WO2016148186A1 - 太陽電池 - Google Patents
太陽電池 Download PDFInfo
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- WO2016148186A1 WO2016148186A1 PCT/JP2016/058313 JP2016058313W WO2016148186A1 WO 2016148186 A1 WO2016148186 A1 WO 2016148186A1 JP 2016058313 W JP2016058313 W JP 2016058313W WO 2016148186 A1 WO2016148186 A1 WO 2016148186A1
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- WIPO (PCT)
- Prior art keywords
- layer
- resin layer
- resin
- solar cell
- anode
- Prior art date
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- 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
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- 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
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a solar cell excellent in high temperature and high humidity durability.
- a photoelectric conversion element including a stacked body in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between opposing electrodes.
- photocarriers are generated by photoexcitation, and an electric field is generated by electrons moving through an N-type semiconductor and holes moving through a P-type semiconductor.
- An object of this invention is to provide the solar cell excellent in high temperature, high humidity durability.
- the present invention is a solar cell having a cathode, an anode, and a photoelectric conversion layer disposed between the cathode and the anode, wherein the photoelectric conversion layer has the general formula RMX 3 (provided that , R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom.) And a resin layer is disposed on either the cathode or the anode.
- An inorganic layer is disposed on the resin layer, the glass transition temperature of the resin layer is 70 ° C. or higher and 200 ° C. or lower, and the linear expansion coefficient is 9.0 ⁇ 10 ⁇ 6 K ⁇ 1 or higher, 1.5 ⁇ It is a solar cell that is 10 ⁇ 4 K ⁇ 1 or less.
- the present invention is described in detail below.
- the present inventors have examined the use of an organic / inorganic perovskite compound for the photoelectric conversion layer in a solar cell having a cathode, an anode, and a photoelectric conversion layer disposed between the cathode and the anode.
- an organic inorganic perovskite compound for the photoelectric conversion layer in a solar cell having a cathode, an anode, and a photoelectric conversion layer disposed between the cathode and the anode.
- the present inventors perform sealing by disposing a resin layer on either the cathode or the anode and disposing an inorganic layer on the resin layer (for example, by sputtering) We studied to improve the durability of solar cells.
- the present inventors adjust the glass transition temperature and the linear expansion coefficient of the resin layer within a specific range, so that the fineness of the inorganic layer and the resin layer can be achieved even in a high-temperature and high-humidity atmosphere. It has been found that the occurrence of surface irregularities can be suppressed, and the high-temperature and high-humidity durability of the solar cell can be improved by suppressing the peeling or cracking of the inorganic layer even in a high-temperature and high-humidity atmosphere.
- the present inventors have clarified that the resin layer in which the glass transition temperature and the linear expansion coefficient are adjusted within a specific range is peeled from the photoelectric conversion layer, particularly when the photoelectric conversion layer contains an organic-inorganic perovskite compound. As a result, the present invention has been completed.
- the solar cell of this invention has a cathode, an anode, and the photoelectric converting layer arrange
- the term “layer” means not only a layer having a clear boundary but also a layer having a concentration gradient in which contained elements gradually change.
- the elemental analysis of the layer can be performed, for example, by performing FE-TEM / EDS line analysis measurement of the cross section of the solar cell and confirming the element distribution of the specific element.
- a layer means not only a flat thin film-like layer but also a layer that can form a complicated and complicated structure together with other layers.
- a to B mean A or more and B or less.
- the materials for the cathode and the anode are not particularly limited, and conventionally known materials can be used.
- the anode is often a patterned electrode.
- cathode materials include FTO (fluorine-doped tin oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / Al 2 O 3 mixture, Al / LiF mixture etc. are mentioned.
- Examples of anode materials include metals such as gold, conductive materials such as CuI, ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), and GZO (gallium zinc oxide).
- Conductive transparent materials, conductive transparent polymers, and the like These materials may be used alone or in combination of two or more.
- the refractive index of the cathode material is not particularly limited, but when the cathode is in contact with the resin layer, it is preferable that the difference in refractive index with the resin layer is small.
- the difference in refractive index between the resin layer and the material in contact with the resin layer for example, a cathode or an anode, a substrate, etc.
- sunlight can efficiently reach the inside of the solar cell (inside the photoelectric conversion layer).
- the photoelectric conversion efficiency of the battery can be improved.
- the refractive index of FTO is generally about 1.9 to 2.1
- the refractive index of ITO is generally about 1.8 to 2.3.
- the refractive index of the anode material is not particularly limited, but when the anode is in contact with the resin layer, it is preferable that the refractive index difference with the resin layer is small.
- the refractive index of ITO indium tin oxide
- the refractive index of AZO is generally about 1.8 to 2.2.
- the photoelectric conversion layer includes an organic / inorganic perovskite compound represented by the general formula R-MX 3 (where R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom).
- the solar cell in which the photoelectric conversion layer includes the organic / inorganic perovskite compound is also referred to as an organic / inorganic hybrid solar cell.
- the organic / inorganic perovskite compound has low moisture resistance
- the organic or perovskite compound is used on the cathode or the anode in order to improve the high-temperature and high-humidity durability of the solar cell. It becomes more effective to dispose a resin layer and an inorganic layer as described later on either one of the above.
- the R is an organic molecule, and is preferably represented by C 1 N m H n (l, m, and n are all positive integers). Specifically, R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl.
- ions eg, methylammonium (CH 3 NH 3 )
- methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their ions and phenethylammonium are preferred, and methylamine, ethylamine, propylamine and these ions are more preferred.
- M is a metal atom, for example, lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, Europium etc. are mentioned. These metal atoms may be used independently and 2 or more types may be used together.
- X is a halogen atom or a chalcogen atom, and examples thereof include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms or chalcogen atoms may be used alone or in combination of two or more. Among these, the halogen atom is preferable because the organic / inorganic perovskite compound becomes soluble in an organic solvent and can be applied to an inexpensive printing method by containing halogen in the structure. Furthermore, iodine is more preferable because the energy band gap of the organic-inorganic perovskite compound becomes narrow.
- the organic / inorganic perovskite compound preferably has a cubic structure in which a metal atom M is disposed at the body center, an organic molecule R is disposed at each vertex, and a halogen atom or a chalcogen atom X is disposed at the face center.
- FIG. 1 shows an example of a crystal structure of an organic / inorganic perovskite compound having a cubic structure in which a metal atom M is arranged at the body center, an organic molecule R is arranged at each vertex, and a halogen atom or a chalcogen atom X is arranged at the face center. It is a schematic diagram.
- the organic / inorganic perovskite compound is preferably a crystalline semiconductor.
- the crystalline semiconductor means a semiconductor capable of measuring the X-ray scattering intensity distribution and detecting a scattering peak.
- the organic / inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic / inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the solar cell is improved.
- the degree of crystallization can be evaluated as an index of crystallization.
- the degree of crystallinity is determined by separating the crystalline-derived scattering peak detected by the X-ray scattering intensity distribution measurement and the halo derived from the amorphous part by fitting, obtaining the respective intensity integrals, Can be obtained by calculating the ratio.
- a preferable lower limit of the crystallinity of the organic-inorganic perovskite compound is 30%. When the crystallinity is 30% or more, the mobility of electrons in the organic / inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the solar cell is improved.
- a more preferred lower limit of the crystallinity is 50%, and a more preferred lower limit is 70%. Examples of the method for increasing the crystallinity of the organic / inorganic perovskite compound include thermal annealing, irradiation with intense light such as laser, and plasma irradiation.
- the photoelectric conversion layer contains the organic / inorganic perovskite compound
- the photoelectric conversion layer further includes an organic semiconductor or an inorganic semiconductor in addition to the organic / inorganic perovskite compound as long as the effect of the present invention is not impaired. May be included.
- the organic semiconductor or inorganic semiconductor referred to here may serve as an electron transport layer or a hole transport layer described later.
- the organic semiconductor include compounds having a thiophene skeleton such as poly (3-alkylthiophene).
- conductive polymers having a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, and the like can be given.
- compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, or a benzoporphyrin skeleton, a spirobifluorene skeleton, etc.
- carbon-containing materials such as carbon nanotubes, graphene, and fullerene that may be surface-modified Also mentioned.
- the inorganic semiconductor examples include titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu 2 O, CuI, MoO 3 , V 2 O 5 , WO 3 , MoS 2, MoSe 2, Cu 2 S , and the like.
- the photoelectric conversion layer includes the organic-inorganic perovskite compound and the organic semiconductor or the inorganic semiconductor
- the photoelectric conversion layer is a laminated body in which a thin-film organic semiconductor or an inorganic semiconductor portion and a thin-film organic-inorganic perovskite compound portion are stacked.
- a composite film in which an organic semiconductor or inorganic semiconductor part and an organic / inorganic perovskite compound part are combined may be used.
- a laminated body is preferable in that the production method is simple, and a composite film is preferable in that the charge separation efficiency in the organic semiconductor or the inorganic semiconductor can be improved.
- the preferable lower limit of the thickness of the thin-film organic / inorganic perovskite compound site is 5 nm, and the preferable upper limit is 5000 nm. If the thickness is 5 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 5000 nm or less, since it can suppress that the area
- the more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 20 nm, and the still more preferable upper limit is 500 nm.
- a preferable lower limit of the thickness of the composite film is 30 nm, and a preferable upper limit is 3000 nm. If the thickness is 30 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 3000 nm or less, since it becomes easy to reach
- the more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the still more preferable lower limit is 50 nm, and the still more preferable upper limit is 1000 nm.
- an electron transport layer may be disposed between the cathode and the photoelectric conversion layer.
- the material of the electron transport layer is not particularly limited.
- N-type conductive polymer, N-type low molecular organic semiconductor, N-type metal oxide, N-type metal sulfide, alkali metal halide, alkali metal, surface activity Specific examples include, for example, cyano group-containing polyphenylene vinylene, boron-containing polymer, bathocuproine, bathophenanthrene, hydroxyquinolinato aluminum, oxadiazole compound, benzimidazole compound, naphthalene tetracarboxylic acid compound, perylene derivative, Examples include phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc s
- the electron transport layer may consist of only a thin film electron transport layer, but preferably includes a porous electron transport layer.
- the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor part and an organic / inorganic perovskite compound part are combined, a more complex composite film (a more complicated and complicated structure) is obtained.
- the composite film is formed on the porous electron transport layer.
- the preferable lower limit of the thickness of the electron transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of electron transport, and photoelectric conversion efficiency will become high.
- the more preferable lower limit of the thickness of the electron transport layer is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
- a hole transport layer may be disposed between the anode and the photoelectric conversion layer.
- the material of the hole transport layer is not particularly limited, and examples thereof include a P-type conductive polymer, a P-type low molecular organic semiconductor, a P-type metal oxide, a P-type metal sulfide, and a surfactant.
- Examples include polystyrene sulfonate adduct of polyethylenedioxythiophene, carboxyl group-containing polythiophene, phthalocyanine, porphyrin, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide. , Tin sulfide, fluoro group-containing phosphonic acid, carbonyl group-containing phosphonic acid, copper compounds such as CuSCN and CuI, surface-modified carbon nanotubes, carbon-containing materials such as graphene, and the like.
- the preferable lower limit of the thickness of the hole transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, electrons can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of hole transport, and a photoelectric conversion efficiency will become high.
- the more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
- the solar cell of the present invention may further have a substrate or the like.
- substrate is not specifically limited, For example, transparent glass substrates, such as soda-lime glass and an alkali free glass, a ceramic substrate, a transparent plastic substrate, etc. are mentioned.
- substrate is not specifically limited, When the said board
- the refractive index of soda lime glass is generally about 1.4 to 1.6
- the refractive index of the transparent plastic substrate is generally about 1.52 to 1.60.
- a resin layer is disposed on either the cathode or the anode, and an inorganic layer is disposed on the resin layer.
- the resin layer has a glass transition temperature of 70 ° C. or more and 200 ° C. or less, and a linear expansion coefficient of 9.0 ⁇ 10 ⁇ 6 K ⁇ 1 or more and 1.5 ⁇ 10 ⁇ 4 K ⁇ 1 or less.
- the glass transition temperature and the linear expansion coefficient of the resin layer are within the above ranges.
- the generation of fine surface irregularities in the inorganic layer and the resin layer can be suppressed, and the occurrence of peeling or cracking of the inorganic layer can be suppressed even in a high-temperature and high-humidity atmosphere. Can be improved.
- the resin layer having a glass transition temperature and a linear expansion coefficient within the above ranges are less likely to peel off from the photoelectric conversion layer, particularly when the photoelectric conversion layer contains an organic-inorganic perovskite compound.
- the glass transition temperature and the linear expansion coefficient of the resin layer are within the above ranges, generation of fine surface irregularities of the resin layer can be suppressed, so that the surface of the solar cell has a beautiful gloss. It becomes easy to express and the design property of a solar cell can be improved.
- the minimum with a preferable glass transition temperature of the said resin layer is 85 degreeC, a more preferable minimum is 100 degreeC, a preferable upper limit is 190 degreeC, and a more preferable upper limit is 180 degreeC.
- the glass transition temperature is measured under a tensile condition (25 ° C. to 125 ° C., 20 ° C./min) using a dynamic viscoelasticity measuring apparatus (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.). be able to.
- the resin constituting the resin layer is a thermosetting resin or a photocurable resin
- the glass transition temperature means a glass transition temperature after curing of the thermosetting resin or the photocurable resin.
- the preferable lower limit of the linear expansion coefficient of the resin layer is 6.0 ⁇ 10 ⁇ 5 K ⁇ 1 and the preferable upper limit is 1.0 ⁇ 10 ⁇ 4 K ⁇ 1 .
- the linear expansion coefficient is measured under a tensile condition ( ⁇ 60 ° C. to 300 ° C., 10 ° C./min) using a linear expansion coefficient measuring apparatus (eg, TMA / SS600 manufactured by Seiko Instruments Inc.). Can do.
- the resin constituting the resin layer is not particularly limited as long as the glass transition temperature and the linear expansion coefficient of the resin layer can be adjusted within the above ranges, and may be a thermoplastic resin, a thermosetting resin, or a photocurable resin.
- the thermoplastic resin include butyl rubber, polyester, polyurethane, polyvinyl alcohol, polyvinyl acetate, polybutadiene, polyamide, polyimide, polyisobutylene, cycloolefin resin, and diallyl phthalate resin.
- the thermosetting resin include an epoxy resin, an acrylic resin, a silicone resin, a phenol resin, a melamine resin, a urea resin, and a diallyl phthalate resin.
- the photocurable resin include an epoxy resin, a vinyl resin, and an ene-thiol resin.
- the resin layer preferably contains a resin having an alicyclic skeleton and / or an aromatic skeleton in order to adjust the glass transition temperature and the linear expansion coefficient of the resin layer within the above ranges.
- the alicyclic skeleton is not particularly limited, and examples thereof include skeletons such as norbornene, isobornene, adamantane, cyclohexane, dicyclopentadiene, dicyclohexane, and cyclopentane.
- the aromatic skeleton is not particularly limited, and examples thereof include a phthalate skeleton. These skeletons may be used alone or in combination of two or more.
- a norbornene skeleton, an isobornene skeleton, an adamantane skeleton, a cyclohexane skeleton, and a phthalate skeleton are preferable because a difference in refractive index between the cathode material and the anode material is small.
- the resin having the alicyclic skeleton and / or aromatic skeleton is an alicyclic skeleton and / or aromatic skeleton.
- the content of is preferably 30% by weight or more.
- the content of the alicyclic skeleton and / or aromatic skeleton means that the resin having an alicyclic skeleton and / or an aromatic skeleton is a monomer having an alicyclic skeleton and / or an aromatic skeleton, and an alicyclic ring.
- a copolymer with a monomer having neither a formula skeleton nor an aromatic skeleton it means the content of a component derived from a monomer having an alicyclic skeleton and / or an aromatic skeleton in the copolymer.
- the copolymer may be a thermoplastic resin, or may be a thermosetting resin or a photocurable resin that is cured by reacting with a curing agent, that is, a prepolymer.
- a method for calculating the content of a component derived from a monomer having an alicyclic skeleton and a component derived from a monomer having an aromatic skeleton in the copolymer a method of calculating from the addition weight of raw material monomers, GC- There is a method of calculating from a composition analysis result by MS or the like.
- the resin having an alicyclic skeleton and / or an aromatic skeleton is not particularly limited as long as it has an alicyclic skeleton and / or an aromatic skeleton, and may be a thermoplastic resin or thermosetting. Resin may be sufficient and a photocurable resin may be sufficient. These resins having an alicyclic skeleton and / or an aromatic skeleton may be used alone, or two or more kinds thereof may be used in combination. Further, the resin having the alicyclic skeleton and / or the aromatic skeleton may be a resin obtained by forming a resin having a reactive functional group and then crosslinking the reactive functional group.
- thermoplastic resins such as norbornene resin (TOPAS6017S-04, manufactured by Polyplastics), norbornene resin (TOPAS9014S-04, manufactured by Polyplastics), and adamantane acrylate (Mitsubishi).
- thermosetting resins such as isobornyl acrylate (TS-147, manufactured by Shin-Nakamura Chemical Co., Ltd.), and alicyclic epoxy resins (Celoxide 2021P, manufactured by Daicel).
- resin having an aromatic skeleton include thermosetting resins or photocurable resins such as diallyl phthalate resin (Daisodap, manufactured by Daiso Corporation).
- the resin having the alicyclic skeleton and / or the aromatic skeleton may be mixed with a resin having neither the alicyclic skeleton nor the aromatic skeleton.
- the refractive index of the resin constituting the resin layer is not particularly limited, but is generally smaller than the material (for example, cathode or anode, substrate, etc.) in contact with the resin layer.
- the refractive index of norbornene resin is generally about 1.3 to 1.6
- the refractive index of isobornyl acrylate is generally about 1.3 to 1.6.
- the resin layer preferably contains an inorganic filler in order to adjust the glass transition temperature and the linear expansion coefficient of the resin layer within the above ranges.
- the resin layer has an inorganic filler having a refractive index of 1.80 or more and 2.50 or less, an average particle diameter of 2 nm or more and 50 nm or less, and an average pore diameter of 5 to 5000 mm, and 20% by volume or more, 70 It is more preferable to contain it by volume% or less.
- the resin layer and a material in contact with the resin layer can be reduced, and sunlight can efficiently reach the inside of the solar cell (inside the photoelectric conversion layer) to improve the photoelectric conversion efficiency of the solar cell.
- the inorganic filler can adsorb moisture penetrating into the resin layer and suppress deterioration of the solar cell (deterioration of the photoelectric conversion layer), the high temperature and high humidity durability of the solar cell can be improved. it can.
- the refractive index of the inorganic filler is 1.80 or more, the refractive index of the resin layer is sufficiently increased by blending the inorganic filler, and the resin layer and a material in contact with the resin layer (for example, a cathode or an anode, a substrate, etc.) ) And the refractive index difference. If the refractive index of the said inorganic filler is 2.50 or less, it can suppress that the refractive index of the said resin layer increases too much by the mixing
- a preferable lower limit of the refractive index of the inorganic filler is 1.90, a more preferable lower limit is 2.0, a preferable upper limit is 2.40, and a more preferable upper limit is 2.1.
- the average particle diameter of the inorganic filler is 2 nm or more, the glass transition temperature and the linear expansion coefficient of the resin layer can be easily adjusted within the above range, and the resin layer penetrated into the resin layer by the inorganic filler. Adsorption of moisture becomes sufficient, and the high temperature and high humidity durability of the solar cell is improved. If the average particle diameter of the inorganic filler is 50 nm or less, the inorganic filler can be uniformly dispersed in the resin layer without aggregation.
- the preferable lower limit of the average particle diameter of the inorganic filler is 3 nm, and the preferable upper limit is 20 nm.
- the average particle size of the inorganic filler can be measured using a nanoparticle size distribution measuring device (for example, SALD-7500NANO manufactured by Shimadzu Corporation).
- the inorganic filler is preferably porous in order to sufficiently adsorb moisture that has penetrated into the resin layer. If the average pore diameter of the inorganic filler is 5 to 5000 mm, moisture can be adsorbed sufficiently. A preferable lower limit of the average pore diameter of the inorganic filler is 10%, and a more preferable lower limit is 15%. In addition, it can confirm that the said inorganic filler is porous by scanning electron microscopy (SEM) analysis. The average pore diameter of the inorganic filler can be calculated using a high-functional specific surface area / pore distribution measuring device (for example, ASAP2020 manufactured by Micromeritics Japan).
- the inorganic filler preferably has a specific surface area of a preferred lower limit of 100 g / m 2 , a preferred upper limit of 1000 g / m 2 , and a more preferred lower limit of 200 g / m 2.
- m 2 and a more preferable upper limit is 900 g / m 2 .
- the specific surface area of the inorganic filler can be calculated using a high-functional specific surface area / pore distribution measuring device (for example, ASAP2020 manufactured by Micromeritics Japan).
- the refractive index of the resin layer is sufficiently increased by blending the inorganic filler, and the resin layer and a material in contact with the resin layer (for example, cathode or anode, substrate, etc.) ) And the refractive index difference.
- content of the said inorganic filler is 70 volume% or less, it will be suppressed that the refractive index of the said resin layer increases too much by the mixing
- the minimum with preferable content of the said inorganic filler is 25 volume%, a more preferable minimum is 35 volume%, a preferable upper limit is 60 volume%, and a more preferable upper limit is 50 volume%.
- the said inorganic filler will not be specifically limited if it has the refractive index adjusted in the said range,
- an oxide, sulfide, a sulfide, a silicic oxide is mentioned.
- the oxide include silica, zeolite, glass, calcium oxide, barium oxide, magnesium oxide, zirconium oxide, strontium oxide, and barium titanate.
- the sulfide include zinc sulfide and magnesium sulfide.
- the sulfate include lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, cobalt sulfate, gallium sulfate, and titanium sulfate.
- the silicate examples include zirconium silicate and bismuth silicate. Especially, since it is preferable that it is a compound which has a water
- the surface of the inorganic filler is preferably hydrophobized, and the surface is preferably not hydrophilized.
- the surface of the inorganic filler is hydrophobized and / or the surface of the inorganic filler is not hydrophilized so that the dispersibility of the hygroscopic inorganic filler in the resin is improved, and the sun The high temperature and high humidity durability of the battery is further improved.
- Examples of the surface treatment agent for hydrophobizing the surface of the inorganic filler include a silane coupling agent, and examples of the surface treatment for hydrophilization include a fluorine gas treatment.
- the preferable lower limit of the thickness of the resin layer is 100 nm, and the preferable upper limit is 100000 nm. If the thickness is 100 nm or more, the resin layer can sufficiently cover either the cathode or the anode. When the thickness is 100000 nm or less, water vapor entering from the side surface of the resin layer can be sufficiently blocked.
- the more preferable lower limit of the thickness is 500 nm, the more preferable upper limit is 50000 nm, the still more preferable lower limit is 1000 nm, and the still more preferable upper limit is 2000 nm.
- an inorganic layer is disposed on the resin layer.
- an inorganic layer may be disposed between either the cathode or the anode and the resin layer. Also in this case, since the said inorganic layer has water vapor
- the inorganic layer preferably contains a metal oxide, a metal nitride, or a metal oxynitride.
- the metal oxide, metal nitride or metal oxynitride is not particularly limited as long as it has a water vapor barrier property.
- an oxide, nitride or oxynitride of a metal element containing both metal elements of Zn and Sn is preferable.
- the metal oxide, metal nitride, or metal oxynitride is particularly preferably a metal oxide represented by the general formula Zn a Sn b O c .
- the metal oxide represented by the general formula Zn a Sn b O c for the inorganic layer, the metal oxide contains tin (Sn) atoms, and thus gives the inorganic layer appropriate flexibility. Even when the thickness of the inorganic layer is increased, the stress is reduced, so that peeling of the inorganic layer, the electrode, the semiconductor layer, and the like can be suppressed. Thereby, the water vapor
- the ratio Xs (wt%) of Sn to the sum of Zn and Sn satisfies 70>Xs> 0.
- the element ratio of zinc (Zn), tin (Sn), and oxygen (O) contained in the metal oxide represented by the general formula Zn a Sn b O c in the inorganic layer is determined by X-ray photoelectron spectroscopy ( It can be measured using an XPS) surface analyzer (for example, ESCALAB-200R manufactured by VG Scientific).
- the inorganic layer when containing a metal oxide represented by the general formula Zn a Sn b O c, preferably further contains silicon (Si) and / or aluminum (Al).
- silicon (Si) and / or aluminum (Al) By adding silicon (Si) and / or aluminum (Al) to the inorganic layer, the transparency of the inorganic layer can be increased and the photoelectric conversion efficiency of the solar cell can be improved.
- the preferable lower limit of the thickness of the inorganic layer is 30 nm, and the preferable upper limit is 3000 nm. If the said thickness is 30 nm or more, the said inorganic layer can have sufficient water vapor
- the more preferable lower limit of the thickness is 50 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 100 nm, and the still more preferable upper limit is 500 nm.
- the thickness of the inorganic layer can be measured using an optical interference film thickness measuring device (for example, FE-3000 manufactured by Otsuka Electronics Co., Ltd.).
- FIG. 2 is a cross-sectional view schematically showing an example of the solar cell of the present invention.
- a solar cell 1 shown in FIG. 2 has a cathode 2, an anode 3, and a photoelectric conversion layer 4 disposed between the cathode 2 and the anode 3 on a substrate 7, and a resin layer 5 on the anode 3.
- the inorganic layer 6 is arranged on the resin layer 5.
- the end of the resin layer 5 is closed by being in close contact with the substrate 7.
- the anode 3 is a patterned electrode.
- the method for producing the solar cell of the present invention is not particularly limited.
- the resin layer is disposed on the anode.
- Method of sealing by disposing the inorganic layer on the resin layer, forming the anode, the photoelectric conversion layer, and the cathode in this order on the substrate, and then disposing the resin layer on the cathode
- the method of sealing by arrange
- the method for forming the photoelectric conversion layer is not particularly limited, and examples thereof include a vacuum deposition method, a sputtering method, a gas phase reaction method (CVD), an electrochemical deposition method, and a printing method.
- the solar cell which can exhibit high photoelectric conversion efficiency can be simply formed in a large area by employ
- the printing method include a spin coating method and a casting method, and examples of a method using the printing method include a roll-to-roll method.
- the method of disposing the resin layer on the cathode or the anode is not particularly limited.
- a method of sealing the cathode or the anode using a sheet-like resin layer, a resin constituting the resin layer A method in which a resin solution dissolved in an organic solvent is applied on the cathode or the anode, a liquid monomer to be a resin layer is applied on the cathode or the anode, and then the liquid monomer is polymerized by heat or UV.
- Examples thereof include a method, a method in which the resin layer is melted by applying heat, and then cooled.
- a vacuum deposition method As a method for disposing the inorganic layer on the resin layer, a vacuum deposition method, a sputtering method, a gas phase reaction method (CVD), or an ion plating method is preferable.
- the sputtering method is preferable for forming a dense layer, and the DC magnetron sputtering method is more preferable among the sputtering methods.
- an inorganic layer can be formed by using a metal target and oxygen gas or nitrogen gas as raw materials and depositing the raw material on the resin layer to form a film.
- the solar cell excellent in high temperature, high humidity durability can be provided.
- Example 1 Fabrication of laminate in which cathode / electron transport layer / photoelectric conversion layer / anode are laminated On a glass substrate, an FTO film having a thickness of 1000 nm is formed as a cathode, and pure water, acetone, and methanol are used in this order. After ultrasonic cleaning for 10 minutes, it was dried. A titanium isopropoxide ethanol solution adjusted to 2% was applied on the surface of the FTO film by a spin coating method, followed by baking at 400 ° C. for 10 minutes to form a thin-film electron transport layer having a thickness of 20 nm.
- a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of an average particle size of 10 nm and 30 nm) is applied onto the thin film electron transport layer by a spin coat method, and then heated to 500 ° C. Was fired for 10 minutes to form a porous electron transport layer having a thickness of 500 nm.
- CH 3 NH 3 I and PbCl 2 were dissolved at a molar ratio of 3: 1 using N, N-dimethylformamide (DMF) as a solvent as a solution for forming an organic inorganic perovskite compound, and the total of CH 3 NH 3 I and PbCl 2 The weight concentration was adjusted to 20%.
- This solution was laminated on the electron transport layer by spin coating. Furthermore, a solution in which Poly-TPD (having a triphenylamine skeleton) of 68 mM, Tert-butylpyridine was added to 55 mM, and Lithium Bis (trifluoromethanesulfonyl) imide salt was dissolved in 25 ⁇ L of chlorobenzene to a thickness of 300 nm by spin coating, A photoelectric conversion layer was formed. On the photoelectric conversion layer, a gold film having a thickness of 100 nm was formed as an anode by vacuum vapor deposition to obtain a laminate in which the cathode / electron transport layer / photoelectric conversion layer / anode were laminated.
- Poly-TPD having a triphenylamine skeleton
- Tert-butylpyridine was added to 55 mM
- Lithium Bis (trifluoromethanesulfonyl) imide salt was dissolved in 25 ⁇ L of chlorobenzen
- the linear expansion coefficient of the resin layer was measured under a tensile condition ( ⁇ 60 ° C. to 300 ° C., 10 ° C./min) using a linear expansion coefficient measuring apparatus (TMA / SS600 manufactured by Seiko Instruments Inc.).
- Examples 2 to 10, Comparative Examples 1 to 4 In the same manner as in Example 1 except that the type of photoelectric conversion layer, the resin constituting the resin layer, the glass transition temperature and linear expansion coefficient of the resin layer, the type of inorganic layer, etc. were changed as shown in Table 1, A battery was obtained.
- Example 2 It is a cyclic olefin polymer containing 80% by weight of an alicyclic skeleton on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode in “(2) Formation of resin layer”.
- a 10% cyclohexane solution of TOPAS6015S-04 (norbornene resin, manufactured by Polyplastics Co., Ltd.) was applied with a doctor blade and the organic solvent was dried to form a resin layer having a thickness of 5 ⁇ m. A battery was obtained.
- Example 3 In “(2) Formation of resin layer”, 4 mol% of a peroxide (Park Mill D, Park Mill D, as a curing agent) was formed on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode. A 10% cyclohexane solution of Daiso Dap (diallyl phthalate resin, manufactured by Daiso Corporation), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, added with NOF is applied by a doctor blade, and the temperature is 100 ° C. for 10 minutes. A solar cell was obtained in the same manner as in Example 1 except that a resin layer having a thickness of 5 ⁇ m was formed by heating and curing.
- Daiso Dap diallyl phthalate resin, manufactured by Daiso Corporation
- Example 4 In “(2) Formation of resin layer”, Celoxide 2021P (epoxy) which is an epoxy monomer containing an alicyclic skeleton is formed on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated. Resin, manufactured by Daicel), and a solution containing 1% by weight of a thermal cation catalyst (SI-100L, manufactured by Sanshin Chemical Industry Co., Ltd.) as a curing agent was applied by a doctor blade at 150 ° C. A solar cell was obtained in the same manner as in Example 1 except that the resin layer having a thickness of 5 ⁇ m was formed by curing for 2 hours.
- a thermal cation catalyst SI-100L, manufactured by Sanshin Chemical Industry Co., Ltd.
- Example 5 In “(2) Formation of resin layer”, 4 mol% of a peroxide (Park Mill D, Park Mill D, as a curing agent) was formed on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode.
- a 10% cyclohexane solution of Daiso isopap diallyl phthalate resin, manufactured by Daiso Corporation), which is a diallyl phthalate polymer containing 80% by weight of an aromatic skeleton, to which 100% at 10 ° C. is applied
- a solar cell was obtained in the same manner as in Example 1 except that a resin layer having a thickness of 5 ⁇ m was formed by heating for a few minutes.
- Example 6 In “(2) Formation of resin layer”, 4 mol% of a peroxide (Park Mill D, Park Mill D, as a curing agent) was formed on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode.
- TS-147 isobornyl acrylate resin, manufactured by Shin-Nakamura Chemical Co., Ltd., containing 40% by weight of an alicyclic skeleton), which is a thermosetting resin as a resin constituting the resin layer.
- a solar cell was obtained in the same manner as in Example 1 except that a 10% cyclohexane solution was applied with a doctor blade, and was cured by heating at 100 ° C. for 10 minutes to form a resin layer having a thickness of 5 ⁇ m.
- Example 7 It is a cyclic olefin polymer containing 76% by weight of an alicyclic skeleton on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode in “(2) Formation of resin layer”.
- a 10% cyclohexane solution of TOPAS8007S-04 (norbornene resin, manufactured by Polyplastics, containing 76% by weight of alicyclic skeleton) was applied with a doctor blade, and the organic solvent was dried to form a resin layer having a thickness of 5 ⁇ m. Obtained a solar cell in the same manner as in Example 1.
- Example 8 In “(2) Formation of resin layer”, 4 mol% of a peroxide (Park Mill D, Park Mill D, as a curing agent) was formed on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode.
- Daiso Dup diallyl phthalate resin, manufactured by Daiso Corporation
- cyclohexyl acrylate acrylic resin, Wako Pure Chemical Industries, Ltd.
- a 10% cyclohexane solution of an 8: 2 mixture (containing 70% by weight of an alicyclic skeleton and / or an aromatic skeleton) is applied with a doctor blade, and the organic solvent is dried to obtain a resin having a thickness of 5 ⁇ m.
- a solar cell was obtained in the same manner as in Example 1 except that the layer was formed.
- Example 9 In “(2) Formation of resin layer”, 4 mol% of a peroxide (Park Mill D, Park Mill D, as a curing agent) was formed on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode.
- TS-147 isobornyl acrylate resin, manufactured by Shin-Nakamura Chemical Co., Ltd., containing 40% by weight of an alicyclic skeleton), which is a thermosetting resin as a resin constituting the resin layer.
- a cyclohexane solution containing 10% and dispersing SZR-K (zirconium oxide particles, average particle diameter 4 nm, refractive index 2.1, manufactured by Nippon Shokubai Co., Ltd.) as an inorganic filler was applied with a doctor blade, and the temperature was 100 ° C. for 10 minutes.
- a solar cell was obtained in the same manner as in Example 1 except that a resin layer having a thickness of 5 ⁇ m was formed by heating and curing.
- Example 10 In “(2) Formation of resin layer”, 4 mol% of a peroxide (Park Mill D, Park Mill D, as a curing agent) was formed on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode.
- TS-147 isobornyl acrylate resin, manufactured by Shin-Nakamura Chemical Co., Ltd., containing 40% by weight of an alicyclic skeleton), which is a thermosetting resin as a resin constituting the resin layer.
- a cyclohexane solution containing 10% and dispersed TECHPOW-TIO 2 (titanium oxide particles, average particle diameter 15 nm, refractive index 2.79, manufactured by TECMAN) as an inorganic filler was applied with a doctor blade, and 100 ° C. for 10 minutes.
- a solar cell was obtained in the same manner as in Example 1 except that a resin layer having a thickness of 5 ⁇ m was formed by heating and curing.
- Comparative Example 1 It is a cyclic olefin polymer containing 62% by weight of an alicyclic skeleton on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode in “(2) Formation of resin layer”.
- a 10% cyclohexane solution of TOPAS 9506F-04 (norbornene resin, manufactured by Polyplastics) was applied with a doctor blade and the organic solvent was dried to form a resin layer having a thickness of 5 ⁇ m. A battery was obtained.
- Comparative Example 2 In “(2) Formation of resin layer”, 10 of OPPANOL-B50 (polyisobutylene resin, manufactured by BASF) was formed on the anode of the laminate obtained by laminating the obtained cathode / electron transport layer / photoelectric conversion layer / anode. A solar cell was obtained in the same manner as in Example 1 except that a% cyclohexane solution was applied with a doctor blade and the organic solvent was dried to form a resin layer having a thickness of 5 ⁇ m.
- OPPANOL-B50 polyisobutylene resin, manufactured by BASF
- a high-temperature, high-humidity durability solar cell was placed under conditions of a humidity of 85% and a temperature of 85 ° C. for 24 hours to conduct a high-temperature, high-humidity durability test.
- a solar simulation (Yamashita Denso Co., Ltd.) with a power of 100 mW / cm 2 is connected between the electrodes of the solar cell immediately after the formation of the inorganic layer and the solar cell after the high-temperature and high-humidity durability test (236 model made by KEITHLEY).
- the photoelectric conversion efficiency was measured using the product, and the photoelectric conversion efficiency immediately after forming the photoelectric conversion efficiency / inorganic layer after the high temperature and high humidity durability test was determined.
- the value of photoelectric conversion efficiency immediately after (immediately after sealing) is 0.8 or more and less than 0.9 ⁇ : photoelectric conversion efficiency after high humidity durability test / photoelectric conversion efficiency immediately after formation of inorganic layer (immediately after sealing)
- Example 11 Fabrication of laminate in which cathode / electron transport layer / photoelectric conversion layer / anode are laminated On a glass substrate, an FTO film having a thickness of 1000 nm is formed as a cathode, and pure water, acetone, and methanol are used in this order. After ultrasonic cleaning for 10 minutes, it was dried. A titanium isopropoxide ethanol solution adjusted to 2% was applied on the surface of the FTO film by a spin coating method, followed by baking at 400 ° C. for 10 minutes to form a thin-film electron transport layer having a thickness of 20 nm.
- a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of an average particle size of 10 nm and 30 nm) is applied onto the thin film electron transport layer by a spin coat method, and then heated to 500 ° C. Was fired for 10 minutes to form a porous electron transport layer having a thickness of 500 nm.
- CH 3 NH 3 I and PbCl 2 were dissolved at a molar ratio of 3: 1 using N, N-dimethylformamide (DMF) as a solvent as a solution for forming an organic inorganic perovskite compound, and the total of CH 3 NH 3 I and PbCl 2 The weight concentration was adjusted to 20%.
- This solution was laminated on the electron transport layer by spin coating. Further, a 1 wt% chlorobenzene solution of Poly (4-butylphenyl-diphenyl-amine) (manufactured by 1-Material) was laminated as a hole transport layer on the organic / inorganic perovskite compound site to a thickness of 50 nm by a spin coating method, and photoelectric conversion was performed. A layer was formed. On the photoelectric conversion layer, an ITO film (refractive index of 1.9) having a thickness of 100 nm was formed as an anode by vacuum deposition to obtain a laminate in which the cathode / electron transport layer / photoelectric conversion layer / anode were laminated.
- the obtained resin layer was peeled from the PET film to prepare a sample.
- the glass transition temperature of the resin layer was measured under a tensile condition (25 ° C. to 125 ° C., 20 ° C./min) using a dynamic viscoelasticity measuring apparatus (DVA-200 manufactured by IT Measurement Control Co., Ltd.).
- the linear expansion coefficient of the resin layer was measured under a tensile condition ( ⁇ 60 ° C. to 300 ° C., 10 ° C./min) using a linear expansion coefficient measuring apparatus (TMA / SS600 manufactured by Seiko Instruments Inc.).
- Example 1 except that the type of photoelectric conversion layer, the type of resin constituting the resin layer, the type and content of inorganic filler contained in the resin layer, the type of inorganic layer, etc. were changed as shown in Table 3. Similarly, a solar cell was obtained.
- Example 12 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated.
- an inorganic filler it contains 10% Daisodap (diallyl phthalate resin, Daiso Corp.), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, to which is added a peroxide (Perk Mill D, manufactured by NOF Corporation).
- TECHPOW-TIO 2 titanium oxide particles, average particle size 15 nm, refractive index 2.79, manufactured by TECMAN
- TECMAN refractive index 2.79
- Example 13 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated.
- an inorganic filler it contains 10% Daisodap (diallyl phthalate resin, Daiso Corp.), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, to which is added a peroxide (Perk Mill D, manufactured by NOF Corporation).
- a cyclohexane solution in which SZR-K (zirconium oxide particles, average particle diameter 4 nm, refractive index 2.1, manufactured by Nippon Shokubai Co., Ltd.) was dispersed was applied with a doctor blade, the organic solvent was dried, and the inorganic filler was 70 vol%
- SZR-K zirconium oxide particles, average particle diameter 4 nm, refractive index 2.1, manufactured by Nippon Shokubai Co., Ltd.
- Example 14 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated.
- an inorganic filler it contains 10% Daisodap (diallyl phthalate resin, Daiso Corp.), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, to which is added a peroxide (Perk Mill D, manufactured by NOF Corporation).
- TECHPOW-ZrO 2 zirconium oxide particles, average particle diameter 20 nm, refractive index 2.1, manufactured by TECMAN
- TECMAN refractive index 2.1
- Example 15 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated.
- an inorganic filler it contains 10% Daisodap (diallyl phthalate resin, Daiso Corp.), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, to which is added a peroxide (Perk Mill D, manufactured by NOF Corporation).
- a cyclohexane solution in which magnesium fluoride particles (average particle size 40 nm, refractive index 1.3) are dispersed is applied with a doctor blade, the organic solvent is dried, and a resin layer having a thickness of 5 ⁇ m containing 20% by volume of an inorganic filler is obtained.
- a solar cell was obtained in the same manner as in Example 1 except that it was formed.
- Example 16 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated. And 10% Daiso Dap (diallyl phthalate resin, Daiso Corp.) which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton and sulfurized as an inorganic filler.
- Daiso Dap diallyl phthalate resin, Daiso Corp.
- a cyclohexane solution in which antimony particles (average particle size 40 nm, refractive index 4.06) are dispersed is applied with a doctor blade, and the organic solvent is dried to form a resin layer having a thickness of 5 ⁇ m containing 20% by volume of an inorganic filler. Except for this, a solar cell was obtained in the same manner as in Example 1.
- Example 17 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated.
- an inorganic filler it contains 10% Daisodap (diallyl phthalate resin, Daiso Corp.), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, to which is added a peroxide (Perk Mill D, manufactured by NOF Corporation).
- a cyclohexane solution in which SZR-K (zirconium oxide particles, average particle diameter 4 nm, refractive index 2.1, manufactured by Nippon Shokubai Co., Ltd.) was dispersed was applied with a doctor blade, the organic solvent was dried, and 1% by volume of an inorganic filler A solar cell was obtained in the same manner as in Example 1 except that a 5 ⁇ m thick resin layer was formed.
- SZR-K zirconium oxide particles, average particle diameter 4 nm, refractive index 2.1, manufactured by Nippon Shokubai Co., Ltd.
- Example 18 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated.
- an inorganic filler it contains 10% Daisodap (diallyl phthalate resin, Daiso Corp.), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, to which is added a peroxide (Perk Mill D, manufactured by NOF Corporation).
- SZR-K zirconium oxide particles, average particle diameter 4 nm, refractive index 2.1, manufactured by Nippon Shokubai Co., Ltd.
- SZR-K zirconium oxide particles, average particle diameter 4 nm, refractive index 2.1, manufactured by Nippon Shokubai Co., Ltd.
- Example 19 In “(2) Formation of resin layer”, 4 mol% as a curing agent is used as a resin constituting the resin layer on the anode of the laminate in which the obtained cathode / electron transport layer / photoelectric conversion layer / anode is laminated.
- an inorganic filler it contains 10% Daisodap (diallyl phthalate resin, Daiso Corp.), which is a diallyl phthalate polymer containing 50% by weight of an aromatic skeleton, to which is added a peroxide (Perk Mill D, manufactured by NOF Corporation).
- TA-200 titanium oxide particles, average particle size 610 nm, refractive index 2.79, manufactured by Fuji Titanium Co., Ltd.
- TA-200 titanium oxide particles, average particle size 610 nm, refractive index 2.79, manufactured by Fuji Titanium Co., Ltd.
- Photoelectric conversion efficiency A power source (manufactured by KEITHLEY, 236 model) is connected between the electrodes of the solar cell, and the photoelectric conversion efficiency is measured by using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm 2. The obtained photoelectric conversion efficiency was defined as initial conversion efficiency. The solar cell obtained in Example 3 was normalized based on the initial conversion efficiency. ⁇ : Standardized photoelectric conversion efficiency value is 1.2 or more ⁇ : Standardized photoelectric conversion efficiency value is less than 1.2
- a high temperature and high humidity durability solar cell was placed under conditions of a humidity of 85% and a temperature of 85 ° C. for 24 hours to conduct a high temperature and high humidity durability test.
- a power source (made by KEITHLEY, 236 model) was connected between the electrodes of the solar cell after the high temperature and high humidity durability test, and the photoelectric conversion efficiency was measured using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm 2 .
- the photoelectric conversion efficiency after the high-temperature and high-humidity durability test of the solar cell obtained in Example 3 was standardized.
- Standardized Photoelectric conversion efficiency after high temperature and high humidity durability test is less than 1.05
- the solar cell excellent in high temperature, high humidity durability can be provided.
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Abstract
Description
以下、本発明を詳述する。
しかしながら、上記樹脂層の種類によっては、特に湿度85%程度以上、温度85℃程度以上の高温高湿の雰囲気下では、上記無機層及び樹脂層に微細な表面凹凸(波状)が生じることがわかった。そして、このような微細な表面凹凸(波状)が生じた結果、上記無機層に剥離又はクラックが生じやすくなり、該剥離やクラックを通って水分が樹脂層の内部に入り込み、太陽電池が劣化することがわかった。
これに対して、本発明者らは、上記樹脂層のガラス転移温度と線膨張係数とを特定範囲内に調整することで、高温高湿の雰囲気下においても上記無機層及び樹脂層の微細な表面凹凸の発生を抑えることができ、高温高湿の雰囲気下でも上記無機層の剥離又はクラックの発生を抑えて、太陽電池の高温高湿耐久性を向上できることを見出した。また、本発明者らは、ガラス転移温度と線膨張係数とを特定範囲内に調整した樹脂層は、上記光電変換層が有機無機ペロブスカイト化合物を含む場合に特に、該光電変換層に対して剥離が生じにくいことを見出し、本発明を完成させるに至った。
なお、本明細書中、層とは、明確な境界を有する層だけではなく、含有元素が徐々に変化する濃度勾配のある層をも意味する。なお、層の元素分析は、例えば、太陽電池の断面のFE-TEM/EDS線分析測定を行い、特定元素の元素分布を確認する等によって行うことができる。また、本明細書中、層とは、平坦な薄膜状の層だけではなく、他の層と一緒になって複雑に入り組んだ構造を形成しうる層をも意味する。また、本明細書中、A~Bとは、A以上、B以下を意味する。
陰極材料として、例えば、FTO(フッ素ドープ酸化スズ)、ナトリウム、ナトリウム-カリウム合金、リチウム、マグネシウム、アルミニウム、マグネシウム-銀混合物、マグネシウム-インジウム混合物、アルミニウム-リチウム合金、Al/Al2O3混合物、Al/LiF混合物等が挙げられる。陽極材料として、例えば、金等の金属、CuI、ITO(インジウムスズ酸化物)、SnO2、AZO(アルミニウム亜鉛酸化物)、IZO(インジウム亜鉛酸化物)、GZO(ガリウム亜鉛酸化物)等の導電性透明材料、導電性透明ポリマー等が挙げられる。これらの材料は単独で用いられてもよく、2種以上が併用されてもよい。
上記陽極材料の屈折率も特に限定されないが、上記陽極が上記樹脂層と接する場合には、上記樹脂層との屈折率差が小さいことが好ましい。なお、例えば、ITO(インジウムスズ酸化物)の屈折率は一般的に1.8以上、2.3以下程度、AZOの屈折率は一般的に1.8以上、2.2以下程度である。
上記光電変換層に上記有機無機ペロブスカイト化合物を用いることにより、太陽電池の光電変換効率を向上させることができる。また、上記有機無機ペロブスカイト化合物は耐湿性が低いことから、上記光電変換層に上記有機無機ペロブスカイト化合物を用いる場合には、太陽電池の高温高湿耐久性の向上のために上記陰極上又は上記陽極上のいずれか一方に後述するような樹脂層及び無機層を配置することがより有効となる。
上記Rは、具体的には例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、エチルメチルアミン、メチルプロピルアミン、ブチルメチルアミン、メチルペンチルアミン、ヘキシルメチルアミン、エチルプロピルアミン、エチルブチルアミン、イミダゾール、アゾール、ピロール、アジリジン、アジリン、アゼチジン、アゼト、アゾール、イミダゾリン、カルバゾール及びこれらのイオン(例えば、メチルアンモニウム(CH3NH3)等)やフェネチルアンモニウム等が挙げられる。なかでも、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン及びこれらのイオンやフェネチルアンモニウムが好ましく、メチルアミン、エチルアミン、プロピルアミン及びこれらのイオンがより好ましい。
図1は、体心に金属原子M、各頂点に有機分子R、面心にハロゲン原子又はカルコゲン原子Xが配置された立方晶系の構造である、有機無機ペロブスカイト化合物の結晶構造の一例を示す模式図である。詳細は明らかではないが、上記構造を有することにより、結晶格子内の八面体の向きが容易に変わることができるため、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、太陽電池の光電変換効率が向上すると推定される。
上記有機無機ペロブスカイト化合物の結晶化度の好ましい下限は30%である。結晶化度が30%以上であると、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、太陽電池の光電変換効率が向上する。結晶化度のより好ましい下限は50%、更に好ましい下限は70%である。
また、上記有機無機ペロブスカイト化合物の結晶化度を上げる方法として、例えば、熱アニール、レーザー等の強度の強い光の照射、プラズマ照射等が挙げられる。
上記有機半導体として、例えば、ポリ(3-アルキルチオフェン)等のチオフェン骨格を有する化合物等が挙げられる。また、例えば、ポリパラフェニレンビニレン骨格、ポリビニルカルバゾール骨格、ポリアニリン骨格、ポリアセチレン骨格等を有する導電性高分子等も挙げられる。更に、例えば、フタロシアニン骨格、ナフタロシアニン骨格、ペンタセン骨格、ベンゾポルフィリン骨格等のポルフィリン骨格、スピロビフルオレン骨格等を有する化合物や、表面修飾されていてもよいカーボンナノチューブ、グラフェン、フラーレン等のカーボン含有材料も挙げられる。
上記電子輸送層の材料は特に限定されず、例えば、N型導電性高分子、N型低分子有機半導体、N型金属酸化物、N型金属硫化物、ハロゲン化アルカリ金属、アルカリ金属、界面活性剤等が挙げられ、具体的には例えば、シアノ基含有ポリフェニレンビニレン、ホウ素含有ポリマー、バソキュプロイン、バソフェナントレン、ヒドロキシキノリナトアルミニウム、オキサジアゾール化合物、ベンゾイミダゾール化合物、ナフタレンテトラカルボン酸化合物、ペリレン誘導体、ホスフィンオキサイド化合物、ホスフィンスルフィド化合物、フルオロ基含有フタロシアニン、酸化チタン、酸化亜鉛、酸化インジウム、酸化スズ、酸化ガリウム、硫化スズ、硫化インジウム、硫化亜鉛等が挙げられる。
上記ホール輸送層の材料は特に限定されず、例えば、P型導電性高分子、P型低分子有機半導体、P型金属酸化物、P型金属硫化物、界面活性剤等が挙げられ、具体的には例えば、ポリエチレンジオキシチオフェンのポリスチレンスルホン酸付加物、カルボキシル基含有ポリチオフェン、フタロシアニン、ポルフィリン、酸化モリブデン、酸化バナジウム、酸化タングステン、酸化ニッケル、酸化銅、酸化スズ、硫化モリブデン、硫化タングステン、硫化銅、硫化スズ、フルオロ基含有ホスホン酸、カルボニル基含有ホスホン酸、CuSCN、CuI等の銅化合物、表面修飾されていてもよいカーボンナノチューブ、グラフェン等のカーボン含有材料等が挙げられる。
上記陰極上又は上記陽極上のいずれか一方に樹脂層を配置することにより、太陽電池の高温高湿耐久性を向上させることができる。これは、上記樹脂層を配置することにより、水分が太陽電池の内部に浸透することを抑制できるためと考えられる。ここで、上記樹脂層は、その端部を閉じるようにして、上記陰極と上記光電変換層と上記陽極とを含む積層体全体を覆うことが好ましい。これにより、水分が太陽電池の内部に浸透することを確実に防止することができる。
なお、上記ガラス転移温度は、動的粘弾性測定装置(例えば、アイティー計測制御社製のDVA-200等)を用いて、引っ張り条件(25℃から125℃、20℃/分)で測定することができる。上記樹脂層を構成する樹脂が熱硬化性樹脂又は光硬化性樹脂である場合、上記ガラス転移温度とは、熱硬化性樹脂又は光硬化性樹脂等の硬化後のガラス転移温度を意味する。
なお、上記線膨張係数は、線膨張率測定装置(例えば、セイコーインスツル社製のTMA/SS600等)を用いて、引っ張り条件(-60℃から300℃、10℃/分)で測定することができる。
上記脂環式骨格は特に限定されず、例えば、ノルボルネン、イソボルネン、アダマンタン、シクロヘキサン、ジシクロペンタジエン、ジシクロヘキサン、シクロペンタン等の骨格が挙げられる。上記芳香族骨格は特に限定されず、例えば、フタレート骨格が挙げられる。これらの骨格は単独で用いられてもよく、2種以上が併用されてもよい。なかでも、上記陰極材料及び陽極材料との屈折率差が小さくなることから、ノルボルネン骨格、イソボルネン骨格、アダマンタン骨格、シクロヘキサン骨格、フタレート骨格が好ましい。
なお、脂環式骨格及び/又は芳香族骨格の含有量とは、脂環式骨格及び/又は芳香族骨格を有する樹脂が、脂環式骨格及び/又は芳香族骨格を有するモノマーと、脂環式骨格も芳香族骨格も有さないモノマーとの共重合体である場合において、共重合体中の脂環式骨格及び/又は芳香族骨格を有するモノマーに由来する成分の含有量を意味する。上記共重合体は、熱可塑性樹脂であってもよいし、更に硬化剤と反応させることで硬化する熱硬化性樹脂又は光硬化性樹脂、即ち、プレポリマーであってもよい。
上記共重合体中の脂環式骨格を有するモノマーに由来する成分及び芳香族骨格を有するモノマーに由来する成分の含有量の算出方法としては、原料モノマーの添加重量から計算する方法や、GC-MS等による組成分析結果から算出する方法等がある。
また、上記脂環式骨格及び/又は芳香族骨格を有する樹脂は、反応性官能基を有する樹脂を製膜した後、上記反応性官能基を架橋反応させた樹脂であってもよい。
上記樹脂層に、上記範囲内に調整された屈折率、平均粒子径及び平均細孔径を有する無機フィラーを特定範囲の配合量で配合することで、上記樹脂層と、それに接する材料(例えば、陰極又は陽極、基板等)との屈折率差を低減し、太陽光を効率よく太陽電池の内部(光電変換層の内部)に到達させて太陽電池の光電変換効率を向上させることができる。また、上記樹脂層に、上記範囲内に調整された屈折率及び含有量の無機フィラーを配合することで、上記樹脂層のガラス転移温度と、線膨張係数とを上記範囲内に調整しやすくなるうえ、上記無機フィラーが上記樹脂層の内部に浸透した水分を吸着して太陽電池の劣化(光電変換層の劣化)を抑えることができるため、太陽電池の高温高湿耐久性を向上させることができる。
なお、上記無機フィラーの平均粒子径は、ナノ粒子径分布測定装置(例えば、島津製作所社製のSALD-7500NANO等)を用いて測定することができる。
なお、上記無機フィラーが多孔質状であることは、走査型電子顕微鏡法(SEM)解析により確認できる。また、上記無機フィラーの平均細孔径は、高機能比表面積/細孔分布測定装置(例えばマイクロメリティックスジャパン社製、ASAP2020)を用いて算出できる。
なお、上記無機フィラーの比表面積は、高機能比表面積/細孔分布測定装置(例えばマイクロメリティックスジャパン社製、ASAP2020)を用いて算出できる。
上記酸化物としては、例えば、シリカ、ゼオライト、ガラス、酸化カルシウム、酸化バリウム、酸化マグネシウム、酸化ジルコニウム、酸化ストロンチウム、チタン酸バリウム等が挙げられる。
上記硫化物としては、例えば、硫化亜鉛、硫化マグネシウムが挙げられる。
上記硫酸化物としては、例えば、硫酸リチウム、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸コバルト、硫酸ガリウム、硫酸チタン等が挙げられる。
上記ケイ酸化物としては、例えば、ケイ酸ジルコニウム、ケイ酸ビスマス等が挙げられる。なかでも、水分吸着機能を有し、水分を吸着した後でも固体状態を維持する化合物であることが好ましいことから、上記無機フィラーは、酸化物及び硫酸化物からなる群より選択される少なくとも1種を含有することが好ましい。
なお、本発明の太陽電池においては、上記陰極上又は上記陽極上のいずれか一方と上記樹脂層との間にも無機層が配置されていてもよい。この場合にも、上記無機層が水蒸気バリア性を有し、水分が太陽電池の内部に浸透することを抑制できるため、太陽電池の高温高湿耐久性をより向上させることができる。
なお、上記無機層中の上記一般式ZnaSnbOcで表される金属酸化物に含まれる亜鉛(Zn)、スズ(Sn)及び酸素(O)の元素比率は、X線光電子分光(XPS)表面分析装置(例えば、VGサイエンティフィックス社製のESCALAB-200R等)を用いて測定することができる。
上記無機層にケイ素(Si)及び/又はアルミニウム(Al)を添加することにより、上記無機層の透明性を高め、太陽電池の光電変換効率を向上させることができる。
なお、上記無機層の厚みは、光学干渉式膜厚測定装置(例えば、大塚電子社製のFE-3000等)を用いて測定することができる。
図2に示す太陽電池1は、基板7上に陰極2と、陽極3と、この陰極2と陽極3との間に配置された光電変換層4とを有し、陽極3上に樹脂層5が配置され、樹脂層5上に無機層6が配置されたものである。ここで樹脂層5の端部は、基板7に密着することにより閉じている。なお、図2に示す太陽電池1において、陽極3はパターニングされた電極である。
(1)陰極/電子輸送層/光電変換層/陽極が積層された積層体の作製
ガラス基板上に、陰極として厚み1000nmのFTO膜を形成し、純水、アセトン、メタノールをこの順に用いて各10分間超音波洗浄した後、乾燥させた。
FTO膜の表面上に、2%に調整したチタンイソプロポキシドエタノール溶液をスピンコート法により塗布した後、400℃で10分間焼成し、厚み20nmの薄膜状の電子輸送層を形成した。更に、薄膜状の電子輸送層上に、有機バインダとしてのポリイソブチルメタクリレートと酸化チタン(平均粒子径10nmと30nmとの混合物)とを含有する酸化チタンペーストをスピンコート法により塗布した後、500℃で10分間焼成し、厚み500nmの多孔質状の電子輸送層を形成した。
次いで、有機無機ペロブスカイト化合物形成用溶液として、N,N-ジメチルホルムアミド(DMF)を溶媒としてCH3NH3IとPbCl2をモル比3:1で溶かし、CH3NH3IとPbCl2の合計重量濃度を20%に調製した。この溶液を電子輸送層上にスピンコート法によって積層した。更に、クロロベンゼン25μLにPoly-TPD(トリフェニルアミン骨格を有する)を68mM、Tert-butylpyridineを55mM、Lithium Bis(trifluoromethanesufonyl)imide塩を9mM溶解させた溶液をスピンコート法によって300nmの厚みに積層し、光電変換層を形成した。
光電変換層上に、陽極として真空蒸着により厚み100nmの金膜を形成し、陰極/電子輸送層/光電変換層/陽極が積層された積層体を得た。
得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂としての、脂環式骨格を82重量%含む環状オレフィンポリマーであるTOPAS6017S-04(ノルボルネン樹脂、ポリプラスチックス社製)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み5μmの樹脂層を形成した。
樹脂層を形成したサンプルをスパッタリング装置の基板ホルダーに取り付け、更に、スパッタリング装置のカソードAにZnSn合金(Zn:Sn=95:5重量%)ターゲットを、カソードBにSiターゲットを取り付けた。スパッタリング装置の成膜室を真空ポンプにより排気し、5.0×10-4Paまで減圧した。その後、成膜条件Aに示す条件でスパッタリングし、樹脂層上に無機層としてZnSnO(Si)薄膜を100nm形成し、太陽電池を得た。
(成膜条件A)
アルゴンガス流量:50sccm,酸素ガス流量:50sccm
電源出力:カソードA=500W、カソードB=1500W
離型処理を施したポリエチレンテレフタレート(PET)フィルム上に、樹脂層を構成する樹脂としての、脂環式骨格を82重量%含む環状オレフィンポリマーであるTOPAS6017S-04(ノルボルネン樹脂、ポリプラスチックス社製)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み500μmの樹脂層を形成した。得られた樹脂層をPETフィルムから剥離し、サンプルとした。
動的粘弾性測定装置(アイティー計測制御社製のDVA-200)を用いて、引っ張り条件(25℃から125℃、20℃/分)で樹脂層のガラス転移温度を測定した。また、線膨張率測定装置(セイコーインスツル社製のTMA/SS600)を用いて、引っ張り条件(-60℃から300℃、10℃/分)で樹脂層の線膨張係数を測定した。
光電変換層の種類、樹脂層を構成する樹脂、樹脂層のガラス転移温度及び線膨張係数、無機層の種類等を表1に示すように変更したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、脂環式骨格を80重量%含む環状オレフィンポリマーであるTOPAS6015S-04(ノルボルネン樹脂、ポリプラスチックス社製)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)の10%シクロヘキサン溶液をドクターブレードにより塗布し、100℃、10分加熱して硬化させて厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、脂環式骨格を含むエポキシモノマーであるセロキサイド2021P(エポキシ樹脂、ダイセル社製)を主剤とし、硬化剤として主剤に対し1重量%の熱カチオン触媒(SI-100L、三新化学工業社製)を加えた溶液を、ドクターブレードにより塗布し、150℃で2時間硬化させ、厚さ5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を80重量%含むジアリルフタレートポリマーであるダイソーイソダップ(ジアリルフタレート樹脂、ダイソー社製)の10%シクロヘキサン溶液をドクターブレードにより塗布し、100℃、10分加熱して硬化させて厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、樹脂層を構成する樹脂としての熱硬化性樹脂であるTS-147(イソボルニルアクリレート樹脂、新中村化学社製、脂環式骨格を40重量%含む)の10%シクロヘキサン溶液をドクターブレードにより塗布し、100℃、10分加熱して硬化させて厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、脂環式骨格を76重量%含む環状オレフィンポリマーであるTOPAS8007S-04(ノルボルネン樹脂、ポリプラスチックス社製、脂環式骨格を76重量%含む)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)と熱硬化性樹脂であるシクロヘキシルアクリレート(アクリル樹脂、和光純薬工業社製)との重量比8:2混合物(脂環式骨格及び/又は芳香族骨格を70重量%含む)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、樹脂層を構成する樹脂としての熱硬化性樹脂であるTS-147(イソボルニルアクリレート樹脂、新中村化学社製、脂環式骨格を40重量%含む)を10%含有するとともに無機フィラーとしてのSZR-K(酸化ジルコニウム粒子、平均粒子径4nm、屈折率2.1、日本触媒社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、100℃、10分加熱して硬化させて厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、樹脂層を構成する樹脂としての熱硬化性樹脂であるTS-147(イソボルニルアクリレート樹脂、新中村化学社製、脂環式骨格を40重量%含む)を10%含有するとともに無機フィラーとしてのTECHPOW-TIO2(酸化チタン粒子、平均粒子径15nm、屈折率2.79、TECMAN社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、100℃、10分加熱して硬化させて厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、脂環式骨格を62重量%含む環状オレフィンポリマーであるTOPAS9506F-04(ノルボルネン樹脂、ポリプラスチックス社製)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、OPPANOL-B50(ポリイソブチレン樹脂、BASF社製)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、脂環式骨格を含むエポキシモノマーであるセロキサイド8000(エポキシ樹脂、ダイセル社製)を主剤とし、硬化剤として主剤に対し1重量%の熱カチオン触媒(SI-100L、三新化学工業社製)を加えた溶液を、ドクターブレードにより塗布し、150℃で2時間硬化させ、厚さ5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)と熱硬化性樹脂であるラウリルアクリレート(アクリル樹脂、和光純薬工業社製)との重量比5:5混合物(芳香族骨格を20重量%含む)の10%シクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて厚み5μmの樹脂層を形成した以外は実施例1と同様にして、太陽電池を得た。
実施例1~10及び比較例1~4で得られた太陽電池について、以下の評価を行った。結果を表2に示した。
高温高湿耐久試験後に、無機層の表面の微細な表面凹凸の有無を目視観察した。
○:表面に微細な表面凹凸が見られない
×:表面に微細な表面凹凸が見られる
太陽電池を湿度85%、温度85℃の条件下に24時間置いて高温高湿耐久試験を行った。無機層を形成した直後の太陽電池、及び、高温高湿耐久試験後の太陽電池の電極間に電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、高温高湿耐久試験後の光電変換効率/無機層を形成した直後の光電変換効率の値を求めた。
◎:高湿耐久試験後の光電変換効率/無機層を形成した直後(封止直後)の光電変換効率の値が0.9以上
○:高湿耐久試験後の光電変換効率/無機層を形成した直後(封止直後)の光電変換効率の値が0.8以上、0.9未満
△:高湿耐久試験後の光電変換効率/無機層を形成した直後(封止直後)の光電変換効率の値が0.7以上、0.8未満
×:高湿耐久試験後の光電変換効率/無機層を形成した直後(封止直後)の光電変換効率の値が0.7未満
(1)陰極/電子輸送層/光電変換層/陽極が積層された積層体の作製
ガラス基板上に、陰極として厚み1000nmのFTO膜を形成し、純水、アセトン、メタノールをこの順に用いて各10分間超音波洗浄した後、乾燥させた。
FTO膜の表面上に、2%に調整したチタンイソプロポキシドエタノール溶液をスピンコート法により塗布した後、400℃で10分間焼成し、厚み20nmの薄膜状の電子輸送層を形成した。更に、薄膜状の電子輸送層上に、有機バインダとしてのポリイソブチルメタクリレートと酸化チタン(平均粒子径10nmと30nmとの混合物)とを含有する酸化チタンペーストをスピンコート法により塗布した後、500℃で10分間焼成し、厚み500nmの多孔質状の電子輸送層を形成した。
次いで、有機無機ペロブスカイト化合物形成用溶液として、N,N-ジメチルホルムアミド(DMF)を溶媒としてCH3NH3IとPbCl2をモル比3:1で溶かし、CH3NH3IとPbCl2の合計重量濃度を20%に調整した。この溶液を電子輸送層上にスピンコート法によって積層した。更に、ホール輸送層としてPoly(4-butylphenyl-diphenyl-amine)(1-Material社製)の1重量%クロロベンゼン溶液を有機無機ペロブスカイト化合物部位上にスピンコート法によって50nmの厚みに積層し、光電変換層を形成した。
光電変換層上に、陽極として真空蒸着により厚み100nmのITO膜(屈折率1.9)を形成し、陰極/電子輸送層/光電変換層/陽極が積層された積層体を得た。
得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのSZR-K(酸化ジルコニウム粒子、平均粒子径4nm、屈折率2.1、日本触媒社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを25体積%含有する厚み5μmの樹脂層を形成した。なお、本実施例で用いた無機フィラーの平均細孔径は全て5Å以上、5000Å以下の範囲内であった。
樹脂層を形成したサンプルをスパッタリング装置の基板ホルダーに取り付け、更に、スパッタリング装置のカソードAにZnSn合金(Zn:Sn=95:5重量%)ターゲットを、カソードBにSiターゲットを取り付けた。スパッタリング装置の成膜室を真空ポンプにより排気し、5.0×10-4Paまで減圧した。その後、成膜条件Aに示す条件でスパッタリングし、樹脂層上に無機層としてZnSnO(Si)薄膜を100nm形成し、太陽電池を得た。
(成膜条件A)
アルゴンガス流量:50sccm,酸素ガス流量:50sccm
電源出力:カソードA=500W、カソードB=1500W
離型処理を施したポリエチレンテレフタレート(PET)フィルム上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのSZR-K(酸化ジルコニウム粒子、平均粒子径4nm、屈折率2.1、日本触媒社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを25体積%含有する厚み500μmの樹脂層を形成した。得られた樹脂層をPETフィルムから剥離し、サンプルとした。
動的粘弾性測定装置(アイティー計測制御社製のDVA-200)を用いて、引っ張り条件(25℃から125℃、20℃/分)で樹脂層のガラス転移温度を測定した。また、線膨張率測定装置(セイコーインスツル社製のTMA/SS600)を用いて、引っ張り条件(-60℃から300℃、10℃/分)で樹脂層の線膨張係数を測定した。
光電変換層の種類、樹脂層を構成する樹脂の種類、樹脂層に含有される無機フィラーの種類及び含有量、無機層の種類等を表3に示すように変更したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのTECHPOW-TIO2(酸化チタン粒子、平均粒子径15nm、屈折率2.79、TECMAN社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを25体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのSZR-K(酸化ジルコニウム粒子、平均粒子径4nm、屈折率2.1、日本触媒社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを70体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのTECHPOW-ZrO2(酸化ジルコニウム粒子、平均粒子径20nm、屈折率2.1、TECMAN社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを20体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのフッ化マグネシウム粒子(平均粒子径40nm、屈折率1.3)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを20体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)と、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしての硫化アンチモン粒子(平均粒子径40nm、屈折率4.06)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを20体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのSZR-K(酸化ジルコニウム粒子、平均粒子径4nm、屈折率2.1、日本触媒社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを1体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのSZR-K(酸化ジルコニウム粒子、平均粒子径4nm、屈折率2.1、日本触媒社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを80体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
「(2)樹脂層の形成」において、得られた陰極/電子輸送層/光電変換層/陽極が積層された積層体の陽極上に、樹脂層を構成する樹脂として、硬化剤としての4mol%の過酸化物(パークミルD、日油社製)を添加した、芳香族骨格を50重量%含むジアリルフタレートポリマーであるダイソーダップ(ジアリルフタレート樹脂、ダイソー社製)を10%含有するとともに無機フィラーとしてのTA-200(酸化チタン粒子、平均粒子径610nm、屈折率2.79、富士チタン社製)を分散したシクロヘキサン溶液をドクターブレードにより塗布し、有機溶媒を乾燥させて、無機フィラーを20体積%含有する厚み5μmの樹脂層を形成したこと以外は実施例1と同様にして、太陽電池を得た。
実施例11~19で得られた太陽電池について、以下の評価を行った。結果を表4に示した。
太陽電池の電極間に電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、得られた光電変換効率を初期変換効率とした。実施例3で得られた太陽電池の初期変換効率を基準として規格化した。
○:規格化した光電変換効率の値が1.2以上
△:規格化した光電変換効率の値が1.2未満
高温高湿耐久試験後に、無機層の表面の微細な表面凹凸の有無を目視観察した。
○:表面に微細な表面凹凸が見られない
×:表面に微細な表面凹凸が見られる
太陽電池を湿度85%、温度85℃の条件下に24時間置いて高温高湿耐久試験を行った。高温高湿耐久試験後の太陽電池の電極間に電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定した。実施例3で得られた太陽電池の高温高湿耐久試験後の光電変換効率を基準として規格化した。
◎:規格化した高温高湿耐久試験後の光電変換効率が1.1以上
○:規格化した高温高湿耐久試験後の光電変換効率が1.05以上、1.1未満
△:規格化した高温高湿耐久試験後の光電変換効率が1.05未満
2 陰極
3 陽極(パターニングされた電極)
4 光電変換層
5 樹脂層
6 無機層
7 基板
Claims (5)
- 陰極と、陽極と、前記陰極と前記陽極との間に配置された光電変換層とを有する太陽電池であって、
前記光電変換層は、一般式R-M-X3(但し、Rは有機分子、Mは金属原子、Xはハロゲン原子又はカルコゲン原子である。)で表される有機無機ペロブスカイト化合物を含み、
前記陰極上又は前記陽極上のいずれか一方に樹脂層が配置され、
前記樹脂層上に無機層が配置され、
前記樹脂層のガラス転移温度が70℃以上、200℃以下、かつ、線膨張係数が9.0×10-6K-1以上、1.5×10-4K-1以下である
ことを特徴とする太陽電池。 - 樹脂層のガラス転移温度が85℃以上であることを特徴とする請求項1記載の太陽電池。
- 樹脂層は、脂環式骨格及び/又は芳香族骨格を有する樹脂を含有することを特徴とする請求項1又は2記載の太陽電池。
- 脂環式骨格及び/又は芳香族骨格を有する樹脂は、脂環式骨格及び/又は芳香族骨格の含有量が30重量%以上であることを特徴とする請求項3記載の太陽電池。
- 樹脂層は、無機フィラーを含有することを特徴とする請求項1、2、3又は4記載の太陽電池。
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JP2018163938A (ja) * | 2017-03-24 | 2018-10-18 | 積水化学工業株式会社 | 太陽電池 |
JP2018170382A (ja) * | 2017-03-29 | 2018-11-01 | 積水化学工業株式会社 | 太陽電池 |
CN110392940A (zh) * | 2017-03-30 | 2019-10-29 | 积水化学工业株式会社 | 太阳能电池及其制造方法 |
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