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WO2018181393A1 - Corps stratifié et procédé de fabrication d'une cellule solaire organique - Google Patents

Corps stratifié et procédé de fabrication d'une cellule solaire organique Download PDF

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Publication number
WO2018181393A1
WO2018181393A1 PCT/JP2018/012571 JP2018012571W WO2018181393A1 WO 2018181393 A1 WO2018181393 A1 WO 2018181393A1 JP 2018012571 W JP2018012571 W JP 2018012571W WO 2018181393 A1 WO2018181393 A1 WO 2018181393A1
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WIPO (PCT)
Prior art keywords
resin
organic solar
solar cell
support
adhesive layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/012571
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English (en)
Japanese (ja)
Inventor
聡 前田
祐二 柴田
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Zeon Corp
Original Assignee
Zeon Corp
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Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to JP2019509933A priority Critical patent/JP7070551B2/ja
Priority to CN201880017294.5A priority patent/CN110431648B/zh
Publication of WO2018181393A1 publication Critical patent/WO2018181393A1/fr
Anticipated expiration legal-status Critical
Priority to JP2021205542A priority patent/JP2022049017A/ja
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • 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
    • 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 laminate and a method for producing an organic solar cell.
  • organic solar cells such as dye-sensitized solar cells and perovskite solar cells have attracted attention as photoelectric conversion elements that convert light energy into electric power.
  • a dye-sensitized solar cell includes a working electrode (photoelectrode), a counter electrode (counter electrode), a sensitizing dye layer carried on the working electrode, and an electrolyte layer disposed between the working electrode and the counter electrode.
  • Perovskite solar cells generally have a working electrode (negative electrode), a counter electrode (positive electrode), a perovskite crystal layer, an electron accepting layer, and a hole accepting layer.
  • a resin film is used as a substrate constituting an electrode.
  • handling properties are poor, positioning is difficult, displacement occurs during patterning and bonding, and the production efficiency decreases. .
  • Patent Document 1 proposes holding a working electrode substrate on a transport plate via an ionic liquid.
  • Patent Document 1 if the working electrode substrate is held on the transport plate via the ionic liquid, there is a problem that the back surface of the substrate needs to be cleaned.
  • the resin film when the resin film is fixed on the support by the adhesive layer, it is bent to the resin film of the organic solar cell substrate when the support is peeled off from the resin film after completion of the predetermined manufacturing process of the organic solar cell. There is also a problem that the organic solar cell is damaged.
  • the present invention efficiently reduces the risk of damage to the resin film or the constituent member of the organic solar cell formed on the resin film or the organic solar cell. It aims at providing the manufacturing method of the organic solar cell using the laminated body which can manufacture an organic solar cell, and the said laminated body.
  • the laminate according to the present invention is in turn, Resin film as organic solar cell substrate, It is a laminate including a resin adhesive layer containing a resin adhesive and a support,
  • the said support body is a laminated body which has a through-hole which connects the surface which contacts the said resin adhesive layer of the said support body, and surfaces other than the said surface of the said support body.
  • the laminate according to the present invention has a through-hole that connects the surface of the resin-based pressure-sensitive adhesive layer that contacts the support and the surface that contacts the resin film,
  • the through hole of the resin-based pressure-sensitive adhesive layer is preferably present at a position overlapping with the through-hole existing on the surface of the support that contacts the resin-based pressure-sensitive adhesive layer when viewed from the stacking direction.
  • the through-hole present on the surface of the support that contacts the resin-based adhesive layer does not overlap with the portion that forms the wiring pattern on the resin film when viewed from the lamination direction. Is preferred.
  • the area of the through hole existing on the surface of the support that contacts the resin-based adhesive layer is 0.007 mm 2 or more, and the through hole is 200 cm on the surface. per 2, it is preferable that there are one or more.
  • the method for manufacturing an organic solar cell according to the present invention is a method for manufacturing an organic solar cell, which includes a step of injecting a fluid into the through hole of the support of the laminate described above.
  • the fluid is preferably air.
  • the organic solar cell is preferably a dye-sensitized solar cell.
  • the present invention when a resin film is used as the substrate, the risk of damage to the resin film or the constituent member of the organic solar cell formed on the resin film or the organic solar cell can be reduced efficiently.
  • the laminated body which can manufacture an organic solar cell, and the manufacturing method of the organic solar cell using the said laminated body can be provided.
  • FIG. 1 is a schematic perspective view of an example of a laminate according to the present invention.
  • FIG. 2A is a schematic top view of another example of the laminate according to the present invention.
  • FIG. 2B is a schematic cross-sectional view taken along line AA of the laminate of FIG. 2A.
  • FIG. 3 is a schematic cross-sectional view of another example of a laminate according to the present invention.
  • a numerical range is intended to include the lower limit and the upper limit of the range unless otherwise specified.
  • 2 to 80 nm is intended to include a lower limit of 2 nm and an upper limit of 80 nm, and means 2 nm to 80 nm.
  • a dye-sensitized solar cell typically has a photoelectrode (working electrode), a counter electrode (counter electrode), and an electrolyte layer.
  • the dye-sensitized solar cell may optionally have a known functional layer such as a protective layer, an antireflection layer, or a gas barrier layer on one or both of the photoelectrode and the counter electrode.
  • a well-known separator for short circuit prevention may be used to be used to be used.
  • the photoelectrode may be any electrode that receives light and can emit electrons to an external circuit, and a known photoelectrode for a dye-sensitized solar cell can be used.
  • the photoelectrode typically includes a photoelectrode substrate, a conductive film formed on the photoelectrode substrate, a porous semiconductor fine particle layer formed on the conductive film, and a surface of the porous semiconductor fine particle layer. And a sensitizing dye layer formed by adsorbing a sensitizing dye.
  • the photoelectrode substrate plays a role of supporting a porous semiconductor fine particle layer and the like and a role of a current collector.
  • substrate what laminated
  • a known resin film or glass substrate can be used as the substrate.
  • the resin film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), Examples thereof include those obtained by molding a resin composition containing a synthetic resin such as polyester sulfone (PES), polyetherimide (PEI), transparent polyimide (PI), and cycloolefin polymer (COP).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • SPS syndiotactic polystyrene
  • PPS polyphenylene sulfide
  • PC polycarbonate
  • PAr polyarylate
  • PSF polysulfone
  • Examples thereof include those obtained by molding a resin composition containing a synthetic resin such as polyester sulfone (PES
  • Examples of the material constituting the conductive film include metals such as platinum, gold, silver, copper, aluminum, indium, and titanium; conductive metal oxides such as tin oxide and zinc oxide; indium-tin oxide (ITO), Examples thereof include composite metal oxides such as indium-zinc oxide (IZO).
  • metals such as platinum, gold, silver, copper, aluminum, indium, and titanium
  • conductive metal oxides such as tin oxide and zinc oxide
  • ITO indium-tin oxide
  • ITO indium-tin oxide
  • Examples thereof include composite metal oxides such as indium-zinc oxide (IZO).
  • the porous semiconductor fine particle layer is a porous layer containing semiconductor fine particles.
  • the porous semiconductor fine particle layer is a porous layer containing semiconductor fine particles.
  • semiconductor fine particles examples include metal oxide particles such as titanium oxide, zinc oxide, and tin oxide.
  • the particle diameter of semiconductor fine particles (average particle diameter of primary particles) is preferably 2 to 80 nm, more preferably 2 to 60 nm.
  • the surface area is large and the amount of the sensitizing dye supported is large, so that the electrolytic solution constituting the electrolytic solution layer can diffuse to the details of the porous semiconductor fine particle layer.
  • the solid content concentration contained in the semiconductor fine particle dispersion is 0.1 to 60 wt%, preferably 0.5 to 40 wt%, and more preferably 1.0 to 25 wt%.
  • the thickness of the porous semiconductor fine particle layer is not particularly limited, but is usually 0.1 to 50 ⁇ m, preferably 5 to 30 ⁇ m, more preferably 15 ⁇ m or less.
  • the porous semiconductor fine particle layer may be a single layer or a stack of two or more layers. The particle size and composition of the semiconductor fine particles in these layers may be different.
  • the sensitizing dye layer is a layer formed by adsorbing a compound (sensitizing dye) that can be excited by light to pass electrons to the porous semiconductor fine particle layer on the surface of the porous semiconductor fine particle layer.
  • Sensitizing dyes include organic dyes such as cyanine dyes, merocyanine dyes, oxonol dyes, xanthene dyes, squarylium dyes, polymethine dyes, coumarin dyes, riboflavin dyes, perylene dyes; metal phthalocyanine complexes such as iron, copper, ruthenium, and porphyrins. Metal complex dyes such as complexes; and the like. Two or more kinds of dyes may be mixed and used.
  • the solvent used to dissolve the sensitizing dye is particularly a solvent that can dissolve the sensitizing dye and does not dissolve the porous semiconductor fine particle layer or react with the semiconductor fine particles. Not limited.
  • Preferred examples of the solvent include alcohols, nitriles, halogenated hydrocarbons, ethers, amides, esters, carbonates, ketones, hydrocarbons, aromatics, nitromethanes and the like.
  • Preferred examples of the solvent used for dissolving the sensitizing dye in the present invention include methanol, ethanol, isopropanol, 1-methoxy-2-propanol, n-butanol, t-butanol, butoxyethanol, N, N-dimethylformamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, 3-methoxypropiontonyl, butyronitrile, propiolactone, ⁇ -butyrolactone, toluene, DMSO and the like can be mentioned.
  • the concentration of the sensitizing dye in the dye solution is preferably 0.01 mM to 10 mM, more preferably 0.1 mM to 10 mM.
  • the total amount of dye adsorbed is preferably 0.01 to 100 M per unit surface area (1 m 2 ) of the conductive support.
  • the amount of the dye adsorbed on the semiconductor fine particles is preferably in the range of 0.001M to 1M per gram of semiconductor fine particles.
  • cationic compounds for example, tertiary ammonium compounds, quaternary ammonium compounds, pyridine compounds, imidazolium compounds, acid compounds (for example, cholic acid, deoxychol)
  • carboxylic acid compound such as an acid, a phosphoric acid compound, a phosphonic acid compound, a sulfonic acid compound, etc.
  • concentration of these in the dye solution is preferably 0.1 mM to 100 mM.
  • the molar equivalent is preferably 1 to 1000 molar equivalents.
  • a cleaning method there are a method of spraying a solvent on a dye-sensitized porous semiconductor fine particle layer and washing it away, or a method of immersing a substrate on which a dye-sensitized porous semiconductor fine particle layer is formed in a cleaning solvent tank.
  • the substrate on which the dye-sensitized porous semiconductor fine particle layer thus obtained is formed can be further dried to obtain a photoelectrode.
  • the drying conditions are not particularly limited, but preferably 30 ° C. to 150 ° C. for 0.5 minutes to 30 minutes.
  • the counter electrode includes a counter electrode substrate and a conductive film on the counter electrode substrate.
  • a catalyst layer may be provided on the conductive film.
  • the counter electrode substrate is the same as the resin film or glass mentioned in the photoelectrode.
  • Examples of the material constituting the conductive film include metals such as platinum, gold, silver, copper, aluminum, indium, and titanium; conductive metal oxides such as tin oxide and zinc oxide; indium-tin oxide (ITO), Examples thereof include composite metal oxides such as indium-zinc oxide (IZO); carbon materials such as carbon nanotubes and fullerenes.
  • metals such as platinum, gold, silver, copper, aluminum, indium, and titanium
  • conductive metal oxides such as tin oxide and zinc oxide
  • ITO indium-tin oxide
  • ITO indium-tin oxide
  • Examples thereof include composite metal oxides such as indium-zinc oxide (IZO); carbon materials such as carbon nanotubes and fullerenes.
  • a known catalyst layer such as a conductive polymer such as platinum or polythiophene (PEDOT) or a carbon material such as carbon black, graphene, carbon nanotube, or fullerene may be used.
  • PEDOT polythiophene
  • a carbon material such as carbon black, graphene, carbon nanotube, or fullerene
  • the electrolyte layer is a layer for separating the photoelectrode and the counter electrode and efficiently performing charge transfer.
  • the electrolyte layer is not particularly limited, and examples thereof include an electrolytic solution, a gel electrolyte, or a solid electrolyte.
  • the electrolytic solution contains a supporting electrolyte, a redox couple (a pair of chemical species that can be reversibly converted into an oxidized form and a reduced form in a redox reaction), a solvent, and the like.
  • Examples of the supporting electrolyte include salts containing cations such as lithium ions, imidazolium ions, and quaternary ammonium ions.
  • any known one can be used as long as it can reduce the oxidized sensitizing dye.
  • the redox pair chlorine compound-chlorine, iodine compound-iodine, bromine compound-bromine, thallium ion (III) -thallium ion (I), ruthenium ion (III) -ruthenium ion (II), copper ion (II) -Copper ion (I), Iron ion (III)-Iron ion (II), Cobalt ion (III)-Cobalt ion (II), Vanadium ion (III)-Vanadium ion (II), Manganate ion-Permanganate And ions, ferricyanide-ferrocyanide, quinone-hydroquinone, fumaric acid-succinic acid, and the like.
  • the solvent a known solvent for forming an electrolyte layer of a solar cell can be used.
  • the solvent include acetonitrile, methoxyacetonitrile, methoxypropionitrile, N, N-dimethylformamide, ethylmethylimidazolium bistrifluoromethylsulfonylimide, ⁇ -butyrolactone, propylene carbonate, and the like.
  • the organic solar cell may be a perovskite solar cell in addition to the dye-sensitized solar cell described above.
  • a perovskite solar cell typically has a perovskite crystal layer between a working electrode and a counter electrode. In addition, you may have the positive hole transport layer and electron-accepting layer which are located so that a perovskite crystal layer may be pinched
  • Examples of the perovskite solar cell include the perovskite solar cells described in Japanese Patent Application Laid-Open Nos. 2014-049631, 2015-046583, 2016-009737, and the like.
  • the laminate according to the present invention is in turn, Resin film as organic solar cell substrate, It is a laminate including a resin adhesive layer containing a resin adhesive and a support,
  • the said support body is a laminated body which has a through-hole which connects the surface which contacts the said resin adhesive layer of the said support body, and surfaces other than the said surface of the said support body.
  • FIG. 1 is a perspective view schematically showing an example of a laminate according to the present invention.
  • the resin film 30, the resin adhesive layer 20, and the support body 10 are included in order.
  • the support 10 has a through hole 40.
  • FIG. 2A is a schematic top view of another example of the laminate according to the present invention.
  • a plurality of through holes 40 are arranged in the support 10 at regular intervals.
  • FIG. 2B is a schematic cross-sectional view taken along the line AA of the laminate of FIG. 2A.
  • a through hole 40 is present in the support 10, and the through hole 40 is a surface that contacts the resin-based adhesive layer 20 of the support 10 and a surface opposite to the surface of the support 10. Are connected.
  • FIG. 3 is a schematic cross-sectional view of another example of the laminate according to the present invention.
  • this laminate 1 through holes 40 are present in the support 10 and the resin-based pressure-sensitive adhesive layer 20, and the through-holes 40 of the resin-based pressure-sensitive adhesive layer 20 are viewed from the stacking direction. It exists in the position which overlaps with the through-hole 40 which exists in the surface which contacts the layer 20.
  • FIG. 1 is a schematic cross-sectional view of another example of the laminate according to the present invention.
  • through holes 40 are present in the support 10 and the resin-based pressure-sensitive adhesive layer 20, and the through-holes 40 of the resin-based pressure-sensitive adhesive layer 20 are viewed from the stacking direction. It exists in the position which overlaps with the through-hole 40 which exists in the surface which contacts the layer 20.
  • the material of the support is any selected from the group consisting of glass, plastic and metal.
  • the support may be subjected to a surface treatment or the like.
  • glass of the support material examples include borosilicate glass, silicate glass, silica glass, alkali-free glass, and quartz glass.
  • plastic material of the support examples include, for example, acrylic, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyester such as liquid crystal polyester, polyethylene ( PE), polypropylene (PP), polybutylene, polymethylpentene (PMP) and other polyolefins, cycloolefin polymers (COP, COC) and other cyclic olefin polymers, styrenic resins, polyoxymethylene (POM), polyamide ( PA), polycarbonate (PC), polymethylene methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified P E, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), polyethersulfone, polyketone (PK), polyetherket
  • Examples of the metal of the support material include stainless steel, iron, aluminum, brass and copper.
  • the thickness of the support may be, for example, 0.5 to 10 mm, and the end face may be subjected to C surface processing or R processing as necessary.
  • the support is a surface other than the surface in contact with the resin-based pressure-sensitive adhesive layer of the support (hereinafter sometimes referred to as the “first surface of the support”) and the surface of the support (the first surface of the support). (Hereinafter, also referred to as “the second surface of the support”). There may be one through hole or a plurality of through holes.
  • the arrangement of the through holes is not particularly limited and can be set as appropriate.
  • it may be regularly arranged at a predetermined interval, may be irregularly arranged, or a combination thereof.
  • the combination is, for example, a case where a plurality of through holes in one row are regularly arranged and a plurality of through holes in another row are arranged irregularly.
  • the second surface of the support may be a surface other than the first surface of the support.
  • the second surface may be a surface opposite to the first surface of the support.
  • the number of the second surface may be one, or two or more.
  • the shape, size and number of through-holes existing on the first surface of the support may be the same as the shape, size (hole diameter) and number of through-holes existing on the second surface of the support, respectively. And may be different.
  • the size of the through hole existing on the first surface of the support may be larger than the size of the through hole existing on the second surface of the support.
  • the connection between the through holes in the support body causes the connection of one through hole existing on the first surface of the support member and two through holes existing on the second surface of the support member.
  • the number of through holes present on one surface may be different from the number of through holes present on the second surface of the support.
  • the through-hole present in the surface (first surface) that contacts the resin-based pressure-sensitive adhesive layer of the support overlaps with the portion that forms the wiring pattern on the resin film as viewed from the lamination direction. It is preferable not to be. Thereby, the danger of the damage of the structural member of an organic solar cell formed on the resin film or the resin film, or an organic solar cell can be reduced more, and an organic solar cell can be manufactured efficiently.
  • the area of the through hole present on the surface (first surface) that contacts the resin-based pressure-sensitive adhesive layer of the support is 0.007 mm 2 or more, and the through hole is It is preferable that one or more exists per 200 cm 2 of the surface (first surface).
  • the area of the through hole is more preferably 0.19 mm 2 to 320 mm 2 , and the shape is preferably a circle or a square, but is not particularly limited thereto. If the area of the through-hole is 0.007 mm 2 or more, it becomes easy to inject a fluid into the through-hole during the peeling process, and the organic solar cell component or the organic solar battery formed on the resin film or the resin film at the time of peeling. The risk of breakage can be reduced.
  • the size of the through hole is 320 mm 2 or less, it is possible to suppress a decrease in the strength of the through hole portion, and to reduce the possibility that the through hole portion is deformed and damaged during the production of the organic solar cell. Furthermore, the presence of one or more through-holes per 200 cm 2 of the first surface can suppress the concentration of stress applied to the resin film during the peeling process, and the risk of damage to the constituent members of the organic solar cell or the organic solar cell Therefore, the organic solar cell can be efficiently manufactured.
  • the resin adhesive layer includes a resin adhesive.
  • a resin adhesive a known resin adhesive can be used.
  • the resin-based pressure-sensitive adhesive layer may or may not have a base material. Regardless of the presence or absence of the base material, the resin-based pressure-sensitive adhesive layer preferably has a light transmittance at a wavelength of 400 nm of the resin-based pressure-sensitive adhesive layer including the base material of 40% or more, and preferably 60% or more. More preferred. Moreover, what formed unevenness
  • Examples of the base material for the resin-based pressure-sensitive adhesive layer include base materials such as polyester such as polyethylene terephthalate, polyimide, cycloolefin polymer (COP, COC), polymethylpentene, and thin film glass. In particular, those having excellent heat resistance and transparency are preferable.
  • base materials such as polyester such as polyethylene terephthalate, polyimide, cycloolefin polymer (COP, COC), polymethylpentene, and thin film glass. In particular, those having excellent heat resistance and transparency are preferable.
  • the resin adhesive of the resin adhesive layer is not particularly limited and may be appropriately selected.
  • resin adhesives are silicone resin adhesives, acrylic resin adhesives, urea resin adhesives, melamine resin adhesives, phenol resin adhesives, vinyl acetate resin solvent adhesives, natural rubber adhesives Solvent adhesive, vinyl acetate resin emulsion adhesive, vinyl acetate copolymer resin emulsion adhesive, EVA (ethylene / vinyl acetate copolymer) resin emulsion adhesive, isocyanate adhesive, synthetic rubber latex It is preferably at least one selected from the group consisting of a mold adhesive, an epoxy resin adhesive, a cyanoacrylate adhesive, and a polyurethane adhesive.
  • the resin adhesive is one or more selected from the group consisting of a silicone resin adhesive, an acrylic resin adhesive, and a rubber adhesive.
  • the resin-based pressure-sensitive adhesive is heated in the peeling step (step of peeling the support) after using the laminate according to the present invention or after producing an organic solar cell by the production method according to the present invention described later. It is preferably a resin-based pressure-sensitive adhesive whose peel strength is reduced by irradiation with electromagnetic waves such as ultraviolet rays, electron beams and radiation, and temperature changes such as cooling. These may be used alone or in combination of two or more. Accordingly, in the peeling step, the resin-based pressure-sensitive adhesive layer is heated, cooled, or irradiated with electromagnetic waves such as ultraviolet rays, electron beams, or radiation to reduce the peeling strength, so that the organic solar cell or electrode is removed from the support. The formed resin film can be easily peeled off.
  • a resin-based pressure-sensitive adhesive examples include a temperature-sensitive pressure-sensitive adhesive sheet (Intellimer tape) manufactured by NITTA, and SOMATAC (registered trademark) UV manufactured by SOMAR.
  • a stimulus may be given in a timely manner according to the pressure-sensitive adhesive.
  • a temperature-sensitive sheet a temperature of ⁇ 20 ° C. to 200 ° C. may be given for 0.01 to 10 hours.
  • an electromagnetic wave containing a necessary wavelength in a timely manner may be applied for 0.01 to 10 hours.
  • the support described above may have a through-hole, but the surface of the resin-based pressure-sensitive adhesive layer is also referred to as the “first surface of the resin-based pressure-sensitive adhesive layer”. And a through-hole that connects a surface in contact with the resin film (hereinafter sometimes referred to as “second surface of the resin-based pressure-sensitive adhesive layer”). There may be one or more through-holes in the resin-based pressure-sensitive adhesive layer.
  • the arrangement of the through holes is not particularly limited and can be set as appropriate.
  • it may be regularly arranged at a predetermined interval, may be irregularly arranged, or a combination thereof.
  • the combination is, for example, a case where a plurality of through holes in one row are regularly arranged and a plurality of through holes in another row are arranged irregularly.
  • the shape, size and number of through-holes present on the first surface of the resin-based pressure-sensitive adhesive layer are the same as the shape, size and number of through-holes present on the second surface of the resin-based pressure-sensitive adhesive layer, respectively. It may be different or different.
  • the through-holes present on the first surface and / or the second surface of the resin-based pressure-sensitive adhesive layer do not overlap with the portion forming the wiring pattern on the resin film when viewed from the lamination direction. Is preferred. Thereby, the danger of the damage of the structural member of an organic solar cell formed on the resin film or the resin film, or an organic solar cell can be reduced more, and an organic solar cell can be manufactured efficiently.
  • the resin-based pressure-sensitive adhesive layer has a surface in contact with the support (first surface of the resin-based pressure-sensitive adhesive layer) and a surface in contact with the resin film (second surface of the resin-based pressure-sensitive adhesive layer).
  • the through hole of the resin-based pressure-sensitive adhesive layer is a through hole existing on the surface (first surface of the support) that contacts the resin-based pressure-sensitive adhesive layer of the support as viewed from the stacking direction. It is preferable that it exists in the position which overlaps with a hole. Thereby, a resin adhesive layer can be easily peeled from a resin film, without leaving a resin adhesive layer in a resin film.
  • the size (hole diameter) of the through-holes in the resin-based pressure-sensitive adhesive layer is the same as the size of the through-holes (hole diameter) existing on the first surface of the support. It may be different or different. In one embodiment, the size of the through hole of the resin-based pressure-sensitive adhesive layer is larger than the size of the through hole existing on the first surface of the support.
  • the resin adhesive layer formed from the resin adhesive may be one layer or two or more layers. In the case of two or more layers, each layer may be the same or different from each other.
  • the thickness of the resin-based pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 150 ⁇ m, more preferably 1 to 100 ⁇ m, and still more preferably 1 to 50 ⁇ m.
  • the resin film is a member that becomes a substrate such as a working electrode and a counter electrode of the organic solar cell.
  • a substrate such as a working electrode and a counter electrode of the organic solar cell.
  • one or both of the photoelectrode substrate and the counter electrode substrate is preferably a resin film.
  • the resin film a known resin film can be used.
  • a known resin film can be used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • SPS syndiotactic polystyrene
  • PPS polyphenylene sulfide
  • PC polycarbonate
  • PAr polyarylate
  • PSF polysulfone
  • PET Polyetherimide
  • PI transparent polyimide
  • COP cycloolefin polymer
  • PMP polymethylpentene
  • the light transmittance at a wavelength of 400 nm of the resin film is preferably 40% or more, and more preferably 70% or more.
  • the thickness of the resin film may be appropriately adjusted according to the use.
  • the thickness is 10 to 10,000 ⁇ m.
  • the conductive film described above may be present on the surface of the resin film of the laminate.
  • the method of forming the laminate is a method for obtaining a laminate having a structure of at least three layers including a resin film, a resin-based pressure-sensitive adhesive layer, and a support in this order, and if the support has the above-described through holes, in particular It is not limited, What is necessary is just to select suitably, such as application
  • a resin adhesive is applied to form a resin adhesive layer
  • the method is not particularly limited, and a known printing method can be used. Examples include spin coating, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, extrusion coating using a hopper, and multilayer simultaneous coating.
  • a resin-type adhesive layer When forming a resin-type adhesive layer by bonding, a resin-type adhesive layer can be bonded to a support body or a resin film using a bonding apparatus, for example.
  • the timing for providing the through hole in the support may be before, after laminating the support and the resin adhesive layer, or before or after laminating the support, the resin adhesive layer and the resin film. Good.
  • the manufacturing method of the organic solar cell which concerns on this invention is a manufacturing method of an organic solar cell which has the process of inject
  • the method for producing an organic solar cell according to the present invention is not particularly limited, except that a fluid is injected into the through hole from the second surface side of the support using the above-described laminate, and a known organic solar cell is used.
  • a battery manufacturing method can be employed. That is, in the conventional method for manufacturing an organic solar cell, in the process of using a resin film as a substrate, instead of the resin film alone, using the above-described laminate according to the present invention, film formation, fixation, printing, What is necessary is just to perform each process, such as bonding.
  • a fluid is inject
  • Examples of the fluid to be injected into the through hole of the support include, for example, air, dry air, inert gas such as nitrogen gas and argon gas, water, alcohol, acetonitrile, toluene, tetrahydrofuran (THF) and other common organic materials. A solvent etc. are mentioned.
  • the temperature of the fluid is not particularly limited, but is preferably ⁇ 80 ° C. to 200 ° C.
  • the fluid is preferably air or dry air.
  • the fluid to be injected from the second surface side may be injected over the entire surface, or may be partially injected into the center portion or a specific portion of the support. Further, the timing of injecting the fluid may be shifted depending on the portion to be injected.
  • the fluid may be pressurized when injected, and it is preferable to apply a pressure of 0.001 to 1 MPa.
  • the laminate or the support may be cooled or heated at the time of peeling, and the peeling environment may be carried out in a dry atmosphere or in an inert gas.
  • the organic solar cell is preferably a dye-sensitized solar cell.
  • a method for producing an organic solar cell will be described using a dye-sensitized solar cell having a photoelectrode (working electrode), a counter electrode (counter electrode), and an electrolyte layer as an example.
  • the steps of the method for producing an organic solar cell include, for example, a step of forming a conductive film on the photoelectrode substrate, a step of forming a porous semiconductor fine particle layer on the conductive film on the photoelectrode substrate, and a porous semiconductor fine particle layer
  • Photoelectrode manufacturing process such as a process of forming a sensitizing dye layer on the surface
  • Manufacturing process of a counter electrode such as a process of forming a conductive film on the counter electrode substrate, a process of forming a catalyst layer on the conductive film on the counter electrode substrate Applying a sealant composition on the photoelectrode and / or the counter electrode, irradiating with energy rays and curing to form a sealant; placing an electrolyte layer between the photoelectrode and the counter electrode;
  • the general process of the manufacturing method of well-known organic type solar cells such as; For example, refer to Japanese Unexamined Patent Application Publication No. 2014-120219.
  • the conductive film can be formed by forming a film on a photoelectrode substrate or a counter electrode substrate by a known method such as a sputtering method, a coating method, a vapor deposition method, a spray pyrolysis method, or a chemical vapor deposition (CVD) method. These conductive films may be processed using a laser such as CO 2 or YAG to form conductive patterns.
  • the porous semiconductor fine particle layer can be formed by a known method such as a press method, a hydrothermal decomposition method, an electrophoretic electrodeposition method, a binder-free coating method, and an aerosol deposition (AD) method.
  • a porous semiconductor fine particle layer is obtained by applying a titanium oxide paste using a screen printer or a baker type applicator, drying the coating film at room temperature, and then drying by heating in a thermostatic layer at 150 ° C. Can be formed.
  • the sensitizing dye layer can be formed by, for example, a method of immersing the porous semiconductor fine particle layer in a sensitizing dye solution or a method of applying a sensitizing dye solution on the porous semiconductor fine particle layer.
  • the sensitizing dye layer can be formed by dipping the porous semiconductor fine particle layer in an ethanol solution containing the dye.
  • the catalyst layer can be formed by a known method. For example, in a catalyst layer containing carbon nanotubes (A) as described in JP 2014-120219 A, a dispersion containing carbon nanotubes (A) is prepared, and this dispersion is used as a conductive film on a counter electrode substrate. It can form by apply
  • the electrolyte layer can be formed by applying a solution (electrolyte) containing the constituent components onto the photoelectrode, or by producing a cell having a photoelectrode and a counter electrode, and injecting the electrolyte into the gap. it can.
  • the energy rays for curing the sealing agent may be energy rays such as ultraviolet rays, visible light, infrared rays, and electron beams. Of these, ultraviolet rays and electron beams are preferred.
  • a light source usually containing light in the range of 200 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used.
  • an electron beam accelerator having an energy of usually 100 to 500 eV can be used.
  • Integrated irradiation dose of energy rays is usually 100 ⁇ 5000mJ / cm 2, preferably 200 ⁇ 4000mJ / cm 2.
  • the application method of the sealant composition is not particularly limited, and flexographic printing, gravure printing, screen printing, inkjet printing, offset printing, or bar coating method, dip coating method, flow coating method, spray coating method, spin coating method, Methods such as roller coating, reverse coating, air knife, and dispensing can be used.
  • the structure of the organic solar cell module is not particularly limited, and includes a Z-type, a W-type, a parallel type, a current collection type, a monolithic type, and the like.
  • a plurality of these modules may be connected in series or in parallel by combining one or two or more.
  • you may produce in a module by well-known means, such as a current collection electrode and an extraction electrode.
  • a connection method a known means may be used, and solder, a metal plate, a cable, a flat cable, a flexible base material, a cable, or the like may be appropriately selected.
  • the method for assembling the module is not particularly limited, and the module can be manufactured by a known method such as a vacuum bonding method (One Drop Fill method: ODF method) or an end seal method.
  • ODF method One Drop Fill method
  • end seal method examples include the method described in International Publication No. 2007/046499.
  • end seal method examples include a method described in JP-A-2006-004827.
  • an ultraviolet cut layer, an oxygen or moisture barrier layer, an antireflection layer, an antifouling layer, a hard coat layer, a reinforcing member, or the like may be disposed around the module or on the exterior surface as appropriate. These may be a known method such as vapor deposition, coating, or installing a sheet.
  • the blending amount means parts by mass.
  • the support, resin adhesive, resin film, and UV curable resin used in the examples are as follows.
  • Borosilicate glass Product name Tempax glass (thickness 3 mm, length 300 mm, width 210 mm) manufactured by Schott (Resin adhesive)
  • Silicone resin adhesive silicone rubber double-sided adhesive tape 9030W manufactured by Teraoka Seisakusho Co., Ltd.
  • Resin film A 300 nm long, 210 mm wide, 125 ⁇ m thick PEN film with a 300 nm ITO film.
  • UV curable resin UV curable resin: Liquid polyisobutylene sealant
  • Example 1 A resin-based pressure-sensitive adhesive layer is formed by applying 30 ⁇ m of a silicone resin-based pressure-sensitive adhesive on a support having through-holes with a spacing of 50 mm and a diameter of 1 mm (area 0.79 mm 2 ) on one surface and the opposite surface.
  • the resin film was disposed so that the surface on the ITO film side was opposite to the resin-based pressure-sensitive adhesive layer to form a laminate.
  • the through hole of the support was formed so as to avoid the printed pattern of the resin film.
  • Example 2 In Example 1, after forming the resin-based pressure-sensitive adhesive layer, the resin-based pressure-sensitive adhesive layer having the same diameter as that of the through-hole and the same position as the through-hole existing in the first surface of the support as viewed from the stacking direction A through-hole penetrating to the second surface was provided in the resin-based pressure-sensitive adhesive layer. Thereafter, in the same manner as in Example 1, a resin film was disposed to form a laminate.
  • Example 3 In Example 1, instead of a silicone resin adhesive, NITTA Intellimer Tape CS2325NA2 was used as a resin adhesive layer, and then a resin film was placed in the same manner as in Example 1 to form a laminate. Formed.
  • Example 4 Intellimer Tape CS2325NA2 manufactured by Nitta Co., Ltd. was used as the resin-based adhesive layer instead of the resin-based adhesive. Thereafter, as in Example 2, when viewed from the stacking direction, After the resin adhesive layer is provided with a through hole penetrating to the second surface of the resin-based adhesive layer at the same position as the through-hole that overlaps the through-hole existing on one surface, the resin film is disposed. Thus, a laminate was formed.
  • Example 5 In Example 1, through-holes were provided at intervals of 100 mm and a diameter of 2 mm (area 3.19 mm 2 ), and then a resin film was disposed to form a laminate as in Example 1.
  • Comparative Example 1 In Example 1, a comparative laminate was formed in the same manner as in Production Example 1 except that a support having no through hole was used.
  • organic solar cells were manufactured through the following steps of manufacturing an organic solar cell.
  • ⁇ Step of forming a sensitizing dye layer (immersion step)> A dye solution obtained by dissolving a laminate formed with a porous semiconductor fine particle layer so that a sensitizing dye has a concentration of 3 ⁇ 10 ⁇ 1 mol / liter (sensitizing dye: ruthenium complex (N719, manufactured by Solaronics)) , Solvent: ethanol) at 40 ° C. for 120 minutes to form a sensitizing dye layer to obtain a photoelectrode.
  • ⁇ Process for forming sealing agent (UV curing process)> After drawing a UV curable resin as a sealant composition on a laminate in which a sensitizing dye layer is formed on the porous semiconductor fine particle layer so as to surround the periphery of the porous semiconductor fine particle layer by a dispensing method, the porous semiconductor A UV curable resin is applied by applying an electrolytic solution on the fine particle layer, bonding the prepared photoelectrode and the counter electrode under vacuum using an automatic bonding apparatus, and irradiating 100 mW metal halide light from the photoelectrode side for 60 seconds. Was cured to form a sealant.
  • the present invention when a resin film is used as the substrate, the risk of damage to the resin film or the constituent member of the organic solar cell formed on the resin film or the organic solar cell can be reduced efficiently.
  • the laminated body which can manufacture an organic solar cell, and the manufacturing method of the organic solar cell using the said laminated body can be provided.
  • Laminate 10 Support 20: Resin-based adhesive layer 30: Resin film 40: Through-hole

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)
  • Hybrid Cells (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un corps stratifié permettant de fabriquer une cellule solaire organique avec une grande efficacité, tout en réduisant le risque de dégâts dans cette cellule solaire organique ou dans un matériau de base d'une cellule solaire organique formé d'un film de résine ou sur un film de résine, ce film de résine étant utilisé en tant que substrat. L'invention concerne également un procédé de fabrication d'une cellule solaire organique mettant en oeuvre ledit corps stratifié. Ledit corps stratifié possède, dans l'ordre un film de résine en tant que substrat de cellule solaire organique ainsi qu'un support et qu'une couche adhésive de résine contenant un adhésif de type résine. Le support présente des trous traversants qui relient la surface du support en contact avec la couche adhésive de résine et l'autre surface du support.
PCT/JP2018/012571 2017-03-29 2018-03-27 Corps stratifié et procédé de fabrication d'une cellule solaire organique Ceased WO2018181393A1 (fr)

Priority Applications (3)

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JP2019509933A JP7070551B2 (ja) 2017-03-29 2018-03-27 積層体および有機系太陽電池の製造方法
CN201880017294.5A CN110431648B (zh) 2017-03-29 2018-03-27 层叠体和有机系太阳能电池的制造方法
JP2021205542A JP2022049017A (ja) 2017-03-29 2021-12-17 積層体および有機系太陽電池の製造方法

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JP2017-065565 2017-03-29

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JP7249160B2 (ja) * 2019-01-29 2023-03-30 日東電工株式会社 積層体

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CN110431648A (zh) 2019-11-08
CN110431648B (zh) 2022-05-13
JP2022049017A (ja) 2022-03-28
TW201840403A (zh) 2018-11-16
JPWO2018181393A1 (ja) 2020-02-06

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