Classifications

• • 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
• • 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
  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/50—Photovoltaic [PV] devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/80—Constructional details
  • H10K30/88—Passivation; Containers; Encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
  • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single 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
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates to a laminate, a photoelectric conversion element, and a method for manufacturing a photoelectric conversion element.
• a device that has a laminate including an active layer (also called a photoelectric conversion layer), an electron transport layer, and a hole transport layer as the functional layers of the photoelectric conversion element (Patent Document 1), and efforts are being made to improve solar cells, such as organic thin-film solar cells, that include such devices.
• an active layer also called a photoelectric conversion layer
• an electron transport layer also called a electron transport layer
• a hole transport layer as the functional layers of the photoelectric conversion element
• organic thin-film solar cells When manufacturing organic thin-film solar cells, functional layers can be formed by coating, making them easy to manufacture on flexible resin film substrates.
• Organic thin-film solar cells formed on resin film substrates are characterized by their flexibility and light weight.
• the various layers formed on the resin film substrate are sometimes sealed by applying a film with barrier properties to prevent them from being deteriorated by moisture and oxygen in the air.
• Resin film substrates used in organic thin-film solar cells are generally thin, at 300 ⁇ m or less.
• the laminate can sag at the suction points.
• the side of the resin film substrate that is suctioned is the light-receiving surface, and repeated vacuum chucking and stress release, for example, can easily cause scratches on the light-receiving surface due to this sagging. Scratches on the light-receiving surface can reduce the efficiency with which the laminate captures light. Furthermore, significant sagging can cause cracks in the functional layers of the laminate, reducing photoelectric conversion efficiency.
• This invention was made in light of the above circumstances, and its purpose is to provide a laminate in which deflection due to vacuum suction or the like is suppressed, a photoelectric conversion element using said laminate, and a method for manufacturing a photoelectric conversion element using said laminate.
• the present invention can include the following aspects.
• a laminate comprising a resin film substrate, a first resin film, and a photoelectric conversion layer between the resin film substrate and the first resin film,
• the tensile modulus E1 (GPa) and thickness T1 ( ⁇ m) of the laminate are expressed by the following formula (A): 1000 ⁇ E1 ⁇ T1 (A) Fulfilling
• the tensile modulus E2 (GPa) and thickness T2 ( ⁇ m) of the laminate are expressed by the following formula (B): 1500 ⁇ E2 ⁇ T2 (B) Meet the laminate.
• [4] A laminate described in any one of [1] to [3] above, wherein the tensile modulus of each of the first resin film and the second resin film is 3.0 GPa or more and 9.0 GPa or less, and the thickness of each of the first resin film and the second resin film is 80 ⁇ m or more and 300 ⁇ m or less.
• [5] The laminate described in any one of [1] to [4] above, wherein the absolute value of the amount of warping when heated at 110°C for 30 minutes is 200 ⁇ m or less when the laminate does not have a resin film on the opposite side of the resin film substrate from the side on which the photoelectric conversion layer is provided.
• a laminate comprising a resin film substrate, a first resin film, and a photoelectric conversion layer between the resin film substrate and the first resin film, wherein the laminate does not have a resin film on the side opposite to the side on which the photoelectric conversion layer is provided with respect to the resin film substrate, and the tensile modulus E1 (GPa) and thickness T1 ( ⁇ m) of the laminate satisfy the following formula (A): 1000 ⁇ E1 ⁇ T1 (A) Meet the laminate. [7] The laminate according to [6] above, wherein the thickness T1 is 200 ⁇ m or more and 600 ⁇ m or less.
• a laminate comprising a resin film substrate, a first resin film, and a photoelectric conversion layer between the resin film substrate and the first resin film, wherein the laminate has a second resin film on the opposite side of the resin film substrate from the side on which the photoelectric conversion layer is provided, and the tensile modulus E2 (GPa) and thickness T2 ( ⁇ m) of the laminate are expressed by the following formula (B): 1500 ⁇ E2 ⁇ T2 (B) Meet the laminate.
• the thickness T1 is 200 ⁇ m or more and 600 ⁇ m or less
• the thickness T2 is 400 ⁇ m or more and 1000 ⁇ m or less.
• FIG. 2 is a diagram illustrating an example of a configuration of a stacked body according to the first embodiment.
• 4A and 4B are diagrams illustrating another example of the configuration of the stacked body according to the first embodiment.
• FIG. 2 is a diagram schematically illustrating the configuration of an apparatus for measuring the amount of warpage of a laminate according to the first embodiment.
• component B being provided on component A
• component B being provided on top of component A
• component B being in contact with component A
• Such descriptions are intended to allow not only cases where components A and B are in direct contact with each other, but also cases where another component is interposed between them to the extent that the effect is not impaired.
• the upper or lower limit of a numerical range in one stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage.
• the upper or lower limit of that numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example.
• a numerical range connected with " ⁇ " means a numerical range that includes the numbers before and after " ⁇ " as the upper and lower limits.
• ⁇ Laminate> 1 shows an example of the configuration of a laminate 1 according to the first embodiment.
• the laminate 1 includes a resin film substrate 11 and a resin film (also referred to as a first resin film) 12, and further includes a photoelectric conversion layer 133 between the resin film substrate 11 and the resin film 12.
• the resin film 12 is provided, for example, on the resin film substrate 11 so as to cover the photoelectric conversion layer 133.
• the photoelectric conversion layer 133 is capable of photoelectric conversion, and by providing a structure for extracting electricity generated by photoelectric conversion, the laminate 1 can be used as a photoelectric conversion element.
• An example of a photoelectric conversion element is an organic thin-film solar cell.
• the laminate 1 does not have a resin film on the side of the resin film substrate 11 opposite the side on which the photoelectric conversion layer 133 is provided. In this case, it is preferable that no other layers are provided on the surface of the resin film substrate 11 opposite the side on which the photoelectric conversion layer 133 is provided. That is, it is preferable that the surface of the resin film substrate 11 opposite the side on which the photoelectric conversion layer 133 is provided is exposed in the laminate 1. In the example of Figure 1, it is preferable that the surface of the resin film 12 opposite the side on which the photoelectric conversion layer 133 is provided is exposed in the laminate 1.
• a barrier layer described below
• Figure 1 shows a case where the laminate 1 further includes a first conductive layer 131, a first transport layer 132, a second transport layer 134, and a second conductive layer 135.
• the first conductive layer 131, the first transport layer 132, the photoelectric conversion layer 133, the second transport layer 134, and the second conductive layer 135 are provided on the resin film substrate 11 in that order.
• the first transport layer 132, the photoelectric conversion layer 133, and the second transport layer 134 may be collectively referred to as the "functional layers.”
• the first conductive layer 131, the first transport layer 132, the photoelectric conversion layer 133, the second transport layer 134, and the second conductive layer 135 may be covered by the resin film 12 on the resin film substrate 11, but when the laminate 1 includes the first conductive layer 131, a portion of the first conductive layer 131 may be extended outside the resin film 12 to serve as an extraction electrode, as shown in FIG. 1 .
• the intermediate layer includes a photoelectric conversion layer 133, and may optionally include one or more of a first conductive layer 131, a first transport layer 132, a second transport layer 134, and a second conductive layer 135.
• FIG. 2 shows another example of the configuration of the laminate 1 according to the first embodiment.
• the following explanation will mainly focus on the differences from the explanation given with reference to FIG. 1.
• the explanation given with reference to FIG. 1 also applies to the example in FIG. 2 to the extent that it does not contradict the following explanation.
• the following explanation may include explanations regarding the laminate 1 without specifying whether it relates to FIG. 1 or FIG. 2, such explanations will apply to both the examples in FIG. 1 and FIG. 2.
• the laminate 1 has a resin film (also referred to as a second resin film) 14 on the side opposite the side on which the photoelectric conversion layer 133 is provided, relative to the resin film substrate 11.
• the resin film 14 is provided so as to contact the surface of the resin film substrate 11 opposite the side on which the photoelectric conversion layer 133 is provided.
• the surface of the resin film 14 opposite the side on which the resin film substrate 11 is provided is exposed in the laminate 1.
• the first resin film 12 and the second resin film 14 are each larger than the resin film substrate 11 when viewed in the thickness direction of the resin film substrate 11 (a direction perpendicular to the resin film substrate 11), and that the first resin film 12 and the second resin film 14 cover the resin film substrate 11 so as to sandwich it all around.
• the laminate 1 of the example of FIG. 2 can be used as a photoelectric conversion element, as in the example of FIG. 1.
• the size of the first resin film 12 may be such that the first conductive layer 131 is exposed when the resin film substrate 11 is covered and sandwiched between the first resin film 12 and the second resin film 14.
• the constituent material of the resin film substrate 11 is not particularly limited and is appropriately selected depending on the application of the photoelectric conversion element.
• Examples of the constituent material of the resin film substrate 11 include polyester films such as PET film and PEN film, PES (polyethersulfone) film, polyamide films such as nylon film, polycarbonate film, and cycloolefin film, with polyester film being preferred, and PET film or PEN film being more preferred.
• the thickness of the resin film substrate 11 is preferably 50 ⁇ m or more and 350 ⁇ m or less, more preferably 75 ⁇ m or more and 300 ⁇ m or less, and even more preferably 100 ⁇ m or more and 250 ⁇ m or less.
• a barrier layer for blocking the photoelectric conversion layer 133 and other layers from the outside air may be provided on the surface of the resin film substrate 11 facing the photoelectric conversion layer 133 or on the surface opposite to that surface.
• a material with low oxygen permeability and water vapor permeability is preferred as the material for the barrier layer, and a transparent material is also preferred.
• the barrier layer is, for example, an inorganic thin film, not a resin film.
• One method for forming a resin film substrate 11 with a barrier layer is to form a transparent inorganic thin film such as silicon oxide or aluminum oxide as a barrier layer on a polymer film serving as the resin film substrate 11.
• Methods for forming a transparent inorganic thin film on a film include the sol-gel method, PVD (Physical Vapor Deposition), electron beam evaporation, plasma CVD (Chemical Vapor Deposition), and reactive sputtering.
• One example of a method for forming the barrier layer is to form a film of silicon-based compounds such as silicon nitride, silicon oxide, silicon oxynitride, and silicon carbide; aluminum-based compounds such as aluminum oxide and aluminum nitride; aluminum silicate, zirconium oxide, tantalum oxide, titanium oxide, indium tin oxide (ITO), titanium nitride, or the like on a resin film substrate 11 (preferably a PEN film) using a method such as plasma CVD, Cat-CVD, or vacuum deposition.
• the thickness of the barrier layer is preferably approximately 0.05 to 2 ⁇ m.
• the thickness of the barrier layer is sufficiently thin compared to the thickness of the resin film substrate 11, and has little effect on the elastic modulus, etc., of the resin film substrate 11.
• the cathode and anode which may be the first conductive layer 131 and the second conductive layer 135, are made of a conductive material.
• the cathode is preferably made of a conductive material with a smaller work function than the anode.
• the cathode functions to extract electrons generated in the photoelectric conversion layer 133.
• materials that can be used to make the cathode include conductive metal oxides such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zirconium oxide (IZO), titanium oxide, indium oxide, and zinc oxide; metals such as gold, platinum, silver, chromium, and cobalt, and alloys thereof.
• conductive metal oxides such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zirconium oxide (IZO), titanium oxide, indium oxide, and zinc oxide
• metals such as gold, platinum, silver, chromium, and cobalt, and alloys thereof.
• the cathode is a transparent electrode, it is preferable to use a translucent conductive metal oxide such as ITO, zinc oxide
• the anode is preferably made of a conductive material with a larger work function than the cathode.
• the anode functions to extract holes generated in the photoelectric conversion layer.
• materials that can be used to form the anode include metals and alloys thereof, such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, and magnesium; inorganic salts, such as lithium fluoride and cesium fluoride; and metal oxides, such as nickel oxide, aluminum oxide, lithium oxide, and cesium oxide.
• a conductive n-type semiconductor compound such as zinc oxide
• a material with a small work function such as ITO, may be used as the anode material.
• each of the cathode and anode is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 40 nm or more, and is preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 500 nm or less.
• the photoelectric conversion layer 133 is a layer where photoelectric conversion takes place, and contains, for example, a p-type semiconductor compound and an n-type semiconductor compound.
• the photoelectric conversion element receives light, the light is absorbed by the photoelectric conversion layer 133, electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is extracted from the cathode and anode.
• the cathode and anode correspond to the first conductive layer 131 and the second conductive layer 135.
• the p-type semiconductor compound is preferably a polymer compound, and examples thereof include conjugated copolymer semiconductor compounds such as polythiophene, polyfluorene, polyphenylene vinylene, polythienylene vinylene, polyacetylene, and polyaniline; copolymer semiconductor compounds such as oligothiophene substituted with an alkyl group or other substituent; and the like, and polythiophene which may have a substituent is preferred.
• a copolymer semiconductor compound obtained by copolymerizing two or more types of monomer units may be used.
• the p-type semiconductor compound that is a polymer compound examples include PDPPBDT, PDPPDTT, PFs, KP115, PCDTBT, DPPT-TT, PDPP2FT, F82T, F8TBT, F8BT, P3HT-Br10, PPP-P3HT, P3HT (poly(3-hexylthiophene-2,5-diyl)), PhxSDT-DTZ, PBDTDPP-1, P3DDT, PPDTBT, PPDT2FBT, PBDTDPP-2, PCPDTBT-1, PCPDTBT-2, and PBDBT2F(PM6), with P3HT being preferred.
• n-type semiconductor compounds include low molecular weight compounds such as fullerene or a derivative thereof, octaazaporphyrin, and perfluoro compounds in which hydrogen atoms of p-type semiconductor compounds are substituted with fluorine atoms (for example, perfluoropentacene and perfluorophthalocyanine), and fullerene or a derivative thereof is preferred.
• n-type semiconductor compound a polymer compound containing an aromatic carboxylic acid anhydride or an imide thereof as a skeleton, such as naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic diimide, perylene tetracarboxylic anhydride, or perylene tetracarboxylic diimide, can also be used.
• Specific examples of the polymer n-type semiconductor compound include MEH-CN-PPV, F8TBT, PZ1, DCNBT-IDT, P-BNBP-fBT, PF2-DTSi, PDI-V, PYT M , PJ1-H, N2200, and Y6.
• the layer structure of the photoelectric conversion layer 133 can be a thin-film stacked structure in which p-type and n-type semiconductor compounds are stacked, or a bulk heterojunction structure having a layer in which p-type and n-type semiconductor compounds are mixed.
• a bulk heterojunction structure has a layer (i-layer) in which p-type and n-type semiconductor compounds are mixed.
• the i-layer has a structure in which the p-type and n-type semiconductor compounds are phase-separated, with carrier separation occurring at the phase interface, and the resulting carriers (holes and electrons) being transported to the electrode.
• the mass ratio of the p-type and n-type semiconductor compounds in the i-layer is preferably 0.5 or more, more preferably 1 or more, and preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less.
• the photoelectric conversion layer 133 may contain additives in addition to p-type and n-type semiconductor compounds.
• the phase-separated structure between the p-type and n-type semiconductor compounds in a bulk heterojunction photoelectric conversion layer affects light absorption, exciton generation and diffusion, exciton dissociation (carrier separation), carrier transport, and other properties. Therefore, optimizing the phase-separated structure is expected to achieve good photoelectric conversion efficiency.
• an additive with high affinity for p-type or n-type semiconductor compounds in the photoelectric conversion layer 133 By including an additive with high affinity for p-type or n-type semiconductor compounds in the photoelectric conversion layer 133, a photoelectric conversion layer with a favorable phase-separated structure can be obtained, potentially improving photoelectric conversion efficiency.
• Additives include aliphatic hydrocarbon compounds having 8 to 20 carbon atoms and aromatic compounds having 8 to 20 carbon atoms. These aliphatic hydrocarbon compounds and aromatic compounds may have a substituent. Substituents that may be present on aliphatic hydrocarbon compounds include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, amino groups, carbamoyl groups, carbonyloxy groups, carboxyl groups, carbonyl groups, and aromatic groups.
• Substituents that may be present on aromatic compounds include halogen atoms, hydroxyl groups, cyano groups, amino groups, amide groups, carbonyloxy groups, carboxy groups, carbonyl groups, oxycarbonyl groups, silyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and aromatic groups.
• Specific examples of preferred additives include benzene that may have a substituent, naphthalene that may have a substituent, and octane that may have a substituent. Halogen atoms are particularly preferred as the substituent.
• the photoelectric conversion layer 133 contains an organic semiconductor compound, more preferably a polymer p-type semiconductor compound and/or an n-type semiconductor compound, and even more preferably a polymer p-type semiconductor compound and a small molecule n-type semiconductor compound.
• the photoelectric conversion layer 133 may contain a polymer compound having a benzobisthiazole structural unit as a p-type semiconductor compound, and specifically, it preferably contains a polymer compound having a benzobisthiazole structural unit represented by the following formula (1) (hereinafter referred to as "polymer compound P").
• T1 and T2 each independently represent an alkoxy group; a thioalkoxy group; a thiophene ring which may be substituted with a hydrocarbon group or an organosilyl group; a thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group; or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group.
• B1 and B2 each independently represent a thiophene ring which may be substituted with a hydrocarbon group, a thiazole ring which may be substituted with a hydrocarbon group, or an ethynylene group.
• the organosilyl group refers to a monovalent group in which one or more hydrocarbon groups are substituted on the Si atom, and the number of hydrocarbon groups substituted on the Si atom is preferably 2 to 3, more preferably 3.
• polymer compound P can deepen the HOMO level while narrowing the band gap, thereby increasing photoelectric conversion efficiency.
• T1 and T2 may be the same or different, but are preferably the same from the viewpoint of ease of production.
• B1 and B2 may be the same or different, but are preferably the same from the viewpoint of ease of production.
• T1 and T2 are preferably groups represented by the following formulas (t1) to (t5), respectively.
• the alkoxy group of T1 and T2 is preferably a group represented by the following formula (t1)
• the thioalkoxy group is preferably a group represented by the following formula (t2)
• the thiophene ring optionally substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t3)
• the thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t4)
• the phenyl group optionally substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group is preferably a group represented by the following formula (t5).
• T1 and T2 are groups represented by the following formulas (t1) to (t5), they are capable of absorbing short-wavelength light and have high planarity, thereby efficiently forming ⁇ - ⁇ stacking, and therefore, the photoelectric conversion efficiency can be improved.
• the groups represented by formulae (t1) to (t3) exhibit electron-donating properties, and the groups represented by formulae (t4) and (t5) exhibit electron-withdrawing properties.
• R 13 and R 14 each independently represent a hydrocarbon group having 6 to 30 carbon atoms.
• R 15 and R 16 each independently represent a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by *-Si(R 18 ) 3.
• R 15' represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by *-Si(R 18 ) 3.
• R 17 represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, *-O-R 19 , *-S-R 20 , *-Si(R 18 ) 3 , or *-CF 3.
• R 18 each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Among the multiple R 18 , some R 18 may be the same as each other, or some R 18 may be different from each other.
• R 19 and R 20 represent a hydrocarbon group having 6 to 30 carbon atoms. * represents a bond bonded to the thiazole ring of benzobisthiazole.
• the hydrocarbon groups having 6 to 30 carbon atoms represented by R 13 to R 17 , R 19 , R 20 , and R 15′ are preferably branched hydrocarbon groups, more preferably branched saturated hydrocarbon groups.
• the branched hydrocarbon groups represented by R 13 to R 17 , R 19 , R 20 , and R 15′ can increase the solubility in organic solvents.
• the hydrocarbon groups represented by R 13 to R 17 , R 19 , R 20 , and R 15′ preferably have 8 to 25 carbon atoms, more preferably 8 to 20 carbon atoms, and even more preferably 8 to 16 carbon atoms.
• the number of carbon atoms in the aliphatic hydrocarbon group for R 18 is preferably 1 to 18, more preferably 1 to 8.
• the number of carbon atoms in the aromatic hydrocarbon group for R 18 is preferably 6 to 8, more preferably 6 to 7, and even more preferably 6.
• Examples of the aromatic hydrocarbon group for R 18 include a phenyl group.
• R 18 is preferably an aliphatic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group, and even more preferably an isopropyl group.
• R 15 to R 17 and R 15′ are a group represented by *-Si(R 18 ) 3
• R 15 to R 17 and R 15′ are a group represented by *-Si(R 18 ) 3
• the solubility of the polymer compound P in organic solvents is improved.
• alkylsilyl groups are preferred, with trimethylsilyl and triisopropylsilyl groups being more preferred.
• R 17 when R 17 is a halogen atom, any of fluorine, chlorine, bromine, and iodine can be used.
• R 17 is preferably a halogen atom or *-CF 3 .
• R 15' is preferably a hydrogen atom.
• T1 and T2 groups represented by formulas (t1), (t3), and (t5) are more preferred, and a group represented by formula (t3) is even more preferred, in terms of excellent planarity of the structural unit represented by formula (1) as a whole.
• B 1 and B 2 are preferably groups represented by any one of the following formulae (b1) to (b3):
• B 1 and B 2 are groups represented by the following formulae (b1) to (b3), the polymer compound P has good planarity and can have an increased photoelectric conversion efficiency.
• R 21 , R 22 , and R 21′ represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. * represents a bond, and in particular, the * on the left represents a bond bonded to the benzene ring of benzobisthiazole.
• R 21 , R 22 , and R 21′ are hydrocarbon groups having 6 to 30 carbon atoms, since this may further increase the photoelectric conversion efficiency.
• R 21 , R 22 , and R 21′ are hydrogen atoms, the formation of a donor-acceptor type semiconducting polymer is facilitated.
• B1 and B2 are groups represented by either formula (b1) or (b2), respectively.
• B1 and B2 are groups represented by either formula (b1) or (b2), respectively.
• an interaction between the S atom and the N atom occurs in the benzobisthiazole structural unit, further improving the planarity.
• the planarity of the resulting polymer compound P can be improved.
• the polymer compound P is preferably a donor-acceptor type semiconducting polymer, and therefore preferably has a benzobisthiazole structural unit represented by formula (1) as well as a specific structural unit that provides a donor unit or an acceptor unit.
• a donor unit refers to an electron-donating structural unit
• an acceptor unit refers to an electron-accepting structural unit.
• the donor units and acceptor units are preferably arranged alternately, and therefore the donor-acceptor type semiconducting polymer is preferably a polymer compound in which the benzobisthiazole structural unit represented by formula (1) and the specific structural unit are arranged alternately.
• the polymer compound P can be suitably used as a p-type semiconductor compound.
• the specific structural unit may be a conventionally known structural unit that provides a donor unit or an acceptor unit.
• Specific examples of the specific structural unit include structural units of the following formulae (c1) to (c43). Of these, structural units represented by formulae (c1), (c3) to (c5), (c7), (c9), (c12), (c21), (c27), (c37), and (c42) are preferred, and structural units represented by formulae (c1), (c5), (c9), (c21), (c37), and (c42) are more preferred.
• R 30 to R 76 each independently represent a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms.
• a 30 and A 31 each independently represent the same groups as T 1 and T 2 , and j represents an integer of 1 to 4. represents a bond bonding to B 1 or B 2 of the structural unit represented by formula (1).
• the groups represented by the above formulae (c1) to (c30) function as acceptor units, and the groups represented by the formulae (c32) to (c43) function as donor units.
• the group represented by formula (c31) may function as an acceptor unit or as a donor unit depending on the types of A 30 and A 31 .
• the repeating ratio of the benzobisthiazole structural unit represented by formula (1) in polymer compound P is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, and even more preferably 30 mol% or more, and is usually 99 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, and even more preferably 70 mol% or less.
• the repeating ratio of the specific structural unit in polymer compound P is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, and even more preferably 30 mol% or more, and is usually 99 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, and even more preferably 70 mol% or less.
• polymer compound P the arrangement of the benzobisthiazole structural unit represented by formula (1) and the specific structural unit may be alternating, block, or random. That is, polymer compound P may be an alternating copolymer, block copolymer, or random copolymer. Preferably, the benzobisthiazole structural unit represented by formula (1) and the specific structural unit are arranged alternately.
• the weight-average molecular weight and number-average molecular weight of polymer compound P are preferably 2,000 or more and 500,000 or less, and more preferably 3,000 or more and 200,000 or less.
• the weight-average molecular weight and number-average molecular weight of polymer compound P can be calculated using gel permeation chromatography based on a calibration curve created using polystyrene as a standard sample.
• the thickness of the photoelectric conversion layer 133 is preferably 70 nm or more, more preferably 90 nm or more, even more preferably 100 nm or more, and preferably 1000 nm or less, more preferably 750 nm or less, even more preferably 500 nm or less, and particularly preferably 300 nm or less.
• One of the first transport layer 132 and the second transport layer 134 is an electron transport layer, and the other is a hole transport layer.
• the electron transport layer, photoelectric conversion layer, and hole transport layer may be stacked in this order from the side closest to the resin film substrate 11, or the hole transport layer, photoelectric conversion layer, and electron transport layer may be stacked in this order. While FIGS. 1 and 2 show an example in which the laminate 1 includes the first transport layer 132 and the second transport layer 134, this embodiment is not limited thereto.
• the laminate 1 may not include at least one of the first transport layer 132 and the second transport layer 134.
• the electron transport layer is a layer that extracts electrons from the photoelectric conversion layer 133 to the cathode.
• the constituent material of the electron transport layer is preferably an electron transporting material that improves the efficiency of electron extraction, and may be either an organic compound or an inorganic compound, but an inorganic compound is preferred.
• the inorganic compound that constitutes the electron transport layer is preferably a metal compound, such as salts of alkali metals such as lithium, sodium, potassium, and cesium, as well as metal oxides.
• a metal compound such as salts of alkali metals such as lithium, sodium, potassium, and cesium, as well as metal oxides.
• fluoride salts such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride are preferred as alkali metal salts
• metal oxides with n-type semiconductor properties such as titanium oxide (TiOx) and zinc oxide (ZnO) are preferred.
• Organic compounds that constitute the electron transport layer include conductive organic compounds, such as polyethyleneimine ethoxylate.
• the thickness of the electron transport layer is preferably 0.1 nm or more, more preferably 0.5 nm or more, and even more preferably 1.0 nm or more, and is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less.
• the hole transport layer is a layer that extracts holes from the photoelectric conversion layer 133 to the anode.
• the constituent material of the hole transport layer is not particularly limited as long as it is a hole transport material that can improve the efficiency of hole extraction, and examples of the material include conductive organic compounds and metal compounds.
• Conductive organic compounds that constitute the hole transport layer include, for example, conductive polymers in which polymers such as polythiophene, polypyrrole, polyacetylene, triphenylenediamine, and polyaniline are doped with sulfonic acid and/or iodine, polythiophene derivatives with sulfonyl groups as substituents, and arylamines.
• Metal compounds that constitute the hole transport layer include metal oxides with p-type semiconductor properties, such as molybdenum trioxide, vanadium pentoxide, and nickel oxide, as well as metals such as gold, indium, silver, and palladium.
• the hole transport layer may also be formed from a p-type semiconductor compound.
• conductive polymers in which sulfonic acid is doped into a polymer are preferred, and poly(3,4-ethylenedioxythiophene)poly(styrenesulfonic acid) (PEDOT:PSS), in which polythiophene derivatives are doped with polystyrenesulfonic acid, are more preferred.
• PEDOT:PSS poly(3,4-ethylenedioxythiophene)poly(styrenesulfonic acid)
• Metal oxides such as molybdenum oxide and vanadium oxide may also be used.
• the thickness of the hole transport layer is preferably 0.2 nm or more, more preferably 0.5 nm or more, and even more preferably 1.0 nm or more, and is preferably 500 nm or less, and more preferably 400 nm or less.
• the resin films 12 and 14 are used, for example, as barrier films capable of sealing and blocking the photoelectric conversion layer 133 and the like from the outside air, but the present embodiment is not limited thereto.
• a barrier layer may be provided on the resin film 12 or 14, and the resin film 12 or 14 and the barrier layer may be used together as a barrier film capable of sealing and blocking the photoelectric conversion layer 133 and the like from the outside air.
• Such a barrier film can reduce the penetration of oxygen and moisture into the photoelectric conversion layer 133 and the like, thereby improving the long-term durability of a photoelectric conversion element using the laminate 1.
• the barrier layer is preferably provided on the surface of the resin film 12 facing the resin film substrate 11 and/or the surface of the resin film 14 facing the resin film substrate 11.
• the resin films 12 and 14 may each be a polyester film such as PET film or PEN film; a PES (polyethersulfone) film; a polyamide film such as nylon film; a polycarbonate film; or a cycloolefin film, with a polyester film being preferred, and a PET film or PEN film being more preferred.
• a polyester film such as PET film or PEN film
• PES polyethersulfone
• barrier layer that can be provided on the resin film substrate 11 applies to the barrier layer that can be provided on the resin film 12 and/or 14.
• the thicknesses of the resin films 12 and 14 are not limited, but are preferably 30 ⁇ m to 300 ⁇ m, more preferably 40 ⁇ m to 280 ⁇ m, and even more preferably 50 ⁇ m to 250 ⁇ m.
• an inorganic thin film made of silicon nitride or the like is used as the barrier layer, and the thickness of the inorganic thin film is preferably approximately 0.05 to 2 ⁇ m.
• the thickness of the barrier layer is sufficiently thin compared to the thickness of resin film 12, so that it has little effect on the elastic modulus of resin film 12, etc.
• an inorganic thin film made of silicon nitride or the like is used as the barrier layer, and the thickness of the inorganic thin film is preferably approximately 0.05 to 2 ⁇ m.
• the thickness of the barrier layer is sufficiently thin compared to the thickness of resin film 14, so that it has little effect on the elastic modulus of resin film 14, etc.
• an adhesive method suitable for each material can be used. Examples include a method of attaching the barrier film with an adhesive, or a method of attaching the barrier film by thermocompression bonding using a heat press or laminator. Using a barrier film with a hot melt layer or adhesive layer on one side makes it easy to attach the barrier film to the resin film substrate 11. Olefin-based resins, rubber-based resins, silicone-based resins, and acrylic-based resins are preferred adhesives.
• the adhesive itself can have a low water vapor permeability, or if the water vapor permeability is high, the sealing properties of the photoelectric conversion layer 133, etc. can be improved by adding a moisture scavenger or reducing the coating thickness.
• the adhesive can be applied in a frame-like pattern around the four sides of the surface to which the barrier film will be attached, or it can be applied to the entire surface. If it is applied to the entire surface, it must be applied in a manner that does not affect the photoelectric conversion element due to shrinkage when the adhesive hardens.
• the resin films 12 and 14 used in the laminate 1 in the example of Figure 2 preferably have the same configuration (composition and thickness). This is because warping when the laminate 1 is heated is due to differences in the thermal contraction and coefficient of thermal expansion (CTE) of the resin films 12 and 14, and when the laminate 1 is heated, warping is canceled out across the entire laminate 1 between the resin films 12 and 14, which have the same configuration.
• CTE coefficient of thermal expansion
• the shape of the laminate 1 is not particularly limited, and may be a square or a rectangle when viewed in the thickness direction of the resin film substrate 11 (direction perpendicular to the resin film substrate 11).
• the shape of the laminate 1 is square or rectangular, for example, the shape of the resin film substrate 11 when viewed in the thickness direction of the resin film substrate 11 (direction perpendicular to the resin film substrate 11) is also square or rectangular.
• the long side and the short side are assumed to be the same length.
• the long and short sides of the resin film substrate 11 are each, for example, 20 mm or more and 2000 mm or less, and may be 30 mm or more and 1500 mm or less, preferably 45 mm or more and 1000 mm or less, more preferably 50 mm or more and 200 mm or less, even more preferably 65 mm or more and 150 mm or less, even more preferably 80 mm or more and 120 mm or less, particularly preferably 85 mm or more and 110 mm or less, and most preferably 90 mm or more and 105 mm or less.
• the resin films 12 and 14 are preferably also square or rectangular.
• the two sides of the square or rectangle will be described using the terms “long side” and “short side” for convenience.
• the lengths of the two sides of each of the resin films 12 and 14 here are those in a planar state before the formation of the laminate 1.
• the long side and short side are assumed to be the same length.
• the long and short sides of each of the resin films 12 and 14 are, for example, 20 mm to 2000 mm, and may be 30 mm to 1500 mm, preferably 45 mm to 1000 mm, more preferably 50 mm to 200 mm, even more preferably 65 mm to 150 mm, even more preferably 80 mm to 120 mm, particularly preferably 85 mm to 110 mm, and most preferably 90 mm to 105 mm.
• the long and short sides of the resin film 12 are, for example, smaller than the long and short sides of the resin film substrate 11.
• the long and short sides of each of the resin films 12 and 14 are, for example, larger than the long and short sides of the resin film substrate 11.
• E1 ⁇ T1 is more preferably 1100 or more, even more preferably 1150 or more, and particularly preferably 1250 or more. While the upper limit is not particularly limited, E1 ⁇ T1 is preferably 6000 or less, more preferably 4500 or less, even more preferably 3000 or less, and particularly preferably 2200 or less.
• E1 ⁇ T1 is preferably 1000 or more and 6000 or less, more preferably 1100 or more and 4500 or less, even more preferably 1150 or more and 3000 or less, and particularly preferably 1250 or more and 2200 or less.
• E1 ⁇ T1 satisfies the above formula (A)
• deformation (deflection) when the laminate 1 is vacuum-chucked, for example is suppressed, thereby suppressing the occurrence of scratches on the light-receiving surface.
• the occurrence of cracks in the functional layer of the laminate 1 can also be suppressed. This can suppress the deterioration of photoelectric conversion efficiency. Therefore, the laminate 1 satisfying formula (A) is useful when manufacturing a photoelectric conversion element through the handling process described above using the laminate 1.
• the tensile modulus of the laminate structure from the resin film substrate 11 to the other layer provided on the opposite side is taken as the tensile modulus E1 in formula (A)
• the thickness of the laminate structure is taken as the thickness T1 in formula (A). That is, in the above case, the portion corresponding to the laminate structure is considered to be the laminate 1.
• the tensile modulus E1 of the laminate 1 is preferably 4.5 GPa or more and 6.0 GPa or less, more preferably 4.8 GPa or more and 5.8 GPa or less, and even more preferably 5.0 GPa or more and 5.5 GPa or less.
• the thickness T1 of the laminate 1 is preferably 200 ⁇ m or more and 600 ⁇ m or less, more preferably 230 ⁇ m or more and 500 ⁇ m or less, and even more preferably 250 ⁇ m or more and 400 ⁇ m or less.
• the tensile modulus E1 and thickness T1 of the laminate 1 are measured by the methods described in the examples.
• the tensile modulus E1 of the laminate 1 can be controlled, for example, by the tensile modulus and thickness of the resin film substrate 11 that constitutes the laminate 1, and the tensile modulus and thickness of the resin film 12.
• the tensile modulus of the resin film substrate 11 is, for example, 3.0 GPa to 9.0 GPa, preferably 3.5 GPa to 8.0 GPa, and more preferably 3.8 GPa to 6.3 GPa.
• the thickness of the resin film substrate 11 is, for example, 100 ⁇ m to 300 ⁇ m, preferably 110 ⁇ m to 280 ⁇ m, and more preferably 120 ⁇ m to 260 ⁇ m.
• the tensile modulus of the resin film 12 is preferably 3.0 GPa or more and 9.0 GPa or less, more preferably 3.5 GPa or more and 8.0 GPa or less, and even more preferably 3.8 GPa or more and 6.3 GPa or less.
• the thickness of the resin film 12 is preferably 80 ⁇ m or more and 300 ⁇ m or less, more preferably 85 ⁇ m or more and 280 ⁇ m or less, and even more preferably 90 ⁇ m or more and 260 ⁇ m or less.
• the ratio of the thickness of the resin film substrate 11 to the thickness T1 of the laminate 1 is preferably 0.25 or more and 0.80 or less, more preferably 0.30 or more and 0.75 or less, and even more preferably 0.32 or more and 0.70 or less.
• the tensile modulus E1 of the laminate 1 is easily determined by the tensile modulus and thickness of the resin film substrate 11 and the tensile modulus and thickness of the resin film 12.
• the ratio of the thickness of the resin film 12 to the thickness T1 of the laminate 1 is preferably 0.20 to 0.75, more preferably 0.23 to 0.70, and even more preferably 0.27 to 0.65.
• the tensile modulus E1 of the laminate 1 is easily determined by the tensile modulus and thickness of the resin film substrate 11 and the tensile modulus and thickness of the resin film 12.
• the ratio of the thickness of the resin film 12 to the thickness of the resin film substrate 11 is preferably 0.30 or more and 3.0 or less, more preferably 0.35 or more and 2.7 or less, and even more preferably 0.38 or more and 2.2 or less.
• the thickness of the layer (intermediate layer) provided between the resin film substrate 11 and the resin film 12 included in the laminate 1 of the example of Figure 1 is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 1 ⁇ m or less, and particularly preferably 800 nm or less.
• the thickness of the first conductive layer 131 is preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 100 nm or less.
• the thickness of the intermediate layer there is no particular lower limit to the thickness of the intermediate layer, and it is, for example, preferably 70 nm or more, and more preferably 90 nm or more.
• the thickness of the intermediate layer relative to the thickness of the laminate 1 is preferably 0.0001 to 0.1, more preferably 0.0005 to 0.05, even more preferably 0.0007 to 0.01, and particularly preferably 0.001 to 0.005. Note that when the intermediate layer is composed of multiple layers (when a layer other than the photoelectric conversion layer is included between the resin film substrate 11 and the resin film 12), this refers to the total thickness. By being within this range, the tensile modulus E1 and thickness T1 of the laminate 1 are hardly affected by the layer configuration other than the resin film substrate 11 and the resin film 12 included in the laminate 1.
• the laminate 1 satisfying the above formula (A) is heated at 110°C for 30 minutes, the absolute value of the amount of warping is, for example, 200 ⁇ m or less, preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 70 ⁇ m or less.
• the method for measuring the amount of warping of the laminate 1 at 110°C is the method described in the Examples.
• E2 ⁇ T2 is more preferably 1800 or more, even more preferably 2000 or more, and particularly preferably 2500 or more. While the upper limit is not particularly limited, E2 ⁇ T2 is preferably 6000 or less, more preferably 5000 or less, even more preferably 4000 or less, and particularly preferably 3500 or less.
• E2 ⁇ T2 is preferably 1500 or more and 6000 or less, more preferably 1800 or more and 5000 or less, even more preferably 2000 or more and 4000 or less, and particularly preferably 2500 or more and 3500 or less.
• E2 ⁇ T2 satisfies the above formula (B)
• deformation (deflection) when the laminate 1 is vacuum-chucked, for example is suppressed, thereby suppressing the occurrence of scratches on the light-receiving surface.
• the occurrence of cracks in the functional layer of the laminate 1 can also be suppressed. This can suppress the deterioration of photoelectric conversion efficiency. Therefore, the laminate 1 satisfying formula (B) is useful when manufacturing a photoelectric conversion element through the handling process described above using the laminate 1.
• the tensile modulus of the laminate structure from the layer other than the second resin film 14 provided on the opposite surface to the resin film 12 is the tensile modulus E2 in formula (B), and the thickness of the laminate structure is the thickness T2 in formula (B). That is, in the above case, the portion corresponding to the laminate structure is considered to be the laminate 1.
• the tensile modulus E2 of the laminate 1 is preferably 3.5 GPa or more and 7.0 GPa or less, more preferably 4.0 GPa or more and 6.5 GPa or less, and even more preferably 5.0 GPa or more and 6.0 GPa or less.
• the thickness T2 of the laminate 1 is preferably 400 ⁇ m or more and 1000 ⁇ m or less, more preferably 450 ⁇ m or more and 900 ⁇ m or less, and even more preferably 500 ⁇ m or more and 800 ⁇ m or less.
• the tensile modulus E2 and thickness T2 of the laminate 1 are measured by the methods described in the examples.
• the tensile modulus E2 of the laminate 1 can be controlled, for example, by the tensile modulus and thickness of the resin film substrate 11 that constitutes the laminate 1, and the tensile modulus and thickness of the resin films 12 and 14.
• the tensile modulus of the resin film substrate 11 is, for example, 3.0 GPa to 9.0 GPa, preferably 3.5 GPa to 8.0 GPa, and more preferably 3.8 GPa to 6.1 GPa.
• the thickness of the resin film substrate 11 is, for example, 100 ⁇ m to 300 ⁇ m, preferably 110 ⁇ m to 280 ⁇ m, and more preferably 120 ⁇ m to 260 ⁇ m.
• the tensile modulus of each of the resin films 12 and 14 is preferably 3.0 GPa to 9.0 GPa, more preferably 3.8 GPa to 8.0 GPa, and even more preferably 5.7 GPa to 6.3 GPa.
• the thickness of each of the resin films 12 and 14 is preferably 80 ⁇ m to 300 ⁇ m, more preferably 100 ⁇ m to 280 ⁇ m, and even more preferably 120 ⁇ m to 260 ⁇ m.
• the ratio of the thickness of the resin film substrate 11 to the thickness T2 of the laminate 1 is preferably 0.10 or more and 0.65 or less, more preferably 0.15 or more and 0.60 or less, and even more preferably 0.19 or more and 0.50 or less.
• the tensile modulus E2 of the laminate 1 is easily determined by the tensile modulus and thickness of the resin film substrate 11 and the tensile modulus and thickness of the resin films 12 and 14.
• the ratio of the total thickness of the resin films 12 and 14 to the thickness T2 of the laminate 1 is preferably 0.35 or more and 0.90 or less, more preferably 0.43 or more and 0.85 or less, and even more preferably 0.49 or more and 0.79 or less.
• the tensile modulus E2 of the laminate 1 is easily determined by the tensile modulus and thickness of the resin film substrate 11 and the tensile modulus and thickness of the resin films 12 and 14.
• the ratio of the total thickness of resin films 12 and 14 to the thickness of resin film substrate 11 is preferably 0.50 or greater and 6.0 or less, more preferably 0.70 or greater and 5.0 or less, and even more preferably 0.90 or greater and 4.2 or less.
• the thickness of the layer (intermediate layer) provided between the resin film substrate 11 and the resin film 12 included in the laminate 1 of the example in Figure 2 is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 1 ⁇ m or less, and particularly preferably 800 nm or less. There is no particular lower limit to the thickness of the intermediate layer, and it is preferably 70 nm or more, more preferably 90 nm or more.
• the thickness of the intermediate layer relative to the thickness of the laminate 1 (thickness of intermediate layer/thickness of laminate 1) is preferably 0.0001 to 0.1, more preferably 0.0005 to 0.05, even more preferably 0.0007 to 0.01, and particularly preferably 0.001 to 0.005.
• the intermediate layer is composed of multiple layers (when layers other than the photoelectric conversion layer are included between the resin film substrate 11 and the resin film 12), this refers to the total thickness.
• the tensile modulus E2 and thickness T2 of the laminate 1 are hardly affected by the layer structure other than the resin film substrate 11, resin film 12, and resin film 14 contained in the laminate 1.
• S1 Teonex Q51 (PEN film manufactured by Toyobo Co., Ltd., thickness 125 ⁇ m, tensile modulus 5.9 GPa)
• S2 Teonex Q51 (PEN film manufactured by Toyobo Co., Ltd., thickness 250 ⁇ m, tensile modulus 6.1 GPa)
• S3 A4160 (PET film manufactured by Toyobo Co., Ltd., thickness 125 ⁇ m, tensile modulus 4.0 GPa)
• S4 A4360 (PET film manufactured by Toyobo Co., Ltd., thickness 250 ⁇ m, tensile modulus 4.0 GPa)
• S5 PEN film with ITO (thickness 125 ⁇ m, 50 nm ITO film formed on one side of S1 by sputtering, tensile modulus 5.9 GP
• B1 E5100 (PET film manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m, tensile modulus 4.0 GPa)
• B2 Teonex Q51 (PEN film manufactured by Toyobo Co., Ltd., thickness 125 ⁇ m, tensile modulus 5.9 GPa)
• B3 Teonex Q51 (PEN film manufactured by Toyobo Co., Ltd., thickness 250 ⁇ m, tensile modulus 6.1 GPa)
• B4 Torayfan BO (PP film manufactured by Toray Industries, Inc., thickness 40 ⁇ m, tensile modulus 0.2 GPa)
• B5 Toretek R213 (polyolefin film manufactured by Toray Industries, Inc., thickness 60 ⁇ m, tensile modulus 0.3 GPa)
• ⁇ Resin film thickness measurement> The thicknesses of the resin film substrate, the first resin film, and the second resin film were measured using a macrometer (Militron 1245D, manufactured by Fine Leaf Co., Ltd.). The results are shown in Table 1.
• T1 and T2 ⁇ Measurement of Laminate Thickness (T1 and T2)>
• the thicknesses (T1 and T2) of the laminates of the examples and comparative examples were measured using a high-precision Digimatic Micrometer (MDH-25M, manufactured by Mitutoyo Corporation). The results are shown in Table 1.
• the amount of warpage was measured using a laser displacement meter 31.
• the distance from the corner of the top surface of the resin film 12 (the surface opposite the resin film substrate 11) to the hot plate 36 was measured, and the thickness of the resin film substrate 11 and the glass beads 37 was subtracted from this measurement to determine the amount of warpage.
• the position of the laser displacement meter 31 was changed using the rail-equipped angle 32, and the amount of warpage was measured at the four corners of the upper surface of the resin film substrate in the laminate, and the average value was taken as the amount of warpage of the laminate when heated to 110° C.
• Table 1 A Keyence LK-H-055 was used as the laser displacement meter 31.
• Example 1 The resin film substrate S1 was cut to a size of 100 mm x 100 mm using a cutter. A resin film B1 cut to 95 mm x 95 mm was attached to the center of the cut resin film substrate S1 as a first resin film using Aron Alpha EXTRA 2000 manufactured by Toagosei. An adhesive was applied to the entire surface of the first resin film, and the thickness of the adhesive was controlled to 10 ⁇ m by immediately passing it through a laminator using a spacer. This produced a laminate including the resin film substrate and the first resin film.
• Example 2 The same procedure as in Example 1 was carried out except that the resin film substrate was changed to S2.
• Example 3 The same procedure as in Example 1 was carried out except that the resin film substrate was S3 and the first resin film was B2.
• Example 4 The same procedure as in Example 3 was carried out except that the first resin film was changed to B3.
• Example 5 The same procedure as in Example 3 was carried out except that the resin film substrate was S5 and the first resin film was B1.
• Example 6 A resin film substrate S5 (size 100 mm x 100 mm) was washed with acetone and then dried with clean dry air. A ZnO nanoparticle dispersion manufactured by Avantama was dripped onto the substrate, and the substrate was coated with a coating gap of 25 ⁇ m using a No. 0 bar and heated at 80°C for 10 minutes. This resulted in an electron transport layer approximately 50 nm thick. After wiping the coating film with acetone, leaving a 95 mm x 95 mm area, the photoelectric conversion layer solution was dripped onto the substrate, coated with a coating gap of 50 ⁇ m, and heated at 100°C for 5 minutes. This resulted in a photoelectric conversion layer approximately 250 nm thick.
• the photoelectric conversion layer solution was prepared by dissolving equal amounts of poly(3-hexylthiophene-2,5-diyl) and the fullerene derivative Nanom Spectra (E100H manufactured by Frontier Carbon Corporation) in chlorobenzene. After wiping the coating with chlorobenzene, leaving a 95 mm x 95 mm area, HTL solar (PEDOT:PSS manufactured by Heraeus-Epirio) was dripped onto the substrate, coated with a coating gap of 50 ⁇ m, and heated at 80°C for 30 minutes. This resulted in a hole transport layer approximately 400 nm thick. The coating was then wiped with pure water, leaving a 95 mm x 95 mm area.
• PDOT:PSS manufactured by Heraeus-Epirio
• Resin film B1 cut to 98 mm x 98 mm, was then attached to the substrate as a first resin film using Aron Alpha EXTRA 2000 manufactured by Toagosei.
• An adhesive was applied to the entire surface of the first resin film, and the adhesive thickness was controlled to 10 ⁇ m by immediately passing it through a laminator using a spacer. This produced a laminate comprising a resin film substrate, a first resin film, and a photoelectric conversion layer.
• Example 7 Two pieces of resin film B1 were prepared by cutting them to a size of 100 mm x 100 mm with a cutter. One of the cut B1 pieces was used as the second resin film, and a resin film substrate S4 cut to 95 mm x 95 mm was placed in the center. The other cut B1 was used as the first resin film, and its entire surface was coated with Aron Alpha EXTRA 2000 manufactured by Toagosei. The other B1, which was the second resin film, was then bonded to the resin film substrate S4. The thickness of the adhesive was controlled to 10 ⁇ m by immediately passing it through a laminator using a spacer. This produced a laminate in which the resin film substrate was sandwiched between the first and second resin films on both sides.
• Example 8 A laminate was produced in the same manner as in Example 7, except that the first resin film and the second resin film were changed to B2.
• Example 9 A laminate was produced in the same manner as in Example 7, except that the first resin film and the second resin film were changed to B3.
• Example 10 A laminate was produced in the same manner as in Example 9, except that the resin film substrate was changed to S5.
• a laminate including a photoelectric conversion layer when the magnitude of the deformation amount during vacuum suction is small, the occurrence of scratches on the light-receiving surface and the occurrence of cracks in the functional layer of the laminate are suppressed, and the deterioration of photoelectric conversion efficiency is suppressed.
• the absolute value of the warpage amount during heating is small, the deterioration of photoelectric conversion efficiency due to damage caused by warpage is suppressed.
• the laminate of Example 6 has a configuration similar to that of Example 5, except that multiple layers, including a photoelectric conversion layer, are further provided between the resin film substrate and the first resin film.
• the total thickness of these multiple layers is thought to be approximately 700 nm, which is minute compared to the thickness T1 of the laminate.
• the laminate of Example 6 has similar amounts of deformation during vacuum suction and warpage during heating as the laminate of Example 5. Therefore, from the results of Examples 6 and 5, it can be seen that the intermediate layer, such as the photoelectric conversion layer provided between the resin film substrate and the first resin film, is an extremely thin layer compared to the resin film substrate and the first resin film, and therefore the presence or absence of the intermediate layer has almost no effect on the amount of deformation during vacuum suction or the amount of warpage during heating.

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