Laminate, photoelectric conversion element, and method for manufacturing photoelectric conversion element

Abstract

Provided is a laminate in which a blur width during handling is reduced. In an embodiment of this invention, a laminate includes an inorganic substrate, a resin film, and a photoelectric conversion layer between the inorganic substrate and the resin film. The thickness T1 (μm) and the tensile elastic modulus E1 (GPa) of the laminate satisfy 40000 ≤ E1 × T1.

Description

LAMINATE, PHOTOELECTRIC CONVERSION ELEMENT, AND METHOD FOR MANUFACTURING PHOTOELECTRIC CONVERSION ELEMENT

[0001] The present invention relates to a laminate, a photoelectric conversion element, and a method for manufacturing a photoelectric conversion element.

[0002] For example, a device is known that has a laminate including an active layer (also referred to as a photoelectric conversion layer), an electron transport layer, and a hole transport layer as functional layers of a 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.

[0003] JP 2012-114424 A

[0004] In the manufacture of such solar cells, hard rigid substrates such as inorganic substrates are often used, on which various layers are coated, and then sealed by applying a barrier film to prevent the coated layers from being deteriorated by moisture and oxygen in the air.

[0005] The laminate, in which various layers are formed on an inorganic substrate and sealed with a barrier film, is then handled using a robot fork or vacuum lifter for transportation. Glass substrates, typically used as inorganic substrates for organic thin-film solar cells, are thin, measuring 700 μm or less. When transported and handled using a robot fork or the like, the edges vibrate in the thickness direction due to the movement. In particular, when the laminate is large in size, specifically when one side of the shape viewed in the thickness direction of the substrate (the direction perpendicular to the substrate) is 400 mm or more, the amplitude of vibration fluctuation increases. This large amplitude of vibration fluctuation can cause problems such as poor transfer of the laminate between robot forks or significant vibration of the laminate when lifted by a lift pin within the device, resulting in misalignment. Furthermore, the inorganic substrate side of an organic thin-film solar cell is the light-receiving surface, and scratches on the light-receiving surface due to such vibration or misalignment during handling can result in poor light capture efficiency.

[0006] The present invention has been made in light of the above-mentioned circumstances, and an object of the present invention is to provide a laminate in which the wobble width during handling is suppressed, a photoelectric conversion element using the laminate, and a method for manufacturing a photoelectric conversion element using the laminate.

[0007] That is, the present invention may include the following aspects. [1] A laminate comprising an inorganic substrate, a resin film, and a photoelectric conversion layer between the inorganic substrate and the resin film, wherein the tensile modulus E1 (GPa) and thickness T1 (μm) of the laminate satisfy the following formula (A): 40000≦E1×T1 (A). [2] The laminate according to [1] above, wherein the shape of the inorganic substrate as viewed in the thickness direction of the inorganic substrate is square or rectangular, and the diameter of a circumscribing circle of the square or rectangle is 130 mm or more. [3] The laminate according to [1] or [2] above, wherein the tensile modulus of the inorganic substrate is 60 GPa or more and 90 GPa or less, and the thickness of the inorganic substrate is 350 μm or more and 800 μm or less. [4] The laminate according to any one of [1] to [3] above, wherein the resin film has a tensile modulus of 3.0 GPa or more and 8.0 GPa or less, and a thickness of 30 μm or more and 300 μm or less. [5] The laminate according to 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 140 μm or less. [6] A photoelectric conversion element using the laminate according to any one of [1] to [5] above. [7] The photoelectric conversion element according to [6] above, wherein the photoelectric conversion element is an organic thin-film solar cell. [8] A method for producing a photoelectric conversion element using the laminate according to any one of [1] to [5] above.

[0008] In the laminate of the present invention, the above formula (A) is satisfied, thereby suppressing the wobble width during handling. Therefore, it is possible to suppress misalignment during mechanical transfer and processes using lift pins. As a result, it is possible to suppress the occurrence of scratches on the light-receiving surface due to vibration and misalignment during handling. This suppresses deterioration of photoelectric conversion efficiency. In particular, the present invention is effective when using a large-sized inorganic substrate that has a large wobble width. Furthermore, in the laminate of the present invention, the formula (A) is satisfied, thereby suppressing warpage during heating and making it less susceptible to damage due to warpage.

[0009] 1 is a diagram illustrating an example of the configuration of a laminate according to the first embodiment, and is a diagram schematically illustrating the configuration of an apparatus for measuring the amount of warpage of the laminate according to the first embodiment.

[0010] The present invention will be described in more detail below based on the following embodiments. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the above and below-described purposes, and all such modifications are within the technical scope of the present invention. In each drawing, hatching and component symbols may be omitted for convenience. In such cases, reference should be made to the specification and other drawings. Furthermore, the dimensions of various components in the drawings may differ from their actual dimensions, as priority is given to helping understand the features of the present invention.

[0011] For ease of reference, examples are shown in the drawings, and descriptions in this specification may use the notation "up" and "down," but the present embodiment is not necessarily limited thereto. For example, products and methods that can be realized by the ideas disclosed in this specification even when the orientation is changed, such as upside down, are considered to be within the scope of the disclosure of this embodiment. In this specification, the expressions "contain" and "comprise" include the concepts of "contain," "comprise," "substantially consist," and "consist only of." In this specification, "A and / or B" means "one of A and B" or "both A and B," and specifically means "A," "B," or "A and B."

[0012] In this specification, the relationship between two components A and B may be described as "component B is provided on component A" or "component B is provided on the upper surface of 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 therebetween to the extent that the effect is not impaired.

[0013] With respect to the numerical ranges described in stages in this specification, 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. With respect to the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example. In this specification, a numerical range connected with "to" means a numerical range that includes the numbers before and after "to" as the lower and upper limits.

[0014] <Laminate> Fig. 1 shows an example of the configuration of a laminate 1 according to the first embodiment. The laminate 1 includes an inorganic substrate 11 and a resin film 12, and further includes a photoelectric conversion layer 133 between the inorganic substrate 11 and the resin film 12. The resin film 12 is provided, for example, on the inorganic substrate 11 so as to cover the photoelectric conversion layer 133. As will be described later, the photoelectric conversion layer 133 is capable of photoelectric conversion, and by providing a configuration 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.

[0015] In the example of FIG. 1 , it is preferable that the laminate 1 does not have a resin film on the side opposite to the side on which the photoelectric conversion layer 133 is provided, relative to the inorganic substrate 11. It is more preferable that no other layer is provided on the surface of the inorganic substrate 11 opposite to the side on which the photoelectric conversion layer 133 is provided. That is, it is more preferable that the surface of the inorganic substrate 11 opposite to the side on which the photoelectric conversion layer 133 is provided is exposed in the laminate 1. In the example of FIG. 1 , it is preferable that the surface of the resin film 12 opposite to the side on which the photoelectric conversion layer 133 is provided is exposed in the laminate 1. When the term "exposed" is used in this specification, it is intended to also include cases where other structures, such as a barrier layer described below, are provided on the surface to the extent that the effect is not impaired.

[0016] 1 shows an example in which 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 in this order on the inorganic substrate 11. 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 a resin film 12 on the inorganic substrate 11. However, 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 as shown in FIG. 1 to serve as an extraction electrode. It is preferable that the first transport layer 132, the photoelectric conversion layer 133, the second transport layer 134, and the second conductive layer 135 are each covered by the resin film 12 on the inorganic substrate 11 so as not to be exposed outside the resin film 12. The layers provided between the inorganic substrate 11 and the resin film 12 are sometimes collectively referred to as the "intermediate layer." The intermediate layer includes the photoelectric conversion layer 133, and may optionally include one or more layers of the first conductive layer 131, the first transport layer 132, the second transport layer 134, and the second conductive layer 135.

[0017] <Inorganic Substrate> There are no particular limitations on the constituent material of the inorganic substrate 11, and it is appropriately selected depending on the application of the photoelectric conversion element. Examples of the constituent material of the inorganic substrate 11 include inorganic materials such as quartz, glass, sapphire, and titania, and glass is preferred.

[0018] The thickness of the inorganic substrate 11 is preferably 50 μm or more and 20 mm or less, more preferably 100 μm or more and 10 mm or less, even more preferably 200 μm or more and 2 mm or less, even more preferably 350 μm or more and 800 μm or less, particularly preferably 400 μm or more and 800 μm or less, and most preferably 500 μm or more and 700 μm or less.

[0019] <(Transparent) Conductive Layer> The cathode and anode, which may be the first conductive layer 131 and the second conductive layer 135, are made of a conductive material.

[0020] The cathode is preferably made of a conductive material having a work function smaller than that of the anode. The cathode has the function of extracting electrons generated in the photoelectric conversion layer 133. Examples of materials constituting 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. When the cathode is a transparent electrode, it is preferable to use a light-transmitting conductive metal oxide such as ITO, zinc oxide, or tin oxide, and ITO is particularly preferable.

[0021] The anode is preferably made of a conductive material having a work function greater than that of the cathode. The anode has the function of extracting holes generated in the photoelectric conversion layer. Examples of materials constituting the anode include metals such as platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium, and magnesium, and alloys thereof; inorganic salts such as lithium fluoride and cesium fluoride; and metal oxides such as nickel oxide, aluminum oxide, lithium oxide, and cesium oxide. Furthermore, when a conductive n-type semiconductor compound such as zinc oxide is used as a material for the hole transport layer described below, a material having a small work function such as ITO may be used as the anode material.

[0022] The thickness of each of the cathode and anode is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 50 nm or more, and is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 500 nm or less.

[0023] <Photoelectric Conversion Layer> The photoelectric conversion layer 133 is a layer where photoelectric conversion occurs, and contains, for example, a p-type semiconductor compound and an n-type semiconductor compound. When 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.

[0024] Known compounds can be used as the p-type semiconductor compound and the n-type semiconductor compound. 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; and copolymer semiconductor compounds such as oligothiophenes substituted with alkyl groups or other substituents, with polythiophenes that may have substituents being preferred. Furthermore, the p-type semiconductor compound may also be a copolymer semiconductor compound obtained by copolymerizing two or more types of monomer units. Specific examples of the p-type semiconductor compound that is a polymer compound 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.

[0025] Examples of n-type semiconductor compounds include low molecular weight compounds such as fullerene or its derivatives, octaazaporphyrin, and perfluoro compounds in which hydrogen atoms of p-type semiconductor compounds are substituted with fluorine atoms (e.g., perfluoropentacene and perfluorophthalocyanine), with fullerene or its derivatives being preferred. Furthermore, examples of n-type semiconductor compounds that can be used include polymeric compounds containing aromatic carboxylic acid anhydrides or imidized products thereof, such as naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic diimide, perylene tetracarboxylic anhydride, and perylene tetracarboxylic diimide, as their skeletons. Specific examples of polymeric n-type semiconductor compounds include MEH-CN-PPV, F8TBT, PZ1, DCNBT-IDT, P-BNBP-fBT, PF2-DTSi, PDI-V, and PYT. Ｍ , PJ1-H, N2200, Y6, etc.

[0026] Examples of the layer structure of the photoelectric conversion layer 133 include a thin-film stacked structure in which p-type semiconductor compounds and n-type semiconductor compounds are stacked, and a bulk heterojunction structure having a layer in which p-type semiconductor compounds and n-type semiconductor compounds are mixed. The bulk heterojunction structure has a layer (i-layer) in which p-type semiconductor compounds and n-type semiconductor compounds are mixed. The i-layer has a structure in which p-type semiconductor compounds and n-type semiconductor compounds are phase-separated, and carrier separation occurs at the phase interface, and the generated carriers (holes and electrons) are transported to the electrode. From the viewpoint of improving photoelectric conversion efficiency by obtaining a good phase-separated structure, the mass ratio of the p-type semiconductor compounds to the n-type semiconductor compounds in the i-layer (p-type semiconductor compounds / n-type semiconductor compounds) 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.

[0027] The photoelectric conversion layer 133 may contain an additive in addition to the p-type semiconductor compound and the n-type semiconductor compound. The phase-separated structure between the p-type semiconductor compound and the n-type semiconductor compound in a bulk heterojunction photoelectric conversion layer affects light absorption, exciton generation and diffusion, exciton dissociation (carrier separation), carrier transport, etc., so optimizing the phase-separated structure is expected to achieve good photoelectric conversion efficiency. By including an additive having a high affinity for the p-type semiconductor compound or the n-type semiconductor compound in the photoelectric conversion layer 133, a photoelectric conversion layer having a preferable phase-separated structure can be obtained, and photoelectric conversion efficiency can be improved.

[0028] Examples of 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. Examples of the substituent that the aliphatic hydrocarbon compound may have include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, an amino group, a carbamoyl group, a carbonyloxy group, a carboxyl group, a carbonyl group, and an aromatic group. Examples of the substituent that the aromatic compound may have include a halogen atom, a hydroxyl group, a cyano group, an amino group, an amido group, a carbonyloxy group, a carboxyl group, a carbonyl group, an oxycarbonyl group, a silyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an aromatic group. Specific examples of preferred additives include benzene which may have a substituent, naphthalene which may have a substituent, and octane which may have a substituent. A halogen atom is particularly preferred as the substituent.

[0029] In order to obtain a photoelectric conversion element such as an organic thin-film solar cell that exhibits high conversion efficiency, the photoelectric conversion layer 133 preferably contains an organic semiconductor compound, more preferably contains a polymeric p-type semiconductor compound and / or an n-type semiconductor compound, and further preferably contains a polymeric p-type semiconductor compound and a low-molecular-weight n-type semiconductor compound.

[0030] 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").

[0031]

[0032] In the above formula (1), T １ and T ２each independently represents 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. １ and B ２ each independently represents a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally 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 a Si atom, and the number of hydrocarbon groups substituted on the Si atom is preferably 2 to 3, and more preferably 3.

[0033] The polymer compound P has a benzobisthiazole structural unit represented by formula (1), and thus can narrow the band gap while deepening the HOMO level, thereby increasing the photoelectric conversion efficiency.

[0034] In the benzobisthiazole structural unit represented by formula (1), T １ and T ２ may be the same or different from each other, but are preferably the same from the viewpoint of ease of production. １ , B ２ may be the same or different from each other, but are preferably the same from the viewpoint of ease of production.

[0035] In the benzobisthiazole structural unit represented by formula (1), T １ and T ２ are preferably groups represented by the following formulae (t1) to (t5), respectively. １ and T ２As the alkoxy group, a group represented by the following formula (t1) is preferred, as the thioalkoxy group, a group represented by the following formula (t2) is preferred, as the thiophene ring which may be substituted with a hydrocarbon group or an organosilyl group, a group represented by the following formula (t3) is preferred, as the thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group, a group represented by the following formula (t4) is preferred, and as the 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, a group represented by the following formula (t5) is preferred. １ and T ２ is a group represented by the following formulae (t1) to (t5), it is possible to absorb light of a short wavelength, and since it has high planarity, π-π stacking is efficiently formed, thereby improving the photoelectric conversion efficiency. 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.

[0036]

[0037] In the above formulas (t1) to (t5), R １３ and R １４ R each independently represents a hydrocarbon group having 6 to 30 carbon atoms. １５ and R １６ are each independently a hydrocarbon group having 6 to 30 carbon atoms, or *-Si(R １８ ) ３ R represents a group represented by the formula: １５’ is a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or *-Si(R １８ ) ３ R represents a group represented by the formula: 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 Represents R １８ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. １８Among them, there are the same R １８ There may be different R １８ There may be R １９ and R ２０ represents a hydrocarbon group having 6 to 30 carbon atoms. * represents a bond bonded to the thiazole ring of benzobisthiazole.

[0038] In the above formulas (t1) to (t5), R １３ ~R １７ , R １９ , R ２０ , and R １５’ The hydrocarbon group having 6 to 30 carbon atoms is preferably a branched hydrocarbon group, more preferably a branched saturated hydrocarbon group. １３ ~R １７ , R １９ , R ２０ , and R １５’ The hydrocarbon group R has a branched structure, which can increase the solubility in organic solvents. １３ ~R １７ , R １９ , R ２０ , and R １５’ The hydrocarbon group preferably has 8 to 25 carbon atoms, more preferably 8 to 20 carbon atoms, and even more preferably 8 to 16 carbon atoms.

[0039] In the above formulas (t1) to (t5), R １５ ~R １７ , and R １５’ *-Si(R １８ ) ３ In the group represented by １８ The aliphatic hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms. １８ The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 8, more preferably 6 to 7, and even more preferably 6. １８ Examples of the aromatic hydrocarbon group include a phenyl group. １８ As the R, an aliphatic hydrocarbon group is preferable, a branched aliphatic hydrocarbon group is more preferable, and an isopropyl group is even more preferable. １８ Among them, there are the same R １８There may be different R １８ There may be multiple R １８ are preferably the same. １５ ~R １７ , and R １５’ *-Si(R １８ ) ３ When the group is represented by *—Si(R １８ ) ３ Among these, the group represented by the formula (I) is preferably an alkylsilyl group, more preferably a trimethylsilyl group or a triisopropylsilyl group.

[0040] In the above formula (t5), R １７ When R is a halogen atom, any of fluorine, chlorine, bromine, and iodine can be used. １７ is a halogen atom or *-CF ３ is preferred.

[0041] R １５’ is preferably a hydrogen atom.

[0042] T １ and T ２ As the group represented by formula (t1), groups represented by formula (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.

[0043] In the benzobisthiazole structural unit represented by formula (1), B １ and B ２ is preferably a group represented by any one of the following formulas (b1) to (b3): １ and B ２ When is a group represented by the following formulae (b1) to (b3), the polymer compound P has good planarity and can have an increased photoelectric conversion efficiency.

[0044]

[0045] In the above formulas (b1) to (b3), R ２１ , R ２２ , and R ２１’represents 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 to the benzene ring of benzobisthiazole.

[0046] R ２１ , R ２２ , and R ２１’ is preferably a hydrocarbon group having 6 to 30 carbon atoms, since this may further increase the photoelectric conversion efficiency. ２１ , R ２２ , and R ２１’ When is a hydrogen atom, the formation of a donor-acceptor type semiconducting polymer is facilitated.

[0047] B １ and B ２ are each more preferably a group represented by formula (b1) or (b2). １ and B ２ are groups represented by either formula (b1) or (b2), an interaction occurs between the S atom and the N atom in the benzobisthiazole structural unit, further improving the planarity, thereby enhancing the planarity of the resulting polymer compound P.

[0048] The polymer compound P is preferably a donor-acceptor type semiconducting polymer, and therefore, it is preferable that the polymer compound P 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. The donor unit means an electron-donating structural unit, and the acceptor unit means an electron-accepting structural unit. In the donor-acceptor type semiconducting polymer, the donor unit and the acceptor unit 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. By having such a structure, the polymer compound P can be suitably used as a p-type semiconductor compound.

[0049] 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 represented by the following formulae (c1) to (c43). Among these, structural units represented by the formulae (c1), (c3) to (c5), (c7), (c9), (c12), (c21), (c27), (c37), and (c42) are preferred, and structural units represented by the formulae (c1), (c5), (c9), (c21), (c37), and (c42) are more preferred.

[0050]

[0051]

[0052] In the above formulas (c1) to (c43), R ３０ ~R ７６ each independently represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms. ３０ and A ３１ are each independently T １ and T ２ represents the same group as in the structural unit represented by formula (1), and j represents an integer of 1 to 4. １ or B ２ represents a bond bonded to

[0053] The groups represented by the formulae (c1) to (c30) above are groups that act as acceptor units, and the groups represented by the formulae (c32) to (c43) are groups that act as donor units. ３０ and A ３１ Depending on the type of unit, it may act as an acceptor unit or as a donor unit.

[0054] The repeating ratio of the benzobisthiazole structural unit represented by formula (1) in the 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.

[0055] The repeating ratio of the specific structural unit in the 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.

[0056] In the polymer compound P, the arrangement of the benzobisthiazole structural unit represented by formula (1) and the specific structural unit may be any of alternate, block, and random. That is, the polymer compound P may be any of an alternate copolymer, a block copolymer, and a random copolymer. Preferably, the benzobisthiazole structural unit represented by formula (1) and the specific structural unit are arranged alternately.

[0057] The weight-average molecular weight and number-average molecular weight of the 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 the polymer compound P can be calculated using gel permeation chromatography based on a calibration curve prepared using polystyrene as a standard sample.

[0058] The thickness of the photoelectric conversion layer 133 is preferably 70 nm or more, more preferably 90 nm or more, and even more preferably 100 nm or more, and is preferably 1000 nm or less, more preferably 750 nm or less, still more preferably 500 nm or less, and particularly preferably 300 nm or less.

[0059] <Transport Layer> 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. In the laminate 1, the electron transport layer / photoelectric conversion layer / hole transport layer may be stacked in this order from the side closest to the inorganic substrate 11, or the hole transport layer / photoelectric conversion layer / electron transport layer may be stacked in this order. While FIG. 1 illustrates 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.

[0060] (Electron Transport Layer) 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.

[0061] The inorganic compound constituting the electron transport layer is preferably a metal compound, and examples thereof include salts of alkali metals such as lithium, sodium, potassium, and cesium, as well as metal oxides. Among these, examples of alkali metal salts include fluoride salts such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride, and examples of metal oxides include titanium oxide (TiO ｘ Metal oxides having n-type semiconductor properties, such as ZnO (ZnO), are preferred. Examples of organic compounds constituting the electron transport layer include conductive organic compounds, such as polyethyleneimine ethoxylate.

[0062] 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.

[0063] (Hole transport layer) 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.

[0064] Examples of conductive organic compounds constituting the hole transport layer include conductive polymers obtained by doping polymers such as polythiophene, polypyrrole, polyacetylene, triphenylenediamine, and polyaniline with sulfonic acid and / or iodine, polythiophene derivatives having sulfonyl groups as substituents, and arylamines. Metal compounds constituting 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. Among these, conductive polymers obtained by doping a polymer with sulfonic acid are preferred, and poly(3,4-ethylenedioxythiophene)poly(styrenesulfonic acid) (PEDOT:PSS), obtained by doping a polythiophene derivative with polystyrenesulfonic acid, are more preferred. Metal oxides such as molybdenum oxide and vanadium oxide may also be used.

[0065] 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.

[0066] <Resin Film> The resin film 12 is used, for example, as a barrier film 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, and the resin film 12 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, and can improve the long-term durability of a photoelectric conversion element using the laminate 1. When a barrier layer is provided, it is preferable that the barrier layer be provided on the surface of the resin film 12 facing the inorganic substrate 11 in the laminate 1.

[0067] Examples of the resin film 12 include polyester films such as PET film and PEN film; PES (polyethersulfone) film; polyamide films such as nylon film; polycarbonate film; cycloolefin film, etc., and polyester film is preferred, with PET film or PEN film being more preferred.

[0068] The material for the barrier layer is preferably a material with low oxygen permeability and water vapor permeability, and is preferably a transparent material. The barrier layer is, for example, an inorganic thin film. For example, a method for forming the resin film 12 provided with a barrier layer can be a method of forming a transparent inorganic thin film such as silicon oxide or aluminum oxide as a barrier layer on a polymer film as the resin film 12. Examples of methods for forming a transparent inorganic thin film on a film include a sol-gel method, a PVD (Physical Vapor Deposition) method, an electron beam evaporation method, a plasma CVD (Chemical Vapor Deposition) method, and a reactive sputtering method. An example of a method for forming the barrier layer includes a method in which a silicon-based compound such as silicon nitride, silicon oxide, silicon oxynitride, or silicon carbide, an aluminum-based compound such as aluminum oxide or aluminum nitride, aluminum silicate, zirconium oxide, tantalum oxide, titanium oxide, or titanium nitride is formed on the resin film 12 (preferably a PEN film) by plasma CVD, Cat-CVD, vacuum deposition, or the like.

[0069] The thickness of the resin film 12 is not particularly limited, and is preferably 30 μm or more and 300 μm or less, more preferably 40 μm or more and 280 μm or less, and even more preferably 50 μm or more and 250 μm or less. When the resin film 12 and a barrier layer provided on the resin film 12 are used as the barrier film, 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 about 0.05 to 2 μm. The thickness of the barrier layer is sufficiently thin compared to the thickness of the resin film 12, and has almost no effect on the elastic modulus, etc. of the resin film 12.

[0070] When attaching the resin film 12 to the laminated structure including the inorganic substrate 11 and intermediate layers such as the photoelectric conversion layer 133, an adhesive method suitable for each material can be applied. Examples include a method of adhering the resin film 12 to the laminated structure using an adhesive, and a method of adhering the resin film 12 to the laminated structure by thermocompression bonding using a heat press or a laminator. Preferred adhesives include olefin-based resins, rubber-based resins, silicone-based resins, and acrylic-based resins, and commercially available products may also be used.

[0071] When attaching the barrier film to the resin film 12, an adhesive method suitable for each material can be applied. Examples include a method of attaching the barrier film to the resin film 12 with an adhesive, or a method of attaching the barrier film to the resin film 12 by thermocompression bonding using a heat press or laminator. Using a barrier film having a hot melt layer or adhesive layer on one side allows the barrier film to be easily attached to the laminated structure. Olefin-based resins, rubber-based resins, silicone-based resins, and acrylic-based resins are preferably used as adhesives. The adhesive itself may have a low water vapor permeability, or if the water vapor permeability is high, adding a moisture scavenger or reducing the coating thickness can improve the sealing properties of the photoelectric conversion layer 133 and the like.

[0072] The adhesive may be applied in a frame-like manner to the four sides of the surface to which the barrier film is attached, or may be applied to the entire surface. If the adhesive is applied to the entire surface, it must be within a range that does not affect the photoelectric conversion element due to shrinkage when the adhesive hardens.

[0073] <Shape and Elastic Modulus of Laminate> The shape of the laminate 1 is not particularly limited, and may be a square or a rectangle when viewed from the thickness direction of the inorganic substrate 11 (direction perpendicular to the inorganic substrate 11). When the shape of the surface of the laminate 1 viewed from the thickness direction is square or rectangular, for example, the shape of the inorganic substrate 11 when viewed from the thickness direction of the inorganic substrate 11 is also square or rectangular.

[0074] When the surface of the inorganic substrate 11 viewed in the thickness direction has the above-mentioned square or rectangular shape, the diameter of the circumscribing circle of the square or rectangle is, for example, 130 mm to 1000 mm, more preferably 270 mm to 1000 mm, even more preferably 450 mm to 800 mm, and particularly preferably 550 mm to 800 mm. When producing the laminate 1, it is more productive to produce it in such a large size and then cut it down to an appropriate size.

[0075] When the surface of the inorganic substrate 11 viewed in the thickness direction has a square or rectangular shape, the two sides of the square or rectangle are described as the long side and the short side for convenience. In the case of a square, the long side and the short side are assumed to be the same length. The long side of the inorganic substrate 11 is, for example, 50 mm or more and 1000 mm or less, preferably 70 mm or more and 700 mm or less, more preferably 90 mm or more and 600 mm or less, even more preferably 150 mm or more and 550 mm or less, and particularly preferably 300 mm or more and 500 mm or less. The short side of the inorganic substrate 11 is, for example, 50 mm or more and 1000 mm or less, preferably 70 mm or more and 650 mm or less, more preferably 90 mm or more and 550 mm or less, even more preferably 150 mm or more and 500 mm or less, and particularly preferably 300 mm or more and 400 mm or less.

[0076] When the surface of the inorganic substrate 11 viewed in the thickness direction is the above-mentioned square or rectangular shape, it is preferable that the surface of the resin film 12 viewed in the thickness direction also be a square or rectangular shape. When the surface of the resin film 12 viewed in the thickness direction is a square or rectangular shape, the two sides of the square or rectangle will be described using the terms long side and short side for convenience. Here, the lengths of the two sides of the resin film 12 refer to the length in the planar state before the formation of the laminate 1. As described above, in the case of a square, the long side and short side are assumed to be the same length. The long side of the resin film 12 is, for example, shorter than the long side of the inorganic substrate 11, and is preferably 50 mm to 1000 mm, more preferably 70 mm to 700 mm, even more preferably 90 mm to 600 mm, even more preferably 150 mm to 550 mm, and particularly preferably 300 mm to 500 mm. The short side of the resin film 12 is, for example, shorter than the short side of the inorganic substrate 11, and is preferably 50 mm or more and 1000 mm or less, more preferably 70 mm or more and 650 mm or less, even more preferably 90 mm or more and 550 mm or less, even more preferably 150 mm or more and 500 mm or less, and particularly preferably 300 mm or more and 400 mm or less.

[0077] The tensile modulus E1 and thickness T1 of the laminate 1 satisfy the formula (A). E1 is expressed in GPa, and T1 is expressed in μm. 40000≦E1×T1 (A) E1×T1 is preferably 40,500 or more, more preferably 42,000 or more, and even more preferably 43,500 or more. There is no particular upper limit, but E1×T1 is preferably 60,000 or less, more preferably 55,000 or less, and even more preferably 52,000 or less. That is, E1×T1 is preferably 40,000 or more and 60,000 or less, more preferably 40,500 or more and 60,000 or less, even more preferably 42,000 or more and 55,000 or less, and particularly preferably 43,500 or more and 52,000 or less. When E1 × T1 satisfies the above formula (A), the width of the deviation when handling the laminate is suppressed, and the positional deviation during transfer by machine and the process using a lift pin can also be suppressed. As a result, the occurrence of scratches on the light receiving surface due to vibration and positional deviation during handling can be suppressed. This suppresses the deterioration of photoelectric conversion efficiency. Therefore, the laminate 1 satisfying the formula (A) is useful when using the laminate 1 to manufacture a photoelectric conversion element through the handling process described above.

[0078] The tensile modulus E1 of the laminate 1 is preferably 20 GPa or more and 120 GPa or less, more preferably 40 GPa or more and 100 GPa or less, even more preferably 55 GPa or more and 80 GPa or less, and particularly preferably 55 GPa or more and 70 GPa or less. The thickness T1 of the laminate 1 is preferably 200 μm or more and 2000 μm or less, more preferably 500 μm or more and 1500 μm or less, even more preferably 600 μm or more and 1000 μm or less, and particularly preferably 750 μm or more and 900 μm or less. The tensile modulus E1 and thickness T1 of the laminate 1 are measured by the methods described in the examples. In addition, when another layer is provided on the surface of inorganic substrate 11 opposite to the side on which photoelectric conversion layer 133 is provided, or when another layer is provided on the surface of resin film 12 opposite to the side on which photoelectric conversion layer 133 is provided, the tensile modulus of the laminate structure from inorganic substrate 11 to resin film 12 is taken as tensile modulus E1 in formula (A), and the thickness of the laminate structure is taken as thickness T1 in formula (A). That is, in the above cases, the portion corresponding to the laminate structure is considered to be laminate 1.

[0079] The tensile modulus E1 of the laminate 1 can be controlled by, for example, the tensile modulus and thickness of the inorganic substrate 11 constituting the laminate 1 and the tensile modulus and thickness of the resin film 12.

[0080] The tensile modulus of the inorganic substrate 11 is preferably 40 GPa or more and 100 GPa or less, more preferably 60 GPa or more and 90 GPa or less, and even more preferably 70 GPa or more and 80 GPa or less. The thickness of the inorganic substrate 11 is, for example, 150 μm or more and 1000 μm or less, preferably 350 μm or more and 800 μm or less, and more preferably 450 μm or more and 750 μm or less. The tensile modulus of the resin film 12 is preferably 3.0 GPa or more and 8.0 GPa or less, more preferably 3.5 GPa or more and 7.0 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 30 μm or more and 300 μm or less, more preferably 40 μm or more and 280 μm or less, and even more preferably 45 μm or more and 260 μm or less.

[0081] The ratio of the thickness of the inorganic substrate 11 to the thickness T1 of the laminate 1 (thickness of the inorganic substrate 11 / thickness T1) is preferably 0.50 or more and 0.90 or less, more preferably 0.60 or more and 0.87 or less, and even more preferably 0.64 or more and 0.85 or less. This range makes it easier for the tensile modulus E1 of the laminate 1 to be determined by the tensile modulus and thickness of the inorganic 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 (thickness of the resin film 12 / thickness T1) is preferably 0.050 or more and 0.50 or less, more preferably 0.080 or more and 0.40 or less, and even more preferably 0.085 or more and 0.33 or less. This range makes it easier for the tensile modulus E1 of the laminate 1 to be determined by the tensile modulus and thickness of the inorganic substrate 11 and the tensile modulus and thickness of the resin film 12.

[0082] The ratio of the thickness of the resin film 12 to the thickness of the inorganic substrate 11 (thickness of the resin film 12 / thickness of the inorganic substrate 11) is preferably 0.050 or more and 0.5 or less, more preferably 0.090 or more and 0.25 or less, even more preferably 0.092 or more and 0.22 or less, and particularly preferably 0.095 or more and 0.21 or less.

[0083] The thickness of the layer (intermediate layer) provided between the inorganic substrate 11 and the resin film 12 included in the laminate 1 is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 1 μm or less, and particularly preferably 800 nm or less. The lower limit of the thickness of the intermediate layer is not particularly limited, and is preferably, for example, 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 the intermediate layer / 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 layers other than the photoelectric conversion layer are included between the inorganic substrate 11 and the resin film 12), this refers to the total thickness. 1 , when the laminate 1 includes the first conductive layer 131 and the first conductive layer 131 has a portion that is not covered with the resin film 12, the thickness of the first conductive layer 131 is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 500 nm or less, as described above. When the thickness is within such a range, the tensile modulus E1 and thickness T1 of the laminate 1 are hardly affected by the layer configuration other than the inorganic substrate 11 and the resin film 12 included in the laminate 1.

[0084] When the above formula (A) is satisfied, warpage of the laminate 1 is suppressed. If the absolute value of the amount of warpage when the laminate 1 is heated is small, the laminate 1 or a photoelectric conversion element using the laminate 1 is less likely to be damaged by warpage when exposed to sunlight and heated, or when heated in a process of connecting the laminate 1 or a photoelectric conversion element using the laminate 1 to an electronic device. This suppresses deterioration of photoelectric conversion efficiency. When the laminate 1 satisfying the above formula (A) is heated at 110°C for 30 minutes, the absolute value of the amount of warpage is, for example, 140 μm or less, preferably 120 μm or less, more preferably 100 μm or less, even more preferably 80 μm or less, and particularly preferably 65 μm or less. The absolute value of the amount of warpage may be 60 μm or less or 40 μm or less. The method for measuring the amount of warpage of the laminate 1 at 110°C is the method described in the Examples.

[0085] This application claims the benefit of priority based on Japanese Patent Application No. 2024-009706, filed on January 25, 2024. The entire contents of the specification of Japanese Patent Application No. 2024-009706, filed on January 25, 2024, are incorporated herein by reference.

[0086] The present invention will be described in detail below using examples, but the present invention is not limited to the following examples as long as it does not deviate from the gist of the invention. In the following, for the purpose of ease of reference, the names of the components described with reference to Figure 1 may be used, but the reference numerals described with reference to Figure 1 may be omitted in the description.

[0087] <Preparation of Resin Films> The following commercially available films were used for films B1 to B5 in the examples and comparative examples: B1: E5100 (PET film manufactured by Toyobo Co., Ltd., thickness 100 μm, tensile modulus 4.0 GPa) B2: Teonex Q51 (PEN film manufactured by Toyobo Co., Ltd., thickness 50 μm, tensile modulus 5.9 GPa) B3: Teonex Q51 (PEN film manufactured by Toyobo Co., Ltd., thickness 250 μm, tensile modulus 6.1 GPa) B4: Torayfan BO (PP film manufactured by Toray Industries, Inc., thickness 40 μm, tensile modulus 0.2 GPa) B5: Toretec R213 (polyolefin film manufactured by Toray Industries, Inc., thickness 60 μm, tensile modulus 0.3 GPa)

[0088] <Inorganic Substrate> The following commercially available inorganic substrates (glass substrates) G1 to G3 were used as inorganic substrates: G1: OA-10G (manufactured by Nippon Electric Glass Co., Ltd., thickness 500 μm, tensile modulus 73.8 GPa) G2: OA-10G (manufactured by Nippon Electric Glass Co., Ltd., thickness 700 μm, tensile modulus 73.8 GPa) G3: OA-10G (manufactured by Nippon Electric Glass Co., Ltd., thickness 300 μm, tensile modulus 73.8 GPa)

[0089] <Measurement of Resin Film Thickness> The thickness of the resin film was measured using a macrometer (Militron 1245D, manufactured by Fine Leaf Co., Ltd.). The results are shown in Table 1.

[0090] <Measurement of Thickness (T1) of Laminate> The thickness (T1) of each laminate of the examples and comparative examples was measured using a high-precision Digimatic micrometer (MDH-25M, manufactured by Mitutoyo Corporation). The results are shown in Table 1.

[0091] <Tensile Modulus of Elasticity (E1) of Laminate> Each laminate of the Examples and Comparative Examples was cut into a 100 mm x 10 mm strip in the machine direction of the film using a glass cutter to prepare a test piece. Using a tensile tester (Shimadzu Corporation, Autograph Model AG-5000A), the tensile modulus of elasticity (E1) was measured in both the MD and TD directions at a tension speed of 50 mm / min and a chuck distance of 40 mm, and the average value was taken as the tensile modulus of elasticity (E1) of the laminate. The results are shown in Table 1.

[0092] <Warp Amount When Heated at 110°C> The amount of warp of each laminate of the Examples and Comparative Examples at 110°C was measured using the apparatus shown in FIG. 2 . For this measurement, a line was drawn with a black marker on the surface of the laminate where the displacement was to be measured (the portion directly below the slits in the slit-equipped insulating cover 33). Glass beads 37 were placed on the heating section of the hot plate 36, and the laminate was placed with the inorganic substrate side in contact with the glass beads 37 and heated to 110°C. The hot plate 36 and the entire laminate were covered with the slit-equipped insulating cover 33. The glass beads were used to suppress the influence of one-sided heating of the laminate by the hot plate. After 30 minutes had elapsed since the start of heating, the amount of warp 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 to the side where the inorganic substrate 11 was provided) to the hot plate 36 was measured, and the value obtained by subtracting the thicknesses of the inorganic substrate 11 and the glass beads 37 from this measurement was used to determine the amount of warp. 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 inorganic substrate in the laminate, and the average value was taken as the amount of warpage of the laminate when heated to 110° C. The results are shown in Table 1. A Keyence LK-H-055 was used as the laser displacement meter 31.

[0093] <Scratches on the Light-Receiving Surface Caused by Lift Pin Raising and Lowering> A lift stage was prepared with MC nylon lift pins (5 mm diameter) set at 50 mm intervals. Each laminate of the Examples and Comparative Examples was placed on the lift stage and raised and lowered 10 times by 50 mm. The locations where the pins would contact were marked in advance, and the increase in scratches on the light-receiving surface (inorganic substrate surface) before and after lift pin raising and lowering was evaluated. Scratches were measured using a Keyence VHX-1000 digital microscope, observing 10 random points within the area where the pins contacted. The increase in scratches was evaluated as follows: A: The increase in scratches before and after lift pin raising was 0% or more but less than 15%; B: The increase in scratches before and after lift pin raising and lowering was 15% or more but less than 30%; C: The increase in scratches before and after lift pin raising and lowering was 30% or more. Samples with 25 to 35 scratches on the light-receiving surface of the laminate before lift pin raising and lowering were selected for use.

[0094] Example 1: An inorganic substrate G1 was cut to a size of 100 mm x 100 mm using a glass cutter. A resin film B1 cut to 95 mm x 95 mm was attached to the center of the cut inorganic substrate G1 using Aron Alpha EXTRA 2000 manufactured by Toagosei. An adhesive was applied to the entire surface of the resin film, and the thickness of the adhesive was controlled to 30 μm by immediately passing it through a laminator using a spacer. This produced a laminate including an inorganic substrate and a resin film. From glass cutting to lamination, clean paper was laid on the side of the glass that would come into contact with the lift pin during handling to prevent scratches.

[0095] Example 2 The same procedure as in Example 1 was carried out, except that the size of the inorganic substrate was 200 mm x 200 mm and the size of the resin film was 195 mm x 195 mm.

[0096] Example 3 The same procedure as in Example 1 was carried out, except that the size of the inorganic substrate was 370 mm x 470 mm and the size of the resin film was 365 mm x 465 mm.

[0097] Example 4 The same procedure as in Example 3 was carried out except that B2 was used as the resin film.

[0098] Example 5 The same procedure as in Example 3 was carried out except that B3 was used as the resin film.

[0099] Example 6 The same procedure as in Example 3 was carried out except that G2 was used as the inorganic substrate.

[0100] Example 7: An inorganic substrate G1 (size: 370 mm x 470 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 μm using a No. 0 bar. The substrate was then heated at 120°C for 10 minutes. As a result, an electron transport layer approximately 50 nm thick was obtained on the glass. After wiping off the coating with acetone, leaving an area of ​​345 mm x 445 mm, a photoelectric conversion layer solution was dripped onto the substrate, and the coating was performed with a coating gap of 50 μm. The substrate was then heated at 140°C for 15 minutes. As a result, a photoelectric conversion layer approximately 250 nm thick was obtained. The photoelectric conversion layer solution was prepared by dissolving equal masses 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 345mm x 445mm area, HTL solar (PEDOT:PSS manufactured by Heraeus-Epirio) was dripped onto the substrate, coated with a coating gap of 50μm, and heated at 80°C for 30 minutes. This resulted in a hole transport layer approximately 400nm thick. The coating was then wiped with pure water, leaving a 345mm x 445mm area. Resin film B1, cut to 365mm x 465mm, was then attached to the substrate using Aron Alpha EXTRA 2000 manufactured by Toagosei. An adhesive was applied to the entire surface of the resin film, and the adhesive thickness was controlled to 30μm by immediately passing it through a laminator using a spacer. This resulted in the production of a laminate comprising an inorganic substrate, a resin film, and a photoelectric conversion layer. From glass cutting to lamination, clean paper was placed on the side of the glass that would come into contact with the lift pins during handling to prevent scratches.

[0101] Comparative Example 1: Inorganic substrate G1 was cut to a size of 370 mm x 470 mm using a glass cutter. Resin film B4, cut to 365 mm x 465 mm, was attached to the center of the cut inorganic substrate G1 using a 3M Super Multipurpose 2. An adhesive was applied to the entire surface of the resin film, and the thickness of the adhesive was controlled to 30 μm by immediately passing it through a laminator using a spacer. This produced a laminate including an inorganic substrate and a resin film.

[0102] Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Comparative Example 1, except that B5 was used as the resin film.

[0103] Comparative Example 3 Comparative Example 3 was carried out in the same manner as in Comparative Example 1, except that G3 was used as the inorganic substrate and B5 was used as the resin film.

[0104]

[0105] In the laminates of Examples 1 to 7, the tensile modulus E1 (GPa) and thickness T1 (μm) satisfy the above formula (A). On the other hand, in the laminates of Comparative Examples 1 to 3, the above formula (A) is not satisfied. Therefore, the following relationship exists between scratches on the light-receiving surface and the amount of warpage upon heating. In the laminates of Examples 1 to 7, the evaluation of scratches on the light-receiving surface was better than that of the laminates of Comparative Examples 1 to 3. Furthermore, in the laminates of Examples 1 to 7, the absolute value of the amount of warpage upon heating was significantly smaller than that of the laminates of Comparative Examples 1 to 3. In a laminate including a photoelectric conversion layer, when the evaluation of scratches on the light-receiving surface was good, deterioration of photoelectric conversion efficiency due to scratches on the light-receiving surface was suppressed, and when the absolute value of the amount of warpage upon heating was small, deterioration of photoelectric conversion efficiency due to damage caused by warpage was suppressed.

[0106] The laminate of Example 7 has a configuration in which multiple layers, including a photoelectric conversion layer, are provided between the inorganic substrate and the resin film in the laminate of Example 3. The total thickness of the multiple layers is thought to be approximately 700 nm, which is minute compared to the thickness T1 of the laminate. The laminate of Example 7 has the same evaluation of scratches on the light-receiving surface (even better) as the laminate of Example 3, and the amount of warping upon heating is also similar. The results of Examples 3 and 7 show that the intermediate layer, such as the photoelectric conversion layer provided between the inorganic substrate and the resin film, is a very thin layer compared to the inorganic substrate and the resin film, and therefore the presence or absence of the intermediate layer has little effect on scratches on the light-receiving surface or the amount of warping upon heating.

[0107] As in Example 3, in Examples 1, 2, 4, 5, and 6, the evaluation of scratches on the light-receiving surface was better than that of the laminates of Comparative Examples 1 to 3. Therefore, it can be said that even in Examples 1, 2, 4, 5, and 6, when an intermediate layer was additionally provided between the inorganic substrate and the resin film, the evaluation of scratches on the light-receiving surface was better than that of the laminates of Comparative Examples 1 to 3, and the absolute value of the amount of warpage upon heating was significantly smaller than that of the laminates of Comparative Examples 1 to 3. From the above, it was found that, since the evaluation of a laminate that does not include an intermediate layer is similar to the evaluation of a laminate that includes an intermediate layer, when the evaluation of scratches on the light-receiving surface and the evaluation of the amount of warpage upon heating are excellent in a laminate that does not include an intermediate layer, the evaluation of scratches on the light-receiving surface and the evaluation of the value of warpage upon heating are also excellent even when an intermediate layer is additionally provided.

[0108] REFERENCE SIGNS LIST 1 Laminate 11 Inorganic substrate 12 Resin film 131 First conductive layer 132 First transport layer 133 Photoelectric conversion layer 134 Second transport layer 135 Second conductive layer 31 Laser displacement meter 32 Angle with rail 33 Slit-equipped heat insulating cover 36 Hot plate 37 Glass beads

Claims

1. A laminate comprising an inorganic substrate, a resin film, and a photoelectric conversion layer between the inorganic substrate and the resin film, wherein the tensile elastic modulus E1 (GPa) and the thickness T1 (μm) of the laminate satisfy the following formula (A): 40000 ≦ E1 × T1 (A).

2. The laminate according to claim 1, wherein the shape of the inorganic substrate as viewed in the thickness direction of the inorganic substrate is square or rectangular, and the diameter of the circumscribed circle of the square or rectangle is 130 mm or more.

3. The laminate according to claim 1 or 2, wherein the tensile elastic modulus of the inorganic substrate is 60 GPa or more and 90 GPa or less, and the thickness of the inorganic substrate is 350 μm or more and 800 μm or less.

4. The laminate according to claim 1 or 2, wherein the tensile elastic modulus of the resin film is 3.0 GPa or more and 8.0 GPa or less, and the thickness of the resin film is 30 μm or more and 300 μm or less.

5. The laminate according to claim 1 or 2, wherein the absolute value of the amount of warpage during heating at 110° C. for 30 min is 140 μm or less.

6. A photoelectric conversion element using the laminate according to claim 1 or 2.

7. The photoelectric conversion element according to claim 6, wherein the photoelectric conversion element is an organic thin film solar cell.

8. A method for manufacturing a photoelectric conversion element using the laminate according to claim 1 or 2.

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