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WO2005029571A1 - Agent de revetement de formation d'un film semi-conducteur, film semi-conducteur, convertisseur photoelectrique, et pile solaire - Google Patents

Agent de revetement de formation d'un film semi-conducteur, film semi-conducteur, convertisseur photoelectrique, et pile solaire Download PDF

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Publication number
WO2005029571A1
WO2005029571A1 PCT/JP2004/013379 JP2004013379W WO2005029571A1 WO 2005029571 A1 WO2005029571 A1 WO 2005029571A1 JP 2004013379 W JP2004013379 W JP 2004013379W WO 2005029571 A1 WO2005029571 A1 WO 2005029571A1
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Prior art keywords
semiconductor film
metal oxide
coating agent
oxide semiconductor
forming
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English (en)
Japanese (ja)
Inventor
Tingli Ma
Eiichi Abe
Xiaoming Fang
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National Institute of Advanced Industrial Science and Technology AIST
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National Institute of Advanced Industrial Science and Technology AIST
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Priority to JP2005514034A priority Critical patent/JP4631000B2/ja
Publication of WO2005029571A1 publication Critical patent/WO2005029571A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a coating agent for forming a semiconductor film, a semiconductor film, a photoelectric conversion element, and a solar cell used for forming a metal oxide semiconductor film, and in particular, to a dye-sensitized solar cell suitably used.
  • the present invention relates to a coating agent for forming a semiconductor film, a semiconductor film, a photoelectric conversion element, and a dye-sensitized solar cell.
  • a dye-sensitized solar cell composed of a photoelectrode or the like in which a Ru dye (ruthenium-biviridine complex) is adsorbed on the surface of porous titanium dioxide is disclosed in 1991 by Grezwell et al. Since then, it has attracted great attention worldwide.
  • titanium dioxide can be efficiently used mainly for only ultraviolet light among sunlight, but this dye-sensitized solar cell can absorb light in the visible light range.
  • this dye-sensitized solar cell is an inexpensive material that does not require the use of a large amount of energy for manufacturing like silicon solar cells, which have a higher theoretical limit value of photoelectric conversion efficiency than conventional silicon solar cells.
  • the band gap of ordinary anatase type or rutile type titanium dioxide is 3.2 eV or 3. OeV, respectively, and only ultraviolet light of sunlight can be used.
  • Methods such as doping metal ions such as um (V) and chromium (Cr) are used (for example, reference 2: International Publication WO 01 Z 048833 Pamphlet (2001 (July 2001) July 5) Published))).
  • a solar cell having an electrode using titanium dioxide having a small band gap is improved in photoelectric conversion efficiency as compared with the one using ordinary titanium dioxide.
  • the photoelectric conversion efficiency is very low.
  • a method using a modified porous titanium dioxide to improve the photoelectric conversion efficiency in a dye-sensitized solar cell For example, a dye-sensitized solar cell using a fluorine (F) -doped titanium dioxide titanium electrode has been proposed (for example, reference 3: Japanese Patent Laid-Open No. 2002-25637 (2002 (2002 (2002)). Year) January 25)).
  • the fluorine-doped titanium dioxide electrode has a titanium dioxide porous crystal film produced using a paste consisting of titanium dioxide, a fluorine atom donor compound, water or N, N-dimethylformamide. . And, it is reported that the photoelectric conversion efficiency of a solar cell using this electrode is improved up to 5.29%.
  • a semiconductor film formed on an electrode of a solar cell is formed by applying or printing a coating agent in which semiconductor particles are dispersed in an aqueous solution mainly in the presence of a surfactant on a substrate.
  • C is manufactured by firing at around 500 ° C.
  • the properties of the coating agent for forming a semiconductor film to be used are important in order to improve the performance of the solar cell, including the photoelectric conversion efficiency.
  • the viscosity is very important, and when the viscosity is too low, when forming a film, it may cause a buildup or a flow, making film formation difficult.
  • the viscosity is too high, a crack is generated on the surface of the formed semiconductor film, and the sensitizing dye and the electrolyte directly contact the transparent conductive substrate through the crack, resulting in a decrease in photoelectric conversion efficiency.
  • the semiconductor film may be peeled off due to a crack, which may cause a trouble such as shortening of the life of the solar cell.
  • the photoelectric conversion efficiency is 5.29%, and the improvement of the electron transportability is not sufficient yet.
  • the present invention has been made in view of the above-mentioned conventional problems, and its object is to form a metal oxide semiconductor film which improves the photoelectric conversion efficiency of a dye-sensitized solar cell.
  • An object of the present invention is to provide a coating agent for forming a semiconductor film, a semiconductor film using the same, a photoelectric conversion element, and a solar cell.
  • the inventors of the present invention conducted intensive studies to solve the above problems, and as a result, as a coating agent for forming a semiconductor film, alkylene glycol, polyalkylene glycol, alkyl ether of alkylene glycol, and alkyl of polyalkylene glycol
  • a dispersion medium containing 10% by mass or more and 100% by mass or less of at least one compound selected from the group consisting of ethers, based on 100% by mass of the total dispersion medium, is 0.1 parts by mass with respect to 100 parts by mass of the metal oxide semiconductor. It has been found that, by blending 2000 parts by mass, adjustment of the viscosity is easy and a more porous semiconductor film can be obtained.
  • the coating agent for forming a semiconductor film according to the present invention is a metal oxide semiconductor 100 material.
  • the total dispersion medium is 100% by mass of at least one compound selected from the group consisting of alkylene glycols, polyalkylene glycols, alkyl ethers of alkylene glycols, and alkyl ethers of polyalkylene glycols based on 10 parts by mass.
  • a dispersion medium containing 0.1% to 2000% by mass of a dispersion medium containing 100% by mass or less of 100% by mass, and the above metal oxide semiconductor is a metal oxide semiconductor modified to be able to respond to visible light. And is characterized. Thereby, the photoelectric conversion efficiency of the solar cell having a semiconductor film formed using the coating agent for forming a semiconductor film can be improved.
  • the metal oxide semiconductor is characterized by having an oxygen vacancy structure. Furthermore, the metal oxide semiconductor may contain impurities.
  • the inventor of the present invention uses a metal oxide semiconductor doped with nitrogen (N) as an impurity, which has been known as a photocatalyst and has not been used for solar cells.
  • N nitrogen
  • the coating agent for forming a semiconductor film according to the present invention is prepared by blending 0.1 to 2000 parts by mass of a dispersion medium with 100 parts by mass of a metal oxide semiconductor, and the metal oxide semiconductor is It is characterized in that it contains nitrogen as an impurity.
  • the dispersing medium is alkylene glycol, It is preferable to include at least one compound selected from the group consisting of polyalkylene glycols, alkyl ethers of alkylene glycols, and alkyl ethers of polyalkylene glycols.
  • the metal oxide semiconductor is preferably titanium dioxide (TiO 2).
  • a semiconductor film useful in the present invention is formed using the above-mentioned coating agent for forming a semiconductor film, and has a specific surface area force of 0 m 2 / g ⁇ 500 m 2 / g.
  • the photoelectric conversion element according to the present invention is characterized by comprising a semiconductor electrode having the above-mentioned semiconductor film, a counter electrode, and a charge transfer layer provided between the semiconductor electrode and the counter electrode. And It is preferable that a sensitizing dye be adsorbed to the semiconductor film.
  • a solar cell comprises the above photoelectric conversion element.
  • FIG. 1 is a view showing a photocurrent density-voltage curve of solar cells manufactured in Examples and Comparative Examples.
  • the coating agent for forming a semiconductor film according to the present invention comprises an alkylene glycol, a polyalkylene glycol, an alkyl ether of an alkylene glycol, and an alkyl ether of a polyalkylene glycol per 100 parts by mass of a metal oxide semiconductor.
  • the proportion of water contained in the dispersion medium is preferably less than 40% by mass, and more preferably less than 20% by mass, based on 100% by mass of the total dispersion medium which is preferably small.
  • the non-aqueous system is more preferably less than 10% by mass.
  • “dispersion medium” refers to all components other than the metal oxide semiconductor in the coating agent for forming a semiconductor film. Therefore, the dispersion aid described later is also included in the "dispersion medium" in the present specification.
  • the coating agent for forming a semiconductor film that is mainly used conventionally, it is difficult to adjust the amount of addition to obtain the desired viscosity and the ability to add a small amount of polyethylene glycol with an average molecular weight of 20000 as a thickener. It is.
  • the dispersion medium is less likely to evaporate as compared to the conventional aqueous dispersion medium, and therefore, the problem of evaporation of the dispersion medium during storage, coating or printing may be overcome.
  • it can. That is, for example, titanium dioxide paste using an aqueous dispersion medium obtained by kneading titanium dioxide powder, thickener, surfactant and the like in an aqueous solution has poor storage stability and film forming property. There are disadvantages such as cracking during sintering and easy peeling of the film. This is due to evaporation of the dispersion medium during storage, application or printing.
  • the dispersion medium evaporates during application or printing, it is not possible to maintain the appropriate viscosity of the applied or printed semiconductor film-forming coating agent. As a result, a crack is generated during firing, or the semiconductor film is peeled off, resulting in poor film formability.
  • the storage stability and film forming property of the coating agent for forming a semiconductor film are improved.
  • the coating agent for forming a semiconductor film to which the present invention can be applied can be suitably used for screen printing.
  • Screen printing is a coating method suitable for industrialization and practical use because it has high productivity and excellent applicability to fine patterns and irregular patterns.
  • a component of the dispersion medium is volatilized at the time of firing, whereby a semiconductor film with improved porosity can be obtained.
  • the carrying amount of the sensitizing dye per unit area is increased, and the mobility of the charge transfer layer is also improved, whereby the photoelectric conversion efficiency of the solar cell using the semiconductor film can be improved.
  • a semiconductor film having excellent uniformity, adhesiveness, and porosity after firing can be obtained.
  • a metal oxide semiconductor which is improved to be able to respond to visible light
  • the photoelectric conversion efficiency when used in a solar cell is improved.
  • a metal oxide semiconductor improved to be able to respond to visible light for example, a metal oxide semiconductor having an oxygen defect structure and a metal oxide semiconductor containing impurities can be mentioned.
  • the metal oxide semiconductor is not particularly limited as long as it is a metal oxide used in conventional photoelectric conversion devices. Specifically, for example, as an example, titanium dioxide (TiO 2), tin dioxide (SnO 2), zinc oxide (ZnO), niobium oxide (Nb 2 O 5), acid oxide, etc.
  • the above metal oxide semiconductor is a compound of the above.
  • the substance may be a single substance! /, Or a combination of two or more of the above-mentioned compounds.
  • At least one selected from the group consisting of alkylene glycol, polyalkylene glycol, alkyl ether of alkylene glycol, and alkyl ether of polyalkylene glycol as a dispersion medium is used. That is, the dispersion medium may contain any one of the above compounds alone, or may be contained as a combination of two or more kinds.
  • Examples of the above alkylene glycol include ethylene glycol and propylene glycol.
  • Examples of the polyalkylene glycol include, for example, acetylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol and the like.
  • Examples of the alkyl ether include monomethyl ether, monoethyl ether, monopropyl ether and the like. Among these, it is more preferable to use polyethylene glycol.
  • the proportion of at least one compound selected from the group of the above compounds is preferably 10% by mass or more. More preferably, it is 40% by mass or more, which is more preferably above.
  • the above dispersion medium may contain other components other than the above compounds.
  • the above-mentioned other components refer to all the components other than the above-mentioned compounds in the above-mentioned dispersion medium, and include solvents and dispersion assistants described later.
  • the solvent include ethanol, propanol, and ethyl acetate. The solvents may be used alone or in combination of two or more.
  • the polyalkylene glycol and the alkyl ether of the polyalkylene glycol various ones from low molecular weight to high molecular weight can be used according to the desired viscosity and the like.
  • the average molecular weight of the polyalkylene glycol is 10 6 to 400000, more preferably 200 to 20000, and further preferably! Also, those having different average molecular weights may be used in combination.
  • high molecular weight powdery ones and liquid ones may be used in combination. The powdery product may be used by dissolving it in a suitable solvent.
  • the dispersion medium is used in a proportion of 0.1 to 2000 parts by mass, preferably 100 to 400 parts by mass, and more preferably 200 to 400 parts by mass with respect to 100 parts by mass of the metal oxide semiconductor. . If it becomes smaller than this range, the coating agent for forming a semiconductor film becomes too viscous to handle. In addition, when it is larger than this range, the amount of the metal oxide semiconductor is small, and it is difficult to form a film, so that sufficient photoelectric conversion efficiency can not be obtained.
  • a chelating agent for forming a semiconductor film
  • a particle aggregation inhibitor for forming a semiconductor film
  • a stabilizer for a chelating agent
  • a thickener for a chelating agent
  • ZrO 2 zirconium oxide
  • the dispersion aid is also included in the dispersion medium.
  • the particle diameter of the primary particle of the metal oxide semiconductor before being dispersed in the dispersion medium is preferably 4 nm or more and 200 nm or less, and more preferably 10 nm or more and 50 nm or less.
  • the particle diameter of the secondary particles of the metal oxide semiconductor in the dispersion medium is preferably 10 nm or more and 100 m or less, and more preferably 10 nm or more and 700 nm or less.
  • secondary particles refer to aggregated primary particles.
  • the method for producing the coating agent for forming a semiconductor film is not particularly limited as long as it is a method in which the improved metal oxide semiconductor is homogeneously dispersed, but a specific example thereof is as follows.
  • a sol-gel method, a method of grinding with a mortar, a method of dispersing while pulverizing using a mill, a method of depositing fine particles in a solvent when synthesizing titanium dioxide, and the like can be mentioned.
  • the above-mentioned solvent contained as the above-mentioned other components may be removed by heating or the like after production from the coating agent for forming a semiconductor film produced by the above method.
  • the metal oxide semiconductor preferably has an oxygen vacancy structure.
  • the electron and charge transfer of the solar cell using the metal oxide semiconductor is improved, and the photoelectric conversion efficiency can be improved.
  • the method for synthesizing titanium dioxide having the above oxygen defect structure is not particularly limited. Specifically, for example, hydrogen plasma treatment under high pressure reduction, rare gases under high pressure reduction, etc. It can be obtained by elemental plasma treatment, ion implantation of a rare gas element, or the like. In addition, it may be synthesized by heating at high temperature under vacuum, may be synthesized by hydrogen reduction treatment at high temperature, or may be heat treated in an atmosphere of ammonia gas. Alternatively, use titanium tetrachloride (TiCl You may treat it with your aqueous solution.
  • the metal oxide semiconductor preferably contains an impurity! /, And more preferably.
  • impurities include metal ions such as vanadium and chromium, nitrogen, fluorine, sulfur (S) and the like.
  • the metal oxide semiconductor may have an oxygen defect structure and may contain an impurity.
  • another coating agent for forming a semiconductor film according to the present invention is obtained by blending 0.1 to 2000 parts by mass of a dispersion medium with 100 parts by mass of a metal oxide semiconductor, and the metal oxide semiconductor described above However, it contains nitrogen as an impurity.
  • a metal oxide semiconductor doped with nitrogen as an impurity the photoelectric conversion efficiency of a solar cell using this is improved.
  • the photocatalytic activity is improved because visible light can be absorbed in titanium dioxide which contains nitrogen as an impurity.
  • sensitizing dyes can absorb visible light, it is necessary to use the above-mentioned modified titanium dioxide for absorption of visible light.
  • the photoelectric transfer efficiency can be improved by improving the electron and charge transfer by the change of the crystal structure rather than the absorption of visible light.
  • the metal oxide semiconductor may further have an oxygen defect structure.
  • the dispersion medium is not particularly limited as long as it contains water or a conventionally known organic solvent used for a coating agent for forming a semiconductor film.
  • the organic solvent include methanol, ethanol, isopropyl alcohol, dichloromethane, acetone, acetonitrile, ethyl acetate and the like.
  • water or the above-mentioned organic solvent may be contained alone, or may be contained as a combination of two or more.
  • the above-mentioned dispersion medium may further comprise a chelating agent, a particle aggregation inhibitor, a stabilizer, a thickener, zirconium oxide (ZrO 2)
  • Acids, surfactants and the like may be included as dispersion aids.
  • the above-mentioned dispersion medium may be a conventionally known one containing water and the above-mentioned organic solvent, as described above.
  • the dispersion medium found by the present inventors is more preferable. That is, the dispersion medium is It is more preferable to include at least one compound selected from the group consisting of alkylene glycols, polyalkylene glycols, alkyl ethers of alkylene glycols, and alkyl ethers of polyalkylene glycols.
  • This makes it easy to adjust the viscosity of the coating agent for forming a semiconductor film, and the storage stability and the film forming property are improved.
  • a semiconductor film having excellent uniformity, adhesiveness, and porosity after firing can be obtained.
  • the coating agent for forming a semiconductor film containing nitrogen as an impurity is also a group consisting of metal oxide semiconductors; alkylene glycols, polyalkylene glycols, alkyl ethers of alkylene glycols, and alkyl ethers of polyalkylene glycols.
  • a dispersion medium containing at least one compound selected from the group of materials; a ratio of the dispersion medium to the metal oxide semiconductor; a particle diameter of the metal oxide semiconductor; and a method of producing a coating agent for forming a semiconductor film are the same as described above. is there.
  • nitrogen (N) contained as the above-mentioned impurity is preferably contained in an atomic percentage of 0.01% or more and 50% or less, and 0.1% or more and 20% or less. It is more preferable that the content is 0.5% or more and 5% or less. This improves the electron and charge mobility of the metal oxide semiconductor.
  • the atomic percentage refers to the ratio of the number of nitrogen atoms to the total number of atoms of the metal oxide semiconductor containing nitrogen as an impurity.
  • the atomic percentage is represented by the formula ⁇ nN / (nN + nM), where nM is the number of all metal atoms in the metal oxide semiconductor, nO is the number of all oxygen atoms, and nN is the number of all nitrogen atoms contained as impurities. + nO) ⁇ X 100 (%) is represented.
  • a method of synthesizing the metal oxide semiconductor containing nitrogen as an impurity specifically, for example, a method of hydrolyzing a solution of titanium dioxide in an aqueous ammonia solution, a solution of titanium dioxide or A method of heating the powder in ammonia gas, a method of RF magnetron sputtering a titanium dioxide target in nitrogen and a rare gas mixed atmosphere, and a method of synthesizing titanium dioxide containing nitrogen as an impurity on a glass substrate, etc.
  • Ca in the present invention ⁇ Cal semiconductor film is formed using the semiconductor film-forming coating agent, the specific surface area is in the 40m 2 Zg- 500m 2 Zg.
  • the loading amount of the sensitizing dye is increased, and the mobility of the charge transfer layer is further enhanced.
  • the photoelectric conversion efficiency of a solar cell using a body film can be improved.
  • the sensitizing dye is adsorbed to the above semiconductor film and sensitized to visible light
  • the adsorption amount of the sensitizing dye can be preferably increased by 10% to 50% by increasing the area to which the sensitizing dye is adsorbed.
  • the photoelectric conversion efficiency of the battery can be improved.
  • the pore distribution of the semiconductor film according to the present invention is preferably In m or more and 100 nm or less.
  • pore distribution refers to the distribution of pore volume with respect to the pore radius.
  • the method for forming the semiconductor film using the coating agent for forming a semiconductor film can be a conventionally known method which is not particularly limited. Specifically, for example, a coating method of coating the above-mentioned coating agent for forming a semiconductor film on a substrate, a printing method of printing, a sol-gel method and the like can be mentioned. Among them, it is preferable to use a coating method and a printing method. This is an advantageous force in terms of mass production of photoelectric conversion elements and flexibility of the substrate.
  • Examples of the coating method include a roll method, an immersion method, an air knife method, a blade method, a wire bar method, a slide hopper method, an erosion method, a curtain method, a spin method, a spray method, a knife coater method, Various coating methods such as the doctor blade method and the shower method can be mentioned.
  • a printing method for example, various printing methods such as a letterpress printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, and a screen printing method can be used.
  • the coating agent for forming a semiconductor film according to the present invention can be suitably used particularly for a screen printing method suitable for mass production.
  • the substrate on which the coating agent for forming a semiconductor film is to be applied is not particularly limited, and the material, size, shape, and the like can be appropriately selected according to the purpose of use, application, and the like.
  • examples of the material include glass, a polymer film, a plastic and the like as an example, and examples of the shape include a plate, a sphere, and a column.
  • the semiconductor film coated or printed on the substrate is preferably fired. This volatilizes the components of the dispersion medium, thereby improving the porosity of the semiconductor film.
  • the adhesion between the particles of the metal oxide semiconductor and between the substrate and the particles of the metal oxide semiconductor can be improved, and the film strength can be improved.
  • the range of the firing temperature is preferably 100 ° C.-700 ° C., more preferably 180 ° C.-5 It is 50 ° C, more preferably 450 ° C-500 ° C.
  • the firing time is preferably 10 minutes to 10 hours, and more preferably 30 minutes to 1 hour.
  • the thickness of the semiconductor film is preferably 0.1 to 100 ⁇ m, and more preferably 5 to 25 ⁇ m. If the thickness is larger than this range, the diffusion distance of electrons increases, and the loss due to charge recombination increases. On the other hand, if the thickness is smaller than this range, the loading amount of the sensitizing dye becomes lower.
  • a photoelectric conversion device comprises a semiconductor electrode having the above-mentioned semiconductor film, a counter electrode, and a charge transfer layer provided between the semiconductor electrode and the counter electrode.
  • the semiconductor electrode in which the sensitizing dye is adsorbed to the semiconductor film the light excites the sensitizing dye, excited electrons are injected into the conduction band of the semiconductor film, and move in the semiconductor electrode. Move to the opposite pole through an external circuit.
  • the electrons transferred to the counter electrode are carried by ions, holes, etc. in the charge transfer layer, and return to the sensitizing dye in the semiconductor electrode. In this way, light energy can be converted to electrical energy.
  • the semiconductor electrode is obtained by forming the semiconductor film on a conductive layer of a transparent conductive substrate.
  • the transparent conductive substrate refers to a transparent substrate on which a conductive layer is formed on at least one surface of a transparent substrate which also has a light transmitting material force.
  • the transparent substrate is not particularly limited as long as it has a light transmitting property. Specifically, for example, glass, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone and the like can be mentioned.
  • the transparent substrate may be plate-like or film-like.
  • examples of the conductive layer include metals, carbon, conductive metal oxide layers, and the like. Examples of the conductive metal oxide layer include indium-tin oxide (ITO), tin dioxide (SnO 2), fluorine-doped tin dioxide (SnO 2), and the like.
  • the transparent conductive substrate is fluorine-doped tin dioxide (SnO).
  • ITO is preferably a conductive glass substrate formed as a conductive layer.
  • the counter electrode is not particularly limited as long as it is used as an electrode.
  • a conductive substrate on which a conductive layer is formed on a substrate is formed by vapor deposition or sputtering of a layer of carbon, platinum or the like, or after application of chloroplatinic acid, and then thermal decomposition is performed.
  • charge transfer layer for example, an electrolyte containing an oxidizing species and a reducing species, an electrolyte obtained by gelling an electrolyte containing an acid species and a reducing species with a polymer matrix, and the like
  • examples include hole transport layers made of polymers and p-type semiconductors.
  • oxidizing species and reducing species are not particularly limited, but it is more preferable to use lithium iodide or potassium iodide and iodine.
  • a sensitizing dye be adsorbed to the semiconductor film of the photoelectric conversion element according to the present invention.
  • Sensitizing dyes are dyes having absorption in the visible light region and in the Z or infrared light region. By adsorbing a sensitizing dye to a metal oxide semiconductor without absorbing light in the region, absorption of light can be sensitized to the region. Thereby, the photoelectric conversion efficiency can be improved.
  • a metal complex dye or an organic dye can be used as the sensitizing dye.
  • the metal complex dye include metal complexes such as phthalocyanine and porphyrin; chlorophyll or a derivative thereof; hemin; a ruthenium complex containing a biviridine structure etc. as a ligand, osmium, iron, zinc etc. And complexes.
  • the organic dyes include phenylxanthene dyes, coumarins, eosin Y, metal free phthalocyanines, cyanine dyes, merocyanine dyes, xanthene dyes, and trifluoromethane-based dyes.
  • the sensitizing dye preferably has a bonding group to the surface of the metal oxide semiconductor in the molecule.
  • the above-mentioned linking group include a carboxyl group; a sulfonic acid group; a cyano group;- ⁇ ( ⁇ ) group;- ⁇ ( ⁇ ) group and the like.
  • a method of adsorbing the sensitizing dye to the semiconductor film a conventionally known method can be used. Specifically, for example, a method of immersing the semiconductor film in a sensitizing dye solution, a gas And the like. For example, there is a method of flowing the sensitizing dye of
  • the solvent for dissolving the sensitizing dye is not particularly limited as long as it dissolves the sensitizing dye. Examples thereof include water, alcohol, toluene, dimethylformamide and the like.
  • the above-mentioned semiconductor film to which the sensitizing dye is adsorbed may be washed, dried, and heated if necessary.
  • a solar cell working in the present invention is a solar cell using the above-mentioned photoelectric conversion element.
  • the above-described photoelectric conversion element is used as a solar cell that generates an electromotive force and current in an external circuit under irradiation of sunlight, and is used for ⁇ j.
  • a coating agent for forming a semiconductor film is prepared using a metal oxide semiconductor modified to be able to respond to visible light!
  • a metal oxide semiconductor modified to be able to respond to visible light
  • it is not particularly limited thereto. It is also possible to improve the metal oxide semiconductor during film formation by film formation with the coating agent for semiconductor film formation using the previous metal oxide semiconductor.
  • the measurement evaluation method in each example and comparative example is as follows.
  • the specific surface area of the titanium dioxide dioxide semiconductor film was measured by the BET method (gas adsorption method) using a fully automatic gas adsorption measuring device (Auto Soap 1, manufactured by Yuasa-Iotas).
  • the specific surface area was calculated by the BET one-point method and the multipoint method, and the pore distribution was calculated by the BJH method.
  • the electrode on which the sensitizing dye was adsorbed was immersed in an alkaline solution of ethanol for 2 hours to decolorize the sensitizing dye.
  • the UV-visible spectrum of the alkaline solution of ethanol was measured using a UV-visible spectrophotometer (U-3310, manufactured by Hitachi, Ltd.). Next, based on the calibration curve of the sensitizing dye, the adsorbed amount was converted from the absorption intensity.
  • titanium dioxide powder (3 g) having an oxygen defect structure polyethylene glycol (5. Olg) with an average molecular weight of 600, ethanol (7.5 mL) and zirconium dioxide (30 g) are added, and a paint shaker is used. After shaking and dispersing for 4 hours, ethanol was removed by heating to prepare a paste as a coating agent for forming a titanium dioxide semiconductor film.
  • fluorine-doped SnO becomes a conductive metal oxide layer
  • the obtained semiconductor film was immersed in a solution in which a ruthenium-biviridine complex (N719, Solaronix) was dissolved in methyl alcohol at a concentration of 3 ⁇ 10 ⁇ 4 molZL, and left to stand at room temperature for 12 hours. . Thereafter, the semiconductor film on which the ruthenium-biviridine complex was adsorbed was washed with methyl alcohol and dried to manufacture a first part. Adsorption amount of ruthenium chatter Jin complex in 4. 81 X 10- 8 mol / cm 2, as compared with the case of using the diacid I spoon titanium before improvements were increased 22%.
  • a platinum film was formed by sputtering on a glass substrate on which another conductive film was provided, and a second part was produced as a counter electrode. Between the first part and the second part described above, an electrolyte solution consisting of 0.1 ML1 I and 0.1 M iodine was injected, and a solar cell A was manufactured.
  • the manufactured solar cell A was irradiated with light having an intensity of 100 mW Z cm 2 (AM 1.5) using a xenon light source to evaluate the cell performance.
  • the results are shown in Figure 1 and Table 1.
  • titanium dioxide particles P25, Nippon Aerosil, average particle size about 25 nm, specific surface area 55 m 2 Zg, anatase 75%, rutile 25%
  • ammonia Nitrogen-doped titanium dioxide dioxide powder was synthesized by heating in a flask. Heating in ammonia gas is carried out in ammonia (NH 2) (67%) Z argon gas (Ar) atmosphere, 60
  • a nitrogen-doped titanium oxide powder (nitrogen doping amount: 1% by atomic percentage, 3 g), polyethylene glycol (5. Olg) having an average molecular weight of 600, ethanol (7.5 mL), and zirconium dioxide After stirring for 4 hours with a paint shaker and dispersing, ethanol was removed by heating to prepare a base as a coating agent for forming a titanium dioxide semiconductor film. Next, using this paste, a solar cell B was produced in the same manner as in Example 1.
  • the pore size distribution is 36 nm (22 nm when using the coating agent for forming a semiconductor film in which the modified titanium dioxide is dispersed in an aqueous solution), and the specific surface area is 92 m 2 Zg, and the porosity is improved.
  • a semiconductor film was obtained.
  • the adsorption amount of the ruthenium-biviridine complex was 4.72 ⁇ 10 18 mol Z cm 2 , which was increased by 20% as compared with the case of using titanium dioxide before modification.
  • the solar cell B produced was evaluated for cell performance in the same manner as in Example 1. The results are shown in Figure 1 and Table 1.
  • titanium dioxide particles P25, Nippon Aerosil, average particle size about 25 nm, specific surface area 55 m 2 Zg, anatase 75%, rutile 25%
  • polyethylene glycol with an average molecular weight of 600 5. Olg
  • Ethanol 7.5 mL
  • zirconium dioxide 30 g
  • the solar cell C produced was evaluated for cell performance in the same manner as in Example 1. The results are shown in Figure 1 and Table 1.
  • a solar cell D was produced in the same manner as in Example 1 using a commercially available anatase type titanium paste (Solaronix, Ti-Nanoxide D). The produced solar cell D was evaluated for cell performance in the same manner as in Example 1. The results are shown in Figure 1 and Table 1. Comparative Example 3
  • the solar cell E produced was evaluated for cell performance in the same manner as in Example 1. The results are shown in Figure 1 and Table 1.
  • Example 1 To a mixed solution of alpha monoterbineol (3.65 g) and ethyl cellulose (0.45 g), add titanium oxide powder (lg) having the oxygen deficient structure obtained in the above [Example 1], A paste as a coating agent for forming a titanium dioxide semiconductor film was prepared by shaking and dispersing for 4 hours in an into shiacre. Next, using this paste, a solar cell F was produced in the same manner as in Example 1.
  • the manufactured solar cell F was evaluated for cell performance in the same manner as in Example 1. The results are shown in Figure 1 and Table 1.
  • FIG. 1 is a graph showing a photocurrent density-voltage curve, in which the vertical axis represents photocurrent density (mAZcm 2) and the horizontal axis represents voltage (mV). Table 1 also shows the open circuit voltage Voc of the manufactured solar cells.
  • a solar cell A manufactured using a paste in which titanium dioxide having an oxygen defect structure is dispersed as polyethylene glycol as a dispersion medium, and a diacid containing nitrogen as an impurity It can be seen that, in a solar cell B manufactured using a paste in which titanium is dispersed with polyethylene glycol as a dispersion medium, the photocurrent density and the photoelectric conversion efficiency are improved. Compared with the case of using a commercially available anatase type titanium dioxide paste, the photoelectric conversion efficiency is 33% when using a paste in which titanium dioxide dioxide having an oxygen defect structure is dispersed in polyethylene glycol as a dispersion medium. In the case of using a paste in which titanium dioxide containing nitrogen as an impurity is dispersed as polyethylene glycol as a dispersion medium, it is dramatically improved to 26%.
  • the coating agent for forming a semiconductor film of the present invention is an alkylene glycol, a polyalkylene glycol, an alkyl ether of an alkylene glycol, and an alkyl ether of a polyalkylene glycol with respect to 100 parts by mass of a metal oxide semiconductor.
  • a dispersion medium containing 0.1 to 2000 parts by mass of a dispersion medium using at least one compound selected from the group consisting of the above, is modified to be able to respond to visible light by the metal oxide semiconductor.
  • Such a metal oxide semiconductor improved to be able to respond to visible light is preferably one having an oxygen defect structure or one containing nitrogen as an impurity.
  • the above coating agent for forming a semiconductor film is easy to adjust the viscosity and does not cause sag, flow, or cracks, and enables formation of a semiconductor film having excellent uniformity, adhesiveness, and porosity by firing. . Therefore, a solar cell manufactured using the coating agent for forming a semiconductor film exhibits an effect of improving the photoelectric conversion efficiency.
  • the crystal structure of the metal oxide semiconductor has an open circuit voltage value, an electron value, and an electron value. Injection effect Rate, affect the electron charge transport properties.
  • metal oxide semiconductors having an oxygen vacancy structure and metal oxide semiconductors containing nitrogen as impurities are subject to electron injection into the metal oxide semiconductor, or in the metal oxide semiconductor, due to changes in crystal structure. It is believed that the electron transport properties will be improved. Therefore, the electron and charge transfer of the solar cell using the metal oxide semiconductor can be improved, and the photoelectric conversion efficiency can be improved.
  • the coating agent for forming a semiconductor film according to the present invention has easy adjustment of viscosity, no flow, no cracks, and excellent uniformity, adhesiveness, and porosity by firing. It enables the formation of a semiconductor film.
  • metal oxide semiconductors are improved to be able to respond to visible light. Therefore, the solar battery manufactured using the coating agent for forming a semiconductor film exhibits an effect of improving the photoelectric conversion efficiency.
  • This dye-sensitized solar cell can be used as a small cell for a room, a transparent cell for window glass, a wall, a cell for outdoor power generation, and the like.
  • These semiconductor films can also be used as photocatalysts, sensors, and the like.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Abstract

L'invention concerne un agent de revêtement de formation d'un film semi-conducteur obtenu par mélange de 0,1-2000 % en masse d'un milieu de dispersion contenant au moins un composé sélectionné dans le groupe comprenant les alkylène glycols, les polyalkylène glycols, des éthers d'alkylène des alkylène glycols et des éthers d'alkyle des polyalkylène glycols avec 100 % en masse d'un semi-conducteur d'oxyde métallique. Un semi-conducteur d'oxyde métallique présentant une structure avec un déficit en oxygène, et/ou un semi-conducteur contenant de l'azote parmi ses impuretés, est utilisé comme semi-conducteur d'oxyde métallique. L'efficacité de conversion photoélectrique d'une pile solaire sensibilisée par un colorant peut être améliorée par utilisation d'un tel agent de revêtement dans la formation d'un film semi-conducteur.
PCT/JP2004/013379 2003-09-19 2004-09-14 Agent de revetement de formation d'un film semi-conducteur, film semi-conducteur, convertisseur photoelectrique, et pile solaire Ceased WO2005029571A1 (fr)

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JP2005336573A (ja) * 2004-05-28 2005-12-08 Toppan Printing Co Ltd 金属酸化物膜およびその製造方法
JP2006279018A (ja) * 2005-01-14 2006-10-12 Seiko Epson Corp 光電変換素子の製造方法、光電変換素子および電子機器
JP2007026994A (ja) * 2005-07-20 2007-02-01 Sumitomo Osaka Cement Co Ltd スクリーン印刷用の酸化物光半導体ペースト、そのペーストを用いた酸化物光半導体多孔質薄膜電極及び光電変換素子、並びにスクリーン印刷用の酸化物光半導体ペーストの製造方法
JP2008115055A (ja) * 2006-11-07 2008-05-22 Electric Power Dev Co Ltd 酸化チタン膜、酸化チタン膜電極膜構造および色素増感太陽電池
JP2011054572A (ja) * 2005-01-14 2011-03-17 Seiko Epson Corp 光電変換素子、光電変換素子の製造方法および電子機器
WO2014057942A1 (fr) * 2012-10-09 2014-04-17 シャープ株式会社 Élément de conversion photoélectrique, son procédé de production et module de conversion photoélectrique
JP2015050003A (ja) * 2013-08-30 2015-03-16 住友大阪セメント株式会社 色素増感型太陽電池用ペースト、酸化物半導体膜、酸化物半導体電極、及び色素増感型太陽電池
JP2018093198A (ja) * 2016-12-06 2018-06-14 旭化成株式会社 半導体膜、及びそれを用いた半導体素子、並びに分散液

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JP2001072419A (ja) * 1999-06-30 2001-03-21 Sumitomo Chem Co Ltd 酸化チタン、それを用いてなる光触媒体及び光触媒体コーティング剤
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005336573A (ja) * 2004-05-28 2005-12-08 Toppan Printing Co Ltd 金属酸化物膜およびその製造方法
JP2006279018A (ja) * 2005-01-14 2006-10-12 Seiko Epson Corp 光電変換素子の製造方法、光電変換素子および電子機器
JP2011054572A (ja) * 2005-01-14 2011-03-17 Seiko Epson Corp 光電変換素子、光電変換素子の製造方法および電子機器
JP2007026994A (ja) * 2005-07-20 2007-02-01 Sumitomo Osaka Cement Co Ltd スクリーン印刷用の酸化物光半導体ペースト、そのペーストを用いた酸化物光半導体多孔質薄膜電極及び光電変換素子、並びにスクリーン印刷用の酸化物光半導体ペーストの製造方法
JP2008115055A (ja) * 2006-11-07 2008-05-22 Electric Power Dev Co Ltd 酸化チタン膜、酸化チタン膜電極膜構造および色素増感太陽電池
WO2014057942A1 (fr) * 2012-10-09 2014-04-17 シャープ株式会社 Élément de conversion photoélectrique, son procédé de production et module de conversion photoélectrique
JP2015050003A (ja) * 2013-08-30 2015-03-16 住友大阪セメント株式会社 色素増感型太陽電池用ペースト、酸化物半導体膜、酸化物半導体電極、及び色素増感型太陽電池
JP2018093198A (ja) * 2016-12-06 2018-06-14 旭化成株式会社 半導体膜、及びそれを用いた半導体素子、並びに分散液

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