 90, and the second conductive film 46 are provided. Configure the cell. The transparent electrode 3 and the first conductive film 44 correspond to all cells.

  Although not shown in FIG. 4, the lead wires 9 are connected in series to a load (external load) in a state of being connected in parallel to each other, and the second conductive films 46 are also connected in parallel to each other. Connected in series to the load. Carriers (electrons) generated in each cell by photoelectric conversion are collected by the transparent electrode 3 and then taken out from the transparent electrode 3 in parallel by the lead wires 9.

  Since the dye-sensitized solar cell 100 described above is one of the dye-sensitized solar cells of the present invention described above, the technical description described in the description of the dye-sensitized solar cell of the present invention is provided. There is an effect.

<Dye-sensitized solar cell (second form)>
FIG. 5 is a schematic view showing another basic principle of the dye-sensitized solar cell of the present invention. In the illustrated dye-sensitized solar cell 110, (1) a dye-sensitized solar cell electrode substrate 60 (hereinafter referred to as "electrode substrate 60") is used as the second electrode substrate; 2) It is greatly different from the dye-sensitized solar cell 100 of the first embodiment described above in that the electrolyte layer 90 is not divided by the plurality of spacers 48 and is interposed between the electrode substrate 20 and the electrode substrate 60. Since the other configuration is the same as the configuration of the dye-sensitized solar cell 100, the description of the common configuration is omitted here.

  In the electrode substrate 60 used as the second electrode substrate, one first conductive film 54, a plurality of second conductive films 56, and a plurality of lead wires 58 are formed on one surface of the transparent base 52, and each lead wire 58 is formed. Is covered with a protective layer 59.

  The transparent substrate 52 and the first conductive film 54 can be formed in the same manner as the transparent substrate 42 or the transparent electrode 44 in the dye-sensitized solar cell 100 of the first embodiment, respectively. Each of the second conductive films 56 can also be formed using the same material as that of the second conductive film 46 in the dye-sensitized solar cell 100 of the first embodiment, but these second conductive films 56 are adjacent to each other. The two porous semiconductor electrodes 5 are arranged in parallel on the first conductive film 54 so as to correspond to each other. Each of the second conductive films 56 covers a gap between the two porous semiconductor electrodes 5 corresponding to the second conductive film 56 in a plan view, and each of the corresponding two porous semiconductor electrodes 5 in a plan view. Overlap partially.

  Each lead wire 58 is for supplying carriers (electrons) to the first conductive film 54, and corresponds to one second conductive film 56 one by one so that the corresponding second conductive film 56 Located in the vicinity. Each lead wire 58 extends in a direction substantially parallel to the extending direction of the corresponding second conductive film 56. These lead wires 58 can be formed in the same manner as the lead wires 9 in the dye-sensitized solar cell 100 of the first embodiment.

  The protective layer 59 covering the lead wire 58 is for protecting the lead wire 58 from the electrolyte, and can be formed in the same manner as the protective layer 11 in the dye-sensitized solar cell 100 of the first embodiment. it can.

  In the dye-sensitized solar cell 110 having the above-described configuration, one second conductive film 56, two porous semiconductor electrodes 5 corresponding to the second conductive film 56, and the two porous semiconductor electrodes 5 respectively. The dye 7 supported on the surface of each constitutes one cell. The transparent electrode 3, the first conductive film 54, and the electrolyte layer 90 correspond to all cells.

  Although not shown in FIG. 5, each lead wire 9 is connected in series to a load (external load) in a state of being connected in parallel to each other, and each lead wire 58 is also connected to the load in a state of being connected in parallel to each other. Connected in series. Carriers (electrons) generated in each cell by photoelectric conversion are collected by the transparent electrode 3 and then taken out from the transparent electrode 3 in parallel by the lead wires 9.

  Since the dye-sensitized solar cell 110 described above is a kind of the dye-sensitized solar cell of the present invention, like the dye-sensitized solar cell 100 of the first embodiment described above, the dye-sensitized solar cell of the present invention. The technical effect described in the description of the solar cell is obtained.

<Dye-sensitized solar cell (third embodiment)>
FIG. 6 is a schematic view showing still another basic principle of the dye-sensitized solar cell of the present invention. In the illustrated dye-sensitized solar cell 120, the electrode substrate 30 of the second form described above is used as the first electrode substrate, and a plurality of first conductive films 64 and a plurality of second conductors are provided on one side of the transparent base material 62. A dye-sensitized solar cell electrode substrate 70 (hereinafter, referred to as “electrode substrate 70”) formed with 66 is used as the second electrode substrate.

  Since the configuration of the electrode substrate 30 has already been described, the description thereof is omitted here. Moreover, as the transparent base material 62 in the electrode substrate 70, the 1st electrically conductive film 64, and the 2nd electrically conductive film 66, respectively, the transparent base material 42 in the dye-sensitized solar cell 100 of the 1st form mentioned above, and the 1st. A conductive film similar to the conductive film 44 or the second conductive film 46 can be used. However, a plurality of first conductive films 64 are formed in parallel on one side of the transparent substrate 62, and the second conductive film 66 is formed on each of the first conductive films 64 one by one.

  The plurality of first conductive films 64 are formed, for example, by providing a large vapor-deposited film on the transparent substrate 62 and etching the vapor-deposited film into a desired shape using, for example, an etching mask formed by photolithography. A vapor deposition film of a desired material can be formed on the transparent substrate 62 by physical vapor deposition or chemical vapor deposition using a mask having a shape. The plurality of second conductive films 66 can be formed in a similar manner.

  The electrode substrate 30 and the electrode substrate 70 are disposed so that the porous semiconductor electrode 25 in the electrode substrate 30 and the second conductive film 66 in the electrode substrate 70 face each other. In between, the spacers 68 and the wirings 69 are arranged so as to correspond to one transparent electrode 23 one by one. An electrolyte layer 90 is interposed between each porous semiconductor electrode 25 and the second conductive film 66 corresponding to the porous semiconductor electrode 25.

  One end of each spacer 68 (one end in the thickness direction of the dye-sensitized solar cell 120) is joined to the region 23a (see FIG. 2) of the corresponding transparent electrode 23, and the other end (dye sensitization) of each spacer 68. The other end in the thickness direction of the sensitive solar cell 120 is bonded to the surface of the transparent base material 62 exposed from between the corresponding second conductive film 66 and the adjacent second conductive film 66.

  Each wiring 69 has one end (one end in the thickness direction of the dye-sensitized solar cell 120) connected to the region 23a (see FIG. 2) in the corresponding transparent electrode 23, and next to the corresponding second conductive film 66. The other end (one end in the thickness direction of the dye-sensitized solar cell 120) is connected to the second conductive film 66, and one surface of the corresponding spacer 68 (opposite to the surface in contact with the porous semiconductor electrode) Side surface).

  Although not shown, in the dye-sensitized solar cell 120, the periphery of the electrode substrates 30 and 70 is sealed with a sealant in order to prevent the electrolyte forming the electrolyte layer 90 from leaking out. Sealed.

  Each spacer 68 described above can be formed, for example, in the same manner as the spacer 48 (see FIG. 4) in the dye-sensitized solar cell 100 of the first embodiment described above. Each wiring 69 is formed of a conductive material having corrosion resistance to the electrolyte. Similar to the spacer 48 described above, the spacer 68 can also serve as a sealant.

  Since the electrolyte layer 90 can be formed by the same method using the same material as the electrolyte layer 90 in the dye-sensitized solar cell 100 of the first embodiment described above, the reference numerals used in FIG. 4 are used here. The same reference numerals as those in FIG.

  In the dye-sensitized solar cell 120 having the above-described configuration, one transparent electrode 23, the porous semiconductor electrode 25 corresponding to the transparent electrode 23, the dye 27, the electrolyte layer 90, the second conductive film 66, and the first The conductive film 64 constitutes one cell. Adjacent cells are electrically connected in series by wiring 69.

  Although not shown in FIG. 6, the transparent electrode 23 in one cell located at the end of the serial connection among the cells electrically connected in series is in series with the load (external load). This load is connected in series to the first conductive film 64 in one cell located at the end of the series connection among the cells electrically connected in series. Carriers (electrons) generated in each cell by photoelectric conversion are electrically extracted from each cell in series.

  Since the dye-sensitized solar cell 120 described above is one of the dye-sensitized solar cells of the present invention described above, the technical description described in the description of the dye-sensitized solar cell of the present invention is provided. There is an effect.

<Dye-sensitized solar cell (fourth embodiment)>
FIG. 7 is a schematic view showing still another basic principle of the dye-sensitized solar cell of the present invention. In the illustrated dye-sensitized solar cell 130, (1) a dye-sensitized solar cell electrode substrate 80 (hereinafter referred to as "electrode substrate 80") is used as the second electrode substrate; 2) It differs greatly from the dye-sensitized solar cell 120 of the third embodiment described above in that the wiring 69 has a structure sandwiched by two spacers 68a and 68b. Since the other configuration is the same as the configuration of the dye-sensitized solar cell 120, the description of the common configuration is omitted here.

  In the electrode substrate 80, as shown in the figure, a plurality of first conductive films 74 are formed on one surface of the transparent base material 72, and each one of the first conductive films 74 is separated from the first conductive film 74. A small second conductive film 76 is formed. As the transparent base material 72, the first conductive film 74, and the second conductive film 76, the transparent base material 62, the first conductive film 64, or the first conductive film in the dye-sensitized solar cell 120 of the third embodiment described above, respectively. The same material as the two conductive films 66 can be used.

  Each spacer 68a has one end (one end in the thickness direction of the dye-sensitized solar cell 130) joined to the region 23a (see FIG. 2) in the corresponding transparent electrode 23, and from between adjacent first conductive films 74. The other end (the other end in the thickness direction of the dye-sensitized solar cell 130) is joined to the exposed surface of the transparent base material 72, and corresponds to one porous semiconductor electrode 25 one by one. And is arranged.

  Each wiring 69 is formed on the surface opposite to the surface in contact with the porous semiconductor electrode 25 in the corresponding spacer 68a. One end of each wiring 69 (one end in the thickness direction of the dye-sensitized solar cell 130) is connected to the region 23a (see FIG. 2) in the corresponding transparent electrode 23, and the other end (the dye-sensitized solar cell 130). Is connected to the first conductive film 74 adjacent to the corresponding first conductive film 74.

  Each spacer 68b is formed on the surface of the corresponding wiring 69 opposite to the surface in contact with the spacer 68a. One end of each spacer 68b (one end in the thickness direction of the dye-sensitized solar cell 130) is on the surface of the transparent substrate 21 exposed from between the corresponding transparent electrode 23 and the adjacent transparent electrode 23. The other end (the other end in the thickness direction of the dye-sensitized solar cell 130) is joined to the first conductive film 74 adjacent to the corresponding first conductive film 74.

  In the dye-sensitized solar cell 130 having the above-described configuration, similarly to the dye-sensitized solar cell 120 of the third embodiment, one transparent electrode 23, a porous semiconductor electrode 25 corresponding to the transparent electrode 23, a dye 27, the electrolyte layer 90, the second conductive film 76, and the first conductive film 74 constitute one cell. Adjacent cells are electrically connected in series by wiring 69.

  Although not shown in FIG. 7, the transparent electrode 23 in one cell located at the end of the series connection among the cells electrically connected in series is in series with the load (external load). This load is connected in series to the first conductive film 74 in one cell located at the end of the series connection among the respective cells electrically connected in series. Carriers (electrons) generated in each cell by photoelectric conversion are electrically extracted from each cell in series.

  The dye-sensitized solar cell 130 described above is one of the dye-sensitized solar cells of the present invention, similar to the dye-sensitized solar cell 120 of the third embodiment described above, and therefore the dye-sensitized solar cell of the present invention. The technical effect described in the description of the solar cell is obtained.

  In addition, instead of the spacer 68 and the corresponding wiring 69 shown in FIG. 6, or instead of the spacer 68a and the corresponding wiring 69 and spacer 68b shown in FIG. 7, it has corrosion resistance to the electrolyte. It is also possible to use one conductive material layer.

<Example 1>
[Formation of porous semiconductor electrode]
(Preparation process)
First, a PET film (A4100 manufactured by Toyobo Co., Ltd .; total light transmittance 90.9%) having a film thickness of 125 μm was prepared as a transparent substrate. Next, this PET film was placed in a chamber of an ion plating apparatus, and a mask having a predetermined shape was placed on the surface of the PET film on the evaporation source side.

Thereafter, indium tin oxide (ITO) as a sublimation material is applied onto the PET film under the conditions of a film formation pressure of 1.5 × 10 ⁻¹ Pa, an argon gas flow rate of 18 sccm, an oxygen gas flow rate of 28 sccm, and a film formation current value of 60 A. A plurality of transparent electrodes made of an ITO film having a film thickness of 150 nm were formed in a row. The size and shape of each transparent electrode in plan view is a rectangle of 8 cm × 1 cm, and the interval between adjacent transparent electrodes is 2 mm.

(Semiconductor electrode formation process)
First, as a coating liquid for forming a porous semiconductor electrode, titanium oxide (TiO ₂ ) fine particles (F-6 manufactured by Showa Denko KK) having a primary particle diameter of 15 nm are mixed with water, polypropylene glycol monomethyl ether, isopropyl alcohol, The coating solution (paste agent) containing 20.5% by mass of the TiO ₂ fine particles was prepared by dissolving and dispersing in the mixed solution using a homogenizer. The viscosity of the paste was measured with a Brookfield viscometer (manufactured by Brookfield) under the conditions of a liquid temperature of 20 ° C. and a rotation speed of 12 rpm, and was 120 mN · s / m ² . Moreover, when the electrical conductivity of the coating liquid was measured, it was 2.6 × 10 ⁻⁶ / Ω · m.

  Next, the above paste agent was sequentially applied onto each transparent electrode by an electric field jet method, and one coating film was formed on each transparent electrode.

The coating machine used at this time was provided with a total of ten Teflon (registered trademark) discharge sections each having a discharge opening with an inner diameter of 500 μm, and these discharge sections had a discharge opening interval of 500 μm. It is arranged to be. In addition, the paste agent is in the form of a rectangular pulse with an amplitude of 7 kV and a frequency of 600 Hz on the electrodes provided around each discharge unit while applying a negative pressure of ² kg / cm ² to the paste agent container in the coating machine. While applying an AC voltage, each discharge part was moved at a speed of 35 mm / second in a state where the distance between the coated surface and the tip of the discharge part was kept at 0.75 mm, and coating was continuously performed. The design size and shape when each coating film was viewed in plan was a rectangle of 8 cm × 0.8 cm.

Thereafter, each coating film is dried at 150 ° C. for 30 minutes to fix the TiO ₂ fine particles in the coating film on the transparent electrode, and one porous semiconductor electrode having a thickness of 11.7 μm is formed on the upper surface of each transparent electrode. Formed one by one. At this time, the in-plane distribution of film thickness was good within ± 5%.

  Under the same conditions as in the preparation step described above, a total of four transparent base materials having a plurality of transparent electrodes formed on one side are prepared, and the above-mentioned semiconductor electrodes are formed on each transparent electrode in these transparent base materials. One porous semiconductor electrode was formed under the same conditions as those in the forming step. When the application area (size in plan view) of each porous semiconductor electrode formed at this time was measured with an XY length measuring machine, the average application area was 8.08 cm × 0.83 cm, which was almost as designed. Met.

<Example 2>
[Production of dye-sensitized solar cell electrode substrate]
(Preparation process and semiconductor electrode formation process)
A preparation step and a semiconductor electrode formation step are performed under the same conditions as in Example 1, and a plurality of transparent electrodes (ITO electrodes) are formed on one side, and one porous semiconductor electrode is formed on each transparent electrode. A formed transparent substrate (PET film) was obtained.

(Dye support process)
First, a ruthenium complex (manufactured by Kojima Chemical Co., Ltd.) as a sensitizing dye was dissolved in ethyl alcohol so that its concentration was 3 × 10 ⁻⁴ mol / l to prepare a dye-supporting coating solution. Next, the above-mentioned PET film formed up to the porous semiconductor electrode was immersed in this dye-supporting coating solution, and left for 1 hour under the condition of a liquid temperature of 40 ° C. Thereafter, the PET film was lifted from the dye-supporting coating solution, and the dye-supporting coating solution adhering to each porous semiconductor electrode was dried using nitrogen gas. Thereby, said pigment | dye was carry | supported by each porous semiconductor electrode, and the electrode substrate for dye-sensitized solar cells which has the structure shown in FIG. 1 was obtained.

<Example 3>
[Manufacture of dye-sensitized solar cells]
From the electrode substrate for the dye-sensitized solar cell obtained in Example 2, a length of 9 cm including a porous semiconductor electrode portion (size in plan view: 8.08 cm × 0.83 cm) carrying the dye, A substrate having a width of 1.4 cm (hereinafter referred to as “electrode substrate A”) was cut out. In the electrode substrate A, there are regions where the porous semiconductor electrodes are not formed at both ends in the width direction. The surface of the transparent electrode has a 9 cm long and 0.17 cm wide area that is exposed without being covered by the porous semiconductor electrode.

  Separately, a transparent electrode (ITO electrode) is formed on one side of a PET film having a size of 9 cm × 1.4 cm under the same conditions as in the preparation step of Example 1, and platinum is formed on the transparent electrode. A thin film (film thickness: 50 nm) was formed by a sputtering method to obtain a dye-sensitized solar cell electrode substrate (hereinafter referred to as “electrode substrate B”). In the electrode substrate B, the transparent electrode corresponds to the first conductive film, and the platinum thin film corresponds to the second conductive film.

  Next, the electrode substrate A and the electrode substrate B described above are bonded together using a 20 μm thick heat-sealing film (Surlin (trade name) manufactured by DuPont) and pressurized at 140 ° C. for 10 minutes to form an electrode. The substrate A and the electrode substrate B were bonded to each other, and when the two electrode substrates A and B were bonded together, the long sides (two in total) in plan view of the electrode substrates A and B were respectively The heat-fusible film was arranged along one of the short sides (two in total) in plan view of the electrode substrates A and B.

  After that, after filling the gap between the two electrode substrates A and B with the microsyringe from the place where the heat-fusible film is not disposed, the above-mentioned heat-fusible film is filled. The portion where no dye was disposed was sealed with an epoxy adhesive to obtain a dye-sensitized solar cell having the same configuration as that of the dye-sensitized solar cell 250 shown in FIG.

  The electrolyte layer forming coating solution is methoxyacetonitrile, 0.1 mol / l lithium iodide, 0.05 mol / l iodine, 0.3 mol / l dimethylpropylimidazolium iodide, and tertiary. A solution in which butylpyridine was dissolved at a rate of 0.5 mol / l was used.

In measuring the performance of the obtained dye-sensitized solar cell, the current-voltage characteristics when using artificial sunlight (AM1.5, irradiation intensity 100 mW / cm ² ) as a light source are shown as a source measure unit (Keutley Model 2400). Determined by As a result, the conversion efficiency as battery characteristics was 5.28%, the short-circuit current density was 12.0 mA / cm ² , the open-circuit voltage was 0.71 V, and the fill factor was 0.62.

It is the schematic which shows the basic cross-section of the electrode substrate for dye-sensitized solar cells of this invention. It is sectional drawing which shows roughly an example of the dye-sensitized solar cell in which the patterning layer was provided between the transparent electrode and the porous semiconductor electrode. It is the schematic which shows the other basic cross-section of the electrode substrate for dye-sensitized solar cells of this invention. It is the schematic which shows the basic cross-section of the dye-sensitized solar cell of this invention. It is the schematic which shows the other basic cross-section of the dye-sensitized solar cell of this invention. It is the schematic which shows the other basic cross-section of the dye-sensitized solar cell of this invention. It is the schematic which shows the other basic cross-section of the dye-sensitized solar cell of this invention. It is the schematic which shows the cross-section of the conventional dye-sensitized solar cell.

Explanation of symbols

1,21 Transparent base material 3, 23 Transparent electrode 5, 25 Porous semiconductor electrode 5a, 25a Semiconductor fine particle 7, 27 Dye 13 Patterning layer 20, 30 Dye-sensitized solar cell electrode substrate (first electrode substrate)
50, 60, 70, 80 Dye-sensitized solar cell electrode substrate (second electrode substrate)
90 Electrolyte layer 100, 110, 120, 130 Dye-sensitized solar cell

Claims (7)

A coating solution containing a large number of semiconductor fine particles is applied to an object to be coated by an electric field jet method, which is a method of discharging a coating solution by applying a voltage to an electrode provided at or near the coating solution discharge port. A first step of forming a coating film;
A second step of fixing the semiconductor fine particles in the coating film to the object to be coated;
A method for forming a porous semiconductor electrode, comprising: Preparing a transparent substrate with a transparent electrode formed on one side; and
A semiconductor electrode forming step of forming a porous semiconductor electrode by the method according to claim 1 using a large number of semiconductor fine particles on the transparent electrode;
A dye carrying step of carrying a dye on the surface of the semiconductor fine particles forming the porous semiconductor electrode;
The manufacturing method of the electrode substrate for dye-sensitized solar cells characterized by including this.   A transparent substrate having one transparent electrode formed on one side is prepared in the preparing step, and a plurality of porous semiconductor electrodes are formed on the one transparent electrode in the semiconductor electrode forming step. The manufacturing method of the electrode substrate for dye-sensitized solar cells of Claim 2.   Preparing a transparent substrate having a plurality of transparent electrodes formed on one side in the preparation step, and forming one porous semiconductor electrode on each of the plurality of transparent electrodes in the semiconductor electrode formation step; The manufacturing method of the electrode substrate for dye-sensitized solar cells of Claim 2 characterized by the above-mentioned.   5. The transparent substrate in which a transparent electrode is formed on one side and a patterning layer whose surface wettability is changed by light irradiation is formed on the transparent electrode in the preparation step. The manufacturing method of the dye-sensitized solar cell board | substrate of any one of these.   A dye-sensitized solar cell electrode substrate manufactured by the method according to any one of claims 2 to 5. A first electrode substrate having a semiconductor electrode having a dye supported on the surface; a second electrode substrate disposed opposite to the first electrode substrate; the first electrode substrate and the second electrode; A dye-sensitized solar cell comprising an electrolyte layer interposed between the substrate and
The dye-sensitized solar cell, wherein the first electrode substrate is the electrode substrate for a dye-sensitized solar cell according to claim 6.

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