WO2012029780A1 - 太陽電池および太陽電池モジュール - Google Patents

太陽電池および太陽電池モジュール Download PDF

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Publication number
WO2012029780A1
WO2012029780A1 PCT/JP2011/069607 JP2011069607W WO2012029780A1 WO 2012029780 A1 WO2012029780 A1 WO 2012029780A1 JP 2011069607 W JP2011069607 W JP 2011069607W WO 2012029780 A1 WO2012029780 A1 WO 2012029780A1
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Prior art keywords
layer
solar cell
photoelectric conversion
inorganic
transparent resin
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PCT/JP2011/069607
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English (en)
French (fr)
Japanese (ja)
Inventor
木原　健
明典 橋口
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大日本印刷株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
    • H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solar cell and a solar cell module using a barrier film.
  • solar cells include single crystal silicon solar cells, polycrystalline silicon solar cells, silicon solar cells such as amorphous silicon solar cells, compound semiconductor solar cells, organic thin film solar cells, dye-sensitized solar cells, etc. And organic solar cells.
  • organic solar cells such as organic thin-film solar cells and dye-sensitized solar cells, which are attracting attention and are being researched and developed as solar cells that have a low environmental impact and can reduce manufacturing costs, are long.
  • Output stability and durability during the period are important issues.
  • organic thin-film solar cells organic semiconductor materials, and in dye-sensitized solar cells, dye sensitizers, oxide semiconductor materials, electrolyte materials, etc., deteriorate due to external factors such as moisture and oxygen, and their performance tends to deteriorate over time. Therefore, it can be said that the necessity to use a barrier film is high.
  • the barrier film one in which an inorganic barrier layer is formed on one side or both sides of a plastic film is generally known.
  • a barrier film as a support substrate having flexibility.
  • the barrier film is damaged such as cracks due to expansion / contraction during heating / cooling in the manufacturing process.
  • the barrier properties will be reduced.
  • scratches or the like may occur in the barrier film due to physical factors, which may reduce the barrier property.
  • a resin base material is used as a flexible support base material, and after forming an element directly on the resin base material, a barrier film is formed on the surface opposite to the element side of the resin base material. It is possible to paste.
  • the inorganic barrier layer is present on the outermost surface (the outermost surface opposite to the element side) and is exposed during use. Since there is a possibility that the barrier property may be deteriorated due to damage, the barrier film is generally arranged so that the inorganic barrier layer is on the element side. Therefore, when a barrier film is bonded to the surface opposite to the element side of the resin base material that is a support base material, the inorganic barrier layer is inorganic regardless of whether it is formed on one side or both sides of the plastic film.
  • a barrier film will be arrange
  • the present invention has been made in view of the above problems, and has as its main purpose to improve the adhesion reliability between the resin base material and the barrier film on the light receiving surface of the solar cell.
  • the present invention provides a transparent resin base material, a photoelectric conversion element formed on the transparent resin base material, and a surface of the transparent resin base material opposite to the photoelectric conversion element side.
  • the inorganic layer for adhesion is formed on the surface of the transparent resin substrate opposite to the photoelectric conversion element side, and the surface of the transparent resin substrate on the adhesive inorganic layer side and the inorganic barrier of the barrier film Since the layer is bonded through the adhesive layer, the adhesive inorganic layer and the inorganic barrier layer are bonded through the adhesive layer, and good adhesiveness can be obtained. Therefore, adhesion reliability can be improved, moisture and oxygen can be prevented from entering from the adhesion interface, and the durability of the solar cell can be improved. Further, according to the present invention, the transparent resin base material and the barrier film can have flexibility, and a photoelectric conversion element can be formed on the transparent resin base material by RollRto Roll, or a photoelectric conversion element. In addition, the surface of the transparent resin base material on which the adhesive inorganic layer is formed and the inorganic barrier layer of the barrier film can be bonded to each other, so that cost reduction and productivity / mass productivity can be reduced. Improvements can be realized.
  • the adhesive inorganic layer has light transmittance and is formed on the entire surface of the transparent resin substrate. It becomes possible to bond the transparent resin substrate and the barrier film more firmly, prevent moisture and oxygen from entering from the bonding interface, and further improve the durability of the solar cell.
  • the adhesive inorganic layer is made of silicon oxynitride or silicon oxide. This is because a film made of silicon oxynitride or silicon oxide is excellent in light transmittance and barrier properties.
  • the thickness of the adhesive inorganic layer is preferably in the range of 10 nm to 60 nm. This is because when the thickness of the bonding inorganic layer is thin, the stress is reduced, and thus the adhesion can be enhanced.
  • the photoelectric conversion element is preferably an organic solar cell element having a photoelectric conversion layer containing an organic compound. Since the organic solar cell element is significantly deteriorated by moisture, the durability can be further improved by adopting the above-described configuration.
  • the present invention provides a solar cell module in which a plurality of the above-described solar cells are connected in series or in parallel.
  • an adhesive inorganic layer is formed on the surface of the transparent resin substrate opposite to the photoelectric conversion element side, and the surface of the transparent resin substrate on the adhesive inorganic layer side and the barrier film inorganic barrier layer Are bonded via the adhesive layer, so that the adhesion reliability can be increased and the durability of the solar cell can be improved.
  • the solar cell of the present invention is formed on the surface of the transparent resin substrate, the photoelectric conversion element formed on the transparent resin substrate, and the surface of the transparent resin substrate opposite to the photoelectric conversion element side.
  • FIG. 1 is a schematic cross-sectional view showing an example of the solar cell of the present invention.
  • a solar cell 1 shown in FIG. 1 is formed on a transparent resin substrate 2 and a transparent resin substrate 2, and a photoelectric conversion element in which a first electrode layer 11, a photoelectric conversion layer 12, and a second electrode layer 13 are sequentially stacked.
  • an adhesive inorganic layer 3 formed on the surface of the transparent resin substrate 2 opposite to the photoelectric conversion element 10
  • an adhesive layer 4 disposed on the adhesive inorganic layer 3 and an adhesive layer 4 and a barrier film 7 in which an inorganic barrier layer 5 is formed on a plastic film 6.
  • the inorganic layer 3 for bonding and the inorganic barrier layer 5 of the barrier film 7 are bonded via the adhesive layer 4.
  • the solar cell 1 has a light-receiving surface on the transparent resin base material 2 and the barrier film 7 side.
  • the 1st electrode layer, photoelectric conversion layer, and 2nd electrode layer which comprise a photoelectric conversion element may not be laminated
  • the bonding inorganic layer 3 and the inorganic barrier layer 5 are both made of an inorganic material, good bonding strength can be secured at the interface between the bonding inorganic layer 3 and the inorganic barrier layer 5. Therefore, moisture permeation from the adhesion interface can be prevented.
  • the inorganic layer for adhesion is formed in the surface on the opposite side to the photoelectric conversion element side of a transparent resin base material, the surface by the side of the inorganic layer for adhesion of a transparent resin base material, and a barrier film Since the inorganic barrier layer is bonded via the adhesive layer, the bonding inorganic layer and the inorganic barrier layer are bonded via the adhesive layer, and moisture and oxygen from the bonding interface Can be prevented, adhesion reliability can be increased, and the durability of the solar cell can be improved.
  • both the transparent resin substrate and the barrier film can have flexibility, and a roll-to-roll can form a photoelectric conversion element on the transparent resin substrate,
  • the surface of the transparent inorganic resin substrate on which the conversion element and the inorganic layer for adhesion are formed can be bonded to the inorganic barrier layer of the barrier film, and a highly reliable solar cell can be manufactured at low cost. It becomes possible to manufacture efficiently.
  • the barrier film when the barrier film has an inorganic barrier layer as one of the outermost layers, the barrier film is disposed so that the inorganic barrier layer is on the element side, and therefore the outermost layer on the light-receiving surface side of the solar cell.
  • An inorganic barrier layer does not exist on the surface, and damage to the barrier film due to external factors such as scratches during production and use can be reduced.
  • Adhesive Inorganic Layer The adhesive inorganic layer in the present invention is formed on the surface of the transparent resin substrate opposite to the photoelectric conversion element side.
  • the material used for the inorganic layer for adhesion is not particularly limited as long as it is an inorganic material.
  • the material may have conductivity or insulation. Specific examples include metals, alloys, oxides, nitrides, carbides, borides, sulfides, fluorides, and carbon. These materials may be used alone or in combination of two or more.
  • the inorganic layer for adhesion may or may not have optical transparency, and is appropriately selected according to the formation position of the inorganic layer for adhesion.
  • the bonding inorganic layer 3 when the bonding inorganic layer 3 is formed in the photoelectric conversion element forming region where the photoelectric conversion element 10 is provided, the bonding inorganic layer 3 is particularly formed on the entire surface of the transparent resin substrate 2.
  • the transparent resin base material 2 and the barrier film 7 side serve as a light receiving surface in the present invention, the material used for the bonding inorganic layer 3 needs to have light transmittance.
  • the bonding inorganic layer 3 is formed so as to surround the periphery of the photoelectric conversion element forming region 20 in which the photoelectric conversion element 10 is provided. In the case where the material is not formed in the photoelectric conversion element forming region 20, the material used for the bonding inorganic layer 3 may not have light transmittance.
  • 2B is a cross-sectional view taken along the line AA in FIG. 2A. In FIG. 2A, the photoelectric conversion element, the adhesive layer, and the barrier film are omitted, and the photoelectric conversion element forming region is shown. Is indicated by a broken line. Especially, it is preferable that the inorganic layer for adhesion
  • Examples of materials used for the light-transmitting adhesive inorganic layer include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium ( Examples thereof include compounds containing Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and the like.
  • oxides containing these elements and oxygen are preferably used. This is because the oxide has light transmittance and is stable in the air atmosphere.
  • a silicon compound or an aluminum compound is preferable, and a silicon compound is particularly preferable.
  • silicon compound examples include silicon oxynitride (SiON), silicon oxide (SiO 2 ), silicon oxynitride carbide (SiONC), silicon oxide carbide (SiOC), silicon nitride (SiN), and silicon nitride carbide (SiNC).
  • silicon oxynitride (SiON) or silicon oxide (SiO 2 ) is preferable. This is because these materials are excellent not only in light transmittance but also in barrier properties.
  • aluminum compound examples include aluminum oxide (Al 2 O 3 ), aluminum oxynitride (AlON), aluminum oxynitride carbide (AlONC), aluminum nitride (AlN), and aluminum nitride carbide (AlNC).
  • the material of the inorganic layer for adhesion may be the same as or different from the material of the inorganic barrier layer of the barrier film.
  • the material of the bonding inorganic layer is preferably the same as the material of the inorganic barrier layer of the barrier film. This is because the bonding inorganic layer and the inorganic barrier layer made of the same material are bonded via the adhesive layer, thereby enabling stronger bonding.
  • the material of the bonding inorganic layer is preferably different from the material of the inorganic barrier layer of the barrier film.
  • the inorganic layer for bonding is formed on the surface of the transparent resin substrate opposite to the photoelectric conversion element side, and the transparent resin substrate and the barrier film are bonded by the bonding inorganic layer.
  • the adhesive inorganic layer may be formed on the entire surface of the transparent resin substrate or may be formed in a pattern.
  • attachment is formed in the whole surface of a transparent resin base material. This is because the transparent resin substrate and the barrier film can be more firmly bonded, moisture and oxygen can be prevented from entering from the bonding interface, and the durability of the solar cell can be further improved.
  • the bonding inorganic layer 3 is formed of the photoelectric conversion element 10 as illustrated in FIGS. 2 (a) and 2 (b). It is preferably formed so as to surround the periphery of the provided photoelectric conversion element formation region 20.
  • the adhesive inorganic layer is formed so as to surround the photoelectric conversion element formation region, and thus the adhesion in the photoelectric conversion element formation region. Intrusion of moisture and oxygen from the interface can be prevented, and barrier properties from the transparent resin substrate side can be secured by the barrier film.
  • the adhesive inorganic layer is usually formed so as to surround the entire periphery of the photoelectric conversion element formation region.
  • the bonding inorganic layer 3 may be formed so as to surround the periphery of the element forming region 20, and as illustrated in FIG. 4, the bonding inorganic layer 3 so as to surround the periphery of the plurality of photoelectric conversion element forming regions 20, respectively. May be formed. 3 and 4, the photoelectric conversion element, the adhesive layer, and the barrier film are omitted, and the photoelectric conversion element formation region is indicated by a broken line.
  • the shape of the adhesive inorganic layer is appropriately selected according to the formation position of the adhesive inorganic layer.
  • the thickness of the adhesive inorganic layer is not particularly limited as long as it can secure the adhesive strength of the barrier film with the inorganic barrier layer, but is preferably 60 nm or less, preferably 30 nm or less. It is more preferable that This is because when the thickness of the bonding inorganic layer is thin, the stress is reduced, and thus the adhesion can be enhanced. Generally, the thicker the deposited film, the greater the variation in thickness and the greater the surface roughness. Therefore, when the adhesive inorganic layer is a deposited film, the thickness of the adhesive inorganic layer is small, so the stress is smaller. Thus, the adhesion can be further improved.
  • the lower limit of the thickness of the bonding inorganic layer is not particularly limited as long as the adhesion strength of the barrier film to the inorganic barrier layer is ensured, but is usually 10 nm or more.
  • the adhesive inorganic layer does not need to have a barrier property, and therefore the thickness may be small.
  • the width of the adhesive inorganic layer should be a width that can secure the adhesive strength of the barrier film with the inorganic barrier layer. There is no particular limitation.
  • the method for forming the bonding inorganic layer is not particularly limited as long as it can form the bonding inorganic layer on the transparent resin substrate, and any of wet process and dry process can be adopted. It is appropriately selected according to the type and position of formation. Among these, a dry process is preferable. Examples of the dry process include vacuum film forming methods such as vacuum deposition, sputtering, ion plating, and plasma CVD. That is, the adhesive inorganic layer is preferably a vapor deposition film. This is because the vapor-deposited film is a continuous film that is dense and has few gaps and is rich in flexibility, and thus can provide barrier properties. Among the vacuum film forming methods, the sputtering method is preferable.
  • the barrier film used in the present invention has an inorganic barrier layer, is disposed on the adhesive layer, and is bonded to the surface of the transparent resin substrate on the side of the inorganic layer for adhesion via the adhesive layer. Is.
  • the barrier film is at least one of the outermost layers.
  • the barrier film is not particularly limited as long as it has an inorganic barrier layer in at least one of the outermost layers.
  • the inorganic barrier layer 5 is formed on one side of the plastic film 6 as shown in FIG.
  • an inorganic barrier layer may be formed on both sides of the plastic film, or a plurality of types of inorganic barrier layers may be laminated on one side or both sides of the plastic film.
  • an organic layer and an inorganic barrier layer may be alternately laminated on one side or both sides of a plastic film.
  • an inorganic barrier layer since the transparent resin base material side becomes a light-receiving surface, an inorganic barrier layer has light transmittance. Further, the inorganic barrier layer may have conductivity or may have insulating properties.
  • the material used for the inorganic barrier layer constituting the barrier film is not particularly limited as long as it is an inorganic substance that exhibits barrier properties, and a general inorganic barrier layer material can be used. Examples include alloys, oxides, and nitrides. These materials may be used alone or in combination of two or more.
  • a silicon compound or an aluminum compound is preferable.
  • the silicon compound and the aluminum compound are the same as those described in the section of the adhesive inorganic layer, and thus the description thereof is omitted here.
  • an oxide is preferable. This is because the oxide has light transmittance and is stable in the air atmosphere.
  • silicon oxide (SiO 2 ), silicon oxynitride (SiON), titanium oxide (TiO 2 ), indium tin oxide (ITO), antimony tin oxide (ATO), aluminum zinc oxide (AZO), Gallium zinc oxide (GZO), zinc oxide (ZnO), aluminum oxide (Al 2 O 3 ), or the like can be used.
  • a silicon compound is preferable, and silicon oxide (SiO 2 ) and silicon oxynitride (SiON) are preferable. This is because these materials are excellent in light transmittance and barrier properties.
  • the barrier film since the transparent resin substrate side is the light receiving surface, the barrier film has light transmittance. Moreover, the barrier film may have electroconductivity and may have insulation.
  • the barrier film preferably has flexibility. Roll to Roll enables bonding of the surface of the transparent resin substrate on the inorganic layer side for adhesion and the inorganic barrier layer of the barrier film, which can improve productivity and mass productivity and reduce costs. Because it becomes.
  • the barrier film “having flexibility” means that it is bent when a force of 5 KN is applied according to the fine ceramic bending test method of JIS R 1601.
  • the barrier film is not particularly limited as long as it has an inorganic barrier layer in at least one of the outermost layers, and a general barrier film can be used. Commercially available barrier films can also be used. Especially, it is preferable that a barrier film has an inorganic barrier layer in any one outermost layer. In the present invention, since the barrier film is arranged so that the inorganic barrier layer is on the element side, when the barrier film has an inorganic barrier layer on either outermost layer, the outermost surface on the light receiving surface side of the solar cell This is because there is no inorganic barrier layer, and damage to the barrier film due to external factors such as scratches during production and use can be reduced.
  • the thickness of the barrier film is appropriately selected depending on the use of the solar cell, but is usually about 10 ⁇ m to 2000 ⁇ m, preferably in the range of 50 ⁇ m to 1800 ⁇ m, more preferably in the range of 100 ⁇ m to 1500 ⁇ m.
  • Transparent resin base material The transparent resin base material used for this invention supports a photoelectric conversion element etc.
  • the transparent resin substrate side serves as the light receiving surface
  • the transparent resin substrate has light transmittance.
  • a transparent resin base material has flexibility. With Roll to Roll, a photoelectric conversion element can be produced on a transparent resin substrate, and the surface of the transparent resin substrate on the side of the inorganic layer for adhesion and the inorganic barrier layer of the barrier film can be bonded, This is because productivity and mass productivity can be improved and costs can be reduced.
  • flexible transparent resin base materials are excellent in processability, and are useful in realizing lightweight, thin, and hard-to-break solar cells, and can be applied to various applications such as curved surfaces. Because it spreads.
  • Examples of the resin used for such a transparent resin substrate include fluorine resin, polyethylene, polypropylene, polyvinyl chloride, polyvinyl fluoride, polystyrene, ABS resin, polyamide, polyacetal, polyester, polycarbonate, modified polyphenylene ether, and polysulfone.
  • Polyarylate polyetherimide, polyethersulfone, polyamideimide, polyimide, polyphenylene sulfide, liquid crystalline polyester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polymicroxylene dimethylene terephthalate, polyoxymethylene, polyether Sulfone, polyether ether ketone, polyacrylate, acrylonitrile-styrene resin, phenol resin, urine Resins, melamine resins, unsaturated polyester resins, epoxy resins, polyurethane, silicone resin, amorphous polyolefins, and the like. You may use these as a 1 type, or 2 or more types of copolymer.
  • the thickness of the transparent resin substrate is appropriately selected depending on the use of the solar cell, etc., but is usually about 50 ⁇ m to 2000 ⁇ m, preferably within the range of 100 ⁇ m to 1800 ⁇ m, more preferably within the range of 100 ⁇ m to 200 ⁇ m. is there.
  • Adhesive layer The adhesive layer in this invention is arrange
  • attachment of a transparent resin base material and the inorganic barrier layer of a barrier film are bonded through an adhesive bond layer.
  • the adhesive bond layer has light transmittance.
  • an adhesive used for the adhesive layer the surface of the transparent resin base material on the side of the inorganic layer for adhesion and the inorganic barrier layer of the barrier film can be bonded to obtain an adhesive layer having light transmittance.
  • a general adhesive used for sealing a solar cell can be used, and among them, a synthetic resin adhesive is preferable.
  • the synthetic resin adhesive for example, a thermosetting adhesive or a photocurable adhesive can be used.
  • epoxy resin, acrylic resin, ionomer resin, urethane resin, ethylene vinyl acetate copolymer resin, and the like can be mentioned.
  • High Milan thermosetting adhesive
  • UV curable adhesive manufactured by ThreeBond Co., Ltd.
  • the position where the adhesive layer is formed is not particularly limited as long as the adhesive layer is disposed on the surface of the transparent resin base material on the side of the inorganic layer for adhesion, but is not limited to the entire surface of the transparent resin base material or the barrier film. Preferably they are arranged.
  • the method of arranging the adhesive is not particularly limited as long as it is a method capable of arranging the adhesive on the entire surface of the transparent resin substrate or the barrier film.
  • positioning an adhesive agent is mentioned.
  • the method for applying the liquid adhesive is not particularly limited as long as it can apply the liquid adhesive to the entire surface of the transparent resin substrate or the barrier film.
  • the micro gravure coating method, the gravure Examples thereof include a coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a flexographic printing method, an offset printing method, and a screen printing method.
  • the target for placing the adhesive may be on the inorganic barrier layer of the barrier film or the surface of the transparent resin substrate on the side of the inorganic layer for adhesion.
  • Photoelectric conversion element The photoelectric conversion element in the present invention is formed on a transparent resin substrate.
  • any solar cell can be used as long as it constitutes a solar cell and sealing is necessary or suitable.
  • silicon such as a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, and an amorphous silicon solar cell element.
  • Organic solar cell elements such as solar cell elements, compound semiconductor solar cell elements, organic thin film solar cell elements, and dye-sensitized solar cell elements. Among these, organic solar cell elements having a photoelectric conversion layer containing an organic compound are preferable because deterioration due to moisture is remarkable.
  • organic solar cell elements as described above, for example, organic thin film solar cell elements and Examples thereof include a dye-sensitized solar cell element. In particular, an organic thin film solar cell element is suitable.
  • FIG. 5 is a schematic sectional view showing an example of the solar cell of the present invention provided with a general organic thin film solar cell element.
  • the photoelectric conversion element 10 shown in FIG. 5 is an organic thin film solar cell element 30.
  • the first electrode layer 11, the hole extraction layer 31, and the photoelectric conversion are formed on the transparent resin substrate 2.
  • the layer 12, the electron extraction layer 32, and the second electrode layer 13 are sequentially stacked. Note that the configuration other than the photoelectric conversion element is the same as that of the solar cell shown in FIG.
  • FIG. 6 is a schematic cross-sectional view showing an example of the solar cell of the present invention provided with a general dye-sensitized solar cell element.
  • the photoelectric conversion element 10 shown in FIG. 6 is a dye-sensitized solar cell element 40, and the dye-sensitized solar cell element 40 includes a first electrode layer 11 formed on the transparent resin substrate 2, and a first electrode.
  • a porous layer 41 (photoelectric conversion layer 12) formed on the layer 11 and containing oxide semiconductor fine particles carrying a dye sensitizer; and an electrolyte layer 42 formed so as to be in contact with the porous layer 41;
  • the second electrode layer 13 formed on the counter substrate 45 and disposed on the porous layer 41 and the electrolyte layer 42 has a sealing agent layer 43 for sealing.
  • the configuration other than the photoelectric conversion element and the counter substrate is the same as that of the solar cell shown in FIG.
  • the photoelectric conversion element will be described.
  • the case where the first electrode layer, the photoelectric conversion layer, and the second electrode layer constituting the photoelectric conversion element are formed in this order will be described.
  • the layers are not necessarily laminated in this order, and the layers may be arranged side by side without being laminated.
  • any one of the first electrode layer, the photoelectric conversion layer, and the second electrode layer may also serve as another layer.
  • the 1st electrode layer used for this invention is formed on a transparent resin base material.
  • the first electrode layer is not particularly limited as long as it becomes an electrode on the light receiving surface side, and may be a transparent electrode layer. It may be a metal electrode layer having a shape, or a transparent electrode layer and a metal electrode layer having a pattern shape laminated in any order.
  • the first electrode layer is a patterned metal electrode layer or when the transparent electrode layer and the patterned metal electrode layer are laminated, the resistance can be reduced and the generated power can be efficiently used. It can collect current well.
  • the transparent electrode layer and the patterned metal electrode layer will be described.
  • the material of the transparent electrode layer used in the present invention is not particularly limited as long as it has conductivity and light transmittance.
  • ITO indium tin oxide
  • ITO indium Conductive inorganic oxides such as zinc oxide (IZO), aluminum zinc oxide (AZO), fluorine-containing tin oxide (FTO), tin oxide and zinc oxide
  • IZO zinc oxide
  • AZO aluminum zinc oxide
  • FTO fluorine-containing tin oxide
  • tin oxide and zinc oxide polythiophene, polyaniline, polypyrrole, polyethylenedioxythiophene-polystyrenesulfone
  • conductive polymers such as acid (PEDOT-PSS).
  • the transparent electrode layer may be a single layer or a multilayer in which materials having different work functions are laminated.
  • the thickness of the transparent electrode layer is appropriately selected according to the type of photoelectric conversion element.
  • the thickness of the transparent electrode layer should be within a range of 0.1 nm to 500 nm when the thickness is a single layer and the total thickness when the layer is a multilayer. In particular, the thickness is preferably in the range of 1 nm to 300 nm. If the thickness of the transparent electrode layer is thinner than the above range, the sheet resistance of the transparent electrode layer may become too large and the generated charge may not be sufficiently transmitted to the external circuit, while the thickness of the transparent electrode layer is within the above range.
  • the transparent electrode layer has a thickness in the range of 5 nm to 2000 nm in the case of a single layer and the total thickness in the case of a multilayer. In particular, the thickness is preferably in the range of 10 nm to 1000 nm. When the thickness of the transparent electrode layer is thinner than the above range, the conductivity may be insufficient. On the other hand, when the thickness of the transparent electrode layer is thicker than the above range, it is difficult to form a homogeneous film. This is because it may be difficult to obtain good photoelectric conversion efficiency due to a decrease in the total light transmittance.
  • the transparent electrode layer may be formed on one surface on the transparent resin substrate or may be formed in a pattern.
  • a method for forming the transparent electrode layer a general method for forming an electrode can be used.
  • the metal electrode layer used in the present invention is formed in a pattern on a transparent resin substrate.
  • the metal electrode layer usually has a smaller resistance than the transparent electrode layer.
  • a metal or an alloy is usually used as a material of the metal electrode layer.
  • a metal or an alloy is usually used.
  • Al, Au, Ag, and Cu are preferable.
  • the metal electrode layer may be a single layer made of the above-described metal or alloy, and in order to improve adhesion to the transparent resin substrate or the transparent electrode layer, contact with the layer made of the above-mentioned metal or alloy.
  • a layer may be appropriately laminated.
  • the material for the contact layer include nickel (Ni), chromium (Cr), nickel chromium (Ni—Cr), titanium (Ti), and tantalum (Ta).
  • the contact layer is provided to obtain adhesion between the metal electrode layer and the transparent resin base material or transparent electrode layer, and may be formed only on one side of the above-mentioned metal or alloy layer. May be.
  • the shape of the metal electrode layer is not particularly limited as long as it is a pattern, and is appropriately selected depending on desired conductivity, light transmittance, strength, and the like.
  • the metal electrode layer may have a mesh-like mesh portion and a frame portion arranged around the mesh portion, or may be composed of a mesh-like mesh portion.
  • the frame part is arranged so as to surround the four sides of the mesh part.
  • it may be arranged so as to surround three sides of the mesh part, may be arranged so as to surround two sides of the mesh part, or may be arranged on one side of the mesh part.
  • the frame part is arrange
  • the shape of the mesh portion is not particularly limited as long as it is a mesh shape, and is appropriately selected depending on desired conductivity, light transmittance, strength, and the like.
  • a polygon such as a triangle, a quadrangle, and a hexagon, a circular lattice, and the like can be given.
  • Polygonal or circular “lattice” refers to a shape in which polygonal or circular openings are periodically arranged.
  • polygonal or circular lattice shape for example, polygonal openings may be arranged in a straight line or zigzag.
  • the shape of the mesh portion is preferably a hexagonal lattice shape or a parallelogram lattice shape. This is because the current flowing through the mesh portion can be prevented from being concentrated locally.
  • the hexagonal openings are arranged in a zigzag (so-called honeycomb shape).
  • the acute angle of the parallelogram is preferably within the range of 40 ° to 80 °, more preferably within the range of 50 ° to 70 °, and even more preferably 55 ° to 65 °. Within the range of °.
  • the metal electrode layer itself basically does not transmit light, light enters the photoelectric conversion layer from the opening of the mesh portion of the metal electrode layer. Therefore, it is preferable that the opening part of the mesh part of a metal electrode layer is comparatively large. Specifically, the ratio of the openings in the mesh portion of the metal electrode layer is preferably about 50% to 98%, more preferably in the range of 70% to 98%, and still more preferably 80% to 98%. Is within the range.
  • the pitch of the openings in the mesh part of the metal electrode layer and the line width of the mesh part are appropriately selected according to the area of the entire metal electrode layer and the like.
  • the line width of the frame part is appropriately selected according to the area of the entire metal electrode layer and the like.
  • the thickness of the metal electrode layer is not limited as long as it does not cause a short circuit between the first electrode layer and the second electrode layer, and is formed between the first electrode layer and the second electrode layer. It is appropriately selected according to the thickness of the photoelectric conversion layer or the like and the type of the photoelectric conversion element.
  • the thickness of the metal electrode layer is preferably in the range of 100 nm to 1000 nm, more preferably in the range of 200 nm to 800 nm, more preferably in the range of 200 nm to 500 nm. It is preferably in the range of 200 nm to 400 nm.
  • the thickness of the metal electrode layer is preferably in the range of 10 nm to 10000 nm, particularly in the range of 100 nm to 5000 nm, and more preferably in the range of 200 nm to 1000 nm. It is preferable that It is because the sheet resistance of a metal electrode layer may become too large when the thickness of a metal electrode layer is thinner than the said range. In addition, if the thickness of the metal electrode layer is larger than the above range, it takes a long time to form a film, so that the production efficiency may be reduced or the production cost may be increased.
  • the lamination order of the transparent electrode layer and the patterned metal electrode layer is not particularly limited, A transparent electrode layer and a patterned metal electrode layer may be laminated in this order on the transparent resin substrate, or a patterned metal electrode layer and a transparent electrode layer may be laminated in this order on the transparent resin substrate. Especially, it is preferable that it is laminated
  • the method for forming the metal electrode layer is not particularly limited, and examples thereof include a method in which a metal thin film is formed on one surface and then patterned in a mesh shape, and a method in which a mesh conductor is directly formed. These methods are appropriately selected according to the material and configuration of the metal electrode layer.
  • the method for forming the metal thin film is preferably a vacuum film forming method such as a vacuum deposition method, a sputtering method, or an ion plating method.
  • the metal species formed by the vacuum film formation method has less inclusions than the plating film and can reduce the specific resistance, and can also reduce the specific resistance as compared with those formed using Ag paste or the like.
  • a vacuum film formation method is also suitable as a method for forming a metal thin film having a thickness of 1 ⁇ m or less, preferably 500 nm or less, with a precise thickness and a uniform thickness.
  • the method for patterning the metal thin film is not particularly limited as long as it can be accurately formed into a desired pattern, and examples thereof include a photoetching method.
  • Second electrode layer The second electrode layer used in the present invention is an electrode facing the first electrode layer.
  • the second electrode layer since the transparent resin substrate side is the light receiving surface, the second electrode layer may or may not have light transmittance.
  • the second electrode layer may be a metal substrate. This is because when the second electrode layer is a metal substrate, it is possible to prevent moisture and oxygen from being transmitted from the second electrode layer side. In this case, it is not necessary to perform sealing using a sealing base material from the second electrode layer, and the structure of the solar cell can be simplified and the manufacturing process can be simplified.
  • the metal substrate When the second electrode layer is a metal substrate, the metal substrate preferably has flexibility. This is because the second electrode layer, which is a metal substrate, can be disposed on the photoelectric conversion layer by roll-to-roll, so that productivity and mass productivity can be improved and costs can be reduced.
  • a metal base material has flexibility refers to bending when a force of 5 KN is applied in the metal material bending test method of JIS Z 2248. As such a metal base material, a metal foil is preferably used.
  • the material of the second electrode layer is not particularly limited as long as it has conductivity, and is appropriately selected according to the form of the second electrode layer.
  • the second electrode layer is not a metal substrate
  • examples of the material of the second electrode layer include Au, Ag, Co, Ni, Pt, Li, In, Al, Ag, Ca, Mg, Sm, Tb, and Yb. , Zr, LiF and the like.
  • the second electrode layer may be a single layer or a multilayer in which materials having different work functions are stacked.
  • Examples of the second electrode layer in which different materials are laminated include those in which any one of Ca, LiF, LiCa, MoO 3 or VO 5 and any one of Al or Ag is laminated.
  • the material of the second electrode layer is not particularly limited as long as it functions as an electrode and can be a metal foil.
  • the material of the second electrode layer is not particularly limited as long as it functions as an electrode and can be a metal foil.
  • the thickness of the second electrode layer is appropriately selected according to the form of the second electrode layer and the type of the photoelectric conversion element.
  • the thickness of the second electrode layer is a single layer, and the thickness is a multilayer.
  • the total film thickness is preferably in the range of 0.1 nm to 500 nm, more preferably in the range of 1 nm to 300 nm.
  • the thickness of the second electrode layer is, in the case of a single layer, the thickness of the multi-layer.
  • the total film thickness is preferably in the range of 5 nm to 2000 nm, and more preferably in the range of 10 nm to 1000 nm.
  • the thickness of the second electrode layer is not particularly limited as long as it functions as an electrode and has a barrier property. Specifically, the thickness is 10 ⁇ m or more. I just need it. The thicker the metal substrate, the better the conductivity and barrier properties. On the other hand, the thinner the metal substrate, the richer the flexibility. In consideration of flexibility, the thickness of the metal substrate is preferably in the range of 10 ⁇ m to 300 ⁇ m, and more preferably in the range of 30 ⁇ m to 300 ⁇ m.
  • the second electrode layer may be formed on one surface of the photoelectric conversion layer or may be formed in a pattern.
  • the method for forming the second electrode layer is appropriately selected according to the form of the second electrode layer.
  • a general electrode forming method can be used as a method for forming the second electrode layer.
  • the second electrode layer is a metal substrate, as a method of arranging the second electrode layer on the photoelectric conversion layer, the second electrode layer made of the metal substrate is arranged on the photoelectric conversion layer with good adhesion.
  • the method is not particularly limited as long as it can be used, and examples thereof include a method in which a metal substrate is thermocompression bonded onto the photoelectric conversion layer.
  • Photoelectric conversion layer used for this invention is suitably selected according to the kind of photoelectric conversion element.
  • the photoelectric conversion element is a silicon-based solar cell element such as a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, or an amorphous silicon solar cell element
  • the photoelectric conversion layer is formed of single crystal silicon or polycrystalline silicon, respectively.
  • a layer containing amorphous silicon is a layer containing gallium-arsenic, copper-indium-selenium, copper-indium-gallium-selenium, cadmium-tellurium, or the like.
  • the photoelectric conversion layer is a layer containing an organic semiconductor, and the organic compound contained in the photoelectric conversion layer is an organic semiconductor.
  • the photoelectric conversion layer is a layer containing an oxide semiconductor on which a dye sensitizer is supported, and the organic compound contained in the photoelectric conversion layer is a dye sensitizer. It is.
  • the photoelectric conversion layer of the photoelectric conversion element used in the present invention a known layer can be appropriately used depending on the type of the photoelectric conversion element.
  • the case where the photoelectric conversion element is an organic thin-film solar cell element and the case where it is a dye-sensitized solar cell element will be described as examples of the photoelectric conversion layer.
  • Photoelectric conversion layer in organic thin film solar cell element contributes to charge separation of the organic thin film solar cell, and the generated electrons and holes are used as electrodes in opposite directions, respectively.
  • the photoelectric conversion layer may be a single layer having both an electron-accepting function and an electron-donating function (first aspect), or an electron-accepting layer having an electron-accepting function and an electron-donating function.
  • a layer in which an electron donating layer having n is laminated may be used (second embodiment).
  • the 1st aspect of the photoelectric converting layer in an organic thin-film solar cell element is a single layer which has both an electron-accepting function and an electron-donating function, and an electron-donating material and an electron-accepting material are used. It contains.
  • this photoelectric conversion layer since charge separation occurs using a pn junction formed in the photoelectric conversion layer, it functions as a photoelectric conversion layer alone.
  • the electron donating material is not particularly limited as long as it has a function as an electron donor, but it is preferable that the material can be formed by a wet coating method.
  • a polymer material is preferred.
  • a conductive polymer is a so-called ⁇ -conjugated polymer, which is composed of a ⁇ -conjugated system in which double bonds or triple bonds containing carbon-carbon or hetero atoms are alternately linked to single bonds, and exhibits semiconducting properties. It is. In the conductive polymer material, ⁇ conjugation is developed in the polymer main chain, so that charge transport in the main chain direction is basically advantageous.
  • the electron transfer mechanism of the conductive polymer is mainly hopping conduction between molecules by ⁇ stacking, it is advantageous not only for the main chain direction of the polymer but also for the charge transport in the film thickness direction of the photoelectric conversion layer. is there.
  • the conductive polymer material can be easily formed by a wet coating method using a coating solution in which the conductive polymer material is dissolved or dispersed in a solvent, a large-area organic thin film solar cell Can be manufactured at low cost without requiring expensive equipment.
  • Examples of the electron-donating conductive polymer material include polyphenylene, polyphenylene vinylene, polysilane, polythiophene, polycarbazole, polyvinyl carbazole, porphyrin, polyacetylene, polypyrrole, polyaniline, polyfluorene, polyvinyl pyrene, polyvinyl anthracene, and derivatives thereof. And copolymers thereof, or phthalocyanine-containing polymers, carbazole-containing polymers, organometallic polymers, and the like.
  • thiophene-fluorene copolymer polyalkylthiophene, phenylene ethynylene-phenylene vinylene copolymer, phenylene ethynylene-thiophene copolymer, phenylene ethynylene-fluorene copolymer, fluorene-phenylene vinylene copolymer
  • a thiophene-phenylene vinylene copolymer is preferably used. This is because the energy level difference is appropriate for many electron-accepting materials.
  • a phenylene ethynylene-phenylene vinylene copolymer Poly [1,4-phenyleneethynylene-1,4- (2,5-dioctadodecyloxyphenylene) -1,4-phenyleneethene-1,2-diyl-1,4- ( 2,5-dioctadodecyloxyphenylene) ethene-1,2-diyl]
  • the electron-accepting material is not particularly limited as long as it has a function as an electron acceptor, but it is preferable that it can be formed into a film by a wet coating method.
  • a conductive polymer material is preferable. This is because the conductive polymer material has the advantages as described above.
  • Examples of the electron-accepting conductive polymer material include polyphenylene vinylene, polyfluorene, and derivatives thereof, and copolymers thereof, or carbon nanotubes, fullerene derivatives, CN group or CF 3 group-containing polymers, and the like. And —CF 3 substituted polymer.
  • polyphenylene vinylene derivative examples include CN-PPV (Poly [2-Methoxy-5- (2′-ethylhexyloxy) -1,4- (1-cyanovinylene) phenylene]), MEH-CN-PPV (Poly [2 -Methoxy-5- (2′-ethylhexyloxy) -1,4- (1-cyanovinylene) phenylene]) and the like.
  • an electron accepting material doped with an electron donating compound, an electron donating material doped with an electron accepting compound, or the like can be used.
  • a conductive polymer material doped with an electron donating compound or an electron accepting compound is preferably used.
  • Conductive polymer materials are basically advantageous in charge transport in the direction of the main chain because of the development of ⁇ conjugation in the polymer main chain, and are doped with electron-donating compounds and electron-accepting compounds. This is because electric charges are generated in the ⁇ -conjugated main chain, and the electrical conductivity can be greatly increased.
  • Examples of the electron-accepting conductive polymer material doped with the electron-donating compound include the above-described electron-accepting conductive polymer material.
  • a Lewis base such as an alkali metal such as Li, K, Ca, or Cs or an alkaline earth metal can be used.
  • the Lewis base acts as an electron donor.
  • the electron-donating conductive polymer material doped with the electron-accepting compound include the above-described electron-donating conductive polymer material.
  • a Lewis acid such as FeCl 3 (III), AlCl 3 , AlBr 3 , AsF 6 or a halogen compound can be used. In addition, Lewis acid acts as an electron acceptor.
  • the film thickness of the photoelectric conversion layer As the film thickness of the photoelectric conversion layer, the film thickness generally employed in bulk heterojunction organic thin-film solar cells can be employed. Specifically, it can be set within the range of 0.2 nm to 3000 nm, and preferably within the range of 1 nm to 600 nm. This is because when the film thickness is thicker than the above range, the volume resistance in the photoelectric conversion layer may increase. On the other hand, if the film thickness is thinner than the above range, light may not be sufficiently absorbed.
  • the mixing ratio of the electron-donating material and the electron-accepting material is appropriately adjusted to an optimal mixing ratio depending on the type of material used.
  • the method for forming the photoelectric conversion layer is not particularly limited as long as it can be uniformly formed in a predetermined film thickness, but a wet coating method is preferably used. This is because if the wet coating method is used, the photoelectric conversion layer can be formed in the air, and the cost can be reduced and the area can be easily increased.
  • the method for applying the photoelectric conversion layer forming coating liquid is not particularly limited as long as it is a method capable of uniformly applying the photoelectric conversion layer forming coating liquid.
  • a die coating method or a spin coating method is used. Dip coating method, roll coating method, bead coating method, spray coating method, bar coating method, gravure coating method, ink jet method, screen printing method, offset printing method and the like.
  • coating method of the coating liquid for photoelectric conversion layer formation is a method which can adjust thickness mainly according to an application amount.
  • Methods that can adjust the thickness mainly according to the coating amount include, for example, a die coating method, a bead coating method, a bar coating method, a gravure coating method, an ink jet method, a screen printing method, and an offset printing method. Can be mentioned.
  • the printing method is suitable for increasing the area of the organic thin film solar cell.
  • a drying treatment for drying the formed coating film may be performed. It is because productivity can be improved by removing the solvent etc. which are contained in the coating liquid for photoelectric conversion layer formation at an early stage.
  • a drying method for example, a general method such as heat drying, air drying, vacuum drying, infrared heat drying, or the like can be used.
  • the second aspect of the photoelectric conversion layer in the organic thin film solar cell element is a laminate of an electron accepting layer having an electron accepting function and an electron donating layer having an electron donating function. It is.
  • the electron-accepting layer and the electron-donating layer will be described.
  • the electron-accepting layer used in this embodiment has an electron-accepting function and contains an electron-accepting material.
  • the electron-accepting material is not particularly limited as long as it has a function as an electron acceptor, but is preferably a material that can be formed into a film by a wet coating method.
  • a polymer material is preferred. This is because the conductive polymer material has the advantages as described above. Specific examples include the same electron-accepting conductive polymer materials used for the photoelectric conversion layer of the first aspect.
  • a film thickness generally employed in a bilayer type organic thin film solar cell can be employed. Specifically, it can be set within a range of 0.1 nm to 1500 nm, and preferably within a range of 1 nm to 300 nm. This is because if the film thickness is larger than the above range, the volume resistance in the electron-accepting layer may be increased. On the other hand, if the film thickness is thinner than the above range, light may not be sufficiently absorbed.
  • the method for forming the electron-accepting layer can be the same as the method for forming the photoelectric conversion layer of the first aspect.
  • the electron donating layer used in this embodiment has an electron donating function and contains an electron donating material.
  • the electron donating material is not particularly limited as long as it has a function as an electron donor, but it is preferable that the material can be formed by a wet coating method.
  • a polymer material is preferred. This is because the conductive polymer material has the advantages as described above. Specific examples include the same electron donating conductive polymer materials used for the photoelectric conversion layer of the first aspect.
  • a film thickness generally employed in a bilayer type organic thin film solar cell can be employed. Specifically, it can be set within a range of 0.1 nm to 1500 nm, and preferably within a range of 1 nm to 300 nm. This is because if the film thickness is larger than the above range, the volume resistance in the electron donating layer may be increased. On the other hand, if the film thickness is thinner than the above range, light may not be sufficiently absorbed.
  • the method for forming the electron donating layer can be the same as the method for forming the photoelectric conversion layer of the first aspect.
  • (B) Photoelectric conversion layer in dye-sensitized solar cell element for example, a porous layer containing oxide semiconductor fine particles carrying a dye sensitizer on the surface Is used.
  • a porous layer containing oxide semiconductor fine particles carrying a dye sensitizer on the surface Is used.
  • each structure of the porous layer will be described.
  • the oxide semiconductor fine particles used in the dye-sensitized solar cell element are not particularly limited as long as they are made of an oxide having semiconductor characteristics.
  • the oxide constituting the oxide semiconductor fine particles include TiO 2 , ZnO, SnO 2 , ITO, ZrO 2 , MgO, Al 2 O 3 , CeO 2 , Bi 2 O 3 , Mn 3 O 4 , and Y 2 O. 3 , WO 3 , Ta 2 O 5 , Nb 2 O 5 , La 2 O 3 and the like.
  • These oxide semiconductor fine particles are suitable for forming a porous porous layer, and are preferably used because energy conversion efficiency can be improved and cost can be reduced.
  • the oxide semiconductor fine particles may all be made of the same oxide, or two or more kinds of oxide semiconductor fine particles may be used.
  • One kind of oxide semiconductor fine particles may be a core fine particle, and another oxide semiconductor may have a core-shell structure including a core fine particle to form a shell.
  • oxide semiconductor fine particles made of TiO 2 it is most preferable to use oxide semiconductor fine particles made of TiO 2 . This is because TiO 2 is particularly excellent in semiconductor characteristics.
  • the average particle diameter of the oxide semiconductor fine particles is not particularly limited as long as the specific surface area of the porous layer is within a desired range, but is preferably within a range of 1 nm to 10 ⁇ m, and particularly 10 nm to 1000 nm. It is preferable to be within the range. If the average particle size is smaller than the above range, the respective oxide semiconductor fine particles may aggregate to form secondary particles. If the average particle size is larger than the above range, the porous layer becomes thicker. This is because the porosity of the porous layer, that is, the specific surface area may be reduced. Here, when the specific surface area of the porous layer becomes small, for example, it may be difficult to carry a dye sensitizer sufficient for photoelectric conversion on the porous layer. Note that the average particle size of the oxide semiconductor fine particles means a primary particle size.
  • oxide semiconductor fine particles those having the same average particle diameter may be used, or a plurality of oxide semiconductor fine particles having different average particle diameters may be used.
  • oxide semiconductor fine particles having different average particle diameters By using together oxide semiconductor fine particles having different average particle diameters, the light scattering effect in the porous layer can be enhanced, and there is an advantage that the dye-sensitized solar cell can be made more excellent in power generation efficiency.
  • the combination of the different average particle diameters is, for example, oxide semiconductor fine particles having an average particle diameter in the range of 10 nm to 50 nm and an average particle diameter of 50 nm.
  • oxide semiconductor fine particles in the range of ⁇ 800 nm can be exemplified.
  • the dye sensitizer used in the dye-sensitized solar cell element is not particularly limited as long as it can absorb light and generate an electromotive force.
  • a dye sensitizer include organic dyes and metal complex dyes.
  • the organic dye include acridine, azo, indigo, quinone, coumarin, merocyanine, and phenylxanthene dyes.
  • a ruthenium dye as the metal complex dye, and it is particularly preferable to use a ruthenium bipyridine dye and a ruthenium terpyridine dye, which are ruthenium complexes. This is because such a ruthenium complex has a wide wavelength range of light to be absorbed, so that the wavelength range of light that can be photoelectrically converted can be greatly expanded.
  • the porous layer in the dye-sensitized solar cell element may contain an optional component in addition to the oxide semiconductor fine particles.
  • binder resin can be mentioned, for example. It is because a porous layer can be made into a thing with low brittleness by containing binder resin in a porous layer.
  • the binder resin is not particularly limited as long as the brittleness of the porous layer can be set to a desired level. However, since the porous layer is formed in contact with the electrolyte layer as described later, it is necessary to use a binder resin having resistance to the electrolyte layer.
  • a binder resin include polyvinyl pyrrolidone, ethyl cellulose, caprolactan, and the like. There may be only one type of binder resin, or two or more types.
  • the thickness of the porous layer in the dye-sensitized solar cell element is appropriately selected according to the use of the dye-sensitized solar cell and is not particularly limited.
  • the thickness of the porous layer is preferably in the range of 1 ⁇ m to 100 ⁇ m, and particularly preferably in the range of 3 ⁇ m to 30 ⁇ m. This is because if the thickness of the porous layer is larger than the above range, the porous layer itself tends to cause cohesive failure, which tends to cause membrane resistance.
  • the thickness of the porous layer is thinner than the above range, it becomes difficult to form a porous layer having a uniform thickness, or the amount of the dye sensitizer carried is reduced, so that the sunlight is sufficiently absorbed. This is because there is a possibility that performance may be deteriorated because it is not possible.
  • the porous layer may be formed on one surface or a pattern on the transparent resin base material.
  • the method for forming the porous layer can be the same as the general method for forming a porous layer in a dye-sensitized solar cell.
  • the photoelectric conversion element in this invention may have another layer as needed other than a 1st electrode layer, a photoelectric converting layer, and a 2nd electrode layer.
  • the photoelectric conversion element is an organic thin film solar cell element and the case where the photoelectric conversion element is a dye-sensitized solar cell element will be described as examples.
  • the first electrode layer is usually an electrode for extracting holes generated in the photoelectric conversion layer (hole extraction electrode), the second electrode The layer serves as an electrode (electron extraction electrode) for extracting electrons generated in the photoelectric conversion layer.
  • a hole extraction layer 31 may be formed between the photoelectric conversion layer 12 and the first electrode layer 11 as illustrated in FIG.
  • An electron extraction layer 32 may be formed between the layer 12 and the second electrode layer 13.
  • the hole extraction layer is a layer provided so that holes can be easily extracted from the photoelectric conversion layer to the hole extraction electrode. Thereby, since the hole extraction efficiency from the photoelectric conversion layer to the hole extraction electrode is increased, the photoelectric conversion efficiency can be improved.
  • the material used for the hole extraction layer is not particularly limited as long as it is a material that stabilizes the extraction of holes from the photoelectric conversion layer to the hole extraction electrode.
  • conductive organic compounds such as doped polyaniline, polyphenylene vinylene, polythiophene, polypyrrole, polyparaphenylene, polyacetylene, triphenyldiamine (TPD), or electron donation such as tetrathiofulvalene, tetramethylphenylenediamine, etc.
  • An organic material that forms a charge transfer complex composed of an organic compound and an electron-accepting compound such as tetracyanoquinodimethane and tetracyanoethylene.
  • a thin film of metal such as Au, In, Ag, Pd, etc. can be used.
  • a thin film of metal or the like may be formed alone or in combination with the above organic material.
  • PEDOT polyethylenedioxythiophene
  • TPD triphenyldiamine
  • the film thickness of the hole extraction layer is preferably within a range of 10 nm to 200 nm when the organic material is used, and within a range of 0.1 nm to 5 nm when the metal thin film is used. Is preferred.
  • the electron extraction layer is a layer provided so that electrons can be easily extracted from the photoelectric conversion layer to the electron extraction electrode. Thereby, since the electron extraction efficiency from the photoelectric conversion layer to the electron extraction electrode is increased, the photoelectric conversion efficiency can be improved.
  • the material used for the electron extraction layer is not particularly limited as long as it is a material that stabilizes the extraction of electrons from the photoelectric conversion layer to the electron extraction electrode.
  • TPD triphenyldiamine
  • An organic material that forms a charge transfer complex composed of an organic compound and an electron-accepting compound such as tetracyanoquinodimethane and tetracyanoethylene.
  • the metal dope layer with an alkali metal or alkaline-earth metal is mentioned.
  • Suitable materials include bathocuproin (BCP) or bathophenantrone (Bphen) and metal doped layers such as Li, Cs, Ba, Sr.
  • Electrolyte layer In the dye-sensitized solar cell element, the electrolyte layer is in contact with the porous layer between the first electrode layer and the second electrode layer. It is formed as follows.
  • the electrolyte layer may be in any form of gel, solid or liquid.
  • the electrolyte layer may or may not contain a redox pair.
  • the redox couple is not particularly limited as long as it is generally used in an electrolyte layer of a dye-sensitized solar cell. A combination, a combination of bromine and bromide is preferred.
  • Examples of the combination of iodine and iodide are used as the redox pair may be, for example, LiI, NaI, KI, and metal iodide such as CaI 2, a combination of I 2.
  • Examples of the combination of bromine and bromide include a combination of a metal bromide such as LiBr, NaBr, KBr, CaBr 2 and Br 2 .
  • the electrolyte layer When the electrolyte layer is in a liquid state, for example, acetonitrile, methoxyacetonitrile, propylene carbonate or the like is used as a solvent, and a redox couple containing the same or an ionic liquid having an imidazolium salt as a cation is used as the solvent. Can do.
  • the electrolyte layer when it is in a gel form, it may be either a physical gel or a chemical gel.
  • the physical gel is gelled near room temperature due to physical interaction
  • the chemical gel is a gel formed by chemical bonding by a crosslinking reaction or the like.
  • a solid electrolyte layer what consists of CuI, a polypyrrole, polythiophene etc. can be mentioned, for example.
  • a catalyst layer may be formed between the second electrode layer, the porous layer, and the electrolyte layer as necessary.
  • the catalyst layer By forming the catalyst layer on the second electrode layer, the dye-sensitized solar cell element can be made more excellent in power generation efficiency.
  • examples of such a catalyst layer include an embodiment in which Pt is vapor-deposited on the second electrode layer, polyethylene dioxythiophene (PEDOT), polystyrene sulfonic acid (PSS), polyaniline (PA), paratoluene sulfonic acid (PTS). Examples of forming the catalyst layer from these and mixtures thereof are not limited thereto.
  • the sealant used for the sealant layer in the dye-sensitized solar cell element is not particularly limited as long as it has durability against the electrolyte layer.
  • heat seal Various possible thermoplastic resins and thermoplastic elastomers, low density polyethylene, high density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, or ethylene, propylene, 1-butene, 4-methyl-1 -Polyolefin resins such as random or block copolymers of ⁇ -olefins such as pentene; ethylene-vinyl compounds such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer Copolymer resin: polystyrene, acrylonitrile-styrene copolymer, ABS, ⁇ Styrenic resins such as methylstyrene-styrene copolymer; polystyrene, acryl
  • the thickness of the sealing agent layer is preferably in the range of 1 ⁇ m to 100 ⁇ m, and more preferably in the range of 1 ⁇ m to 50 ⁇ m.
  • the second electrode layer may be formed on the counter substrate.
  • the opposing base material since it can be set as the said transparent resin base material, description here is abbreviate
  • one photoelectric conversion element 10 may be formed on the transparent resin substrate 2 as illustrated in FIG. 1, and as illustrated in FIG. 3 and FIG.
  • a plurality of photoelectric conversion elements may be formed on the transparent resin substrate 2 (a photoelectric conversion element formation region 20 is shown in FIGS. 3 and 4).
  • the number of photoelectric conversion elements is not particularly limited.
  • the connection of the plurality of photoelectric conversion elements is not limited as long as a desired electromotive force can be obtained, may be only in series, may be only in parallel, or may be a combination of series and parallel.
  • the second adhesive layer is disposed on the transparent resin substrate on which the photoelectric conversion element is formed
  • the sealing substrate is disposed on the second adhesive layer
  • the second adhesive The transparent resin base material in which the photoelectric conversion element was formed and the sealing base material may be bonded through the layer.
  • the photoelectric conversion element can be sealed with the front barrier film and the back sealing substrate.
  • the sealing substrate since the transparent resin substrate side is the light receiving surface, the sealing substrate may or may not have light transmittance. Moreover, the sealing base material may have electroconductivity and may have insulation. Moreover, it is preferable that a sealing base material has flexibility. Roll-to-roll enables the transparent resin base material on which the photoelectric conversion element is formed and the sealing base material to be pasted together, thereby improving productivity and mass productivity and reducing costs. is there.
  • the sealing substrate has “flexibility” means that it bends when a force of 5 KN is applied in the bending test method of fine ceramics of JIS R 1601 or the bending test method of metal materials of JIS Z 2248. .
  • a metal foil and a barrier film can be used as such a sealing substrate. Among these, a metal foil is preferable because of its excellent barrier properties and impact resistance.
  • the second adhesive layer can be the same as the adhesive layer described above, and a description thereof will be omitted here.
  • the photoelectric conversion layer 12 is interposed between the first electrode layer 11 and the second electrode layer 13 as illustrated in FIG.
  • a third adhesive layer 21 having an insulating property may be formed so as to surround the periphery.
  • the first electrode layer and the second electrode layer can be directly bonded together via the third adhesive layer, and the photoelectric conversion layer can be sealed with good airtightness. Thereby, the penetration
  • the adhesive used for the third adhesive layer is not particularly limited as long as it has insulating properties and can bond the first electrode layer and the second electrode layer together.
  • a general adhesive used for fixing can be used.
  • the third adhesive layer is formed so as to surround the photoelectric conversion layer between the first electrode layer and the second electrode layer, and the first electrode layer and the second electrode are formed. If it arrange
  • the method for forming the third adhesive layer is not particularly limited as long as the method can arrange the adhesive layer at a desired position, and a method of applying an adhesive is usually used.
  • the adhesive application method include an inkjet method, a dispenser method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a die coating method, a flexographic printing method, and an offset.
  • Examples thereof include a printing method and a screen printing method. Among these, an inkjet method, a dispenser method, and a screen printing method are preferably used.
  • the adhesive may be applied on the first electrode layer or the second electrode layer, but is usually applied on the first electrode layer.
  • the solar cell of this invention may have another structural member other than the above-mentioned structural member as needed.
  • the solar cell of the present invention may have functional layers such as a protective sheet, a filler layer, a protective hard coat layer, a strength support layer, an antifouling layer, a high light reflection layer, and a light containment layer.
  • an adhesive layer may be formed between the functional layers depending on the layer configuration.
  • the manufacturing method of the solar cell of the present invention is not particularly limited as long as it is a method capable of manufacturing the above-described solar cell, and is appropriately selected according to the type and layer configuration of the photoelectric conversion element. .
  • FIG. 8A the bonding inorganic layer 3 is formed on the transparent resin substrate 2.
  • FIG.8 (b) the 1st electrode layer 11, the photoelectric converting layer 12, and the 2nd electrode layer 13 are provided in the surface on the opposite side to the inorganic layer 3 for adhesion
  • FIG. The photoelectric conversion elements 10 are formed by sequentially stacking.
  • the sheet-like adhesive 4a is disposed between them, laminated, and the adhesive 4a is cured.
  • FIG.8 (d) the surface by the side of the inorganic layer 3 for adhesion of the transparent resin base material 2 and the inorganic barrier layer 5 of the barrier film 7 are bonded through the adhesive bond layer 4.
  • FIGS. 9A to 9D are process diagrams showing another example of the method for manufacturing a solar cell of the present invention.
  • the 1st electrode layer 11, the photoelectric converting layer 12, and the 2nd electrode layer 13 are laminated
  • the bonding inorganic layer 3 is formed on the surface of the transparent resin substrate 2 opposite to the photoelectric conversion element 10 side.
  • the sheet-like adhesive 4a is disposed between them, laminated, and the adhesive 4a is cured. Thereby, as shown in FIG. 9 (d), the surface of the transparent resin substrate 2 on the side of the inorganic layer 3 for bonding and the inorganic barrier layer 5 of the barrier film 7 are bonded via the adhesive layer 4.
  • the inorganic layer for adhesion may be formed before the photoelectric conversion element is formed or after the photoelectric conversion element is formed.
  • the transparent resin substrate can be sufficiently washed when the inorganic layer for adhesion is formed on the transparent resin substrate. A good adhesion inorganic layer can be formed.
  • the adhesive inorganic layer is formed after the photoelectric conversion element is formed, damage such as cracks and scratches can be avoided in the adhesive inorganic layer when the photoelectric conversion element is formed.
  • the solar cell module of the present invention is characterized in that a plurality of the above-described solar cells are connected in series or in parallel.
  • connection of a plurality of solar cells is not limited as long as a desired electromotive force can be obtained, may be only in series, only in parallel, or a combination of series and parallel.
  • the solar cell has been described in detail in the section “A. Solar Cell” above, and thus the description thereof is omitted here.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same function and effect. Are included in the technical scope.
  • the sample which bonded the PEN base material which has not formed SiON film-forming on the same conditions as a comparison control was prepared.
  • the T-shaped peeling test was carried out with Tensilon, and the adhesion was evaluated.
  • the results are shown in Table 1 below.
  • the thickness of the SiON film was 10N at 90nm, 25N at 60nm, 50N at 30nm, 20N at 10nm, and measurement was impossible without the SiON film (peeling by hand).
  • Example (Production of organic thin film solar cells) A Cr / Cu layer having a thickness of 10 nm / 300 nm was formed on the entire surface of one side of a 125 ⁇ m thick PEN substrate by sputtering. Thereafter, the Cr / Cu layer was patterned by a photoetching process so as to leave a Cr / Cu layer located in a photoelectric conversion element formation region where a 50 mm ⁇ photoelectric conversion element was provided, thereby forming a metal electrode. At this time, a mesh-shaped metal electrode layer having an opening ratio of 80% was formed in the 50 mm ⁇ photoelectric conversion element formation region.
  • ITO was patterned on the metal electrode layer located in the 50 mm ⁇ photoelectric conversion element formation region by a sputtering method using a metal mask. As described above, the first electrode layer in which the mesh-shaped metal electrode layer and the transparent electrode layer were laminated was formed.
  • the surface opposite to the metal electrode layer forming surface of the PEN substrate was washed with Ar plasma 300 W for 5 minutes, and a SiON film with a thickness of 25 nm was formed by sputtering to form an adhesive inorganic layer.
  • a hole extraction layer was formed on the first electrode layer by bar coating.
  • PEDOT / PSS HC Starc, Clevious
  • HC Starc HC Starc, Clevious
  • a bar coating was applied as a photoelectric conversion layer in the atmosphere by dissolving P3HT / PCBM at 2 wt% in an orthodichlorobenzene solvent. Vacuum drying was performed for 5 minutes to form a photoelectric conversion layer.
  • pattern evaporation was performed with Ca as the electron extraction layer and Al as the second electrode layer with a thickness of 15 nm / 300 nm using a metal mask.
  • the organic thin film solar cell element was produced as described above.
  • a barrier film was prepared in which an organic layer (acrylic resin) and an inorganic barrier layer (SiON) were sequentially laminated on a PEN substrate having a thickness of 100 ⁇ m.
  • This barrier film exhibited a water vapor transmission rate of about 10 ⁇ 2 g / m 2 ⁇ day.
  • An aluminum foil having a thickness of 15 ⁇ m was prepared.
  • the SiON film surface of the PEN substrate on which the organic thin film solar cell element is formed and the inorganic barrier layer surface of the barrier film are passed through an ionomer resin (Mitsui / DuPont Polychemical Co., Ltd., High Milan, 30 ⁇ m thick), and the organic thin film solar cell
  • an ionomer resin Mitsubishi Chemical Company LLC., High Milan, 30 ⁇ m thick
  • the organic thin film solar cell By bonding the second electrode layer surface of the PEN substrate on which the element was formed and the aluminum foil with a vacuum laminator (150 ° C / 10min) via ionomer resin (Mitsui / DuPont Polychemical Co., Ltd., High Milan, 100 ⁇ m thickness) An organic thin film solar cell was produced.

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WO2019062788A1 (en) * 2017-09-29 2019-04-04 (Cnbm) Bengbu Design & Research Institute For Glass Industry Co., Ltd SEMI-TRANSPARENT THIN FILM SOLAR MODULE
US11515440B2 (en) 2017-09-29 2022-11-29 Cnbm Research Institute For Advanced Glass Materials Group Co., Ltd. Semitransparent thin-film solar module
US11715805B2 (en) 2017-09-29 2023-08-01 Cnbm Research Institute For Advanced Glass Materials Group Co., Ltd. Semitransparent thin-film solar module
EP3574528B1 (en) * 2017-01-25 2024-03-13 Saule Spolka Akcyjna Optoelectronic foil and manufacturing method of optoelectronic foil

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US12119416B2 (en) 2018-10-24 2024-10-15 First Solar, Inc. Buffer layers for photovoltaic devices with group V doping
WO2025053210A1 (ja) * 2023-09-06 2025-03-13 Ａｇｃ株式会社 透過部材及び透過部材の製造方法

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