JP4953615B2 - Method for producing dye-sensitized solar cell semiconductor electrode and method for producing dye-sensitized solar cell - Google Patents

Description

The present invention relates to a manufacturing method and a manufacturing method of the dye-sensitized solar cell of the dye-sensitized solar cell semiconductor electrodes, particularly high photoelectric conversion light ratio, semiconductor electrodes for excellent dye-sensitized solar cell productivity It is related with the manufacturing method .

  In recent years, solar cells that directly convert sunlight into electrical energy have attracted attention and are being developed from the viewpoints of energy saving, effective use of resources, prevention of environmental pollution, and the like. Currently, solar cells that are generally used are pn junction solar cells that use crystalline silicon or amorphous silicon as a photoelectric conversion material. However, in a pn junction solar cell, a large amount of energy is required for producing a photoelectric conversion material such as crystalline silicon, and thus the above-mentioned purpose such as energy saving cannot be achieved. Moreover, since enormous energy is required for manufacture of a photoelectric conversion material, as a result, a pn junction type solar cell must be expensive.

  On the other hand, as a photoelectric conversion material, a dye-sensitized solar cell using an oxide semiconductor sensitized with an organic dye without using silicon or the like is known. Since the dye-sensitized solar cell can use a mass-produced and relatively inexpensive oxide semiconductor and organic dye, in terms of raw materials, compared to a pn junction solar cell using silicon or the like. There are many advantages.

  As the dye-sensitized solar cell, for example, rose bengal is adsorbed as an organic dye on the surface of a disk-shaped sintered body formed by compression molding zinc oxide powder and sintering at 1300 ° C. for 1 hour. A dye-sensitized solar cell using an oxide semiconductor electrode has been proposed (see Non-Patent Document 1). However, the solar cell has a very low current value of about 25 μA at an electromotive voltage of 0.2 V in the current / voltage curve, and is far from practical use.

  On the other hand, those having a spectral sensitizing dye layer such as a transition metal complex on the oxide semiconductor surface (see Patent Document 1), and a spectral sensitizing dye such as a transition metal complex on the surface of the titanium oxide semiconductor layer doped with metal ions. A layer having a layer (see Patent Document 2), a dye-sensitized solar cell using an oxide semiconductor film made of a sintered product of oxide semiconductor fine particle aggregates (see Patent Document 3), and the like are known. Conversion efficiency is gradually improved. However, these dye-sensitized solar cells require a long time for the production of the semiconductor layer, and there is still room for improvement in photoelectric conversion efficiency.

Nature, 268 (1976), p. 402 Japanese Patent Laid-Open No. 1-220380 Japanese National Patent Publication No. 5-504023 Japanese Patent Laid-Open No. 10-92477

Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and to dispose a semiconductor layer on a transparent electrode by a novel method that has not been tried before, and for a dye-sensitized solar cell with high photoelectric conversion efficiency. It is to provide a method for manufacturing a dye-sensitized solar cell having a manufacturing method and a semiconductor electrode for said color Motozo sensitized solar cell of the semiconductor electrode.

  As a result of diligent study to achieve the above object, the present inventor can rapidly form a semiconductor layer by coating the semiconductor layer on the transparent electrode by gas flow sputtering, and dye sensitization with high photoelectric conversion efficiency. The inventors have found that a semiconductor electrode for a solar cell can be obtained, and have completed the present invention.

That is, the manufacturing method of the dye-sensitized solar cell semiconductor electrode of the present invention, arranged a semiconductor layer on the transparent electrode by a gas flow sputtering, characterized in that Ru is adsorbed an organic dye to the semiconductor layer .

In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, it is preferable that one or more metals or metal compounds are simultaneously sputtered to dispose the semiconductor layer on the transparent electrode. Here, in the method for producing a semiconductor electrode for a dye-sensitized solar cell according to the present invention, when sputtering the plurality of metals or metal compounds, a plurality of cathodes are simultaneously discharged, and the semiconductor is formed on the transparent electrode. disposing the layer, and, upon sputtering the plurality of metal or metal compound, attaching a plurality of targets to the cathode of one, the on the transparent electrode by sputtering a plurality of metal simultaneously in the cathode during discharge More preferably, a semiconductor layer is provided. When sputtering the plurality of metals or metal compounds, a plurality of targets are attached to one cathode, and after discharge, a plurality of metals are simultaneously sputtered on the cathode during discharge to dispose the semiconductor layer on the transparent electrode. It is also preferable to remove at least one metal or metal compound in the semiconductor layer with an acid and / or an alkali. Further, when attaching the plurality of targets to one cathode, when there are two targets, the targets are arranged to face each other, and when there are three or more targets, the targets are arranged in a polyhedral shape. Is preferred.

In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, the metal may be Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Ru, Rh, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Tl, Pb, Bi, Ce, Pr, Nd, Sm and Eu are preferred.

In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, a noble metal may be used as the metal. Here, it is preferable that the noble metal is at least one selected from the group consisting of Ag, Pt and Au.

In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, the metal compound is preferably a metal oxide. Here, the metal oxide is at least one selected from the group consisting of TiO _x , CoO _x , NiO _x , CuO _x , ZnO _x , TaO _x and WO _x , and the value of x is determined during sputtering. It is preferable to control by the oxygen flow rate.

In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, the metal compound is also preferably a metal nitride. Here, the metal nitride is at least one selected from the group consisting of TiN _x , CoN _x , NiN _x , CuN _x , ZnN _x , TaN _x and WN _x , and the value of x is determined during sputtering. It is preferable to control by the nitrogen flow rate.

In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, the metal compound is preferably a metal oxynitride. Here, the metal oxynitride is selected from the group consisting of TiO _x N _y , CoO _x N _y , NiO _x N _y , CuO _x N _y , ZnO _x N _y , TaO _x N _y, and WO _x N _y. It is preferable to control the values of x and y by the oxygen flow rate and the nitrogen flow rate during sputtering.

In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, it is preferable that the use efficiency of the target material used in the gas flow sputtering is 80% or more.

In another preferred embodiment of the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, the transparent electrode comprises a transparent substrate and a transparent conductive thin film disposed on the transparent substrate. . Here, the transparent substrate is preferably glass, polyethylene terephthalate (PET), polycarbonate (PC), or polymethyl methacrylate (PMMA). Moreover, it is preferable that the said transparent conductive thin film consists of at least 1 type of metal oxide selected from the group which consists of ITO, FTO, ATO, and AZO. Furthermore, it is preferable that the transparent electrode further includes a mesh-like metal auxiliary electrode on the transparent conductive thin film.

In another preferred embodiment of the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, the transparent electrode comprises a transparent base material, a transparent conductive thin film, the transparent base material, and the transparent conductive thin film. And a mesh-like metal auxiliary electrode disposed between the two.

In another preferred embodiment of the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, the transparent electrode comprises a transparent substrate, a metal oxide thin film, and a multilayer film of a metal thin film.

Further, the method of manufacturing a dye-sensitized solar cell of the present invention includes a semiconductor electrode for dye-sensitized solar cell, and the counter electrode, the manufacturing method of the dye-sensitized solar cell comprising an electrolyte, the dye A semiconductor electrode for a sensitive solar cell is produced by the method described above .

According to the present invention, a semiconductor layer for a dye-sensitized solar cell having a high photoelectric conversion efficiency and high productivity, in which a semiconductor layer is disposed on a transparent electrode by a gas flow sputtering method and an organic dye is adsorbed to the semiconductor layer . it is possible to provide a manufacturing method, and manufacturing method of the dye-sensitized solar cell having a semiconductor electrode for said color Motozo sensitized solar cell.

The present invention is described in detail below. Method for manufacturing a dye-sensitized solar cell semiconductor electrode of the present invention, arranged a semiconductor layer on the transparent electrode by a gas flow sputtering, Ru adsorbed an organic dye to the semiconductor layer. By using the gas flow sputtering method, a semiconductor layer can be rapidly formed on the transparent electrode, so that a dye-sensitized solar cell semiconductor electrode can be manufactured with high productivity. In addition, the dye-sensitized solar cell incorporating the obtained semiconductor electrode has a film formation rate of 10 to 1000 times in the case of a metal compound, particularly a titanium oxide thin film, compared with a normal sputtering method (planar type magnetron sputtering). Can be formed. As a high-speed film formation method, the vacuum deposition method is popular, but the adhesion to the substrate is poor. On the other hand, the film formed by the gas flow sputtering method is rich in the adhesion characteristic of the sputtering method. Yes. In addition, since the film after film formation is milky white because of high-speed film formation, it is a film including a void layer, so the surface area is large and the conversion efficiency is higher than that of the normal magnetron sputtering method. ing.

  The gas flow sputtering method used for forming a semiconductor layer on a transparent electrode in the present invention is a method in which sputtering is performed under a relatively high pressure, and sputtered particles are transported to a carrier by a forced gas flow and deposited. FIG. 1 shows a schematic diagram of a gas flow sputtering apparatus suitable for carrying out the present invention. In the gas flow sputtering apparatus of the illustrated example, a rare gas such as argon is introduced from the sputtering gas inlet 1, and plasma P generated by discharge between the anode 3 and the cathode 4 connected to the DC power source 2 is supplied to the cathode 4. The sputtered particles that collide with the target 5 and are blown off are transported to the transparent electrode 6 and deposited by forced flow of a rare gas such as argon. In the illustrated example, the transparent electrode 6 is supported by a holder 7, and a reactive gas inlet 8 is disposed in the vicinity of the transparent electrode 6 so that reactive sputtering can be performed. . Further, the sputter gas introduction port 1 has a structure in which the sputter gas introduced from the upper part and the lower part flows from the side opening as shown in the side view of FIG.

  The semiconductor layer is usually made of a metal and / or a metal compound. In the present invention, the semiconductor layer is formed by sputtering at least one of a metal and a metal compound. Here, the metal and metal compound to be sputtered may be a single kind or a mixture of two or more kinds. Moreover, when a semiconductor layer is formed on a transparent electrode by sputtering a plurality of metals or metal compounds, it is preferable to simultaneously sputter a plurality of metals or metal compounds.

  When sputtering the plurality of metals or metal compounds, it is preferable that the plurality of cathodes 4 are simultaneously discharged to dispose the semiconductor layer on the transparent electrode. Here, by disposing a target 5 made of a different metal on each cathode 4, it is possible to form a semiconductor layer by simultaneously sputtering a plurality of metals or metal compounds.

  When sputtering the plurality of metals or metal compounds, a plurality of targets 5 are attached to one cathode 4, and a plurality of metals are simultaneously sputtered at the cathode 4 during discharge to dispose a semiconductor layer on the transparent electrode. It is also preferable to do. Here, after a plurality of metals are simultaneously sputtered at the cathode 4 to dispose a semiconductor layer on the transparent electrode, at least one of the metal or metal compound in the semiconductor layer is removed with an acid and / or alkali. Also good. Here, the acid and alkali used for removing the metal or metal compound are appropriately selected according to the type of the metal or metal compound to be removed and the metal or metal compound to be left. For example, the acid is hydrochloric acid. , Sulfuric acid, nitric acid, phosphoric acid, acetic acid, hydrofluoric acid, chromic acid, hydrogen peroxide, perchloric acid, chloric acid, chlorous acid, hypochlorous acid, citric acid, oxalic acid, hydrogen bromide, etc. These can be used as an aqueous solution alone or with a mixed acid obtained by mixing them. Further, depending on the metal to be dissolved, a mixed aqueous solution of a mixed acid, a metal chloride such as ferric chloride, and a metal sulfide can be used. On the other hand, as the alkaline aqueous solution, an aqueous solution such as sodium hydroxide or potassium hydroxide, aqueous ammonia, or the like can be used. In addition, the density | concentration and composition of acid aqueous solution and alkali aqueous solution can be suitably selected according to the kind of metal to melt | dissolve.

  Further, when attaching the plurality of targets 5 to one cathode 4, when there are two targets 5, the targets 5 are arranged facing each other, and when there are three or more targets 5, the targets 5 are in a polyhedral shape. For example, when there are three targets 5, it is preferable to arrange the targets 5 in a triangular shape, and when there are four targets 5, the targets 5 are preferably arranged in a quadrangular shape.

The metals to be sputtered are Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr. , Nb, Mo, Ru, Rh, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Tl, Pb, Bi, Ce, Pr, Nd, Sm And Eu are preferably selected from the group consisting of Eu, and the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention may use these metals alone or in combination of two or more of these metals. It may be used.

Moreover, a noble metal may be used as the metal to be sputtered, and examples of the noble metal include Ag, Pt, and Au. In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention, one or more of these noble metals can be used.

  Examples of the metal compound sputtered in the present invention include metal oxides, metal nitrides, and metal oxynitrides. In addition, when arrange | positioning these metal compounds on a transparent electrode, it is preferable to use the said metal for the target 5, and introduce | transduce reactive gas from the inlet 8, and perform reactive sputtering.

Examples of the metal oxide include TiO _x , CoO _x , NiO _x , CuO _x , ZnO _x , TaO _x and WO _{x. The} method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention includes: These metal oxides may be used alone, or two or more of these metal oxides may be used. Here, according to the reactive sputtering, the value of x in each chemical formula can be controlled to a desired value by adjusting the flow rate of oxygen introduced from the introduction port 8 at the time of sputtering.

Examples of the metal nitride include TiN _x , CoN _x , NiN _x , CuN _x , ZnN _x , TaN _x, WN _{x, and the} like, and the method for producing a dye-sensitized solar cell semiconductor electrode according to the present invention. May use these metal nitrides individually by 1 type, and may use 2 or more types of these metal nitrides. Here, according to the reactive sputtering, the value of x in each chemical formula can be controlled to a desired value by adjusting the flow rate of nitrogen introduced from the introduction port 8 at the time of sputtering.

Furthermore, as the metal oxide _{nitride, TiO x N y, CoO x} N y, NiO x N y, CuO x N y, ZnO x N y, etc. TaO _x N _y and WO _x N _y can be cited, the In the method for producing a semiconductor electrode for a dye-sensitized solar cell of the invention, these metal oxynitrides may be used alone or in combination of two or more of these metal oxynitrides. Here, according to the reactive sputtering, the values of x and y in each chemical formula can be controlled to desired values by adjusting the flow rates of oxygen and nitrogen introduced from the inlet 8 during sputtering. It becomes possible.

  In a preferred embodiment of the present invention, the use efficiency of the target material used in the gas flow sputtering is 80% or more, and in the present invention, the gas flow sputtering method is used for disposing the semiconductor layer on the transparent electrode. The use efficiency of the target material is high.

The thickness of the semiconductor layer in the method for producing a semiconductor electrode for a dye-sensitized solar cell of the present invention is preferably in the range of 0.01 μm to 100 μm. If the thickness of the semiconductor layer is less than 0.01 μm, the amount of dye adsorbed is small, and sunlight cannot be absorbed effectively, so the power generation efficiency does not increase. On the other hand, when the thickness exceeds 100 μm, visible light cannot be taken in effectively, and since the film becomes brittle, its shape cannot be maintained, so that the battery performance is not improved.

  As the organic dye adsorbed on the semiconductor layer, conventionally known ones can be used, and those capable of absorbing sunlight over a wide wavelength range are preferable. Examples of the organic dye include Ru complexes such as bipyridyl Ru complex, terpyridyl Ru complex, phenanthroline Ru complex, and bicinchoninic acid Ru complex, chlorophyll, rhodamine, eosin, phloxine, fluorescein, erythrosine, uranin, rose bengal and the like. These organic dyes may be used alone or in combination of two or more. In order to adsorb the organic dye to the semiconductor layer, the transparent electrode on which the semiconductor layer is formed may be immersed in a solution containing the organic dye. Here, the solvent for dissolving the organic dye is not particularly limited, and alcohol such as ethanol can be used.

In this invention , it is preferable that the transparent electrode which comprises the semiconductor electrode for dye-sensitized solar cells consists of a transparent base material and the transparent conductive thin film arrange | positioned on this transparent base material. Here, examples of the material of the transparent substrate include organic substances such as polyethylene terephthalate (PET), polycarbonate (PC), and polymethyl methacrylate (PMMA) in addition to inorganic substances such as glass. On the other hand, as the material of the transparent conductive thin film, metal oxides such as ITO (indium-tin oxide), FTO (fluorine-doped tin oxide), ATO (antimony-containing tin oxide), and AZO (aluminum-doped zinc oxide) are available. Can be mentioned. Moreover, it is preferable that the said transparent electrode is further equipped with a mesh-shaped metal auxiliary electrode on the said transparent conductive thin film from a viewpoint of resistance reduction. Here, examples of the material for the metal auxiliary electrode include single materials such as silver, copper, aluminum, titanium, chromium, zinc, gold, and platinum, and alloy materials containing them as main components.

  From the viewpoint of reducing resistance, the transparent electrode includes a transparent base material, a conductive thin film, and a mesh-like metal auxiliary electrode disposed between the transparent base material and the transparent conductive thin film. It may be a structure composed of a transparent substrate, a metal oxide thin film, and a multilayer film of metal thin films. Here, the transparent substrate, the conductive thin film, and the metal auxiliary electrode are as described above, and the material of the metal oxide thin film in the metal oxide thin film and the multilayer film of the metal thin film includes silicon oxide, titanium oxide, Examples include zinc oxide, aluminum oxide, indium oxide, ITO, tin oxide, zirconia oxide, niobium oxide, etc. The material of the metal thin film is gold, silver, platinum and alloys containing them, copper, aluminum, titanium, chromium, Examples include zinc and alloys containing them.

The method of manufacturing a dye-sensitized solar cell of the present invention includes a semiconductor electrode for dye-sensitized solar cell, and the counter electrode, the manufacturing method of the dye-sensitized solar cell comprising an electrolyte, the dye-sensitized A semiconductor electrode for a solar cell is manufactured by the method described above . In the present invention , the counter electrode used in the dye-sensitized solar cell is a catalyst in which a conductive thin film is disposed on a transparent substrate, and the reduction reaction of ions in the redox electrolyte is promoted on the conductive thin film. Those in which are arranged are preferable. Here, as the conductive thin film, ITO, SnO ₂ or the like is preferable. Examples of the material for the transparent substrate include glass and transparent plastic. Furthermore, examples of the catalyst that promotes the reduction reaction of ions in the redox electrolyte include Pt, Ru, Rh, Pd, etc. Among these, Pt is preferable. These catalysts can be formed on the conductive thin film by sputtering or the like. Further, after depositing the catalyst by sputtering, a chloroplatinic acid aqueous solution or the like may be further applied, followed by firing reduction.

In the present invention , the electrolyte used for the dye-sensitized solar cell is not particularly limited, and usually contains a redox electrolyte and may further contain an organic solvent. Examples of the redox electrolyte include I ⁻ / I ₃ ⁻ system, Br ⁻ / Br ₃ ⁻ system, and quinone / hydroquinone system. These redox electrolyte can be obtained by known methods, for example, I ^- / I ₃ ^- system redox electrolyte, an ammonium salt or imidazolium salt or LiI iodine, NaI, KI, metal iodide such as CaI ₂ the can be prepared by mixing alone or iodine, Br ^- / Br ₃ ^- system redox electrolyte, a mixed bromine ammonium or imidazolium salt or LiBr, NaBr, KBr, metal bromides, such as CaBr ₂ alone or bromine Can be prepared. In the present invention , the concentration of the redox electrolyte in the dye-sensitized solar cell electrolyte is preferably in the range of 0.1 to 2 mol / L (M).

  Examples of the organic solvent that can be used for the electrolyte include carbonates such as propylene carbonate, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate, esters such as methyl acetate and methyl propionate, tetrahydrofuran, and 1,3. -Ethers such as 1-dioxolane, 1,2-dimethoxyethane, alcohols such as methanol, ethanol, ethylene glycol, propylene glycol and glycerin, lactones such as γ-butyrolactone, amides such as dimethylformamide, 3-methyl-2 -Oxazolidinones such as oxazolidinone, phosphate esters such as trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, tripropyl phosphate, tributyl phosphate, aceto Nitriles such as nitrile and methoxyacetonitrile can be mentioned. These organic solvents may be used alone or in combination of two or more.

Next, the dye-sensitized solar cell produced by the method of the present invention will be described in detail with reference to FIG. FIG. 3 is a partial cross-sectional view of one embodiment of a dye-sensitized solar cell produced by the method of the present invention. In the illustrated dye-sensitized solar cell, transparent conductive thin films 12A and 12B are disposed on transparent substrates 11A and 11B, respectively. Further, a catalyst 13 that promotes a reduction reaction of ions in the redox electrolyte is disposed on the transparent conductive thin film 12A. On the other hand, a semiconductor layer 14 is disposed on the transparent conductive thin film 12B, and an organic dye is adsorbed on the semiconductor layer 14. Further, the counter electrode 15 composed of the transparent base material 11A, the transparent conductive thin film 12A and the catalyst 13 and the semiconductor electrode 16 composed of the transparent base material 11B, the transparent conductive thin film 12B and the semiconductor layer 14 are opposed to each other through the electrolyte 17. The catalyst 13 of the counter electrode 15 and the semiconductor layer 14 of the semiconductor electrode 16 are in contact with the electrolyte 17. Here, in the dye-sensitized solar cell manufactured by the method of the present invention, the photoelectric conversion efficiency can be greatly improved by forming the semiconductor layer 14 by the gas flow sputtering described above.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[Semiconductor layer formation]
(Examples 1-6)
Using the gas flow sputtering apparatus shown in FIG. 1, a Ti target is set as a target, glass coated with fluorine-doped tin oxide (FTO) is set as a substrate in a vacuum chamber, and a roughing pump (rotary pump + mechanical booster pump) ) To 1 × 10 ⁻¹ Pa, and a TiO ₂ film was formed. The sputtering conditions at this time are as follows. In addition, Table 1 and Table 2 show the film forming conditions of each example.
<DC gas flow sputtering conditions>
・ Target dimensions: 80mm × 160mm × 5mmt
・ Cathode shape: Parallel plate (two above targets are arranged in parallel, distance 30mm)
・ Sputtering pressure: 0.01 Torr to 1 Torr
・ Sputtering power: 0 to 5kW
Ar gas flow rate: 1-10SLM
・ O ₂ gas flow rate: 0 ~ 250sccm
-Substrate temperature: No substrate heating or cooling-Substrate position: Fixed (distance between cathode end and substrate: 50 mm)

(Comparative Examples 1-2)
A 4-inch circular metal titanium target was attached to a magnetron sputtering apparatus, the pressure inside the apparatus was set to 5 mTorr, and a titanium oxide film was formed on the FTO-coated glass (transparent electrode). Deposition conditions are shown in Tables 1 and 2.

After forming a TiO ₂ film as described above, firing was performed at 450 ° C. for 60 minutes in a high-temperature firing furnace. Next, a metal oxide semiconductor electrode and a solar cell were produced as follows using both the unfired substrate with the TiO ₂ thin film and the fired substrate with the TiO ₂ thin film.

[Dye adsorption]
As an organic dye solution, 3 × 10 ⁻⁴ mol / L of cis-di (thiocyanato) -bis (2,2′-bipyridyl-4-dicarboxylate-4′-tetrabutylammonium carboxylate) ruthenium (II) — An ethanol solution was prepared, and the substrate on which the TiO ₂ thin film was formed was immersed in this solution at room temperature for 18 hours to adsorb the dye, thereby obtaining a metal oxide semiconductor electrode.

[Production of solar cells]
The metal oxide semiconductor electrode was used as one electrode, and a transparent conductive glass plate coated with platinum doped with fluorine as a counter electrode and further carrying platinum thereon was used. An electrolyte was placed between the two electrodes, the side surfaces were sealed with resin, and then lead wires were attached to produce a dye-sensitized solar cell. As an electrolyte, acetonitrile solvent, lithium iodide 0.1 mol / L, 1,2-dimethyl-3-propylimidazolium iodide 0.3 mol / L, iodine 0.05 mol / L and t-butylpyridine 0.5 mol / L A solution dissolved so as to be used was used. Next, the obtained solar cell was irradiated with light having an intensity of 100 W / cm ² with a solar simulator to evaluate the battery performance. The results are shown in Table 3.

  As is clear from Table 3, the film formation rate of the example is about two to three orders of magnitude faster than the film formation rate of the comparative example, and the dye-sensitized solar cell of the example is converted with the same film thickness. It was found that the efficiency was significantly increased as compared with the comparative example regardless of whether or not baking was performed after film formation. Also in the examples, it was found that the conversion efficiency is higher when the film forming speed is faster even with the same film thickness.

(Examples 7 to 12)
The base material used in Examples 1 to 6 was changed from FTO glass to an ITO film (resistance value: 10Ω / □, base material: PET, conductive thin film: ITO), and the same film formation was attempted, and the conversion efficiency was measured. . The film formation conditions are shown in Table 4, and the conversion efficiency results are shown in Table 5. In addition, since it was film-forming on a film, the baking process after film-forming was not performed.

(Comparative Examples 3-4)
The base material used in Comparative Examples 1 and 2 was changed from FTO glass to the ITO film, and the same film formation was attempted, and the conversion efficiency was measured. The film formation conditions are shown in Table 4, and the conversion efficiency results are shown in Table 5. In addition, since it was film-forming on a film, the baking process after film-forming was not performed.

  Also when it formed into a film on an ITO film like Table 5, it has confirmed that the conversion efficiency of the dye-sensitized solar cell of an Example raised significantly compared with a comparative example.

The schematic of an example of the gas flow sputtering apparatus suitable for the manufacturing method of the semiconductor electrode for dye-sensitized solar cells of this invention is shown. FIG. 2 is a side view of a sputtering gas introduction port of the gas flow sputtering apparatus of FIG. 1. It is a fragmentary sectional view of one embodiment of a dye-sensitized solar cell manufactured by the method of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sputter gas introduction port 2 DC power source 3 Anode 4 Cathode 5 Target 6 Transparent electrode 7 Holder 8 Reactive gas introduction port P Plasma 11A, 11B Transparent base material 12A, 12B Transparent conductive thin film 13 Catalyst 14 Semiconductor layer 15 Counter electrode 16 Semiconductor electrode 17 Electrolyte

Claims (23)

It disposed a semiconductor layer on the transparent electrode by a gas flow sputtering method for manufacturing a dye-sensitized solar cell for a semiconductor electrode, characterized in Rukoto to adsorb the organic dye to the semiconductor layer. The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 1, wherein one or more metals or metal compounds are simultaneously sputtered to dispose the semiconductor layer on the transparent electrode. 3. The dye-sensitized solar according to claim 2, wherein when the plurality of metals or metal compounds are sputtered, the semiconductor layer is disposed on the transparent electrode by simultaneously discharging using a plurality of cathodes. A method for producing a semiconductor electrode for a battery. When sputtering the plurality of metals or metal compounds, a plurality of targets are attached to one cathode, and a plurality of metals are simultaneously sputtered on the cathode during discharge to dispose the semiconductor layer on the transparent electrode. The manufacturing method of the semiconductor electrode for dye-sensitized solar cells of Claim 2. When sputtering the plurality of metals or metal compounds, a plurality of targets are attached to one cathode, and a plurality of metals are simultaneously sputtered on the cathode during discharge to dispose the semiconductor layer on the transparent electrode. The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 4, wherein at least one of a metal or a metal compound in the semiconductor layer is removed with an acid and / or an alkali. The metal is Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, From Mo, Ru, Rh, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Re, Os, Ir, Tl, Pb, Bi, Ce, Pr, Nd, Sm and Eu The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 2, wherein the method is at least one selected from the group consisting of : The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 2, wherein the metal is a noble metal. The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 7, wherein the noble metal is at least one selected from the group consisting of Ag, Pt, and Au. The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 2, wherein the metal compound is a metal oxide. The metal oxide is at least one selected from the group consisting of TiO _x , CoO _x , NiO _x , CuO _x , ZnO _x , TaO _x and WO _x , and the value of x is determined by the oxygen flow rate during sputtering. The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 9, wherein the method is controlled . The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 2, wherein the metal compound is a metal nitride. The metal nitride is at least one selected from the group consisting of TiN _x , CoN _x , NiN _x , CuN _x , ZnN _x , TaN _x and WN _x , and the value of x is determined by the nitrogen flow rate during sputtering. It controlled , The manufacturing method of the semiconductor electrode for dye-sensitized solar cells of Claim 11 characterized by the above-mentioned. The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 2, wherein the metal compound is a metal oxynitride. The metal oxide _{nitride, TiO x N y, CoO x} N y, NiO x N y, CuO x N y, ZnO x N y, at least one selected from the group consisting of TaO _x N _y and WO _x N _y The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 13, wherein the method is a seed, and the values of x and y are controlled by an oxygen flow rate and a nitrogen flow rate during sputtering. The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 1, wherein the use efficiency of the target material used in the gas flow sputtering is 80% or more. When attaching the plurality of targets to one cathode, when there are two targets, the targets are arranged facing each other, and when there are three or more targets, the targets are arranged in a polyhedral shape. The manufacturing method of the semiconductor electrode for dye-sensitized solar cells of Claim 4 or 5. The said transparent electrode consists of a transparent base material and the transparent conductive thin film arrange | positioned on this transparent base material, For dye-sensitized solar cells in any one of Claims 1-16 characterized by the above-mentioned. A method for manufacturing a semiconductor electrode. The said transparent base material is glass, a polyethylene terephthalate (PET), a polycarbonate (PC), or a polymethylmethacrylate (PMMA), The manufacturing method of the semiconductor electrode for dye-sensitized solar cells of Claim 17 characterized by the above-mentioned. . 18. The dye-sensitized solar cell semiconductor electrode according to claim 17, wherein the transparent conductive thin film is made of at least one metal oxide selected from the group consisting of ITO, FTO, ATO, and AZO . Manufacturing method . The method for producing a semiconductor electrode for a dye-sensitized solar cell according to claim 17, wherein the transparent electrode further comprises a mesh-like metal auxiliary electrode on the transparent conductive thin film. The transparent electrode comprises a transparent base material, a transparent conductive thin film, and a mesh-like metal auxiliary electrode disposed between the transparent base material and the transparent conductive thin film. The manufacturing method of the semiconductor electrode for dye-sensitized solar cells in any one of 1-16. The said transparent electrode consists of a transparent base material, and the multilayer film of a metal oxide thin film and a metal thin film, The manufacture of the semiconductor electrode for dye-sensitized solar cells in any one of Claims 1-16 characterized by the above-mentioned. Way . In a method for producing a dye-sensitized solar cell comprising a semiconductor electrode for a dye-sensitized solar cell, a counter electrode, and an electrolyte ,
A method for producing a dye-sensitized solar cell, wherein the semiconductor electrode for a dye-sensitized solar cell is produced by the method according to any one of claims 1 to 22 .

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