Classifications

• • 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
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
• • 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
  • H10K30/84—Layers having high charge carrier mobility
  • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
• • 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
  • H10K30/84—Layers having high charge carrier mobility
  • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers

Definitions

• the present invention relates to a device and a method for manufacturing the device.
• a device that has a laminate including an active layer, an electron transport layer, and a hole transport layer as the 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 this device.
• Patent Document 1 a laminate including an active layer, an electron transport layer, and a hole transport layer as the functional layers of a photoelectric conversion element
• delamination may occur between the active layer and the hole transport layer and/or between the active layer and the electron transport layer. It is desirable to prevent such delamination.
• the present invention aims to provide a device and a method for manufacturing the device in which the adhesion is improved to prevent delamination at least between the active layer and the hole transport layer and between the active layer and the electron transport layer.
• the present invention aims to provide a device and a method for manufacturing the device in which the adhesion is improved in a flexible device, preventing cracks from occurring when the device is repeatedly bent, and reducing changes in power generation efficiency.
• the gist of the present invention which has achieved the above object, is a device having a laminate including an electron transport layer, a hole transport layer, and an active layer between the electron transport layer and the hole transport layer,
• the laminate is a device having a silane coupling agent layer at least one between the electron transport layer and the active layer and between the hole transport layer and the active layer.
• the thickness of the silane coupling agent layer is preferably 1 nm or more and 50 nm or less.
• the laminate includes a transparent conductive layer, the electron transport layer is between the transparent conductive layer and the active layer, and a silane coupling agent layer is provided between the hole transport layer and the active layer, It is preferable that the laminate includes a transparent conductive layer, the hole transport layer is between the transparent conductive layer and the active layer, and a silane coupling agent layer is provided between the electron transport layer and the active layer.
• the active layer is preferably an organic semiconductor.
• the device may further include a substrate, and the laminate may be provided on the substrate.
• Another aspect of the present invention includes a method for manufacturing a device including an electron transport layer, an active layer, and a hole transport layer, the method including the steps of forming the electron transport layer, forming the active layer, forming the hole transport layer, and forming a silane coupling agent layer on at least one of the electron transport layer, the active layer, and the hole transport layer, in which, if a silane coupling agent layer is formed on the electron transport layer in the step of forming the silane coupling agent layer, the active layer is formed on the silane coupling agent layer in the step of forming the active layer, and if a silane coupling agent layer is formed on the active layer in the step of forming the silane coupling agent layer, the electron transport layer is formed on the silane coupling agent layer in the step of forming the electron transport layer, or, if a silane coupling agent layer is formed on the silane coupling agent layer in the step of forming the hole transport layer, the active layer is formed on the silane coupling agent layer in the step of forming
• the silane coupling agent layer it is preferable to use a gas phase method or a spin coating method.
• the silane coupling agent layer is formed to a thickness of 1 nm or more and 50 nm or less.
• the present invention has the effect of improving adhesion between the active layer and the hole transport layer and/or between the active layer and the electron transport layer, thereby preventing delamination.
• improved adhesion prevents cracks from occurring when the device is repeatedly bent, and reduces changes in power generation efficiency.
• FIG. 1 is a diagram illustrating a device according to one embodiment of the present invention.
• FIG. 2 shows a device according to another embodiment of the present invention.
• FIG. 3 is a diagram showing a manufacturing apparatus for a silane coupling agent layer used in a manufacturing method for a device according to one embodiment of the present invention.
• Figure 1 shows a device 10 according to one embodiment of the present invention
• Figure 2 shows a device 20 according to another embodiment of the present invention.
• device 10 includes stack 16, which includes electron transport layer 13, hole transport layer 15, and active layer 14 between electron transport layer 13 and hole transport layer 15.
• device 20 includes stack 26, which includes electron transport layer 23, hole transport layer 25, and active layer 24 between electron transport layer 23 and hole transport layer 25.
• the laminate 16 has a silane coupling agent layer at least one between the electron transport layer 13 and the active layer 14 and between the hole transport layer 15 and the active layer 14.
• the laminate 16 may have a silane coupling agent layer both between the electron transport layer 13 and the active layer 14 and between the hole transport layer 15 and the active layer 14, or may have a silane coupling agent layer only between the electron transport layer 13 and the active layer 14, or may have a silane coupling agent layer only between the hole transport layer 15 and the active layer 14.
• Figure 1 shows an example in which the laminate 16 has a silane coupling agent layer 17 between the hole transport layer 15 and the active layer 14.
• the laminate 26 has a silane coupling agent layer at least one between the electron transport layer 23 and the active layer 24 and between the hole transport layer 25 and the active layer 24.
• the laminate 26 may have a silane coupling agent layer between both the electron transport layer 23 and the active layer 24 and between the hole transport layer 25 and the active layer 24, or may have a silane coupling agent layer only between the electron transport layer 23 and the active layer 24, or may have a silane coupling agent layer only between the hole transport layer 25 and the active layer 24.
• FIG. 2 shows an example in which the laminate 26 has a silane coupling agent layer 27 between the electron transport layer 23 and the active layer 24.
• the silane coupling agent layer thus provided (e.g., silane coupling agent layers 17, 27) is preferably a non-conductive layer formed from a silane coupling agent.
• the current path is provided with, for example, non-conductive silane coupling agent layers 17, 27.
• the silane coupling agent layers 17, 27 at least one between the electron transport layers 13, 23 and the active layers 14, 24 and between the hole transport layers 15, 25 and the active layers 14, 24, the adhesion between the layers is improved and delamination can be prevented.
• the adhesion between at least one of the active layers 14, 24 and the hole transport layers 15, 25 and between the active layers 14, 24 and the electron transport layers 13, 23 is improved, preventing cracks from occurring and reducing changes in power generation efficiency.
• each of the silane coupling agent layers is preferably 1 nm or more and 50 nm or less, more preferably 3 nm or more and 40 nm or less, and further preferably 5 nm or more and 30 nm or less. If the thickness of the silane coupling agent layer is less than 1 nm, there is a risk that the film surface of the silane coupling agent layer will not be uniform and sufficient adhesive strength will not be ensured. On the other hand, if the thickness of the silane coupling agent layer exceeds 50 nm, there is a risk that the electrical characteristics of the device will be deteriorated because the silane coupling agent layer is, for example, a non-conductive layer.
• the thickness of the silane coupling agent layer may be determined, for example, by an ellipsometry method or by calculation from the concentration of the silane coupling agent solution at the time of coating and the coating amount.
• the thickness ratio of the silane coupling agent layer to the total thickness of the laminate composed of the electron transport layer, active layer, hole transport layer, and silane coupling agent layer is preferably 0.3% to 30%, more preferably 0.5% to 20%, and even more preferably 0.5% to 5%.
• the silane coupling agent used in the silane coupling agent layer is, for example, a silicon atom to which a reactive group such as a vinyl group, an epoxy group, a styryl group, a (meth)acrylic group, an amino group, a mercapto group, a ureido group, an isocyanate group, or an isocyanurate group is bonded, and an alkoxy group having 1 to 6 carbon atoms is bonded.
• alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc.
• the number of carbon atoms in the alkoxy group is preferably 1 to 4, and more preferably 1 to 3.
• the number of alkoxy groups bonded to a silicon atom is preferably one or more, more preferably two or more, even more preferably two or three, and even more preferably three.
• Silane coupling agents whose reactive group is a vinyl group include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 7-octenyltrimethoxysilane.
• Silane coupling agents in which the reactive group is an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, aminophenyl
• Silane coupling agents whose reactive group is an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 8-glycidoxyoctyltrimethoxysilane.
• silane coupling agent in which the reactive group is a styryl group is p-styryltrimethoxysilane.
• Silane coupling agents in which the reactive group is a (meth)acrylic group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane.
• silane coupling agent in which the reactive group is a ureido group is 3-ureidopropyltriethoxysilane.
• silane coupling agents in which the reactive group is a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
• silane coupling agent whose reactive group is an isocyanurate group is 3-isocyanatepropyltriethoxysilane.
• silane coupling agent whose reactive group is an isocyanurate group is tris-(3-trimethoxysilylpropyl) isocyanurate.
• silane coupling agents include bis(triethoxysilylpropyl)tetrasulfide, n-propyltrimethoxysilane, chloromethylphenethyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, diethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, ethyltrichlorosilane, hexyltrimethoxysilane, octadecyltri
• silane coupling agent in which an epoxy group or a mercapto group is bonded as a reactive group to one silicon atom in one molecule, and two or three alkoxy groups are bonded to the same, is preferred, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like are more preferred, and from the viewpoint of hydrolysis, silane coupling agents in which the alkoxy group is a methoxy group, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-
• the silane coupling agent may be applied to the surface to be treated as a solution of the silane coupling agent, or a solvent may be added to adjust the pH, etc.
• the laminate 16 includes a transparent conductive layer 12, the electron transport layer 13 is between the transparent conductive layer 12 and the active layer 14, and a silane coupling agent layer 17 is provided between the hole transport layer 15 and the active layer 14.
• the laminate 26 includes a transparent conductive layer 22, a hole transport layer 25 is located between the transparent conductive layer 22 and the active layer 24, and a silane coupling agent layer 27 is provided between the electron transport layer 23 and the active layer 24.
• the silane coupling agent layer 17 is preferably provided on the active layer 14, and is preferably formed entirely or partially on the active layer 14.
• the silane coupling agent layer 17 and the active layer 14 are preferably in contact with each other.
• the hole transport layer 15 is preferably provided on the silane coupling agent layer 17.
• the silane coupling agent layer 17 and the hole transport layer 15 are preferably in contact with each other.
• the silane coupling agent layer 27 is preferably provided on the active layer 24, and is preferably formed entirely or partially on the active layer 24.
• the silane coupling agent layer 27 and the active layer 24 are preferably in contact with each other.
• the electron transport layer 23 is preferably provided on the silane coupling agent layer 27.
• the silane coupling agent layer 27 and the electron transport layer 23 are preferably in contact with each other.
• FIG. 1 shows an example of a laminate 16 having a laminate structure in the order of transparent conductive layer 12/electron transport layer 13/active layer 14/silane coupling agent layer 17/hole transport layer 15.
• the laminate 16 may have a laminate structure in the order of hole transport layer 15/silane coupling agent layer 17/active layer 14/electron transport layer 13/transparent conductive layer 12.
• FIG. 2 shows an example of a laminate 26 having a laminate structure in the order of transparent conductive layer 22/hole transport layer 25/active layer 24/silane coupling agent layer 27/electron transport layer 23.
• the laminate 26 may have a laminate structure in the order of electron transport layer 23/silane coupling agent layer 27/active layer 24/hole transport layer 25/transparent conductive layer 22.
• Device 10 includes, for example, a substrate 11 and a conductive layer 18.
• a stack 16 (preferably a transparent conductive layer 12 of stack 16) may be provided on substrate 11, and conductive layer 18 may be provided on hole transport layer 15.
• Device 20 includes, for example, a substrate 21 and a conductive layer 28.
• a stack 26 (preferably a transparent conductive layer 22 of stack 26) may be provided on substrate 21, and conductive layer 28 may be provided on electron transport layer 23.
• the active layers 14 and 24 are layers where photoelectric conversion takes place, and preferably contain a p-type semiconductor compound and an n-type semiconductor compound.
• the photoelectric conversion element receives light, the light is absorbed by the active layer, electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is taken out from the cathode and anode.
• the cathode and anode correspond to the transparent conductive layer and the conductive layer.
• p-type semiconductor compound can be used as the p-type semiconductor compound and the n-type semiconductor compound.
• p-type semiconductor compounds include conjugated copolymer semiconductor compounds such as polythiophene, polyfluorene, polyphenylene vinylene, polythienylene vinylene, polyacetylene, and polyaniline; and copolymer semiconductor compounds such as oligothiophene substituted with an alkyl group or other substituent. Copolymer semiconductor compounds in which two or more types of monomer units are copolymerized may also be used.
• n-type semiconductor compounds include fullerenes and their derivatives, octaazaporphyrins, and perfluoro compounds in which hydrogen atoms of p-type semiconductor compounds are replaced with fluorine atoms (e.g., perfluoropentacene and perfluorophthalocyanine).
• polymer compounds containing aromatic carboxylic acid anhydrides such as naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic diimide, perylene tetracarboxylic anhydride, and perylene tetracarboxylic diimide as a skeleton, or imides thereof, can also be used as n-type semiconductor compounds.
• the layer structure of the active layers 14, 24 includes a thin-film laminate structure in which a p-type semiconductor compound and an n-type semiconductor compound are laminated, and a bulk heterojunction structure having a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed.
• the bulk heterojunction structure has a layer (i-layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed.
• the i-layer has a structure in which the p-type semiconductor compound and the n-type semiconductor compound are phase-separated, and carrier separation occurs at the phase interface, and the generated carriers (holes and electrons) are transported to the electrode.
• the mass ratio of the p-type semiconductor compound to the n-type semiconductor compound in the i-layer is preferably 0.5 or more, more preferably 1 or more, and also preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less.
• the active layers 14, 24 may contain additives in addition to the p-type and n-type semiconductor compounds.
• the phase separation structure between the p-type and n-type semiconductor compounds in the bulk heterojunction active layer affects light absorption, exciton generation and diffusion, exciton dissociation (carrier separation), carrier transport, etc., so it is expected that good photoelectric conversion efficiency can be achieved by optimizing the phase separation structure.
• an active layer with a favorable phase separation structure can be obtained, and photoelectric conversion efficiency can be improved.
• 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 substituents that may be possessed by the aliphatic hydrocarbon compounds include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, amino groups, carbamoyl groups, carbonyloxy groups, carboxyl groups, carbonyl groups, aromatic groups, etc.
• preferred additives include benzene which may have a substituent, naphthalene which may have a substituent, and octane which may have a substituent.
• halogen atoms are particularly preferred as the substituents.
• the active layers 14, 24 are organic semiconductors, and more preferably contain a p-type semiconductor compound of a polymer compound described later and/or an n-type semiconductor compound of a polymer compound described later or the n-type semiconductor compound.
• Examples of p-type semiconductor compounds that are polymer compounds include PDPPBDT, PDPPDTT, PFs, KP115, PCDTBT, DPPT-TT, PDPP2FT, F82T, F8TBT, F8BT, P3HT-Br10, PPP-P3HT, P3HT, PhxSDT-DTZ, PBDTDPP-1, P3DDT, PPDTBT, PPDT2FBT, PBDTDPP-2, PCPDTBT-1, PCPDTBT-2, and PBDBT2F (PM6).
• n-type semiconductor compounds that are polymer compounds include MEH-CN-PPV, F8TBT, PZ1, DCNBT-IDT, P-BNBP-fBT, PF2-DTSi, PDI-V, PYT M , PJ1-H, N2200, and Y6.
• the active layers 14, 24 may contain a polymeric compound having a benzobisthiazole structural unit, and specifically, it is preferable that the active layers 14, 24 contain a polymeric compound having a benzobisthiazole structural unit represented by the following formula (1) (hereinafter referred to as "polymeric compound P").
• T 1 and T 2 each independently represent a thiophene ring that may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group, or an organosilyl group, a thiazole ring that may be substituted with a hydrocarbon group or an organosilyl group, or a phenyl group that may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group.
• B 1 and B 2 represent a thiophene ring that may be substituted with a hydrocarbon group, a thiazole ring that may be substituted with a hydrocarbon group, or an ethynylene group.
• the organosilyl group means a monovalent group in which one or more hydrocarbon groups are substituted on a Si atom, and the number of hydrocarbon groups that are substituted on a Si atom is preferably 2 or more and 3 or less, more preferably 3.
• the polymer compound P is a type of p-type semiconductor compound, and by having the benzobisthiazole structural unit represented by formula (1), it is possible to narrow the band gap while deepening the HOMO level, thereby improving the photoelectric conversion efficiency.
• T1 and T2 may be the same or different from each other, but are preferably the same from the viewpoint of ease of production.
• B1 and B2 may be the same or different from each other, but are preferably the same from the viewpoint of ease of production.
• T 1 and T 2 are preferably groups represented by the following formulas (t1) to (t5), respectively.
• the alkoxy group of T 1 and T 2 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 which may be substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t3)
• the thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group is preferably a group represented by the following formula (t4)
• 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 is preferably a group represented by the following formula (t5).
• T 1 and T 2 are groups represented by the following formulas (t1) to (t5), they can absorb light of a short wavelength, and have high planarity, so that ⁇ - ⁇ stacking is efficiently formed, thereby improving the photoelectric conversion efficiency.
• the groups represented by the formulae (t1) to (t3) exhibit electron-donating properties
• the groups represented by the formulae (t4) to (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 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and multiple R 18s may be the same or different.
• R 19 to R 20 each represent a hydrocarbon group having a carbon number of 6 to 30.
• the symbol * in each formula represents a bond bonded to the thiazole ring of benzobisthiazole.
• the hydrocarbon group having 6 to 30 carbon atoms for R 13 to R 17 , R 19 to R 20 , and R 15' is preferably a branched hydrocarbon group, more preferably a branched saturated hydrocarbon group.
• the hydrocarbon groups for R 13 to R 17 , R 19 to R 20 , and R 15' can increase the solubility in organic solvents by having a branch.
• the number of carbon atoms for the hydrocarbon groups for R 13 to R 17 , R 19 to R 20 , and R 15' is preferably 8 to 25, more preferably 8 to 20, and even more preferably 8 to 16.
• the carbon number of the aliphatic hydrocarbon group of R 18 is preferably 1 to 18, more preferably 1 to 8.
• the carbon number of the aromatic hydrocarbon group of R 18 is preferably 6 to 8, more preferably 6 to 7, and even more preferably 6.
• the aromatic hydrocarbon group of R 18 can be, for example, 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.
• the multiple R 18 may be the same or different, but are preferably the same.
• R 15 to R 17 and R 15' are groups represented by *-Si(R 18 ) 3
• the solubility of the polymer compound P in an organic solvent is improved.
• the group represented by --Si( R.sup.18 ) .sub.3 is preferably an alkylsilyl group, more preferably a trimethylsilyl group or a triisopropylsilyl group.
• R 17 when R 17 is a halogen atom, any of fluorine, chlorine, bromine, and iodine can be used. As R 17 , a halogen atom or *-CF 3 is preferable.
• R 15' is a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms exemplified as R 15 , or a group similar to the group represented by *-Si(R 18 ) 3 , and is preferably a hydrogen atom.
• T1 and T2 from the viewpoint of excellent planarity of the structural unit represented by formula (1) as a whole, groups represented by formulas (t1), (t3) and (t5) are more preferable, and a group represented by formula (t3) is even more preferable.
• B 1 and B 2 are preferably groups represented by any one of the following formulae (b1) to (b3).
• the polymer compound P has good planarity and can have an improved photoelectric conversion efficiency.
• R 21 , R 22 and R 21′ represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms.
• the symbol ⁇ in each formula represents a bond, and in particular the symbol ⁇ on the left represents a bond bonded to the benzene ring of the benzobisthiazole compound.
• the hydrocarbon group having 6 to 30 carbon atoms for R 21 , R 22 and R 21' the groups exemplified as the hydrocarbon group having 6 to 30 carbon atoms for R 13 to R 17 , R 19 to R 20 and R 15' can be preferably used.
• R 21 , R 22 and R 21' are hydrocarbon groups having 6 to 30 carbon atoms, the photoelectric conversion efficiency can be further improved, which is preferable.
• R 21 , R 22 and R 21' are hydrogen atoms, the formation of a donor-acceptor type semiconductor polymer is facilitated.
• B1 and B2 are more preferably groups represented by formula (b1) and (b2).
• B1 and B2 are groups represented by formula (b1) and (b2)
• an interaction occurs between the S atom and the N atom in the benzobisthiazole structural unit, and the planarity is further improved.
• 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, it is preferable that the polymer compound P has a benzobisthiazole structural unit represented by formula (1) and a specific structural unit that gives a donor unit or an acceptor unit.
• the donor unit means an electron-donating structural unit
• the acceptor unit means an electron-accepting structural unit.
• the donor-acceptor type semiconducting polymer preferably has donor units and acceptor units 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 specific structural unit a conventionally known structural unit that provides a donor unit or an acceptor unit can be used.
• the specific structural unit can be the structural units of the following formulae, of which the structural units represented by the formulae (c1), (c3) to (c5), (c7), (c9), (c12), (c21), (c27), (c37), and (c42) are preferred, and the structural units represented by the 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 bonded to B 1 or B 2 of the structural unit represented by formula (1).
• the groups represented by the above formulae (c1) to (c30) are groups that act as acceptor units, and the groups represented by the formulae (c32) to (c43) are groups that act as donor units.
• the group represented by formula (c31) may act 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 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.
• 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.
• the arrangement of the benzobisthiazole structural unit represented by formula (1) and the specific structural unit may be alternate, block, or random. That is, the 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 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 based on a calibration curve created using gel permeation chromatography with polystyrene as a standard sample.
• the thickness of the active layers 14, 24 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.
• the electron transport layers 13 and 23 are layers that extract electrons from the active layers 14 and 24 to the cathode.
• the constituent material of the electron transport layers 13 and 23 is preferably an electron transporting material that improves the efficiency of electron extraction, and may be either an organic compound or an inorganic compound, although an inorganic compound is preferred.
• the inorganic compound constituting the electron transport layers 13, 23 is preferably a metal compound, such as a salt of an alkali metal, such as lithium, sodium, potassium, or cesium, or a metal oxide.
• the salt of an alkali metal is preferably a fluoride salt, such as lithium fluoride, sodium fluoride, potassium fluoride, or cesium fluoride
• the metal oxide is preferably a metal oxide having n-type semiconductor properties, such as titanium oxide (TiOx) or zinc oxide (ZnO).
• the organic compound constituting the electron transport layers 13, 23 is preferably a conductive organic compound, such as polyethyleneimine ethoxylate.
• the thickness of the electron transport layers 13, 23 is preferably 0.1 nm or more, more preferably 0.5 nm or more, even more preferably 1.0 nm or more, even more preferably 2.0 nm or more, particularly preferably 4.0 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 15, 25 is a layer that extracts holes from the active layer 14, 24 to the anode.
• the constituent material of the hole transport layer 15, 25 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 constituting the hole transport layers 15 and 25 include, for example, conductive polymers in which polythiophene, polypyrrole, polyacetylene, triphenylenediamine, polyaniline, etc. are doped with sulfonic acid and/or iodine, polythiophene derivatives having sulfonyl groups as substituents, arylamines, etc.
• Metal compounds constituting the hole transport layers 15 and 25 include metal oxides having p-type semiconductor properties such as molybdenum trioxide, vanadium pentoxide, nickel oxide, etc., and metals such as gold, indium, silver, and palladium.
• the hole transport layers may also be formed from p-type semiconductor compounds.
• the material constituting the hole transport layers 15 and 25 is preferably a conductive polymer doped with sulfonic acid, more preferably poly(3,4-ethylenedioxythiophene)poly(styrenesulfonic acid) (PEDOT:PSS) in which a polythiophene derivative is doped with polystyrenesulfonic acid, and more preferably a metal oxide such as molybdenum oxide or vanadium oxide.
• PEDOT:PSS poly(3,4-ethylenedioxythiophene)poly(styrenesulfonic acid)
• a metal oxide such as molybdenum oxide or vanadium oxide.
• the thickness of the hole transport layers 15, 25 is preferably 0.2 nm or more, more preferably 0.5 nm or more, even more preferably 1.0 nm or more, even more preferably 2.0 nm or more, and particularly preferably 4.0 nm or more, and is preferably 400 nm or less, more preferably 300 nm or less, even more preferably 200 nm or less, even more preferably 100 nm or less, and particularly preferably 70 nm or less.
• the transparent conductive layers 12, 22, the cathodes and anodes which may be conductive layers 18, 28 are made from conductive materials.
• the cathode is preferably made of a conductive material having a smaller work function than the anode.
• the cathode has the function of extracting electrons generated in the active layers 14, 24.
• Examples of 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.
• a conductive metal oxide with translucency such as ITO, zinc oxide, or tin oxide, and it is particularly preferable to use ITO.
• the anode is preferably made of a conductive material with a work function larger than that of the cathode.
• the anode has the function of extracting holes generated in the active layer.
• materials constituting 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 is used as the material constituting the hole transport layer
• a material with a small work function such as ITO, may be used as the material for the anode.
• the thickness of the cathode and anode is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 50 nm or more, even more preferably 70 nm or more, and is preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 500 nm or less, even more preferably 300 nm or less.
• Substrate Laminates 16,26 are preferably formed on substrates 11,21.
• the constituent material of the substrates 11 and 21 is not particularly limited and is appropriately set according to the application of the photoelectric conversion element.
• Examples of the constituent material of the substrates 11 and 21 include inorganic materials such as quartz, glass, sapphire, and titania; organic materials such as polyethylene (e.g., polyethylene terephthalate, polyethylene naphthalate), polyethersulfone, polyimide, polyamide (e.g., nylon), polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, fluororesin, vinyl chloride, polyolefin (e.g., polyethylene, polypropylene), cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, and epoxy resin; paper materials; and composite materials in which metals such as stainless steel, titanium, and
• substrates 11 and 21 are made of an organic material, it is more preferable that they are made of polyethylene, and it is even more preferable that they are made of polyethylene terephthalate.
• the shapes of the substrates 11 and 21 include, for example, plate-like, film-like, and sheet-like shapes.
• the thickness of the substrates 11 and 21 is preferably 0.3 mm or more, more preferably 0.5 mm or more, and preferably 20 mm or less, more preferably 10 mm or less, and even more preferably 1 mm or less.
• the thickness of the substrates 11 and 21 is preferably 0.05 mm or more, more preferably 0.07 mm or more, and preferably 0.2 mm or less, and more preferably 0.15 mm or less.
• the electron transport layers 13, 23 are preferably made of a metal oxide having n-type semiconductor properties such as titanium oxide (TiOx) or zinc oxide (ZnO)
• the hole transport layers 15, 25 are preferably made of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonic acid) (PEDOT:PSS) in which a polythiophene derivative is doped with polystyrenesulfonic acid
• the active layers 14, 24 are preferably a combination of poly(3-hexylthiophene (P3HT) and a fullerene derivative, or a combination of PM6 and Y6, and the substrates 11, 21 are preferably an inorganic or organic material, more preferably glass or polyethylene.
• the device of the present invention may have a protective layer, which may be provided for the conductive layers (conductive layers 18, 28).
• Materials for the protective layer include polyethylene resin, polypropylene resin, cyclic olefin resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin, fluororesin, polyester resins such as polyethylene terephthalate resin and polyethylene naphthalate resin, phenol resin, polyacrylic resin, polyamide resin, polyimide resin, polyurethane resin, silicone resin, etc.
• the thickness of the protective layer is, for example, 0.5 ⁇ m or more and 100 ⁇ m or less, preferably 1 ⁇ m or more and 50 ⁇ m or less, and more preferably 2 ⁇ m or more and 30 ⁇ m or less.
• the protective layer is preferably transparent to visible light.
• the light transmittance of the protective layer in the visible light range of wavelengths from 360 to 830 nm is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more.
• the protective layer may be formed on the conductive layer via an adhesive layer.
• the formed protective layer may be used as is, or the protective layer and the adhesive layer provided on the protective layer may be peelable layers, or a peeling layer may be provided separately from the adhesive layer.
• peeling off the protective layer leaves the adhesive layer on the conductive layer, for example, and the adhesive strength of the adhesive layer makes it possible to attach a desired object (such as a barrier layer) to the conductive layer, etc.
• a peeling layer peeling off the protective layer can be made easier.
• the manufacturing method of the device of the present invention includes a step of forming an electron transport layer, a step of forming an active layer, a step of forming a hole transport layer, and a step of forming a silane coupling agent layer on at least one of the electron transport layer, the active layer, and the hole transport layer.
• a silane coupling agent layer is formed on the electron transport layer in the step of forming the silane coupling agent layer
• the active layer is formed on the silane coupling agent layer in the step of forming the active layer.
• the electron transport layer is formed on the silane coupling agent layer in the step of forming the electron transport layer, or the hole transport layer is formed on the silane coupling agent layer in the step of forming the hole transport layer.
• the active layer is formed on the silane coupling agent layer in the step of forming the active layer.
• the processes for forming the substrate, transparent conductive layer, electron transport layer, active layer, hole transport layer, conductive layer, and protective layer may be carried out using the materials described above by a conventionally known coating method (e.g., applicator method, bar coating method, spin coating method, mist method, vapor deposition method).
• a conventionally known coating method e.g., applicator method, bar coating method, spin coating method, mist method, vapor deposition method.
• the silane coupling agent layer may be formed by applying a solution containing the silane coupling agent (also called a silane coupling agent solution), by a gas phase method (also called a vapor deposition method), or the like.
• a solution containing the silane coupling agent also called a silane coupling agent solution
• a gas phase method also called a vapor deposition method
• Methods for applying a silane coupling agent solution include spin coating, curtain coating, dip coating, slit die coating, gravure coating, bar coating, comma coating, applicator, screen printing, spray coating, etc., which use a solution of the silane coupling agent diluted with a solvent such as alcohol.
• silane coupling agent solution When using the method of applying a silane coupling agent solution, it is preferable to dry the solution quickly after application and then perform heat treatment at about 100 ⁇ 30°C for several tens of seconds to about 10 minutes. This heat treatment removes the solvent.
• the silane coupling agent and the surface to be applied are bonded by a chemical reaction.
• the silane coupling agent layer is formed by a gas phase method (vapor deposition method)
• vapor deposition method it is preferable to form the silane coupling agent layer by exposing the treated surface to vapor of the silane coupling agent.
• the vapor of the silane coupling agent can be prepared by heating the silane coupling agent in a liquid state to a temperature of from 40° C. to about the boiling point of the silane coupling agent.
• the boiling point of the silane coupling agent is preferably in the range of 100°C to 250°C, more preferably 100°C to 200°C, even more preferably 100°C to 150°C, and even more preferably 100°C to 120°C. Heating at a temperature above 250°C may cause side reactions in the organic groups contained in the silane coupling agent.
• the application of the silane coupling agent may be carried out under increased pressure, normal pressure, or reduced pressure, and is preferably carried out under normal pressure or reduced pressure from the viewpoint of promoting the vaporization of the silane coupling agent.
• the silane coupling agent is a flammable liquid
• the silane coupling agent may be vaporized after the atmosphere in a sealed container, preferably the atmosphere in the container, is replaced with an inert gas.
• the exposure time of the treated surface to the silane coupling agent is, for example, 20 hours or less, preferably 60 minutes or less, more preferably 15 minutes or less, and even more preferably 5 minutes or less, and is, for example, 1 second or more, preferably 5 seconds or more, more preferably 10 seconds or more, and even more preferably 20 seconds or more.
• the temperature at which the surface to be treated is exposed to the silane coupling agent may be appropriately selected from the range of -50°C to 200°C depending on the thickness of the silane coupling agent layer to be formed.
• the object treated with the silane coupling agent is preferably heated to 70°C to 200°C, more preferably 75°C to 125°C. This heating causes the hydroxyl groups on the treated surface to react with the alkoxy groups of the silane coupling agent, completing the silane coupling agent treatment.
• the time required for heating is, for example, 10 seconds or more and 10 minutes or less. If the heating temperature after exposure is too high or the heating time after exposure is too short, there is a risk that sufficient adhesive strength will not be obtained. If the temperature of the treated surface during exposure to the silane coupling agent is 80°C or higher, heating after exposure may be omitted.
• the surface to be treated on which the silane coupling agent layer is to be formed may be held facing down and exposed to the silane coupling agent vapor.
• the surface to be applied faces up during or before and after application, and foreign matter adheres to the treated surface in the working environment. Therefore, by holding the surface to be treated on which the silane coupling agent layer is to be formed facing down, the adhesion of foreign matter can be prevented.
• the silane coupling agent layer in the step of forming the silane coupling agent layer, it is preferable to use a gas phase method or a spin coating method, and it is more preferable to use a gas phase method.
• the silane coupling agent layer may be formed on the surface of either the active layer or the hole transport layer, or on the surfaces of both of these layers, or on the surface of either the active layer or the electron transport layer, or on the surfaces of both of these layers, but it is preferable to form it on the surface of the active layer.
• the silane coupling agent layer is formed to have a thickness of 1 nm or more and 50 nm or less, more preferably that the silane coupling agent layer is formed to have a thickness of 3 nm or more and 40 nm or less, and even more preferably that the silane coupling agent layer is formed to have a thickness of 5 nm or more and 30 nm or less.
• the thickness of the silane coupling agent layer is less than 1 nm, there is a risk that the film surface of the silane coupling agent layer is not uniform and sufficient adhesive strength cannot be ensured, while if the thickness of the silane coupling agent layer exceeds 50 nm, there is a risk that the electrical characteristics of the device will deteriorate because the silane coupling agent layer is, for example, a non-conductive layer.
• FIG. 3 is a diagram showing a silane coupling agent layer manufacturing apparatus 30 used in a device manufacturing method according to one embodiment of the present invention.
• the configuration of the silane coupling agent layer manufacturing apparatus 30 will be described below.
• An object 37 to be treated on which a silane coupling agent layer is to be formed is installed in a treatment chamber 36, and a gas inlet 32 and a silane coupling agent vapor inlet are connected to the treatment chamber 36.
• a silane coupling agent is placed in a chemical tank (silane coupling agent tank) 33, and the outer hot water tank (bath) 34 is heated to 40°C or higher by a heater 35.
• a chemical tank silane coupling agent tank
• bath outer hot water tank
• a carrier gas is supplied from the gas inlet 32 to the chemical tank 33 via a flow meter 31, and the steam generated from the heated silane coupling agent is sent to the treatment chamber 36 together with clean dry air, forming a silane coupling agent layer on the object 37 to be treated (an exhaust port 38 is connected to the treatment chamber 36, and the chamber 36 is placed under negative pressure).
• an inert gas is used as the carrier gas.
• the silane coupling agent layer is formed by removing the workpiece 37 on which the silane coupling agent layer has been formed and heating it.
• the steps are preferably performed in the following order: forming a substrate, forming a transparent conductive layer, forming an electron transport layer, forming an active layer, forming a silane coupling agent layer, forming a hole transport layer, forming a conductive layer, and forming a protective layer. It is also preferable to perform the steps in the following order: forming a substrate, forming a transparent conductive layer, forming a hole transport layer, forming an active layer, forming a silane coupling agent layer, forming an electron transport layer, forming a conductive layer, and forming a protective layer.
• the device and device manufacturing method of the present invention can be suitably used for organic electroluminescence, organic thin-film transistors, organic thin-film solar cells, etc.
• the hole transport layer, silane coupling agent layer, and electron transport layer were formed using the following materials.
• Hole transport layer 3 HTL solar (PEDOT:PSS) manufactured by Ossila
• Silane coupling agent layer 1 KBM802 (3-mercaptopropylmethyldimethoxysilane) manufactured by Shin-Etsu Silicones
• Silane coupling agent layer 2 Shin-Etsu Silicone KBM803 (3-mercaptopropyltrimethoxysilane)
• Silane coupling agent layer 3 KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Silicones
• Silane coupling agent layer 4 KBM402 (3-glycidoxypropylmethyldimethoxysilane) manufactured by Shin-Etsu Silicones
• Electron transport layer 1 ZnO (sol-gel method)
• Electron transport layer 2 ZnO (manufactured by Avantama N-11)
• the active layer was formed using the following active layer solutions A1 and A2.
• a solution was prepared by mixing poly(3-hexylthiophene-2,5-diyl) (P3HT), a fullerene derivative (E100H manufactured by Frontier Carbon), and chlorobenzene in a ratio of 16 mg:16 mg:1 mL.
• Example 1 A PET film (100 mm ⁇ 100 mm, 100 ⁇ m thick) as a substrate on which a patterned transparent conductive layer (ITO, 150 nm thick) was formed was dried with a BEMCOT® soaked in isopropyl alcohol and clean dry air, and then subjected to UV/ O3 treatment. Next, the ZnO solution for the electron transport layer 2 was applied onto the PET film substrate on which the transparent conductive layer was formed using an applicator with a gap of 3 ⁇ m, and heated on a hot plate at 110° C. for 30 minutes (electron transport layer thickness: 50 nm).
• the active layer solution A1 was applied to the film substrate on which the electron transport layer 2 was formed so that the coating gap was 3 ⁇ m, and heated at 110° C. for 15 minutes (active layer thickness 200 nm).
• a silane coupling agent was applied to the obtained active layer (silane coupling agent layer thickness 10 nm, ratio to the thickness of the laminate composed of the electron transport layer, active layer, hole transport layer, and silane coupling agent layer 2%).
• the silane coupling agent was applied using the manufacturing apparatus shown in FIG. 3. 150 g of 3-glycidoxypropylmethyldimethoxysilane, which is the silane coupling agent layer 4, was placed in a chemical tank 33 with a capacity of 1 L, and the outer hot water bath 34 was heated to 43° C.
• the steam coming out was sent to the treatment chamber 36 together with clean dry air.
• the gas flow rate was 25 L/min, and the substrate temperature was 24° C.
• the temperature of the clean dry air was 23° C., and the humidity was 1.2% RH. Since the exhaust was connected to a negative pressure exhaust port, it was confirmed by a differential pressure gauge that the treatment chamber 36 was at a negative pressure of about 10 Pa.
• the laminate of the object to be treated 37 and the silane coupling agent layer was taken out and heated on a hot plate at 100°C for 2 minutes.
• a solution of PEDOT:PSS of the hole transport layer 3 was applied with a coating gap of 3 ⁇ m and heated at 100°C for 10 minutes (hole transport layer thickness 200 nm). Patterned silver (conductive layer) was vacuum-deposited on this laminate to a thickness of 90 nm.
• Example 2 The same procedures as in Example 1 were carried out except that the substrate was glass, that is, a glass substrate (100 mm x 100 mm, thickness 0.7 mm) on which a patterned transparent conductive layer (ITO: thickness 150 nm) was formed was ultrasonically cleaned using isopropyl alcohol, dried with clean dry air, and then subjected to UV/ O3 treatment.
• the substrate was glass, that is, a glass substrate (100 mm x 100 mm, thickness 0.7 mm) on which a patterned transparent conductive layer (ITO: thickness 150 nm) was formed was ultrasonically cleaned using isopropyl alcohol, dried with clean dry air, and then subjected to UV/ O3 treatment.
• ITO thickness 150 nm
• Example 3 The ZnO solution for the electron transport layer 2 was dropped onto the transparent conductive layer surface of a glass substrate with a transparent conductive layer (ITO: thickness 150 nm) and applied at 1500 rpm for 45 seconds (electron transport layer, thickness 50 nm). The substrate was heated on a hot plate at 140° C. for 10 minutes. On the glass substrate on which the electron transport layer 2 was formed, the active layer solution A1 was spin-coated at 1000 rpm for 45 seconds (active layer, thickness 200 nm). The substrate after the coating was heated on a hot plate at 110° C. for 15 minutes.
• ITO transparent conductive layer
• silane coupling agent layer 4 3-glycidoxypropylmethyldimethoxysilane of the silane coupling agent layer 4 was coated and heated in the same manner as in Example 1 (silane coupling agent layer thickness 5 nm, ratio to the thickness of the laminate composed of the electron transport layer, active layer, hole transport layer, and silane coupling agent layer 1%), and the PEDOT:PSS solution of the hole transport layer 3 was dropped thereon, spin-coated at 1000 rpm for 30 seconds, and heated at 100° C. for 10 minutes (hole transport layer thickness 200 nm). Patterned silver (conductive layer) was vacuum-deposited on this laminate to a thickness of 90 nm.
• Example 4 The same procedures as in Example 3 were performed except that electron transport layer 1 was used as the electron transport layer, that is, zinc acetate dianhydride, absolute ethanol, and ethanolamine were mixed in a ratio of 33 mg:1500 ⁇ L:9 ⁇ L, and the mixture was heated and stirred at 70° C. for 2 hours to obtain precursor solution 1, which was then dropped onto the transparent conductive layer and spin-coated at 900 rpm for 30 seconds (electron transport layer, thickness: 50 nm), and then heated on a hot plate at 110° C. for 30 minutes.
• electron transport layer 1 was used as the electron transport layer, that is, zinc acetate dianhydride, absolute ethanol, and ethanolamine were mixed in a ratio of 33 mg:1500 ⁇ L:9 ⁇ L, and the mixture was heated and stirred at 70° C. for 2 hours to obtain precursor solution 1, which was then dropped onto the transparent conductive layer and spin-coated at 900 rpm for 30 seconds (electron transport layer, thickness: 50 n
• Example 5 A substrate on which the active layer solution A1 was formed was prepared in the same manner as in Example 3. A solution of 3-glycidoxypropylmethyldimethoxysilane of the silane coupling agent layer 4 dissolved in isopropyl alcohol at a concentration of 0.1% was dropped onto this substrate, and spin-coated at 3000 rpm for 15 seconds (silane coupling agent layer thickness 10 nm, ratio to the thickness of the laminate composed of the electron transport layer, active layer, hole transport layer, and silane coupling agent layer 2%).
• the substrate was heated for 2 minutes on a hot plate at 100°C, and a PEDOT:PSS solution of the hole transport layer 3 was dropped thereon, spin-coated at 1000 rpm for 30 seconds, and heated at 100°C for 10 minutes (hole transport layer thickness 200 nm).
• a patterned silver (conductive layer) was vacuum-deposited on this laminate to a thickness of 90 nm.
• Example 6 The same procedure as in Example 1 was carried out except that Hole Transport Layer 1 was used as the hole transport layer.
• Example 7 The same procedure as in Example 1 was carried out except that Hole Transport Layer 2 was used as the hole transport layer.
• Example 8 The same procedure as in Example 1 was carried out except that 3-mercaptopropylmethyldimethoxysilane of the silane coupling agent layer 1 was used as the silane coupling agent.
• Example 9 The same procedure as in Example 1 was carried out except that 3-mercaptopropyltrimethoxysilane of the silane coupling agent layer 2 was used as the silane coupling agent.
• Example 10 The same procedure as in Example 1 was carried out except that 3-glycidoxypropyltrimethoxysilane of the silane coupling agent layer 3 was used as the silane coupling agent.
• Example 11 The same procedure as in Example 1 was carried out except that A2 was used as the active layer solution.
• ⁇ Evaluation 2 Evaluation of the number of cracks due to bending> This evaluation was carried out only when a PET film substrate was used. The substrate was bent 10 times in a glove box along a 2.5-inch core (outer diameter 87 mm) so that the light-receiving surface side of the substrate was in contact with the core, and then returned to a flat surface. The non-light-receiving surface of this sample was observed with a white light interference microscope (Hitachi High-Tech VS1800, magnification 10x) and evaluated for the presence or absence of cracks on the surface. Observation was carried out at 30 points per substrate, and the evaluation was as follows. The results are shown in Tables 1 and 2. Number of cracks: 0-2: ⁇ , 3-5: ⁇ , 6 or more: ⁇
• ⁇ Evaluation 3 Evaluation of change in power generation efficiency due to bending>
• the power generation performance of the obtained device was measured using an OTENTO-SUN III manufactured by Bunkoukeiki Co., Ltd. Calibration was performed using an S-500BK Si-based photodiode detector before the measurement.
• the power generation area of the obtained solar cell was masked, and light was irradiated onto an area of 2 mm x 2 mm, and measurements were performed. Thereafter, bending was performed in the same manner as in Evaluation 2, and power generation performance measurements were performed again. The results are shown in Tables 1 and 2.
• Silane coupling agent layer manufacturing apparatus 31: Flow meter 32: Gas inlet 33: Chemical tank (silane coupling agent tank) 34: Hot water bath (bath water bath) 35: heater 36: processing chamber 37: object to be treated 38: exhaust port

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