WO2011158874A1 - Cellule solaire à couche mince organique - Google Patents

Cellule solaire à couche mince organique Download PDF

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WO2011158874A1
WO2011158874A1 PCT/JP2011/063718 JP2011063718W WO2011158874A1 WO 2011158874 A1 WO2011158874 A1 WO 2011158874A1 JP 2011063718 W JP2011063718 W JP 2011063718W WO 2011158874 A1 WO2011158874 A1 WO 2011158874A1
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layer
organic
gas barrier
solar cell
organic thin
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PCT/JP2011/063718
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Japanese (ja)
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東　耕平
塚原　次郎
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富士フイルム株式会社
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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
    • 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
    • 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 an organic thin film solar cell having a resin film as a substrate, and more particularly to an organic thin film solar cell in which a photoelectric conversion part is sealed with a gas barrier film and a gas barrier layer as a substrate.
  • a power generation module that performs solar power generation has a structure in which a portion that performs photoelectric conversion is disposed on a glass that is a substrate on which sunlight is incident, and is protected by sealing it with a gas barrier material.
  • organic thin-film solar cells that are expected to be low-cost, lightweight, and flexible are attracting attention.
  • As a structure of the organic thin film solar cell a structure in which a single layer or a plurality of layers of an organic thin film having a photoelectric conversion function is arranged between two different electrodes is common.
  • This organic thin film solar cell has an advantage that it can be made light and flexible by using a plastic film as a substrate.
  • studies have been made to use a plastic film, which is a resin material, as a substrate for a solar cell.
  • organic optoelectronic devices are considered to have lower durability than inorganic optoelectronic devices.
  • the plastic film cannot transmit water vapor, oxygen, or the like as much as the glass substrate. Deterioration is great and the durability of the solar cell is significantly reduced. For this reason, it has been impossible to mount a resin material while expecting a resin material as a substrate.
  • Organic thin-film solar cells have conventionally used a metal having a low work function, such as aluminum, as the negative electrode because of their high power generation efficiency.
  • a metal having a small work function generally has a large ionization tendency, it is easily corroded by oxygen or water vapor in the atmosphere and is inferior in durability.
  • durability can be improved by using a metal (eg, silver, copper) that has a smaller ionization tendency than aluminum and is less likely to corrode.
  • a metal eg, silver, copper
  • the conversion efficiency decreases. Further, even if a structure in which an inorganic oxide layer such as titanium oxide is provided between aluminum and the organic photoelectric conversion layer, the durability is not sufficient. At present, the technology for improving the durability without reducing the conversion efficiency has not yet been established.
  • the organic thin film solar cell provided with a plastic film as a substrate cannot be said to have sufficient durability even by various devices. There is a disadvantage that it cannot withstand long-term use.
  • the present invention has been made in view of the above, and aims to provide an organic thin-film solar cell that has high durability and can withstand long-term use, and that can maintain high photoelectric conversion efficiency while suppressing a decrease in efficiency. It is an object to achieve the object.
  • the substrate on which the organic thin-film solar cell is formed is a gas barrier film substrate, and only a gas barrier layer is provided outside the electrode on the side away from the gas barrier film substrate.
  • the metal oxide layer is arranged between the negative electrode and the organic photoelectric conversion layer, and the negative electrode is made of a noble metal (less ionization tendency) than iron, so that the negative electrode is simply ionized.
  • a gas barrier film substrate an organic power generation laminate including at least a positive electrode, an organic photoelectric conversion layer, a metal oxide layer, and a negative electrode containing a metal nobler than iron in this order; a first gas barrier layer; It is an organic thin-film solar cell provided with.
  • ⁇ 3> The organic thin-film solar cell according to ⁇ 1> or ⁇ 2>, wherein the negative electrode includes a metal or alloy having a smaller ionization tendency than hydrogen.
  • the negative electrode includes at least one of copper, silver, and an alloy including these.
  • the metal oxide of the metal oxide layer includes at least one of titanium oxide and zinc oxide.
  • the gas barrier film substrate includes a first resin film and a second gas barrier layer, and the second gas barrier layer is provided in contact with the first resin film. And the first inorganic layer provided on the first organic polymer layer.
  • the organic thin-film solar cell according to any one of ⁇ 1> to ⁇ 5>.
  • a second resin film is further provided on the side of the first gas barrier layer where the organic power generation laminate is not disposed, and the first gas barrier layer is in contact with the second resin film.
  • the gas barrier film substrate includes a first resin film and a second gas barrier layer, In the second gas barrier layer, at least two organic polymer layers and at least two inorganic layers are alternately laminated so that the organic polymer layers are in contact with the surface of the first resin film ⁇ 1.
  • the organic thin film solar cell according to any one of> to ⁇ 5>.
  • a second resin film is further provided on the side of the first gas barrier layer where the organic power generation laminate is not disposed; In the first gas barrier layer, at least two organic polymer layers and at least two inorganic layers are alternately laminated so that the organic polymer layers are in contact with the surface of the second resin film ⁇ 1.
  • >- ⁇ 5> and ⁇ 8> The organic thin-film solar cell according to any one of ⁇ 8>.
  • At least two organic polymer layers and at least two inorganic layers are in contact with the organic polymer layer on the surface of the resin film.
  • an organic thin-film solar cell that has high durability and can withstand long-term use, and that can maintain high photoelectric conversion efficiency while suppressing a decrease in efficiency. Furthermore, a flexible organic thin film solar cell can be provided as a solar cell.
  • an organic power generation laminate including a gas barrier film substrate and at least a positive electrode, an organic photoelectric conversion layer, a metal oxide layer, and a negative electrode containing a metal nobler than iron in this order;
  • the organic power generation laminate is shielded from the outside air by the gas barrier film substrate and the gas barrier layer.
  • a metal noble (less ionized) than iron is used for the negative electrode.
  • a metal oxide layer is disposed between the organic photoelectric conversion layer, it is possible to effectively increase durability while not decreasing the release voltage of the element, that is, preventing a decrease in photoelectric conversion efficiency. It becomes possible.
  • the organic thin film solar cell of the present invention typically has, as a basic structure, a resin film / second gas barrier layer / positive electrode / organic layer / metal oxide layer / negative electrode / first gas barrier layer, or resin film / It has a configuration of second gas barrier layer / negative electrode / metal oxide layer / organic layer / positive electrode / first gas barrier layer. Further, the organic thin film solar cell of the present invention has a configuration using two gas barrier film substrates, that is, for example, resin film / second gas barrier layer / positive electrode / organic layer / metal oxide layer / negative electrode / protective layer / adhesive layer. The structure of / first gas barrier layer / resin film may be sufficient. In this case, a protective layer may be provided to protect the organic power generation laminate from the adhesive. Furthermore, in addition to the above configuration, another substrate or an arbitrary functional layer may be included.
  • the organic thin-film solar cell of the present invention has, for example, a conductive layer of a gas barrier film substrate provided with a light-transmitting conductive layer such as ITO (in particular, transparency with low sunlight absorption) as a positive electrode, and an organic layer thereon. It may be manufactured by sequentially installing a metal oxide layer, a negative electrode, and a gas barrier layer. Moreover, the conductive layer of the gas barrier film substrate provided with the conductive layer is used as a positive electrode, and an organic layer, a metal oxide layer, and a negative electrode are provided thereon to form a photoelectric conversion element, and the gas barrier film substrate is interposed therebetween through an adhesive layer. It may be manufactured by pasting together.
  • a light-transmitting conductive layer such as ITO (in particular, transparency with low sunlight absorption)
  • ITO in particular, transparency with low sunlight absorption
  • thermosetting adhesive an ultraviolet curable adhesive, or the like
  • ultraviolet curable adhesive an ultraviolet curable adhesive, or the like
  • the curing conditions of the adhesive can be determined as appropriate according to the type of the adhesive. For example, the description of “Adhesive Data Book 2nd Edition, edited by the Japan Adhesive Society, Nikkan Kogyo Shimbun” can be referred to. it can.
  • the organic thin-film solar cell of this invention is not limited to the structure shown by these.
  • the organic power generation laminated body 2 of laminated structure is formed on the gas barrier film board
  • a gas barrier layer 5 is provided so as to cover the power generation laminate.
  • the organic electric power generation laminated body 2 is provided on the gas barrier film board
  • a gas barrier layer 5 is provided on the surface of the protective layer 3 provided so as to cover the power generation laminate.
  • the organic electric power generation laminated body 2 is provided on the gas barrier film board
  • a gas barrier film substrate 10 is provided via an adhesive layer 4 on the surface of the protective layer 3 provided so as to cover the organic power generation laminate.
  • the gas barrier film substrate 10 includes a base material 10a provided with a gas barrier layer 10b, and is bonded to the adhesive layer 4 on the surface of the gas barrier layer 10b.
  • the organic thin film solar cell of the present invention includes a gas barrier film substrate having gas barrier properties that blocks permeation of oxygen, water vapor, and the like as a support substrate.
  • the gas barrier film substrate may be composed of only a resin film (base material) depending on the film, but it is preferable to provide at least one gas barrier layer on the resin film.
  • the gas barrier layer is preferably provided with at least one organic polymer layer and at least one inorganic layer.
  • the resin film used for the organic thin film solar cell of the present invention is not particularly limited in material, thickness, etc., as long as it is a resin film that can hold an organic polymer layer, an inorganic layer, etc. Can do.
  • polyester resin methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyamideimide resin, polyetherimide Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring
  • thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.
  • the resin film is preferably formed using a material having heat resistance. Specifically, it is preferably formed using a transparent material having a glass transition temperature (Tg) of 100 ° C. or higher and / or a linear thermal expansion coefficient of 40 ppm / ° C. or lower and high heat resistance. Tg and a linear expansion coefficient can be adjusted with an additive.
  • Tg and a linear expansion coefficient can be adjusted with an additive.
  • the thermoplastic resin which is such a material include polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600 manufactured by Nippon Zeon Co., Ltd .: 160 ° C.
  • the resin film used for the organic thin film solar cell of the present invention is usually required to have transparency, and the light transmittance is usually 80% or more, preferably 85% or more, more preferably 90. % Or more.
  • the light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. Is the value to be
  • the thickness of the resin film is not particularly limited, but is typically 1 to 800 ⁇ m, preferably 10 to 200 ⁇ m.
  • the resin film preferably has a gas barrier layer including a laminate having gas barrier properties. A laminate having a gas barrier property suitable for the present invention will be described later.
  • the resin film may have functional layers, such as a conductive layer and a primer layer.
  • the organic thin film solar cell of the present invention includes a gas barrier film substrate using the resin film, but also when a resin film is provided on the side opposite to the side where the gas barrier film substrate is provided (particularly the outermost surface) A resin film similar to the above is preferably used.
  • the gas barrier layer is a layer for preventing permeation of oxygen and water vapor in the atmosphere that adversely affects the organic thin film solar cell (hereinafter, this layer is also referred to as “second gas barrier layer”).
  • the type of the gas barrier layer is not particularly limited, and various organic layers and inorganic layers can be used.
  • at least one organic layer hereinafter also referred to as “organic polymer layer” and at least one.
  • the form which provided the gas barrier layer which has the inorganic layer of a layer is mentioned.
  • the gas barrier layer preferably has a water vapor transmission rate of 0.001 g / m 2 / day or less.
  • such a gas barrier ability has a structure in which at least two organic polymer layers and at least two inorganic layers are alternately laminated like organic layer / inorganic layer / organic layer. It can be achieved by being formed.
  • a gas barrier layer formed in an embodiment having an organic polymer layer in contact with the surface of the resin film described above and an inorganic layer provided on the organic polymer layer is preferable. Furthermore, at least two organic polymer layers and at least two inorganic layers are organic layers / inorganic layers / organic layers so that the organic polymer layers are in contact with the surface of the resin film described above. Thus, the gas barrier layer laminated
  • Organic polymer layer The following description regarding the organic polymer layer applies to all the organic polymer layers described in the present specification.
  • the organic polymer layer in the present invention includes, for example, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate.
  • Thermoplastic resins such as rate, polyurethane, polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, or acryloyl compound, Or a layer using polysiloxane or other organic silicon compound (for example, silicon carbide or silicon oxide carbide produced by a CVD method using an organic silane gas as a raw material) That.
  • the organic polymer layer may be formed of one kind of material or a mixture. Further, two or more organic polymer layers may be laminated. In this case, each layer may have the same composition or a different composition. Further, as described in U.S. Patent Publication No. 2004-46497, the organic polymer layer is a layer whose interface with the inorganic layer is not clear and whose composition changes continuously in the film thickness direction. Good.
  • the organic polymer layer is preferably a layer using a (meth) acrylate polymer.
  • the (meth) acrylate polymer is a polymer obtained by polymerizing a polymerizable composition containing a (meth) acrylate monomer as a main component.
  • the “polymerizable composition containing a (meth) acrylate monomer as a main component” may include one (meth) acrylate monomer or a mixture of several (meth) acrylate monomers. Good.
  • the molecular weight of the (meth) acrylate monomer is preferably 200 to 2000, and more preferably 400 to 1000.
  • the polymerizable composition in the present invention may contain an acidic monomer.
  • an acidic monomer refers to a monomer having an acidic group such as carboxylic acid, sulfonic acid, phosphoric acid, or phosphonic acid.
  • the acidic monomer used in the present invention is preferably a monomer containing a carboxylic acid group or a phosphoric acid group, more preferably a (meth) acrylate containing a carboxylic acid group or a phosphoric acid group, in terms of interlayer adhesion. (Meth) acrylate having an ester group is more preferred.
  • the polymerizable composition containing the (meth) acrylate monomer as a main component includes a monomer other than (meth) acrylate (for example, a styrene derivative, a maleic anhydride derivative, an epoxy compound, and the like within the scope of the present invention).
  • a monomer other than (meth) acrylate for example, a styrene derivative, a maleic anhydride derivative, an epoxy compound, and the like within the scope of the present invention.
  • oxetane derivatives and various polymers (for example, polyester, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane) , Polyether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyethersulfone, polysulfone, fluorene ring-modified polycarbonate, alicyclic ring-modified polycarbonate, fluorene ring-modified polyester, etc.) .
  • polyester methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, cellulose acylate, polyurethane
  • Polyether ketone polycarbonate, alicyclic polyolefin, polyarylate, poly
  • the “polymerizable composition containing a (meth) acrylate monomer as a main component” in the present invention may contain a polymerization initiator.
  • the content thereof is preferably 0.1 mol% or more, more preferably 0.5 to 2 mol%, based on the total amount of the polymerizable compounds.
  • photopolymerization initiator examples include Irgacure series (for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure, commercially available from Ciba Specialty Chemicals. 819), Darocure series (eg, Darocur TPO, Darocur 1173, etc.), Quantacure PDO, Ezacure series (eg, Ezacure TZM, Ezacure TZT, commercially available from Sartomer). ), And also the oligomer type Ezacure KIP series.
  • Irgacure series for example, Irgacure 651, Irgacure 754, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacur
  • the thickness of the organic polymer layer is not particularly limited, but is usually 100 to 5000 nm, preferably 200 to 2000 nm per layer. Moreover, when it has two or more organic polymer layers, each organic polymer layer may be the same layer, or a different layer.
  • -Method for forming organic polymer layer Although there is no restriction
  • the solution coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a slide coating method, or a hopper described in US Pat. No. 2,681,294. It can be applied by an extrusion coating method using-.
  • a polymer may be applied by solution, or a hybrid coating method containing an inorganic substance as described in JP-A Nos. 2000-323273 and 2004-25732 may be used. Good.
  • a composition containing a polymerizable compound is usually cured by irradiation with light, and the irradiation light is usually ultraviolet light from a high-pressure mercury lamp or a low-pressure mercury lamp.
  • the irradiation energy is preferably 0.1 J / cm 2 or more, 0.5 J / cm 2 or more is more preferable.
  • the polymerization is inhibited by oxygen in the air, so that it is preferable to reduce the oxygen concentration or oxygen partial pressure during polymerization.
  • the oxygen concentration is preferably 2% or less, and more preferably 0.5% or less.
  • the total pressure is preferably 1000 Pa or less, and more preferably 100 Pa or less. Further, it is particularly preferable to perform ultraviolet polymerization by irradiating energy of 0.5 J / cm 2 or more under a reduced pressure condition of 100 Pa or less.
  • the inorganic layer in the present invention is not particularly limited as long as it is formed of an inorganic material and has a gas barrier property.
  • inorganic substances generally include boron, magnesium, aluminum, silicon, titanium, zinc, tin oxides, nitrides, oxynitrides, carbides, and hydrides. These may be pure substances, a mixture containing a plurality of compositions, or a gradient material layer. Of these, aluminum oxide, nitride or oxynitride, or silicon oxide, nitride or oxynitride is preferable, and aluminum oxide or silicon oxide is particularly preferable.
  • any method can be applied as long as it can form a target thin film.
  • a sol-gel method, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD method, and the like are suitable, and specifically, Japanese Patent No. 3434344, Japanese Patent Application Laid-Open No. 2002-322561, and Japanese Patent Application Laid-Open No. 2002.
  • the method described in Japanese Patent No. -361774 can be applied.
  • CVD ECR-CVD
  • PVD ECR-PVD
  • a gas source such as silane or a liquid source such as hexamethyldisilazane can be used as a silicon supply source.
  • the average roughness (Ra value) of 1 ⁇ m square is preferably less than 1 nm, and more preferably 0.5 nm or less. For this reason, it is preferable that the inorganic layer is formed in a clean room.
  • the degree of cleanness is preferably class 10,000 or less, and more preferably class 1000 or less.
  • the Ra value is a value measured based on the DFM mode of the scanning probe microscope (SPM).
  • the thickness of the inorganic layer is not particularly limited, but is usually in the range of 5 to 500 nm, preferably 10 to 200 nm per layer.
  • the inorganic layer may have a laminated structure including a plurality of sublayers. In this case, each sublayer may have the same composition or a different composition. Further, as described above, as described in US Publication No. 2004-46497, the inorganic layer has an unclear interface with the organic polymer layer, and the composition continuously changes in the film thickness direction. It may be a layer.
  • the organic polymer layer and the inorganic layer can be carried out by successively and repeatedly forming the organic polymer layer and the inorganic layer in contact with each other according to the desired layer configuration.
  • the inorganic layer is formed by a vacuum film formation method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, or a plasma CVD method
  • the organic polymer layer is also formed by a vacuum film formation method such as the flash vapor deposition method. Is preferred.
  • a vacuum film formation method such as a sputtering method, a vacuum vapor deposition method, an ion plating method, or a plasma CVD method
  • the organic polymer layer is also formed by a vacuum film formation method such as the flash vapor deposition method. Is preferred.
  • the gas barrier layer it is particularly preferable to always laminate the organic polymer layer and the inorganic layer in a vacuum of 1000 Pa or less without returning to atmospheric pressure in the middle.
  • the pressure is more preferably 100 Pa or less, still more preferably 50 Pa or less, and particularly preferably 20 Pa or less.
  • the present invention preferably has an aspect having a layer structure in which at least two organic polymer layers and at least two inorganic layers are alternately laminated.
  • the alternately laminated structure is an organic polymer layer from the resin film side.
  • the layers may be laminated in the order of / inorganic layer / organic polymer layer / inorganic layer, or in the order of inorganic layer / organic polymer layer / inorganic layer / organic polymer layer.
  • At least two layers of organic polymer in the order of organic polymer layer / inorganic layer / organic polymer layer / inorganic layer from the resin film side are most preferable.
  • Organic power generation laminate An organic power generation laminate is provided in the organic thin film solar cell of the present invention.
  • the organic power generation laminate includes at least a pair of electrodes and an organic photoelectric conversion layer and a metal oxide layer provided between the pair of electrodes.
  • one of the paired electrodes is a positive electrode, and the other is a negative electrode.
  • one or more organic photoelectric conversion layers and one or two layers are formed.
  • a metal oxide layer equal to or more than one layer is provided.
  • At least one of the pair of electrodes forming part of the organic power generation laminate has transparency due to the nature of a solar cell.
  • having transparency means the property that sunlight passes through the battery to the extent that power generation can be performed when exposed to sunlight, and the amount of sunlight transmitted is preferably large, as will be described later.
  • the transmittance is 60% or more.
  • the organic photoelectric conversion layer provided between the electrodes has a function of absorbing light and generating electrons and holes.
  • the simplest power generation laminate has a configuration of positive electrode / organic photoelectric conversion layer / metal oxide layer / negative electrode, and the organic photoelectric conversion layer is a mixed layer of a hole transport material and an electron transport material. In this configuration, the hole transport material and the electron transport material are preferably phase separated.
  • the power generation laminate includes positive electrode / hole transport layer / electron transport layer / metal oxide layer / negative electrode structure, positive electrode / hole transport layer / mixed layer / electron transport layer / metal oxide layer / negative electrode. A configuration is also illustrated.
  • the mixed layer is a mixed layer of a hole transport material and an electron transport material, and is preferably phase-separated.
  • the organic thin film solar cell of the present invention may adopt a so-called tandem configuration having a plurality of pairs of a hole transport layer and an electron transport layer.
  • An element configured in a tandem type is particularly preferable in terms of high open-circuit voltage and high conversion efficiency.
  • a recombination layer is disposed as an intermediate layer. That is, as a typical example of the tandem element, a configuration of positive electrode / hole transport layer / electron transport layer / recombination layer / hole transport layer / electron transport layer / metal oxide layer / negative electrode is exemplified.
  • other layers may be provided as necessary.
  • the other layers can be suitably formed by any of dry film forming methods such as vapor deposition and sputtering, transfer methods, and printing methods.
  • a positive electrode a negative electrode, an organic photoelectric conversion layer (an organic layer such as a hole transport layer and an electron transport layer) forming a part of the organic photoelectric conversion layer, and other layers will be described.
  • an organic photoelectric conversion layer an organic layer such as a hole transport layer and an electron transport layer
  • Positive electrode should just have a function as an electrode which receives a hole, and can be suitably selected from well-known electrode materials. Suitable examples of the material for the positive electrode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof.
  • the positive electrode material include conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, indium oxide, indium tin oxide (ITO), zinc indium oxide (IZO), Metals such as gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene and polypyrrole And a laminate of these and a conductive metal oxide.
  • ATO antimony or fluorine
  • FTO tin oxide doped with antimony or fluorine
  • ITO indium oxide
  • IZO zinc indium oxide
  • Metals such as gold, silver, chromium and nickel, and mixtures or laminates of these metals and conductive metal oxides
  • inorganic conductive materials such as copper iodide and copper sulfide
  • organic conductive materials such as
  • the positive electrode When the positive electrode requires transparency, the positive electrode is preferably a conductive metal oxide.
  • the positive electrode from the viewpoints of productivity, high conductivity, transparency, and the like, it is preferable to use ITO, ATO, FTO, IZO, and a composite thereof.
  • the positive electrode preferably has a hole collection layer on the organic photoelectric conversion layer side.
  • the hole collection layer include PEDOT-PSS, molybdenum oxide, tungsten oxide, and vanadium oxide.
  • PEDOT-PSS is preferable in terms of hole mobility and valence band energy levels.
  • Molybdenum oxide, and vanadium oxide are preferred.
  • the energy level of the valence body of the hole collection layer is preferably larger than the work function of the positive electrode and smaller than the level of the valence band of the hole transport material of the photoelectric conversion layer.
  • the positive electrode preferably has a higher work function than the negative electrode described later.
  • the work function of the main component of the material to be the positive electrode is 4. Preferably it is greater than 6 eV.
  • the positive electrode is, for example, a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as a CVD method or a plasma CVD method. It can form on the said gas barrier film board
  • the position where the positive electrode is formed is not particularly limited and can be appropriately selected according to the use of the solar cell.
  • the positive electrode may be formed on the entire one surface of the substrate, or may be formed in part by patterning.
  • the patterning for forming the positive electrode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as a laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.
  • the thickness of the positive electrode can be appropriately selected depending on the material forming the positive electrode and cannot be generally specified, but is usually about 10 nm to 50 ⁇ m, and preferably 50 nm to 20 ⁇ m.
  • the resistance value of the positive electrode is preferably 100 ⁇ / ⁇ or less, and more preferably 20 ⁇ / ⁇ or less.
  • the positive electrode When the positive electrode has transparency, it may be colorless and transparent or colored and transparent.
  • the transmittance In order to capture light from the transparent positive electrode side, the transmittance is preferably 60% or more, and more preferably 70% or more.
  • the transparent positive electrode is described in detail in “New Development of Transparent Electrode Film” (supervised by Yutaka Sawada, published by CMC, 1999), and the matters described here can also be applied to the present invention.
  • Negative electrode The negative electrode is roughly classified into a metal case and a combination of an oxide and a metal as a work function adjusting function.
  • the negative electrode in the present invention contains a metal nobler than iron so that the metal is less susceptible to deterioration due to corrosion.
  • a “metal more precious than iron” is a metal in which the redox potential between the metal and its hydrated ion is greater than that of iron.
  • the standard redox potential is higher than that of a standard hydrogen electrode. This is a metal larger than -0.5V.
  • the standard oxidation-reduction potential is preferably greater than 0V and more preferably greater than 0.5V from the viewpoint of corrosion resistance.
  • the standard oxidation-reduction potential is determined by using the standard hydrogen electrode for the cathode reaction and the oxidation-reduction reaction for which the electrode potential is desired for the anodic reaction, respectively.
  • the activity (or partial pressure) of the substances involved is 1).
  • Examples of metals preferable from the viewpoint of corrosion resistance include indium, cobalt, nickel, tin, copper, silver, and gold.
  • the work function is preferably small.
  • examples of the metal or alloy used for the negative electrode in the present invention include silver (work function: 4.31 eV), copper (work function: 4.65 eV), indium (work function: 4.12 eV), or these An alloy containing is more preferable, and silver, copper, or an alloy containing these is particularly preferable. Similarly, an alloy of silver and indium can be mentioned as a particularly preferable example.
  • a combination of oxide and metal as a work function adjusting function may be used as the negative electrode.
  • a negative electrode in which a conductive oxide such as zinc oxide whose conductivity is improved by doping with zinc oxide, titanium oxide, boron, or aluminum, and a metal nobler than iron is used.
  • the method for forming the negative electrode is not particularly limited and can be performed according to a known method.
  • the negative electrode is formed, for example, from a printing method, a wet method such as a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, and a chemical method such as CVD or plasma CVD method. It can be carried out according to a method appropriately selected in consideration of suitability with the material forming the negative electrode. For example, it can be formed by performing sputtering or the like on one or more metals used as a negative electrode material simultaneously or sequentially. The same method as that for the positive electrode can be used for patterning when forming the negative electrode.
  • the position where the negative electrode is formed is not particularly limited, and it may be formed on the entire organic compound layer or a part thereof. Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the negative electrode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, vacuum deposition, sputtering, or ion plating. The thickness of the negative electrode can be appropriately selected depending on the material for forming the negative electrode and cannot be generally defined, but is usually about 10 nm to 5 ⁇ m, and preferably 50 nm to 1 ⁇ m.
  • Organic photoelectric conversion layer is a mixed layer having a hole transport material and an electron transport material, and is a so-called bulk hetero layer.
  • the organic photoelectric conversion layer may have a structure of (positive electrode) hole transport layer / electron transport layer (negative electrode) or a structure of (positive electrode) hole transport layer / mixed organic layer / electron transport layer (negative electrode).
  • the mixed organic layer is the same as the mixed layer, and details will be described later.
  • An auxiliary layer such as a charge blocking layer, a charge injection layer, or an exciton diffusion preventing layer may be provided between the positive electrode and the hole transport layer or between the negative electrode and the electron transport layer.
  • Each layer may be divided into a plurality of secondary layers.
  • the organic thin film solar cell of the present invention may adopt a so-called tandem configuration having a plurality of pairs of a hole transport layer and an electron transport layer.
  • a tandem element is usually a serial connection type, and is particularly preferable in that it has a high open-circuit voltage and high conversion efficiency. At that time, a recombination layer is disposed as an intermediate layer.
  • the structure is positive electrode / mixed organic layer / recombination layer / mixed organic layer / negative electrode, or positive electrode / hole transport layer / electron transport layer / recombination layer / hole transport layer / electron transport.
  • the structure which is a layer / negative electrode can be illustrated.
  • a tandem element connected in parallel is also possible.
  • organic photoelectric conversion layer a layer using an organic compound such as a mixed organic layer, a hole transport layer, an electron transport layer, a charge blocking layer, a charge injection layer, and an exciton diffusion preventing layer is generally referred to as an “organic photoelectric conversion layer”. Called.
  • Each layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.
  • the hole transport layer is a layer having a function of receiving and transporting holes to the positive electrode or the positive electrode side.
  • the hole transport layer may be a single layer or a laminate of a plurality of layers. It is preferable that at least one layer of the hole transport layer has a charge generating ability to absorb light and generate electrons and holes.
  • the hole transport layer can be formed using one or more hole transport materials.
  • Examples of the hole transport material include carbazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic compounds.
  • Examples include tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, phthalocyanine compounds, polythiophene derivatives, polypyrrole derivatives, and polyparaphenylene vinylene derivatives.
  • Examples of the hole transport material include compounds described as “Hole Transport Material” in Chem. Rev. 2007, 107, 953-1010, and specific examples include the following.
  • Examples of the material of the hole transport layer having charge generation ability include porphyrin compounds, phthalocyanine compounds, polythiophene derivatives, polypyrrole derivatives, and polyparaphenylene vinylene derivatives, and examples thereof include Chem. Rev. 1993, 93, 449-406.
  • Examples of the method for forming the hole transport layer include a solvent coating method and a vacuum deposition method.
  • Examples of the solvent coating method include spin coating, spray coating, bar coating, and die coating.
  • the thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 2 nm to 200 nm, and even more preferably 5 nm to 100 nm.
  • the hole transport layer may have a single-layer structure including one or more of the materials described above, or may have a multilayer structure including a plurality of layers having the same composition or different compositions.
  • Electron transport layer is a layer having a function of transporting electrons to the negative electrode or the negative electrode side.
  • the electron transport layer may be a single layer or a laminate of a plurality of layers. It is preferable that at least one of the electron transport layers has a charge generation capability of absorbing light and generating a charge.
  • the electron transport layer can be formed using one kind or two or more kinds of electron transport materials.
  • electron transport material examples include fullerene derivatives, paraphenylene vinylene derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, phenanthroline derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiols.
  • Pyrandoxide derivatives carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene or perylene, and imides and heterocycles derived therefrom, 8-quinolinol derivatives
  • metal complexes various metal complexes represented by metal complexes having benzoxazole or benzothiazole as a ligand
  • organic silane derivatives examples of the material for the electron transport layer having charge generation ability include fullerenes, polyparaphenylene vinylene derivatives, and imides and heterocycles derived from perylenetetracarboxylic anhydride. Examples thereof include those described as Electron Transport Materials in Chem. Rev. 2007, 107, 953-1010, and specific examples include the following.
  • Examples of the method for forming the electron transport layer include a solvent coating method and a vacuum deposition method. Specific examples of the solvent coating method are as described above.
  • the thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 2 nm to 200 nm, and further preferably 5 nm to 100 nm.
  • the electron transport layer may have a single layer structure including one or more of the above-described materials, or may have a multilayer structure including a plurality of layers having the same composition or different compositions.
  • Mixed organic layer A mixed organic layer containing both a hole transporting material and an electron transporting material can be disposed between the hole transporting layer and the electron transporting layer. This is preferable in terms of improving efficiency.
  • the mixing ratio is adjusted so as to increase the conversion efficiency, but is usually selected from the range of 20:80 to 80:20 in terms of mass ratio (hole transport material: electron transport material). The details of the hole transport material and the electron transport material are as described above.
  • a co-evaporation method by vacuum deposition can be applied.
  • Specific examples of the solvent coating method are as described above.
  • Recombination layer In the case of the tandem element as described above, a recombination layer is provided to connect a plurality of individual photoelectric conversion layers in series.
  • a thin layer of a conductive material can be used.
  • a metal is suitable as the conductive material, and examples of preferable metals include gold, silver, aluminum, platinum, and ruthenium oxide. Of these, silver is preferred.
  • the film thickness of the recombination layer is usually 0.01 to 5 nm, preferably 0.1 to 1 nm, and particularly preferably 0.2 to 0.6 nm.
  • a recombination layer it can form by a vacuum evaporation method, sputtering method, or an ion plating method.
  • the organic thin film solar cell of the present invention may be annealed by various methods for the purpose of crystallization of the organic layer and promotion of phase separation of the organic mixed layer.
  • the annealing method include a method of heating the substrate temperature during vapor deposition to 50 ° C. to 150 ° C., a method of setting the drying temperature after coating to 50 ° C. to 150 ° C., and the like.
  • annealing may be performed by heating to 50 ° C. to 150 ° C. after the electrode formation is completed.
  • a metal oxide layer is disposed between the organic photoelectric conversion layer and the negative electrode as a layer forming the organic power generation laminate.
  • the metal oxide layer in the present invention is located between the organic photoelectric conversion layer and the negative electrode and has a function of passing electrons generated in the organic photoelectric conversion layer to the negative electrode.
  • the energy level of the conduction band of the metal oxide is lower than the LUMO of the electron transport material in the organic photoelectric conversion layer, and the energy level of the negative electrode is preferably lower than the conduction band of the metal oxide.
  • the metal oxide a conventionally known metal oxide can be used.
  • a metal oxide having a conduction band energy level higher than ⁇ 4.5 eV in terms of excellent conversion efficiency when photoelectrically converted is more preferable.
  • titanium oxide (conduction band level: -4.2 eV) and zinc oxide (conduction band level: -4.1 eV) are more preferable.
  • this metal oxide layer is arrange
  • the energy level of the conduction band is measured by obtaining the valence band (VB) of the semiconductor using an ultraviolet photoelectron spectrometer (UPS), and separately from the absorption edge of the diffuse reflection ultraviolet-visible absorption spectrum. ), The energy level of the conduction band (CB) can be calculated from the difference.
  • UPS ultraviolet photoelectron spectrometer
  • the organic power generation laminate in the present invention may be protected by a protective layer.
  • the material contained in the protective layer MgO, SiO, SiO 2, Al 2 O 3, Y 2 O 3, and metal oxides such as TiO 2, metal nitrides such as SiN x, such as SiN x O y metal Examples thereof include metal fluorides such as nitride oxide, MgF 2 , LiF, AlF 3 , and CaF 2 , and polymers such as polyethylene, polypropylene, polyvinylidene fluoride, and polyparaxylylene.
  • the protective layer may be a single layer or a multilayer structure.
  • the method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, vacuum ultraviolet CVD method, coating method, printing method, and transfer method can be applied.
  • a protective layer may be used as the conductive layer.
  • the organic thin film solar cell of the present invention includes a gas barrier layer (also referred to as a first gas barrier layer in the present specification) as a barrier layer for providing a gas barrier function.
  • a gas barrier layer also referred to as a first gas barrier layer in the present specification
  • This gas barrier layer can be formed in the same manner as the second gas barrier layer that forms the gas barrier film substrate described above.
  • the first gas barrier layer can be suitably formed by providing at least one organic polymer layer and at least one inorganic layer.
  • At least two organic polymer layers and at least two inorganic layers are alternately formed as inorganic layer / organic layer / inorganic layer. It is a gas barrier layer which has the laminated structure laminated
  • the organic thin film solar cell of the present invention may have various functional layers on the laminated structure including the gas barrier film substrate / organic power generation laminate / gas barrier layer or at other positions, in addition to the above layers.
  • the functional layer is described in detail in paragraph numbers [0036] to [0038] of JP-A-2006-289627.
  • Examples of functional layers include matting agent layers, protective layers, solvent-resistant layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, Examples thereof include an antifouling layer, a printing layer, and an easy adhesion layer.
  • the thickness of the organic thin film solar cell of the present invention is preferably 50 ⁇ m to 1 mm, and more preferably 100 ⁇ m to 500 ⁇ m.
  • the production of the organic thin film solar cell of the present invention can be carried out with reference to the description of “solar power generation, latest technology and system” (written by Yasuhiro Kajikawa, CMC Co., Ltd.) and the like.
  • ⁇ Production of gas barrier film substrate> -Production of gas barrier film substrate (G-1)- On a polyethylene naphthalate (PEN) film (manufactured by Teijin DuPont, Teonex Q65FA, thickness 100 ⁇ m), 14 parts by mass of the following three polymerizable compounds in total amount and a polymerization initiator (IRGACURE, Ciba Specialty) (Manufactured by Chemicals Co., Ltd.)
  • PEN polyethylene naphthalate
  • IRGACURE Ciba Specialty
  • a composition containing 907 parts by mass and 185 parts by mass of 2-butanone was applied with a wire bar, and cured by irradiation with an ultraviolet ray irradiation amount of 0.5 J / cm 2 in an atmosphere of 100 ppm nitrogen.
  • An organic polymer layer was formed. The thickness of the formed organic polymer layer was 400 nm.
  • Compound A EB-3702 (manufactured by Daicel Cytec Co., Ltd.) ... 60% by mass
  • Compound B EB-150 (manufactured by Daicel Cytec Corporation) 35% by mass
  • Compound C KAYARAD PM-21 (manufactured by Nippon Kayaku Co., Ltd .; the following compound) ... 5% by mass
  • an Al 2 O 3 film (inorganic layer) was formed on the surface of the organic polymer layer by depositing Al 2 O 3 by vacuum sputtering (reactive sputtering) so as to have a film thickness of 35 nm.
  • a gas barrier film substrate (G-1) having a gas barrier layer on a PEN film was produced.
  • gas barrier film substrate (G-2) On the gas barrier layer on the PEN film of the gas barrier film substrate (G-1), one organic polymer layer and one inorganic layer (Al 2 O 3 film) were further formed by the same method as described above. In this way, a gas barrier film substrate (G-2) in which two organic polymer layers and two inorganic layers were alternately laminated was produced.
  • gas barrier film substrate (G-3) On the gas barrier layer on the PEN film of the gas barrier film substrate (G-2), one organic polymer layer and one inorganic layer (Al 2 O 3 film) were further formed by the same method as described above. In this way, a gas barrier film substrate (G-3) in which three organic polymer layers and three inorganic layers were alternately laminated was produced.
  • gas barrier film substrate (G-4) In the production of the gas barrier film substrate (G-3), the gas barrier film substrate (G-3) was prepared in the same manner as in the production of the gas barrier film substrate (G-3) except that the Al 2 O 3 film as the inorganic layer was replaced with a SiO 2 film. A film substrate (G-4) was produced.
  • inorganic gas barrier film substrate (GX)- One inorganic layer (Al 2 O 3 film) was formed in the same manner as the gas barrier film substrate (G-1) except that the organic polymer layer was not applied in the production of the gas barrier film substrate (G-1). An inorganic gas barrier film substrate (GX) having only the same was produced.
  • barrier performance water-vapor-permeation rate
  • barrier performance water-vapor-permeation rate
  • the water vapor permeability (g / m 2 / day) was measured using the method described in G. NISATO, PCPBOUTEN, PJSLIKKERVEER et al. SID Conference Record of the International Display Research Conference, pages 1435-1438 (so-called calcium method). At this time, the temperature was 40 ° C. and the relative humidity was 90%.
  • the gas barrier film substrates (G-1) to (G-4) showed better gas barrier ability than the gas barrier film substrate (GX).
  • the gas barrier film substrates (G-2) to (G-4) have a water vapor permeation ability of 0.001 or less and show extremely high gas barrier ability.
  • ITO film is sputtered on the surface of the inorganic layer (Al 2 O 3 film or SiO 2 film) on the outermost surface of the gas barrier film substrate (G-1 to G-4, GX) so as to have a thickness of 100 nm.
  • a film substrate with a patterned ITO film was obtained.
  • this film substrate is referred to as an ITO-attached film substrate (G-1 to G-4 or GX).
  • PEDOT-PSS polyethylene dioxythiophene / polystyrene sulfonic acid
  • the coated film substrate is dried by heating at 130 ° C. for 10 minutes to form a conductive polymer layer, a transparent conductive film substrate (T-1 to T-4), and a transparent conductive film having no organic polymer layer.
  • a film substrate (TX) was produced.
  • Example 1 Using the transparent conductive film substrate (T-1 to T-4 or TX) obtained above, an organic thin-film solar cell having the configuration shown in FIG. 3 was produced according to the following procedure.
  • the transparent conductive film substrates (T-1 to T-4) prepared above and the comparative transparent conductive film substrate (TX) for comparison were thoroughly blown with a nitrogen gun, and then the conductive polymer layer surface of each film substrate was subjected to the above process.
  • a 0.13 ml coating solution for photoelectric conversion layer was dropped using an Eppendorf pipette and rotated at 2000 rpm for 120 seconds to form a photoelectric conversion layer.
  • the film thickness of the photoelectric conversion layer after drying was 90 nm.
  • Silver was vapor-deposited on the formed titanium oxide layer (electron transport layer) to a thickness of 100 nm with a vacuum evaporator, and heated at 150 ° C. for 10 minutes using a hot plate to obtain a negative electrode.
  • the organic thin film solar cell element substrate (D-1 to D-4) provided with the transparent conductive film substrate (T-1 to T-4) and the transparent conductive film substrate (TX) for comparison.
  • thermosetting adhesive Epotec 310 manufactured by Daizonichi Mori Co., Ltd.
  • the organic thin film solar cell element substrate (D-1 to D-4 or DX) prepared above, and separately from this
  • the prepared gas barrier film substrates (G-1 to G-4 or GX) are arranged and bonded so that the gas barrier layer side of each gas barrier film substrate faces the organic thin-film solar cell element substrate, and at 65 ° C.
  • the adhesive was cured by heating for 3 hours. In this way, organic thin-film solar cells (S-1 to S-4, SX) sealed using two gas barrier film substrates were produced.
  • the produced organic thin-film solar cell has an effective area of 2 mm square and an effective area of 0.04 cm 2 .
  • organic thin film solar cell (S-5)- In the production of the organic thin film solar cell (S-3), an organic thin film solar cell (S-3) was prepared in the same manner as the organic thin film solar cell (S-3) except that Ag used for forming the negative electrode was replaced with Sn. ⁇ 5) was produced.
  • the organic thin film solar cell (S-1) is the same as the organic thin film solar cell (S-1) except that 5 nm of molybdenum oxide is evaporated instead of applying the aqueous dispersion of PEDOT-PSS. Similarly, an organic thin film solar cell (S-6) was produced.
  • Example 2 In the production of the organic thin film solar cell (S-1) of Example 1, two gas barrier film substrates (G-1) were made of polyethylene naphthalate (PEN) film (Teijin DuPont, Teonex Q65FA, thickness 100 ⁇ m).
  • PEN polyethylene naphthalate
  • the organic thin film solar cell is the same as the organic thin film solar cell (S-1) except that a transparent conductive PEN film substrate having no gas barrier capability is formed by forming an ITO film having a thickness of 100 nm by sputtering. (SB) was prepared.
  • Comparative Example 3 In the production of the organic thin film solar cell (SB) of Comparative Example 2, an organic thin film solar cell was obtained in the same manner as the organic thin film solar cell (SB), except that Al used for forming the negative electrode was replaced with Al. A battery (SC) was produced.
  • Comparative Example 4 The organic thin film solar cell (S-B) and the organic thin film solar cell (SC) of Comparative Example 3 were manufactured except that the metal oxide layer was not provided in the production of the organic thin film solar cell (SB) of Comparative Example 2.
  • Organic thin film solar cells (SD) and organic thin film solar cells (SE) were produced in the same manner as in B) or (SC).
  • each organic thin film solar cell is irradiated with simulated sunlight with an air mass of 1.5 and 100 mW / cm 2 using an L12 type solar simulator (manufactured by Pexel Technologies). However, the current value was measured in a voltage range from ⁇ 0.1 V to +0.7 V with a source measure unit (SMU 2400 type, manufactured by KEITHLEY). The current-voltage characteristics obtained by the measurement were evaluated using an IV curve analyzer (manufactured by Pexel Technologies), and the conversion efficiency was calculated. The calculated conversion efficiency is shown in Table 3 below as the initial photoelectric conversion efficiency of each organic thin film solar cell.
  • the value of the conversion efficiency of each organic thin film solar cell was expressed as a relative value obtained by normalizing the conversion efficiency of the organic thin film solar cell (S-1) to 1.
  • the organic thin film solar cell of the present invention showed a high conversion efficiency maintenance ratio after high-temperature and high-humidity aging with respect to the organic thin-film solar cell of the comparative example, and showed excellent durability performance.
  • the organic thin film solar cells S-2 to S-4 and S-5 formed by laminating two or more organic polymer layers and inorganic layers were excellent in durability performance. As described above, it was confirmed that the organic thin film solar cell of the present invention has high durability.
  • the organic thin-film solar cell of the present invention has high temporal stability, it is useful in fields and applications that are expected to be used for a long period of time, particularly in environments with severe temperature and humidity conditions such as outdoors.
  • the disclosure of Japanese application 2010-136429 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

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  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne une cellule solaire à couche mince organique qui comprend : un substrat imperméable aux gaz ; un stratifié organique générant de l'énergie qui contient au moins, dans l'ordre suivant, une électrode positive, une couche de conversion photoélectrique organique, une couche d'oxyde métallique et une électrode négative qui contient un métal plus noble que le fer ; et une première couche de barrière aux gaz.
PCT/JP2011/063718 2010-06-15 2011-06-15 Cellule solaire à couche mince organique WO2011158874A1 (fr)

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WO2016031293A1 (fr) * 2014-08-29 2016-03-03 ローム株式会社 Cellule solaire en couches minces organique à film mince et son procédé de fabrication, et dispositif électronique
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JP2013211473A (ja) * 2012-03-30 2013-10-10 Jx Nippon Oil & Energy Corp 有機薄膜太陽電池モジュールおよびその製造方法
WO2013183548A1 (fr) 2012-06-07 2013-12-12 住友化学株式会社 Procédé de fabrication d'élément de conversion photoélectrique organique
EP4109573A1 (fr) * 2015-03-17 2022-12-28 Nissan Chemical Corporation Élément de photocapteur
WO2018159799A1 (fr) * 2017-03-02 2018-09-07 積水化学工業株式会社 Cellule solaire et procédé de fabrication de cellule solaire

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JP2010087339A (ja) * 2008-10-01 2010-04-15 Fujifilm Corp 有機太陽電池素子

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WO2014077121A1 (fr) 2012-11-13 2014-05-22 積水化学工業株式会社 Cellule solaire
WO2016031293A1 (fr) * 2014-08-29 2016-03-03 ローム株式会社 Cellule solaire en couches minces organique à film mince et son procédé de fabrication, et dispositif électronique
JP2016051805A (ja) * 2014-08-29 2016-04-11 ローム株式会社 有機薄膜太陽電池およびその製造方法、電子機器
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