WO2012141095A1 - 光電変換素子および光電変換モジュール - Google Patents
光電変換素子および光電変換モジュール Download PDFInfo
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- WO2012141095A1 WO2012141095A1 PCT/JP2012/059509 JP2012059509W WO2012141095A1 WO 2012141095 A1 WO2012141095 A1 WO 2012141095A1 JP 2012059509 W JP2012059509 W JP 2012059509W WO 2012141095 A1 WO2012141095 A1 WO 2012141095A1
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- photoelectric conversion
- electrode
- dye
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- collecting electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2081—Serial interconnection of cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a photoelectric conversion element and a photoelectric conversion module.
- Patent Document 1 As a new type of solar cell, there is JP-A-1-220380 (Patent Document 1) as a prior art document disclosing a dye-sensitized solar cell applying photoinduced electron transfer of a metal complex.
- the dye-sensitized solar cell described in Patent Document 1 is visible by adsorbing a photosensitizing dye between a glass substrate on which a first electrode is formed and a glass substrate on which a second electrode is formed. It has a structure in which a photoelectric conversion layer having an absorption spectrum in the optical region and an electrolytic solution are sandwiched.
- the basic structure of the dye-sensitized solar cell described in Patent Document 1 is a structure in which an electrolyte is injected between two glass substrates, a small-area solar cell can be prototyped, but a 1 m square. It is difficult to apply to a large area solar cell. This is because when the area of one solar cell is increased, the short-circuit current increases in proportion to the area, but the resistance in the in-plane direction of the first electrode increases, so that the internal series electrical resistance of the solar cell increases, and the photoelectric This is because the fill factor (FF: fill factor) in the current-voltage characteristics at the time of conversion is lowered, and sufficient photoelectric conversion efficiency cannot be obtained.
- FF fill factor
- Patent Document 2 Japanese Patent Application Laid-Open No. 2003-203681 (Patent Document 2). )
- a grid-shaped current collector made of an alloy of gold and silver is formed on a first electrode between a plurality of strip-shaped photoelectric conversion portions formed on the same plane. An electrode is formed. With this current collecting electrode, the FF and the short-circuit current density can be improved.
- the FF can be improved by forming the current collecting electrode.
- the aperture ratio of the grid is set to 90 to 99%.
- the short-circuit current (Isc) increases in proportion to the area when the size of one photoelectric conversion element is larger than 50 mm square, the amount of the collecting electrode having a high aperture ratio of 90% or more is high. FF cannot be obtained.
- the present invention has been made in view of the above problems, and provides a photoelectric conversion element and a photoelectric conversion module that can achieve high conversion efficiency by realizing high FF while maintaining high short-circuit current (Isc). With the goal.
- a photoelectric conversion element includes a substrate having at least a light receiving surface, a first electrode made of a transparent conductive film located on the substrate, and a current collector made of a metal thin film located at least partially on the first electrode.
- a frame part and a second electrode located above the photoelectric conversion part so as to face the first electrode are provided.
- the short-circuit current value of the photoelectric conversion element is Isc (A)
- the total electric resistance value of the current collecting electrode, the first electrode, and the second electrode is Rh ( ⁇ )
- the open-circuit voltage of the photoelectric conversion element When the value is Voc (V), the relationship of Isc ⁇ Rh ⁇ 0.05 ⁇ Voc is satisfied.
- the photoelectric conversion module according to the present invention has a plurality of the above-described photoelectric conversion elements.
- the plurality of photoelectric conversion elements are electrically connected in series.
- the first electrode or the collector electrode of one photoelectric conversion element and the second electrode of the other photoelectric conversion element are connected.
- the current collecting electrode extends in the direction in which the photoelectric conversion elements connected in series are arranged.
- the photoelectric conversion unit has a rectangular shape having a longitudinal direction in plan view.
- the photoelectric conversion elements connected in series are positioned such that the longitudinal directions of the respective photoelectric conversion units are substantially parallel to each other.
- the length of the longitudinal direction of a photoelectric conversion part is 10 mm or more. In one form of this invention, the width
- the current collecting electrode has parallel portions extending substantially in parallel with an interval of 5 mm to 10 mm in a direction orthogonal to the extending direction.
- the width of the parallel part is 0.1 mm or more and 0.6 mm or less.
- the collecting electrode is formed of a material having corrosion resistance against the carrier transport material.
- the current collecting electrode is formed from any of titanium, nickel and tantalum.
- a high conversion efficiency can be obtained by realizing a high FF while maintaining a high short-circuit current (Isc) in the photoelectric conversion element.
- FIG. 1 is a cross-sectional view showing the structure of a dye-sensitized solar cell that is a photoelectric conversion element according to Embodiment 1 of the present invention.
- FIG. 2 is a view of the dye-sensitized solar cell of FIG. 1 as viewed from the direction of arrow II. In FIG. 2, a part of the structure of the dye-sensitized solar cell is not illustrated.
- the dye-sensitized solar cell 10 includes a translucent substrate 11 having a light receiving surface and a transparent conductive film positioned on the translucent substrate 11.
- a first electrode 12 and a current collecting electrode 17 that is located at least partially on the first electrode 12 and is made of a metal thin film are provided.
- the dye-sensitized solar cell 10 is located on the upper surface of the first electrode 12 or the current collecting electrode 17, carries a photosensitizer, and is immersed in a carrier transport material 13 a, and a photoelectric conversion unit 13. And an insulating frame portion 19 surrounding the side of the conversion portion 13.
- the dye-sensitized solar cell 10 includes a second electrode 16 and a cover 18 that are positioned above the photoelectric conversion unit 13 so as to face the first electrode 12.
- the cover 18 is fixed to the insulating frame portion 19.
- a slight gap is formed between the cover 18 and the second electrode 16, and the gap is filled with the carrier transport material 13a. Note that this gap is not necessarily formed.
- the dye-sensitized solar cell 10 includes a porous insulating layer 14 formed on the photoelectric conversion unit 13 and a catalyst layer formed on the porous insulating layer 14 inside the frame surrounded by the insulating frame 19. 15.
- the second electrode 16 is formed on the catalyst layer 15.
- the photoelectric conversion unit 13 has a rectangular shape having a longitudinal direction in plan view. Specifically, the photoelectric conversion unit 13 is formed with a length X and a width Y. However, the shape of the photoelectric conversion unit 13 is not limited to this, and may be circular or polygonal.
- the collecting electrode 17 extends in a direction orthogonal to the longitudinal direction of the photoelectric conversion unit 13.
- a plurality of current collecting electrodes 17 are formed with a width W. Between the collector electrode 17 adjacent to each other, spaced a distance L x are formed.
- the translucent substrate 11 In the translucent substrate 11, at least a portion serving as a light receiving surface has translucency. Therefore, the translucent substrate 11 is made of a material that transmits light. However, the translucent substrate 11 only needs to be formed of a material that substantially transmits light having a wavelength having effective sensitivity to at least a dye described later, and is not necessarily transparent to light in all wavelength regions. It is not necessary to have sex.
- the thickness of the translucent substrate 11 is preferably 0.2 mm or more and 5 mm or less.
- the material constituting the translucent substrate 11 is not particularly limited as long as it is a material that can generally be used for solar cells and can exhibit the effects of the present invention.
- Examples of such materials include glass substrates such as soda glass, fused silica glass, and crystal quartz glass, and heat resistant resin plates such as flexible films.
- the material constituting the flexible film examples include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PA), and polyetherimide (PEI). Phenoxy resin and Teflon (registered trademark) can be used.
- TAC tetraacetyl cellulose
- PET polyethylene terephthalate
- PPS polyphenylene sulfide
- PC polycarbonate
- PA polyarylate
- PEI polyetherimide
- the translucent substrate 11 may be heated when other members are formed on the translucent substrate 11.
- the material of the light-transmitting substrate 11 is 250 ° C. Teflon (registered trademark) having the above heat resistance is used.
- the translucent substrate 11 is used as a base when the dye-sensitized solar cell 10 is attached to another structure.
- substrate 11 is connected with another structure body by fastening members, such as a screw, via a metal processing component.
- the material constituting the first electrode 12 is not particularly limited as long as it has conductivity and translucency.
- Examples of the material constituting the first electrode 12 include indium tin composite oxide (ITO), tin oxide (SnO 2 ), tin oxide doped with fluorine (FTO), and zinc oxide (ZnO). It is done.
- the first electrode 12 made of such a material is formed on the translucent substrate 11 by a known method such as a sputtering method or a spray method.
- the layer thickness of the first electrode 12 is preferably 0.02 ⁇ m or more and 5 ⁇ m or less.
- the electric resistance of the first electrode 12 is preferably as low as possible, and is preferably 40 ⁇ / sq or less.
- the material which comprises the current collection electrode 17 will not be specifically limited if it is a material which can generally be used for a solar cell and can exhibit the effect of this invention. Examples of such a material include gold, silver, copper, aluminum, nickel, titanium, and tantalum.
- nickel, titanium and tantalum having corrosion resistance to the carrier transport material 13a (electrolytic solution), or gold, silver, copper and aluminum having high electrical conductivity, etc. constitute the current collecting electrode 17.
- the current collecting electrode 17 is made of a material that does not have corrosion resistance to the electrolytic solution, a protective insulating layer made of silicon oxide, zirconium oxide, rutile titanium oxide, or the like is formed on the current collecting electrode 17. Is preferred.
- the current collecting electrode 17 is formed on the first electrode 12 by a known method such as a sputtering method, a spray method, or a screen printing method.
- the insulating frame 19 is made of a material that has electrical insulation and can seal the carrier transport material 13a.
- an ultraviolet curable resin or a thermosetting resin can be used as the material of the insulating frame portion 19.
- the material of the insulating frame portion 19 it is preferable to use a material that can be easily formed into a desired shape on the first electrode 12 and the current collecting electrode 17.
- the material of the insulating frame portion 19 is preferably a silicone resin, an epoxy resin, a polyisobutylene-based resin, a hot melt resin, a glass-based material, or the like, and using these two or more types, the insulating frame portion 19 is used. May have a laminated structure.
- the insulating frame part 19 When forming the photoelectric conversion part 13 after forming the insulating frame part 19, the insulating frame part 19 is comprised with the material which has heat resistance more than the formation temperature of the photoelectric conversion part 13. FIG. Moreover, since the insulating frame part 19 is exposed to the ultraviolet-ray contained in sunlight, it is comprised with the material which is hard to deteriorate with an ultraviolet-ray. Therefore, it is preferable to form the insulating frame portion 19 from a glass-based material.
- the glass-based material for example, a commercially available glass paste or glass frit can be used. Considering the reactivity with the carrier transport material 13a and the burden on the environment, it is preferable to use a lead-free glass-based material.
- the insulating frame 19 is formed above the translucent substrate 11 made of a glass substrate, it is preferable to form the insulating frame 19 at a firing temperature of 550 ° C. or less. For example, it is preferable to use a bismuth glass paste as the glass material.
- the photoelectric conversion unit 13 is composed of a porous semiconductor layer that has adsorbed a dye, and the carrier transporting material 13a can move inside.
- the kind of semiconductor composing the porous semiconductor layer is not particularly limited as long as it is generally used for a photoelectric conversion material.
- the material of the porous semiconductor layer titanium oxide, zinc oxide, tin oxide, iron oxide, niobium oxide, cerium oxide, tungsten oxide, barium titanate, strontium titanate, cadmium sulfide, lead sulfide, zinc sulfide, phosphide
- Semiconductor compounds such as indium, copper-indium sulfide (CuInS 2 ), CuAlO 2 , SrCu 2 O 2 and combinations thereof can be used.
- Titanium oxide suitably used for the porous semiconductor layer includes various narrowly defined titanium oxides such as anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, and hydrous hydroxide There are titanium and the like, and these can be used alone or in combination.
- the two types of crystalline titanium oxide, anatase type and rutile type can be in any form depending on the production method and thermal history, but generally the crystalline titanium oxide is anatase type.
- the titanium oxide those having a high anatase type content, for example, titanium oxide having an anatase type content of 80% or more are preferable from the viewpoint of dye sensitization.
- the form of the semiconductor may be either single crystal or polycrystal, but polycrystal is preferred from the viewpoints of stability, ease of crystal growth, manufacturing cost, and the like.
- As the porous semiconductor it is preferable to use nanoscale or microscale semiconductor fine particles made of polycrystal. Therefore, it is preferable to use fine particles of titanium oxide as the material of the porous semiconductor layer.
- the fine particles of titanium oxide are produced by a known method such as a liquid phase method such as a hydrothermal synthesis method and a sulfuric acid method, or a gas phase method.
- fine particles of titanium oxide may be produced by high-temperature hydrolysis of a chloride developed by Degussa.
- semiconductor fine particles a mixture of fine particles having two or more particle sizes made of the same or different semiconductor compounds may be used. It is considered that semiconductor fine particles having a large particle size scatter incident light and contribute to an improvement in the light capture rate, and semiconductor fine particles having a small particle size contribute to an improvement in the amount of dye adsorbed by increasing the number of adsorption points.
- the ratio of the average particle diameters of the fine particles is preferably 10 times or more.
- the average particle size of the fine particles having a large particle size is, for example, 100 nm or more and 500 nm or less.
- the average particle size of the fine particles having a small particle size is, for example, 5 nm or more and 50 nm or less.
- the layer thickness of the porous semiconductor layer is not particularly limited, and is, for example, 0.1 ⁇ m or more and 100 ⁇ m or less.
- the surface area of the porous semiconductor layer is preferably large.
- the surface area is preferably 10 m 2 / g or more and 200 m 2 / g or less.
- the method for forming the porous semiconductor layer is not particularly limited, and a known method can be used.
- the porous semiconductor layer may be formed by applying a suspension containing the above-described semiconductor fine particles on the first electrode 12 and the current collecting electrode 17 and performing at least one of drying and baking.
- semiconductor fine particles are dispersed in a suitable solvent to obtain a suspension.
- suitable solvents include glyme solvents such as ethylene glycol monomethyl ether, alcohols such as isopropyl alcohol, alcohol-based mixed solvents such as isopropyl alcohol / toluene, and water.
- glyme solvents such as ethylene glycol monomethyl ether
- alcohols such as isopropyl alcohol
- alcohol-based mixed solvents such as isopropyl alcohol / toluene
- a commercially available titanium oxide paste for example, Solaronix, Ti-nanoxide, T, D, T / SP, D / SP
- Ti-nanoxide for example, Solaronix, Ti-nanoxide, T, D, T / SP, D / SP
- the obtained suspension is applied onto the first electrode 12 and the current collecting electrode 17, and at least one of drying and baking is performed to form a porous semiconductor layer.
- known methods such as a doctor blade method, a squeegee method, a spin coating method, and a screen printing method can be used.
- the viscosity of the suspension is reduced. It is preferable to adjust and apply the suspension to a region surrounded by the insulating frame 19 from a dispenser or the like. In this case, since the viscosity of the suspension is low, the suspension spreads to the end of the region by its own weight, so that the upper surface of the photoelectric conversion unit 13 can be easily leveled.
- the conditions such as temperature, time, and atmosphere during drying and firing of the suspension are appropriately set according to the type of semiconductor fine particles.
- the suspension can be dried and calcined by holding it in the temperature range of 50 ° C. to 800 ° C. for 10 seconds to 12 hours in an air atmosphere or an inert gas atmosphere. This drying and baking may be performed once at a single temperature or two or more times while changing the temperature.
- the porous semiconductor layer may have a laminated structure.
- suspensions of different semiconductor fine particles are prepared, each of the suspensions is applied, and at least one of drying and baking is performed.
- post-treatment is performed for the purpose of improving performance such as improving electrical connection between the semiconductor fine particles, increasing the surface area of the porous semiconductor layer, and reducing defect levels on the semiconductor fine particles. Also good.
- the performance of the porous semiconductor layer can be improved by post-treatment with a titanium tetrachloride aqueous solution.
- Examples of the photosensitizer carried on the porous semiconductor layer include sensitizing dyes and quantum dots.
- Examples of the sensitizing dye include various organic dyes and metal complex dyes having absorption in the visible light region and the infrared light region, and one or more of these dyes can be selectively used.
- organic dyes examples include azo dyes, quinone dyes, quinone imine dyes, quinacridone dyes, squarylium dyes, cyanine dyes, merocyanine dyes, triphenylmethane dyes, xanthene dyes, porphyrin dyes, and perylenes. And dyes such as indigo dyes and naphthalocyanine dyes.
- the extinction coefficient of an organic dye is larger than the extinction coefficient of a metal complex dye in which a molecule is coordinated to a transition metal.
- the metal complex dye is a molecule in which a metal is coordinated.
- the molecule include porphyrin dyes, phthalocyanine dyes, naphthalocyanine dyes, ruthenium dyes, and the like.
- metals Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb, La, W, Pt, TA, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Te, Rh, and the like.
- the metal complex dye a phthalocyanine dye or a ruthenium dye with a metal coordinated is preferable, and a ruthenium metal complex dye is particularly preferable.
- a chemical formula of a preferable ruthenium-based metal complex dye is shown below.
- ruthenium-based metal complex dyes examples include Ruthenium 535 dye, Ruthenium 535-bisTBA dye, and Ruthenium 620-1H3TBA dye manufactured by Solaronix.
- a dye having an interlock group such as a carboxyl group, an alkoxy group, a hydroxyl group, a sulfonic acid group, an ester group, a mercapto group, or a phosphonyl group is used in the dye molecule. It is preferable.
- the interlock group is generally present when the dye is fixed to the porous semiconductor layer, and provides an electrical bond that facilitates the movement of electrons between the excited dye and the semiconductor conduction band. To do.
- quantum dots that are photosensitizers include cadmium compounds, lead compounds, and indium compounds. Specific examples include CdS, CdSe, PbS, PbSe, and InAs.
- Examples of the method for adsorbing the dye on the porous semiconductor layer include a method of immersing the porous semiconductor layer in a dye adsorption solution in which the dye is dissolved. When soaking, the dye adsorbing solution may be heated so that the dye adsorbing solution penetrates to the back of the micropores in the porous semiconductor layer.
- the solvent for dissolving the dye may be any solvent that dissolves the dye, and examples thereof include alcohol, toluene, acetonitrile, tetrahydrofuran (THF), chloroform, dimethylformamide, and the like. These solvents are preferably purified and may be used in combination of two or more.
- the dye concentration in the dye adsorption solution can be appropriately set according to the conditions such as the dye to be used, the type of solvent, and the dye adsorption process.
- the dye adsorption solution preferably has a high concentration, for example, 1 ⁇ 10 ⁇ 5 mol / L or more.
- the solution may be heated to improve the solubility of the dye.
- ⁇ Porous insulating layer 14 Examples of the material constituting the porous insulating layer 14 include niobium oxide, zirconium oxide, silicon oxide such as silica glass and soda glass, aluminum oxide, barium titanate, and the like. One or two of these materials are used. The above can be used selectively.
- titanium oxide having a particle size of 100 nm to 500 nm, and among these, rutile type titanium oxide. These materials are preferable because they are in the form of particles, and the average particle diameter is 5 nm to 500 nm, preferably 10 nm to 300 nm.
- the porous insulating layer 14 can be formed by the same method as that for the photoelectric conversion portion 13 described above. That is, a fine particle insulating material is dispersed in a solvent, and a polymer compound such as ethyl cellulose or polyethylene glycol (PEG) is mixed to prepare a paste. The paste is applied onto the surface of the porous semiconductor layer, and at least one of drying and baking is performed. Thereby, the porous insulating layer 14 is formed on the surface of the porous semiconductor layer.
- a polymer compound such as ethyl cellulose or polyethylene glycol (PEG)
- a catalyst layer 15 is formed on the porous insulating layer 14.
- the formation method of the catalyst layer 15 is not specifically limited, A well-known method can be used. Specifically, when platinum is used as the material of the catalyst layer 15, it can be formed on the surface of the porous insulating layer 14 using a method such as sputtering, thermal decomposition of chloroplatinic acid, or electrodeposition.
- the catalyst layer 15 when carbon such as carbon black, ketjen black, carbon nanotube, and fullerene is used as the material of the catalyst layer 15, a paste in which carbon is dispersed in a solvent is applied to the porous insulating layer 14 using a screen printing method or the like. Thus, the catalyst layer 15 can be formed.
- carbon such as carbon black, ketjen black, carbon nanotube, and fullerene
- the second electrode 16 may be formed of the same material as the first electrode 12 or may be formed of a material that does not have translucency.
- the second electrode 16 may be formed of a metal material such as titanium, tungsten, gold, silver, copper, aluminum, or nickel.
- the second electrode 16 is formed by a known method such as a sputtering method or a spray method.
- the thickness of the second electrode 16 is preferably 0.02 ⁇ m or more and 5 ⁇ m or less.
- the electrical resistance is preferably as low as possible and is preferably 40 ⁇ / sq or less.
- the material of the sealing part is preferably a silicone resin, an epoxy resin, a polyisobutylene resin, a hot melt resin, a glass material, or the like.
- the sealing part may be made of these two or more materials and have a laminated structure.
- a material of the sealing part 19a for example, ThreeBond Co., Ltd. model number: 31X-101, ThreeBond Co., Ltd. model number: 31X-088, and a commercially available epoxy resin can be used.
- the sealing portion can be formed using a dispenser.
- the sealing portion can be formed by opening a patterned hole in the sheet-like hot melt resin.
- ⁇ Cover 18> As the material of the cover 18, a material that can seal the carrier transport material 13a and can prevent intrusion of water or the like from the outside is used. When the cover 18 may become the light receiving surface of the dye-sensitized solar cell 10, the cover 18 is formed of a light-transmitting material as with the light-transmitting substrate 11. When the dye-sensitized solar cell 10 is installed outdoors, a material having high mechanical strength such as tempered glass is preferably used as the material of the cover 18.
- Carrier transport material 13a A region surrounded by the first electrode 12, the second electrode 16, the insulating frame portion 19, and the sealing portion is filled with a carrier transport material 13a. Therefore, the gap between the cover 18 and the second electrode 16 and the hole between the porous photoelectric conversion portion 13 and the porous insulating layer 14 are filled with the carrier transport material 13a.
- the carrier transport material 13a is composed of a conductive material capable of transporting ions, and examples of suitable materials include liquid electrolytes, solid electrolytes, gel electrolytes, and molten salt gel electrolytes.
- the liquid electrolyte is not particularly limited as long as it is a liquid substance containing a redox species and can be used in a general battery or a solar battery.
- the liquid electrolyte is composed of a redox species and a solvent capable of dissolving the same, a redox species and a molten salt capable of dissolving the same, and a redox species and a solvent capable of dissolving the same.
- the thing which consists of salt etc. are mentioned.
- the redox species include I ⁇ / I 3 ⁇ series, Br 2 ⁇ / Br 3 ⁇ series, Fe 2 + / Fe 3+ series, and quinone / hydroquinone series.
- metal iodide such as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), calcium iodide (CaI 2 ) and iodine (I 2 )
- LiI lithium iodide
- NaI sodium iodide
- KI potassium iodide
- CaI 2 calcium iodide
- I 2 iodine
- tetraalkylammonium salts such as tetraethylammonium iodide (TEAI), tetrapropylammonium iodide (TPAI), tetrabutylammonium iodide (TBAI), tetrahexylammonium iodide (THAI) and iodine are preferable.
- a combination of a metal bromide such as lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), calcium bromide (CaBr 2 ) and bromine is preferable.
- a combination of LiI and I 2 is particularly preferable.
- redox species solvent examples include carbonate compounds such as propylene carbonate, nitrile compounds such as acetonitrile, alcohols such as ethanol, water, and aprotic polar substances. Among these, carbonate compounds or nitrile compounds are particularly preferable. Two or more kinds of these solvents may be mixed and used.
- the solid electrolyte may be any conductive material that can transport electrons, holes, and ions, and can be used as an electrolyte for solar cells and does not have fluidity.
- a hole transport material such as polycarbazole, an electron transport material such as tetranitrofluororenone, a conductive polymer such as polyroll, a polymer electrolyte obtained by solidifying a liquid electrolyte with a polymer compound, copper iodide and thiocyanate
- Examples thereof include a p-type semiconductor such as copper acid, and an electrolyte obtained by solidifying a liquid electrolyte containing a molten salt with fine particles.
- Gel electrolyte usually consists of an electrolyte and a gelling agent.
- gelling agents include polymer gelation such as crosslinked polyacrylic resin derivatives, crosslinked polyacrylonitrile derivatives, polyalkylene oxide derivatives, silicone resins, and polymers having a nitrogen-containing heterocyclic quaternary compound salt structure in the side chain. Agents and the like.
- the molten salt gel electrolyte is usually composed of the above gel electrolyte and a room temperature molten salt.
- the room temperature molten salt include nitrogen-containing heterocyclic quaternary ammonium salt compounds such as pyridinium salts and imidazolium salts.
- Additives may be added to the above electrolyte as necessary.
- Additives include nitrogen-containing aromatic compounds such as t-butylpyridine (TBP), dimethylpropylimidazole iodide (DMPII), methylpropylimidazole iodide (MPII), ethylmethylimidazole iodide (EMII), ethylimidazoleioio
- TBP t-butylpyridine
- DMPII dimethylpropylimidazole iodide
- MPII methylpropylimidazole iodide
- EMII ethylmethylimidazole iodide
- ethylimidazoleioioio examples thereof include imidazole salts such as dye (EII) and hexylmethylimidazole iodide (HMII).
- the electrolyte concentration in the electrolyte is preferably in the range of 0.001 mol / L to 1.5 mol / L, particularly preferably in the range of 0.01 mol / L to 0.7 mol / L.
- the short-circuit current value of the dye-sensitized solar cell 10 is Isc (A), and the total electric resistance value of the current collecting electrode 17, the first electrode 12, and the second electrode 16 is Rh ( ⁇ ),
- the open-circuit voltage value of the dye-sensitized solar cell 10 is Voc (V)
- it is formed so as to satisfy the relationship of Isc ⁇ Rh ⁇ 0.05 ⁇ Voc.
- the FF of the dye-sensitized solar cell 10 can be reduced to about 0.7 as can be seen from an experimental example described later. Therefore, high FF and conversion efficiency can be maintained in the photoelectric conversion element having a large light receiving surface.
- the collecting electrode 17 has corrosion resistance to the carrier transport material 13a, the stability and life of the dye-sensitized solar cell 10 can be improved.
- FIG. 3 is a cross-sectional view showing the structure of the photoelectric conversion module according to Embodiment 2 of the present invention.
- 4 is a view of the photoelectric conversion module of FIG. 3 as viewed from the direction of the arrow IV. Note that FIG. 3 does not illustrate a partial configuration of the photoelectric conversion module.
- the photoelectric conversion module 20 according to Embodiment 2 of the present invention includes a dye-sensitized solar cell 30 that is a plurality of photoelectric conversion elements.
- the plurality of dye-sensitized solar cells 30 are electrically connected in series.
- the dye-sensitized solar cell 30 includes at least a translucent substrate 21 having a light receiving surface, a first electrode 22 made of a transparent conductive film positioned on the translucent substrate 21, and at least a part of the first electrode 22. And a collector electrode made of a metal thin film.
- the dye-sensitized solar cell 30 is located on the upper surface of the first electrode 22 or the collecting electrode, carries a photosensitizer, and is immersed in a carrier transport material 23a, and a photoelectric conversion unit 23 And an insulating frame portion 29 surrounding the side of the portion 23.
- the dye-sensitized solar cell 30 includes a second electrode 26 positioned above the photoelectric conversion unit 23 so as to face the first electrode 22, and a cover 28. A slight gap is formed between the cover 28 and the second electrode 26, and the gap is filled with the carrier transport material 23a. Note that this gap is not necessarily formed.
- the dye-sensitized solar cell 30 includes a porous insulating layer 24 formed on the photoelectric conversion unit 23 and a catalyst layer formed on the porous insulating layer 24 inside the frame surrounded by the insulating frame 29. 25.
- the second electrode 26 is formed on the catalyst layer 25.
- a plurality of dye-sensitized solar cells 30 are connected in series.
- the first electrode 22 or the collecting electrode of one dye-sensitized solar cell 30 and the second electrode 26 of the other dye-sensitized solar cell 30 are connected. Has been.
- the insulating frame portion 29 electrically insulates the first electrodes 22, the collecting electrodes, and the second electrodes 26 of the dye-sensitized solar cells 30 adjacent to each other.
- the insulating frame portion 29 and the sealing portion are sealed so that the carrier transport material 23a cannot move between the dye-sensitized solar cells 30 adjacent to each other.
- the photoelectric conversion unit 23 has a rectangular shape having a longitudinal direction in plan view. Specifically, the photoelectric conversion unit 23 is formed with a length X and a width Y. The length X is 10 mm or more. The width Y is 5 mm or more and 10 mm or less. However, the shape of the photoelectric conversion unit 23 is not limited to this, and may be circular or polygonal.
- the dye-sensitized solar cells 30 connected in series are positioned so that the longitudinal directions of the photoelectric conversion units 23 are substantially parallel to each other.
- the current collecting electrode includes a parallel part 27 extending in a direction orthogonal to the longitudinal direction of the photoelectric conversion part 23 and a connecting part 31 connecting the ends of the parallel part 27.
- the parallel part 27 of the current collecting electrode extends in the direction in which the dye-sensitized solar cells 30 connected in series are arranged.
- the collector electrode connecting portion 31 extends in a direction orthogonal to the direction in which the dye-sensitized solar cells 30 connected in series are arranged.
- a plurality of parallel portions 27 of the collecting electrode are formed with a width W.
- the parallel portions 27 of the collecting electrodes adjacent to each other are formed with an interval of a distance Lx.
- the width W is not less than 0.1 mm and not more than 0.6 mm.
- the distance Lx is not less than 5 mm and not more than 10 mm.
- the photoelectric conversion module 20 has a short-circuit current value of the dye-sensitized solar cell 30 as Isc (A), a total value of electrical resistance values of the current collecting electrode, the first electrode 22 and the second electrode 26 as Rh ( ⁇ ), and a dye.
- Isc the dye-sensitized solar cell 30
- Rh a total value of electrical resistance values of the current collecting electrode
- Rh a total value of electrical resistance values of the current collecting electrode
- Rh ⁇
- ⁇ a dye.
- Voc (V) When the open-circuit voltage value of the sensitized solar cell 30 is Voc (V), it is formed so as to satisfy the relationship of Isc ⁇ Rh ⁇ 0.05 ⁇ Voc.
- the FF of the dye-sensitized solar cell 30 can be reduced to about 0.7 as can be seen from the experimental examples described later. Therefore, high FF and conversion efficiency can be maintained in the photoelectric conversion module 20 having a large light receiving surface.
- a translucent substrate 21 on which the first electrode 22 was formed was prepared. Specifically, a glass substrate with SnO 2 manufactured by Nippon Sheet Glass Co., Ltd. having a size of 100 mm ⁇ 200 mm was prepared.
- ⁇ Formation of current collecting electrode> Using an electron beam evaporator EI-5 (manufactured by ULVAC, Inc.), a collecting electrode was formed on the first electrode 22 so as to have a thickness of about 1 ⁇ m at a deposition rate of 0.1 ⁇ / S. Metallic titanium was used as a material for the current collecting electrode.
- the current collector electrode was formed by changing the width W of the parallel portion 27 of the current collector electrode under four conditions of 2 mm, 1 mm, 0.5 mm, and 0.2 mm. Further, the distance Lx between the parallel portions 27 of the adjacent collector electrodes is changed to eight conditions of 4 mm, 5 mm, 7.5 mm, 10 mm, 12.5 mm, 17.5 mm, 20 mm, and 30 mm to collect the collector electrodes. Formed.
- ⁇ Formation of insulating frame> A glass frit (manufactured by Noritake Co., Ltd.) was applied on the translucent substrate 21, the first electrode 22 or the collecting electrode using a screen printer (LS-34TVA manufactured by Neurong Seimitsu Kogyo). After preliminary drying at 100 ° C. for 10 minutes, firing was performed at 450 ° C. for 1 hour. The thickness of the formed insulating frame portion 29 was about 25 ⁇ m.
- a paste containing fine particles of zirconium oxide having a particle size of 100 nm (Ci Kasei Co., Ltd.) was prepared by the above method.
- the prepared paste was applied onto the porous semiconductor layer using a screen plate and a screen printing machine (LS-34TVA manufactured by Neurong Seimitsu Kogyo Co., Ltd.) used for the production of the porous semiconductor layer. After leveling at room temperature for 1 hour, it was pre-dried at 80 ° C. for 20 minutes and baked at 450 ° C. for 1 hour. By this step, a porous insulating layer 24 having a layer thickness of 5 ⁇ m was formed.
- an electron beam evaporator EVD-500A (manufactured by ANELVA) was used to deposit platinum at a deposition rate of 0.1 ⁇ / S to form a catalyst layer 25 having a thickness of about 5 nm.
- ⁇ Adjustment of electrolyte> As a redox electrolyte, acetonitrile was used as a solvent, and DMPII (manufactured by Shikoku Kasei) was 0.6 mol / liter, LiI (manufactured by Aldrich Chemical Company) was 0.1 mol / liter, and TBP (Aldrich Chemical). Company (manufactured by Company) was prepared by dissolving 0.5 mol / liter, and I 2 (manufactured by Tokyo Chemical Industry) was dissolved by 0.01 mol / liter.
- DMPII manufactured by Shikoku Kasei
- LiI manufactured by Aldrich Chemical Company
- TBP Aldrich Chemical
- the photoelectric conversion module 20 was produced by injecting a redox electrolyte from an electrolyte injection hole provided in the cover 28.
- Figure 5 is a graph showing the relationship between the distance L x and a dye-sensitized solar cell conversion efficiency between the collector electrode of the photoelectric conversion module (%).
- the vertical axis represents the conversion efficiency (%)
- the horizontal axis represents the distance L x (mm) between the collecting electrodes.
- the conversion efficiency was measured by irradiating four kinds of photoelectric conversion modules 20 produced by the above method with light of 1 kW / m 2 (AM1.5 solar simulator). Note that the conversion efficiency is obtained by dividing the value of the short-circuit current value Isc by the area of the aperture area of the photoelectric conversion module (the area surrounding and connecting the outer frames of several photoelectric conversion elements in the photoelectric conversion module), Voc and It was multiplied by FF.
- the value of the distance L x between the collecting electrodes becomes smaller and the FF increases, but the aperture ratio (light-receiving area ratio) decreases. Determined.
- the width W of the current collecting electrode is larger than 0.5 mm, the aperture ratio decreases as the distance L x between the current collecting electrodes decreases, and the conversion efficiency decreases as the short-circuit current value Isc decreases.
- the width W of the current collecting electrode is 0.5 mm or less, the aperture ratio decreases as the distance L x between the current collecting electrodes decreases, but the degree of improvement in FF is greater and the conversion efficiency has an extreme value. Due to these trade-offs, the conversion efficiency showed a high value when the distance L x between the collecting electrodes was 5 mm or more and 10 mm or less.
- Example 2 Using an electron beam evaporator EI-5 (manufactured by ULVAC, Inc.), a collecting electrode was formed on the first electrode 22 so as to have a thickness of about 1 ⁇ m at a deposition rate of 0.1 ⁇ / S. Metallic titanium was used as a material for the current collecting electrode.
- the current collecting electrode was formed by setting the width W of the parallel portion 27 of the current collecting electrode to 0.5 mm. Further, waving distance L x between the collector electrode between the parallel portion 27 of the adjacent collector electrode 10 mm, 12.5 mm, 25 mm, the four conditions of 50 mm, to form a collecting electrode. Other conditions and configurations are the same as in Experimental Example 1.
- FIG. 6 is a graph showing the relationship between the FF and Rh ⁇ Isc of the photoelectric conversion module.
- the vertical axis represents FF
- the horizontal axis represents Rh ⁇ Isc.
- the conversion efficiency was measured by irradiating four kinds of photoelectric conversion modules 20 produced by the above method with light of 1 kW / m 2 (AM1.5 solar simulator).
- FF 0.7 or more can be achieved by satisfying the relationship of Rh ⁇ Isc ⁇ 0.05 ⁇ Voc. Therefore, high FF and conversion efficiency can be maintained in the photoelectric conversion module 20 having a large light receiving surface.
- Example 3 Using an electron beam evaporator EI-5 (manufactured by ULVAC, Inc.), a collecting electrode was formed on the first electrode 22 so as to have a thickness of about 1 ⁇ m at a deposition rate of 0.1 ⁇ / S. Metallic titanium was used as a material for the current collecting electrode. The width W of the parallel part 27 of the current collecting electrode was set to 0.1 mm.
- a porous semiconductor layer constituting the photoelectric conversion part 23 was formed of titanium oxide.
- the width Y of the direction orthogonal to the longitudinal direction of the photoelectric conversion part 23 was produced at intervals of 1 mm from 3 mm to 15 mm.
- the distance L x between the parallel portion 27 of the adjacent collector electrode was 8 mm.
- Other conditions and configurations are the same as in Experimental Example 1.
- FIG. 7 is a graph showing the relationship between the width Y of the photoelectric conversion part of the photoelectric conversion module and the conversion efficiency (%) of the dye-sensitized solar cell.
- the vertical axis indicates the conversion efficiency (%)
- the horizontal axis indicates the width Y (mm) of the photoelectric conversion unit.
- the conversion efficiency showed a high value when the width Y of the photoelectric conversion portion was 5 mm or more and 10 mm or less.
Abstract
Description
本発明の一形態においては、光電変換部の長手方向と直交する方向の幅が5mm以上10mm以下である。
<光電変換素子>
図1は、本発明の実施形態1に係る光電変換素子である色素増感太陽電池の構造を示す断面図である。図2は、図1の色素増感太陽電池を矢印II方向から見た図である。なお、図2においては、色素増感太陽電池の一部の構成を図示していない。
<透光性基板11>
透光性基板11においては、少なくとも受光面となる部分が透光性を有している。そのため、透光性基板11は、光を透過する材料から形成されている。ただし、透光性基板11は、少なくとも後述する色素に実効的な感度を有する波長の光を実質的に透過させる材料で形成されていればよく、必ずしもすべての波長領域の光に対して透光性を有する必要はない。透光性基板11の厚さは、0.2mm以上5mm以下が好ましい。
第1電極12を構成する材料としては、導電性および透光性を有するものであれば特に限定されない。第1電極12を構成する材料としては、たとえば、インジウム錫複合酸化物(ITO)、酸化錫(SnO2)、酸化錫にフッ素がドープされたもの(FTO)、酸化亜鉛(ZnO)などが挙げられる。このような材料からなる第1電極12は、スパッタ法およびスプレー法などの公知の方法により、透光性基板11上に形成される。
集電電極17を構成する材料は、一般に太陽電池に使用可能で、かつ本発明の効果を発揮し得る材料であれば特に限定されない。このような材料としては、金、銀、銅、アルミニウム、ニッケル、チタンおよびタンタルなどが挙げられる。
絶縁性枠部19は、電気絶縁性を有しかつキャリア輸送材料13aを封止できる材料で構成されている。たとえば、絶縁性枠部19の材料として、紫外線硬化性樹脂または熱硬化性樹脂などを用いることができる。また、絶縁性枠部19の材料として、第1電極12および集電電極17上において所望の形状に形成し易い材料を用いることが好ましい。具体的には、絶縁性枠部19の材料としては、シリコーン樹脂、エポキシ樹脂、ポリイソブチレン系樹脂、ホットメルト樹脂およびガラス系材料などが好ましく、これらの2種類以上を用いて絶縁性枠部19を積層構造にしてもよい。
光電変換部13は、色素を吸着した多孔性半導体層からなり、キャリア輸送材料13aが内部を移動することができる。
多孔性半導体層を構成する半導体の種類は、一般に光電変換材料に使用されるものであれば特に限定されない。たとえば、多孔性半導体層の材料として、酸化チタン、酸化亜鉛、酸化錫、酸化鉄、酸化ニオブ、酸化セリウム、酸化タングステン、チタン酸バリウム、チタン酸ストロンチウム、硫化カドミウム、硫化鉛、硫化亜鉛、リン化インジウム、銅-インジウム硫化物(CuInS2)、CuAlO2、SrCu2O2などの半導体化合物およびこれらを組み合わせたものを用いることができる。これらの中でも、安定性の点から、多孔性半導体層の材料として酸化チタンを用いることが好ましい。
多孔性半導体層に担持される光増感剤としては、増感色素または量子ドットが挙げられる。増感色素としては、可視光領域および赤外光領域に吸収をもつ種々の有機色素および金属錯体色素などが挙げられ、これらの色素の1種または2種以上を選択的に用いることができる。
多孔性絶縁層14を構成する材料としては、たとえば、酸化ニオブ、酸化ジルコニウム、シリカガラスおよびソーダガラスなどの酸化ケイ素、酸化アルミニウム、チタン酸バリウムなどが挙げられ、これらの材料の1種または2種以上を選択的に用いることができる。
多孔性絶縁層14上に触媒層15を形成する。触媒層15の形成方法は特に限定されず、公知の方法を用いることができる。具体的には、触媒層15の材料として白金を用いる場合、スパッタ法、塩化白金酸の熱分解、電着などの方法を用いて、多孔性絶縁層14の表面上に形成することができる。
第2電極16は、第1電極12と同一の材料で形成されていてもよく、または透光性を有さない材料で形成されていてもよい。たとえば、第2電極16は、チタン、タングステン、金、銀、銅、アルミニウム、ニッケルなどの金属材料で形成されていてもよい。
封止部の材料としては、具体的には、シリコーン樹脂、エポキシ樹脂、ポリイソブチレン系樹脂、ホットメルト樹脂、ガラス系材料などが好ましい。封止部は、これらの2種類以上の材料からなり積層構造を有してもよい。封止部19aの材料として、たとえば、スリーボンド社型番:31X-101、スリーボンド社製型番:31X-088および一般に市販されているエポキシ樹脂などを用いることができる。
カバー18の材料としては、キャリア輸送材料13aを封止でき、また外部からの水などの浸入を防止可能なものを用いる。カバー18が色素増感太陽電池10の受光面となることがある場合は、カバー18は透光性基板11と同様に透光性を有する材料で形成される。色素増感太陽電池10が屋外に設置される場合、カバー18の材料として強化ガラスなどの機械強度の高い材料が用いられることが好ましい。
第1電極12、第2電極16、絶縁性枠部19および封止部により囲まれる領域には、キャリア輸送材料13aが充填されている。よって、カバー18と第2電極16との間の隙間、および、多孔性である光電変換部13と多孔性絶縁層14との孔内には、キャリア輸送材料13aが充填されている。
(実施形態2)
図3は、本発明の実施形態2に係る光電変換モジュールの構造を示す断面図である。図4は、図3の光電変換モジュールを矢印IV方向から見た図である。なお、図3においては、光電変換モジュールの一部の構成を図示していない。
図3,4に示す構造を有する光電変換モジュール20を作製するために、第1電極22が形成された透光性基板21を用意した。具体的には、100mm×200mmの大きさの日本板ガラス社製のSnO2付きガラス基板を用意した。
電子ビーム蒸着器EI―5(アルバック社製)を用いて、第1電極22上に集電電極を0.1Å/Sの蒸着速度で約1μmの厚さとなるように形成した。集電電極の材料として金属チタンを用いた。
スクリーン印刷機(ニューロング精密工業製LS-34TVA)を用いて、透光性基板21、第1電極22または集電電極上にガラスフリット(ノリタケ社製)を塗布した。100℃で10分間予備乾燥を行なった後、450℃で1時間焼成を行なった。形成された絶縁性枠部29の厚さは約25μmであった。
スクリーン印刷機(ニューロング精密工業製LS-34TVA)を用いて、市販の酸化チタンペースト(Solaronix社製、商品名Ti-Nanoxide D/SP、平均粒径13nm)を第1電極22または集電電極上に塗布した。室温にて1時間レベリングを行なった後、得られた塗膜を80℃で20分間予備乾燥し、450度で1時間焼成を行なった。この工程を繰り返すことにより、多孔性半導体層として、層厚30μm多孔性半導体層を作製した。
増感色素としてRuthenium620-1H3TBA色素(Solaronix社製)を用い、これのアセトニトリル(Aldrich Chemical Company製)/t-ブチルアルコール(Aldrich Chemical Company製)の1:1溶液(増感色素の濃度;4×10-4モル/リットル)を調製した。この溶液に多孔性半導体層を浸漬し、40度の温度条件のもとで20時間放置した。その後、多孔性半導体層をエタノール(Aldrich Chemical Company製)で洗浄した後、乾燥させた。このようにして、色素を多孔性半導体層に吸着させた。
粒径が100nmの酸化ジルコニウムの微粒子(シーアイ化成製)を含むペーストを上記方法で調整した。多孔性半導体層の作製に用いたスクリーン版とスクリーン印刷機(ニューロング精密工業製LS-34TVA)を用いて、多孔性半導体層上に調整したペーストを塗布した。室温にて1時間レベリングを行なった後、80℃で20分間予備乾燥し、450度で1時間焼成を行なった。この工程により、層厚が5μmの多孔性絶縁層24が形成された。
多孔性絶縁層24上に、電子ビーム蒸着器EVD-500A(ANELVA社製)を用い、白金を0.1Å/Sの蒸着速度で蒸着させて約5nmの厚さの触媒層25を形成した。
酸化還元性電解液として、溶媒にアセトニトリルを用いて、その中にDMPII(四国化成製)を0.6モル/リットル、LiI(Aldrich Chemical Company製)を0.1モル/リットル、TBP(Aldrich Chemical Company製)を0.5モル/リットル、I2(東京化成製)を0.01モル/リットル溶解させたものを用意した。
絶縁性枠部29上に、紫外線硬化材31X-101(スリーボンド社製)を塗布し、50mm×70mmの大きさのガラス基板(Corning7059)からなるカバー28と透光性基板21を貼り合せた。紫外線照射ランプNovacure(EFD社製)を用いて紫外線硬化剤の塗布部分に紫外線を照射することにより、透光性基板21とカバー28とを固定した。
カバー28に設けた電解液注入孔より、酸化還元性電解液を注入することで光電変換モジュール20を作製した。
電子ビーム蒸着器EI―5(アルバック社製)を用いて、第1電極22上に集電電極を0.1Å/Sの蒸着速度で約1μmの厚さとなるように形成した。集電電極の材料として金属チタンを用いた。
電子ビーム蒸着器EI―5(アルバック社製)を用いて、第1電極22上に集電電極を0.1Å/Sの蒸着速度で約1μmの厚さとなるように形成した。集電電極の材料として金属チタンを用いた。集電電極の平行部27の幅Wを0.1mmとした。
Claims (10)
- 少なくとも受光面を有する基板(11)と、
前記基板(11)上に位置する透明導電膜からなる第1電極(12)と、
前記第1電極(12)上の少なくとも一部に位置し、金属薄膜からなる集電電極(17)と、
前記第1電極(12)または前記集電電極(17)の上面に位置して光増感剤を担持し、かつ、キャリア輸送材料(13a)に浸漬された光電変換部(13)と、
前記光電変換部(13)の側方の周囲を囲む絶縁性枠部(19)と、
前記光電変換部(13)の上方で、前記第1電極(12)と対向するように位置する第2電極(16)とを備える光電変換素子であって、
前記光電変換素子の短絡電流値をIsc(A)、前記集電電極(17)と前記第1電極(12)と前記第2電極(16)との電気抵抗値の合計値をRh(Ω)、前記光電変換素子の開放電圧値をVoc(V)とすると、Isc×Rh<0.05×Vocの関係を満たす、光電変換素子。 - 複数の請求項1に記載の光電変換素子を有し、
複数の前記光電変換素子は電気的に直列に接続され、
互いに電気的に接続された前記光電変換素子同士においては、一方の前記光電変換素子の前記第1電極(22)または前記集電電極と他方の前記光電変換素子の前記第2電極(26)とが接続されている、光電変換モジュール。 - 前記集電電極は、直列に接続された前記光電変換素子同士の並ぶ方向に延在している、請求項2に記載の光電変換モジュール。
- 前記光電変換部は、平面視において、長手方向を有する矩形形状を有し、
直列に接続された前記光電変換素子同士は、各々の前記光電変換部の前記長手方向が略平行になるように位置している、請求項2または3に記載の光電変換モジュール。 - 前記光電変換部(23)の前記長手方向の長さが10mm以上である、請求項4に記載の光電変換モジュール。
- 前記光電変換部(23)の前記長手方向と直交する方向の幅が5mm以上10mm以下である、請求項4または5に記載の光電変換モジュール。
- 前記集電電極は、延在方向と直交する方向において5mm以上10mm以下の間隔を空けて略平行に延在する平行部(27)を有する、請求項3から6のいずれかに記載の光電変換モジュール。
- 前記平行部(27)の幅が0.1mm以上0.6mm以下である、請求項7に記載の光電変換モジュール。
- 前記集電電極が前記キャリア輸送材料(23a)に対して耐腐食性を有する材料で形成されている、請求項2から8に記載の光電変換モジュール。
- 前記集電電極が、チタン、ニッケルおよびタンタルのいずれかから形成されている、請求項9に記載の光電変換モジュール。
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JP2015230975A (ja) * | 2014-06-05 | 2015-12-21 | シャープ株式会社 | 光電変換素子、光電変換モジュールおよび光電変換素子の製造方法 |
JP2016505391A (ja) * | 2012-10-27 | 2016-02-25 | フォルシュングスツェントルム・ユーリッヒ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | 基板上にナノ多孔性層を製造する方法 |
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FR3017996A1 (fr) * | 2014-02-25 | 2015-08-28 | Commissariat Energie Atomique | Dispositif a composant electronique |
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