Photoelectric conversion element and photoelectric conversion device

Abstract

To provide a photoelectric conversion element with improved durability when driven while subjected to a heat cycle. [Solution] A photoelectric conversion element comprising a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite structure crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, wherein the electron transport layer contains a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic insulating resin that is not chemically bonded to the cured product.

Description

[Technical Field]

[0001] This disclosure relates to a photoelectric conversion element and a photoelectric conversion device. [Background technology]

[0002] In order to address the depletion of fossil fuels and the environmental problems caused by their use, research is actively being conducted on renewable and clean alternative energy sources such as solar, wind, and hydroelectric power.

[0003] Among these, there is growing interest in solar cells, which directly convert sunlight into electrical energy. Here, a solar cell refers to a battery that absorbs light energy from sunlight and generates current-voltage using the photovoltaic effect, which generates electrons and holes.

[0004] Currently, np diode type silicon (Si) single-crystal based solar cells with light energy conversion efficiencies exceeding 20% ​​are widely known and actually used in photovoltaic power generation. However, these have the problem of high cost per unit of power due to the high-temperature processing required in their manufacture and the high price of the material itself. Furthermore, there are supply issues from the perspective of silicon resources.

[0005] On the other hand, solar cells using organic materials (hereinafter referred to as "organic solar cells") do not require high-temperature processing and can be produced using a so-called roll-to-roll method on sheet substrates, which is expected to reduce costs.

[0006] However, further improvements in power generation efficiency and durability are desired for the practical application of organic solar cells. In particular, perovskite solar cells, which have a perovskite structure crystal as the photoelectric conversion layer, are being developed for practical use because of their excellent photoelectric conversion characteristics. Fullerene compounds are often used as the electron transport layer material for perovskite solar cells. However, since fullerene compounds are extremely expensive, the development of cheaper alternative materials is underway.

[0007] For example, Patent Document 1 describes a technology that achieves excellent conversion efficiency by polymerizing perylenediimide compounds, naphthalenediimide compounds, etc., with a crosslinking agent and a resin. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-2293 [Non-patent literature]

[0009] [Non-Patent Document 1] J.Mater.Chem.A, 2017, 5, 12811. [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] According to the inventors' studies, it was found that the photoelectric conversion elements described in Patent Document 1 and Non-Patent Document 1 have room for improvement in conversion efficiency and short-circuit fault tolerance when the elements are driven while subjected to a heat cycle.

[0011] Therefore, the object of this disclosure is to provide a photoelectric conversion element with improved durability when the element is driven while subjected to a heat cycle. [Means for solving the problem]

[0012] The above objectives are achieved by the present disclosure as follows: The present disclosure is a photoelectric element having a first electrode, a second electrode, a photoelectric conversion layer comprising a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, wherein the electron transport layer comprises a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic insulating resin not chemically bonded to the cured product.

[0013] Furthermore, the present disclosure relates to a photoelectric conversion element comprising a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, wherein the electron transport layer contains a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic resin that is not chemically bonded to the cured product, wherein the mass ratio of conductive portions represented by the following formulas (EB6), (EB7), (EB8), (EB9), (EB10), (EB11), (EB12), (EB13), (EB14), (EB15), (EB16), (EB17), (EB18) contained in the resin is 0.03 or less. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

Chemical Formula

Chemical Formula

[0014] Further, the present disclosure relates to a photoelectric conversion element having a first electrode, a second electrode, a photoelectric conversion layer disposed between the first electrode and the second electrode and containing a crystal with a perovskite structure, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, wherein the electron transport layer contains a cured product of a composition containing an organic electron-transporting compound having a polymerizable functional group, and a thermoplastic resin that is not chemically bonded to the cured product, and the volume resistivity of the resin is 10 12 Ω·cm or more.

[0015] Further, the present disclosure is a photoelectric conversion apparatus comprising any one of the photoelectric conversion elements described above. [Advantageous Effects of the Invention]

[0016] According to the present disclosure, it is possible to provide a photoelectric conversion element with improved conversion efficiency and short-circuit failure resistance when the element is driven while being subjected to heat cycles. [Brief Description of the Drawings]

[0017] [Figure 1]This is a schematic cross-sectional view in the thickness direction of one embodiment of the photoelectric conversion element of the present disclosure. [Figure 2] This is a schematic perspective view showing one embodiment of a mobile body equipped with a photoelectric conversion element of the present disclosure. [Figure 3] This is a schematic perspective view showing one embodiment of a building material equipped with a photoelectric conversion element of the present disclosure. [Modes for carrying out the invention]

[0018] The photoelectric conversion element of the present disclosure comprises a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, wherein the electron transport layer contains a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic insulating resin that is not chemically bonded to the cured product.

[0019] Furthermore, the photoelectric conversion element of the present disclosure is a photoelectric conversion element having a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite structure crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, wherein the electron transport layer contains a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic resin that is not chemically bonded to the cured product, wherein the mass ratio of conductive parts represented by the formulas (EB6), (EB7), (EB8), (EB9), (EB10), (EB11), (EB12), (EB13), (EB14), (EB15), (EB16), (EB17), (EB18) contained in the resin is 0.03 or less.

[0020] Furthermore, the photoelectric conversion element of the present disclosure is a photoelectric conversion element having a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite structure crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, wherein the electron transport layer is a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic resin not chemically bonded to the cured product, wherein the volume resistivity of the resin is 10 12 It is characterized by containing a resin that is Ω·cm or larger.

[0021] As a result of their investigation, the inventors have found that a photoelectric conversion element exhibiting excellent durability can be obtained when the element is driven while applying a heat cycle with the above configuration. The reason why a photoelectric conversion element with excellent durability can be obtained in this disclosure is not entirely clear, but it is thought to be as follows.

[0022] Perovskite solar cells generally have a layered structure consisting of a perovskite layer composed of metal halide crystals and multiple materials with different coefficients of thermal expansion. Therefore, when the device is driven while applying a heat cycle, interfacial delamination occurs, which causes a decrease in conversion efficiency. The "cured product of a composition containing an organic electron-transporting compound having polymerizable functional groups" described in this disclosure and Patent Document 1 reduces the intermolecular distance between electron-transporting compounds through polymerization, thereby maintaining high electron mobility and suppressing the durable degradation of conversion efficiency. However, there was a problem with the decrease in conversion efficiency due to interfacial delamination when heat cycling was applied. Therefore, the inventors have found that by further including the "thermoplastic insulating resin that is not chemically bonded to the cured product" described in this disclosure, the insulating resin enhances the adhesion between the electron-transporting compound and other layers, thereby solving the above problem.

[0023] Furthermore, when the element is driven while a heat cycle is applied, cracks occur at grain boundaries due to changes in the crystal structure of the perovskite layer, halogen ions (especially iodide ions) migrate from the perovskite layer, and conductive paths are formed due to electrode corrosion. When these factors combine, the perovskite layer and the electrode are electrically short-circuited, causing a so-called short-circuit failure in which the conversion efficiency drops to near 0%. The present inventors have found that the feature of this disclosure, which includes a "cured product of a composition containing an organic electron transport compound having polymerizable functional groups" and a "thermoplastic insulating resin not chemically bonded to the cured product," ensures electron transfer by the cured product while simultaneously suppressing short-circuit failures by the insulating resin.

[0024] Furthermore, the passivation effect of the insulating resin against defects in the perovskite crystal also contributes to suppressing the degradation of conversion efficiency and the occurrence of short-circuit failures during thermal cycle endurance.

[0025] Based on the above mechanism, the photoelectric conversion element disclosed herein is thought to improve conversion efficiency and short-circuit failure tolerance when the element is driven while subjected to a heat cycle.

[0026] In this disclosure, an electron-transporting compound may be described as a compound that can efficiently transport electrons, or as an N-type semiconductor compound, or as a compound whose Fermi level approaches the conduction band or lowest unoccupied orbital (LUMO).

[0027] Furthermore, the insulating resin in this disclosure may be described as a resin that does not transport electrons, a resin that does not contain electron-transporting parts, or a resin that contains very few electron-transporting parts, or a resin with high volume resistivity.

[0028] Furthermore, in this disclosure, the electron transport layer may be described as a layer comprising a cured product of a composition containing an electron-transporting compound that efficiently transports electrons and a resin that does not transport electrons; or a layer comprising a cured product of a composition containing an N-type semiconductor compound and a resin that does not contain electron-transporting sites, or contains very few electron-transporting sites; or a layer comprising a cured product of a composition containing a compound whose Fermi level is close to the conduction band or the lowest unoccupied orbital (LUMO) and a resin with high volume resistivity.

[0029] The present disclosure will be described in detail below with reference to preferred embodiments. The present disclosure is not limited to the embodiments described below, and the scope of the present disclosure also includes modifications, improvements, etc., to the extent appropriate to the embodiments described below, based on the ordinary knowledge of those skilled in the art, without departing from the spirit of the present disclosure.

[0030] In this specification, the term "layer" refers not only to layers with clear boundaries or flat, thin films, but also to layers with gradually changing concentrations of constituent elements, and layers that can combine with other layers to form complex, interwoven structures.

[0031] Furthermore, elemental analysis of the layers can be performed, for example, by conducting TOF-SIMS / FE-TEM / EDS line analysis measurements of the cross-section of the photoelectric conversion element to confirm the elemental distribution of specific elements. Analysis of each layer may also be performed by peeling off the completed photoelectric conversion element, exposing the layer to be analyzed, and then measuring it.

[0032] Figure 1 is a schematic cross-sectional view showing the configuration of one embodiment of the photoelectric conversion element of the present disclosure. The photoelectric conversion element 1 has a first electrode 7, a hole transport layer 6, a photoelectric conversion layer 5, an electron transport layer 4, and a second electrode 3 on a substrate 2. One of the first electrode 7 and the second electrode 3 is a positive electrode and the other is a negative electrode, and current can be extracted by connecting the first electrode 7 and the second electrode 3 with an external circuit. The photoelectric conversion layer 5 is excited by light incident through the substrate 2, the first electrode 7, the hole transport layer 6, or the second electrode 3 and electron transport layer 4, generating electrons or holes. That is, the photoelectric conversion layer 5 generates an electric current between the first electrode 7 and the second electrode 3.

[0033] Alternatively, a tandem structure forming a series circuit may be created by repeatedly stacking the layers from the second electrode 3 to the first electrode 7 to provide multiple photoelectric conversion layers 5. In this embodiment, either the first electrode 7 or the second electrode 3 may be made to be in contact with the substrate 2. The following describes each component constituting the photoelectric conversion element of this disclosure.

[0034] [Photoelectric conversion element] The photoelectric conversion element of the present disclosure comprises a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer.

[0035] The photoelectric conversion element of this disclosure comprises an electron transport layer containing a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic insulating resin that is not chemically bonded to the cured product. The organic electron transport compound can produce a cured product by having polymerizable functional groups. The thermoplastic insulating resin, by not having polymerizable functional groups, can form an electron transport layer integrally with the cured product of the composition containing the organic electron transport compound without chemically bonding to the cured product. If the electron transport layer of this disclosure contains additives as a composition, the composition may be considered to become the cured product. The chemical substances of this disclosure can be identified by nuclear magnetic resonance (NMR) spectrometer, gas chromatograph-mass spectrometer (GC-MS), etc.

[0036] Furthermore, to improve photoelectric conversion efficiency, a tandem type with stacked photoelectric conversion elements may be used. The type of photoelectric conversion element to be stacked is not limited to perovskite solar cells that use perovskite crystals as the photoelectric conversion layer, but also includes silicon solar cells, CIGS solar cells, etc.

[0037] Methods for forming the photoelectric conversion layer and charge transport layer of the photoelectric conversion element disclosed herein include coating methods and vapor deposition methods. Examples of coating methods include immersion coating, spin coating, spray coating, inkjet coating, meniscus coating, screen coating, roll coating, die coating, blade coating, curtain coating, and wire bar coating. The coating method involves preparing the coating solution for each layer, which will be described later, coating the layers in the desired order, and drying them. These film formation methods can be selected according to the requirements of each layer. The following explains each layer.

[0038] 〔substrate〕 The photoelectric conversion element 1 of this disclosure may include a substrate 2, for example, a transparent glass substrate such as soda-lime glass or alkali-free glass, a ceramic substrate, or a transparent plastic substrate. When light is taken in from the second electrode 3 side, the substrate 2 can be made of an opaque material, and when light is taken in from the first electrode 3 side, the substrate 2 is made of a transparent material.

[0039] 〔electrode〕 The photoelectric conversion element disclosed herein has a first electrode and a second electrode. The materials of the first electrode 7 and the second electrode 3 are not particularly limited, and conventionally known materials can be used. Examples include metals such as gold, silver, titanium, and copper, sodium, sodium-potassium alloys, lithium, magnesium, carbon, carbon nanotubes, aluminum, magnesium-silver mixtures, magnesium-indium mixtures, aluminum-lithium alloys, Al / Al2O3 mixtures, Al / LiF mixtures, and the like. Examples of transparent electrode materials include conductive transparent materials such as CuI, ITO (indium-doped tin oxide), SnO2, AZO (aluminum-doped zinc oxide), IZO (indium-doped zinc oxide), GZO (gallium-doped zinc oxide), FTO (fluorine-doped tin oxide), and ATO (antimond-doped tin oxide), as well as conductive transparent polymers. These materials may be used individually or in combination of two or more. The first electrode 7 and the second electrode 3 may have at least one electrode on the light incidence side be a transparent electrode, and the other electrode may be a transparent electrode or a reflective layer made of a light-reflective material, or it may be a transparent electrode with a reflective layer on the side opposite to the light incidence side. When the second electrode 3 is on the light incidence side, the second electrode 3 may be a transparent electrode and the substrate 2 may be a reflective layer. The electrodes may be patterned electrodes. Furthermore, the photoelectric conversion element of this disclosure may have a passivation layer formed on the first electrode 7. The passivation material is not particularly limited, but Al2O3 is preferred from the viewpoint of electrode surface treatment ability.

[0040] [Photoelectric conversion layer] The photoelectric conversion layer 5 has a perovskite crystal structure. The perovskite crystal used in this disclosure is preferably represented by the following general formula [1]. A o B p X q [1] In the above general formula [1], A is a cation, B is a cation, and X is an anion.

[0041] o, p, and q satisfy 0 ≤ o ≤ 10, 0 ≤ p ≤ 10, and 0 ≤ q ≤ 20, respectively, and A, B, and X may be composed of a single material or two or more materials may be used in combination. Additives may be added within the range in which the above general formula holds.

[0042] The above general formula generally forms a three-dimensional perovskite crystal. However, if the constituent cation A is too large to fit within the three-dimensional perovskite crystal, it can form a two-dimensional perovskite crystal, a 2.5-dimensional perovskite crystal possessing properties of both two and three dimensions, a two-layer crystal with three-dimensional and two-dimensional perovskite structures, or a mixed three-dimensional / two-dimensional perovskite crystal, all of which function as photoelectric conversion layers.

[0043] A two-layer crystal of 3D and 2D perovskite refers to a crystal in which 3D and 2D perovskite crystals are stacked as independent, separate layers, while a mixed 3D-2D perovskite refers to a crystal in which regions or domains of both 2D or 2.5D layered and 3D perovskite crystals are mixed.

[0044] Crystals of two-dimensional perovskites or 2.5-dimensional perovskite structures may form RP (Ruddlesden-Popper), DJ (Dion-Jacobson), or ACI (Alternating cations in the interlayer) type perovskite structures.

[0045] In the above general formula [1], A is not particularly limited and may be an organic molecule, an inorganic atom, or any other compound. The organic cation A may or may not have substituents, and specific examples include the following formulas (C1) to (C96). [ka] [ka] [ka] [ka]

[0046] Furthermore, while the inorganic atoms are not particularly limited, lithium, cesium, sodium, potassium, and rubidium are preferred. These organic molecules or inorganic atoms may be used individually, or two or more may be used in combination.

[0047] In the general formula [1] above, B is a cation atom, and examples include lead, tin, bismuth, zinc, titanium, antimony, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium. Among these, lead, tin, bismuth, and silver are preferred from the viewpoint of the stability of the perovskite crystal structure. These atoms may be used individually or in combination of two or more.

[0048] In the above general formula [1], X is a halogen or chalcogen atom, such as chlorine, bromine, iodine, oxygen, sulfur, selenium, tellurium, or polonium. These halogen or chalcogen atoms may be used individually or in combination of two or more. In particular, halogen atoms are preferred because the inclusion of halogens in the structure makes the perovskite crystals more soluble in organic solvents, enabling their application to inexpensive printing methods and the like. Furthermore, iodine is more preferred because it narrows the energy band gap of the perovskite crystals.

[0049] Specifically, 3D perovskites, 2D perovskites, and mixed 3D-2D perovskites are MAPbI3, FAPbCl3, FAPbI3, and MAPbI x Br 3-x MAPbI x Cl 3-x , Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb(I 0.83 Br 0.17 )3, {Cs x1 (FA x2 MA 1-x2 ) 1-x1} x3 Pb(I x4 Br 1-x4 ) x5 , Cs 0.05 FA 0.88 MA 0.07 PbI 2.56 Br 0.44 (FAPbI3) 0.95(MAPbBr3) 0.05 、(FAPbI3) 0.85 (MAPbBr3) 0.15 、CsPbI3、CsPbBr3、Cs x (MA) 1-x PbI3、Cs x (FA) 1-x PbI3、MA x (FA) 1-x PbI3、MA 0.17 FA 0.83 Pb(I 0.83 Br 0.17 )3、Cs 0.15 FA 0.85 PbI 2.55 Br 0.45 、Cs 0.05 FA 0.88 MA 0.07 PbI 2.56 Br 0.44 、Cs 0.15 FA 0.85 PbI 2.55 Br 0.45 、(AND)2(MA)2Pb3I 10 、(PTA)2(MA)4Pb5I 16 、(AND)2(MA)4Pb5I 16 、(ThMA)2(MA)2Pb3I 10 、(3BBA)2(MA)2Pb3I 10 、(ThMA)2(FA)4Pb5I 16 、(4FPEA)2(FA 0.3 MA 0.7 )4Pb5I 16 、(PDMA)FA2Pb3I 10 、(3AMPY)(MA)3Pb4I 13 、(PDMA)MA5Pb6I 19 、(PDMA)MA3Pb4I 13 ,(THAT 0.9 AND 0.1 )2MA4Pb5I 16 ,(THAT 0.9 AND 0.1 )2MA3Pb4I 13 、BA)2、MA2Pb3I 10 、(BA)2MA3Pb4I 13 、(BA)2MA4Pb5I 16(BA)2MA3Pb4I 13 , CsSnBr3, CsSnI3, FA 0.75 MA 0.25 Sn 0.95 Ge 0.05 I3, FAMASnGeI3, FASnBr3, FASnI3, MA2Sn3I8, MASnBr3, MASnGeI3, and MASnI3 are preferred. In the above specific examples, "MA" represents methylammonium, "FA" represents formamidinium, "PEA" represents phenethylammonium, "PTA" represents phenyltriethylammonium, "ThMA" represents 2-thiophenemethylammonium, "3BBA" represents 3-bromobenzylammonium, "3AMPY" represents 3-(aminomethyl)pyridine, "PDMA" represents 1,4-phenylenedimethaneammonium, "TTDMA" represents thieno[3,2-b]thiophene-2,5-diyldimethaneammonium, "4FPEA" represents 4-fluorophenethylammonium, and "BA" represents butylammonium.

[0050] Depending on the purpose, sites A, B, and X in the above general formula may be prepared in small or large quantities, and the combinations of x1 to x5 may be changed according to the purpose. Examples of combinations of x1 to x5 are shown in Table 1.

[0051] Particularly preferred ranges are 0.03 ≤ x1 ≤ 0.10, 0.80 ≤ x2 ≤ 0.96, 0.95 ≤ x3 ≤ 1.05, 0.80 ≤ x4 ≤ 0.96, and 2.95 ≤ x5 ≤ 3.05. MACl may also be included as the material for forming the perovskite crystal. [Table 1]

[0052] The perovskite crystal described above preferably has a cubic crystal structure in which a metal atom B is located at the body center, organic molecules A are located at each vertex, and halogen atoms X are located at the face centers. Although the details are not clear, it is presumed that having such a structure allows the orientation of octahedra within the crystal lattice to change easily, thereby increasing the electron mobility in the perovskite crystal and improving the photoelectric conversion efficiency of the photoelectric conversion element.

[0053] The organic-inorganic perovskite compounds used in this disclosure are preferably crystalline semiconductors. A crystalline semiconductor is a semiconductor in which the X-ray scattering intensity distribution can be measured and a scattering peak can be detected. When the organic-inorganic perovskite compound is a crystalline semiconductor, the electron mobility in the organic-inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the photoelectric conversion element is improved.

[0054] The thickness of the photoelectric conversion layer according to this disclosure is preferably 5 nm or more and 2000 nm or less. If the thickness is 5 nm or more, light can be absorbed sufficiently, and if it is 2000 nm or less, the generated charge can be transported to each electrode. A more preferable lower limit is 50 nm or more, a more preferable upper limit is 1200 nm, an even more preferable lower limit is 100 nm, and an even more preferable upper limit is 1000 nm.

[0055] Furthermore, the photoelectric conversion element of this disclosure may have a passivation layer formed in or adjacent to the photoelectric conversion layer 5. The passivation material is not particularly limited and includes organic salts, inorganic salts, ionic liquids, and resins. The conductivity of the passivation material is not particularly limited and may be either insulating or conductive.

[0056] As the organic salt, a compound is preferred that consists of at least one cation selected from the group consisting of compounds represented by the above formulas (C1) to (C96) and at least one anion selected from the group consisting of compounds represented by the following formulas (A1) to (A29). [ka]

[0057] The material of the inorganic salt is not particularly limited, but a compound composed of at least one cation selected from the group consisting of metal atoms and at least one anion selected from the group consisting of compounds represented by the above formulas (A1) to (A29) is preferred.

[0058] Examples of metal atoms include copper, silver, zinc, gallium, bismuth, sodium, potassium, lithium, vanadium, manganese, iron, cobalt, nickel, germanium, arsenic, selenium, lead, tin, iridium, platinum, osmium, cesium, barium, rubidium, molybdenum, and ruthenium.

[0059] The material of the ionic liquid is not particularly limited, but a compound composed of at least one cation selected from the group consisting of compounds represented by the following formulas (ILC1) to (ILC10) and at least one anion selected from the group consisting of compounds represented by the following formulas (ILA1) to (ILA17) is preferred. [ka]

[0060] R 01 ~R 04 Each of these independently represents a hydrogen atom, an optional alkyl group, or an optional aryl group.

[0061] The resin material is not particularly limited and may have substituents, including polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polystyrene (PS), polyimide (PI), fluororesin (PVDF), polyurethane (PU), silicone resin (PDMS), epoxy resin, nanocomposite resin, PEDOT:PSS, poly(9,9-dioctylfluorene-artenalyl) (PFN), P3HT, poly(fluorene-co- Phenylene (PFP), polyvinylcarbazole (PVK), polythiophene (PTh), polyaniline (PANI), polybithiophene (PBTh), polydioxythiophene (PDT), polyoxyethylene (PEO), polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyfumaric acid (PFA), polysuccinic acid (PSA), polyadipic acid (PAdA), polycaprolactam (PCL), polyisophthalic acid (PIPA), polyterephthalic acid (PT) A) Examples include polynaphthalenedicarboxylic acid (PNA), polyamide-imide (PAI), polysilsesquioxane (POSS), polyphenol resin (PF), polycarbonate (PC), poly(styrene-butadiene) (PSB), polysilyl ether (PSE), poly(ether-imide) (PEI), polyvinylpyrrolidone (PVP), polyacrylic acid ester (PAE), polydimethylaminoethyl methacrylate (PDMAEMA), polytrifluoroethylene (PTFE), polyoxymethylene (POM), polyesterimide (PEI), polyacrylonitrile (PAN), polyvinyl acetal (PVAH), polyolefin ether (PIE), polyacetal (PA), polysulfone (PSU), polyurea urethane (PUU), and polyolefin (PO), with polyvinyl acetal, polyolefin, polymethyl methacrylate, polyurethane, polyvinyl alcohol, and polyvinyl butyral being particularly preferred.

[0062] [Hole transport layer] In the photoelectric conversion element of this disclosure, a hole transport layer 6 may be arranged between the first electrode 7 and the photoelectric conversion layer 5, as shown in Figure 1. The thickness of the hole transport layer is preferably 0.1 nm or more and 1000 nm or less, more preferably 0.1 nm or more and 500 nm or less, and particularly preferably 0.1 nm or more and 200 nm or less.

[0063] The hole transport layer can be formed by preparing a coating solution for the hole transport layer containing the above-mentioned materials and solvents, forming this coating film on an ITO electrode, and drying it. Examples of solvents that can be used in the coating solution include amide solvents, aproton solvents, alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

[0064] Among these solvents, amide solvents, aproton solvents, alcohol solvents, or aromatic hydrocarbon solvents are preferred.

[0065] Furthermore, in this disclosure, from the viewpoint of the compatibility of the hole transport layer 6 film, a second charge transport layer may be provided between the hole transport layer 6 and the first electrode 3.

[0066] The material of the hole transport layer 6 or the second charge transport layer is not particularly limited, and examples include spirofluorene compounds, triphenylamine compounds, chrysene compounds, pyrene compounds, phthalocyanine compounds, carbazole compounds, fluorene compounds, phenylcyclohexane compounds, benzidine compounds, phenoxazine compounds, phenylenediamine compounds, thiocyanate compounds, phenothiazine compounds, triazaatorucene compounds, cyclooctatetraene compounds, squalate compounds, etc.

[0067] Specifically, Spiro-OMeTAD, PTAA, TAPyr, TPD, PEDOT:PSS, Meo-TPD, Poly-TPD, EH44, BTT-DPP, NiOx, CuSCN, V2O5, MnO3, CoOx, WO3, Fe2O3, Cu2O, Ag2S, CuI, phenothiazine compounds, carbazole compounds, triphenylamine compounds, triazaalkene compounds, cyclooctatetraene compounds, and squalate compounds are preferred. Among these, Spiro-OMeTAD, PTAA, TAPyr, TPD, PEDOT:PSS, Meo-TPD, Poly-TPD, EH44, BTT-DPP, phenothiazine compounds, carbazole compounds, triphenylamine compounds, triazaalkene compounds, cyclooctatetraene compounds, and squalate compounds are particularly preferred from the viewpoint of compatibility at the membrane interface because they possess aromatic rings.

[0068] A passivation layer may also be provided in or on the hole transport layer 6. The passivation material is not particularly limited and can be an organic salt, an inorganic salt, an ionic liquid, or a resin. The conductivity of the passivation material is not particularly limited and can be either insulating or conductive. As the organic salt, a compound composed of at least one cation selected from the group consisting of compounds represented by formulas (C1) to (C96) and at least one anion selected from the group consisting of compounds represented by formulas (A1) to (A29) is preferred.

[0069] As inorganic salts, compounds composed of at least one cation selected from the group consisting of metal atoms and at least one anion selected from the group consisting of compounds represented by formulas (A1) to (A29) are preferred.

[0070] Examples of metal atoms include copper, silver, zinc, gallium, bismuth, sodium, potassium, lithium, vanadium, manganese, iron, cobalt, nickel, germanium, arsenic, selenium, lead, tin, iridium, platinum, osmium, cesium, barium, rubidium, molybdenum, and ruthenium.

[0071] The material of the ionic liquid is not particularly limited, but a compound composed of at least one cation selected from the group consisting of compounds represented by formulas (ILC1) to (ILC10) and at least one anion selected from the group consisting of compounds represented by formulas (ILA1) to (ILA17) is preferred. 01 ~R 04 Each of these independently represents a hydrogen atom, an optional alkyl group, or an optional aryl group.

[0072] The resin material is not particularly limited and may have substituents, including polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polystyrene (PS), polyimide (PI), fluororesin (PVDF), polyurethane (PU), silicone resin (PDMS), epoxy resin, nanocomposite resin, PEDOT:PSS, poly(9,9-dioctylfluorene-artenalyl) (PFN), P3HT, poly(fluorene-co- Phenylene (PFP), polyvinylcarbazole (PVK), polythiophene (PTh), polyaniline (PANI), polybithiophene (PBTh), polydioxythiophene (PDT), polyoxyethylene (PEO), polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyfumaric acid (PFA), polysuccinic acid (PSA), polyadipic acid (PAdA), polycaprolactam (PCL), polyisophthalic acid (PIPA), polyterephthalic acid (PT) A) Examples include polynaphthalenedicarboxylic acid (PNA), polyamide-imide (PAI), polysilsesquioxane (POSS), polyphenol resin (PF), polycarbonate (PC), poly(styrene-butadiene) (PSB), polysilyl ether (PSE), poly(ether-imide) (PEI), polyvinylpyrrolidone (PVP), polyacrylic acid ester (PAE), polydimethylaminoethyl methacrylate (PDMAEMA), polytrifluoroethylene (PTFE), polyoxymethylene (POM), polyesterimide (PEI), polyacrylonitrile (PAN), polyvinyl acetal (PVAH), polyolefin ether (PIE), polyacetal (PA), polysulfone (PSU), polyurea urethane (PUU), and polyolefin (PO), with polyvinyl acetal, polyolefin, polymethyl methacrylate, polyurethane, polyvinyl alcohol, and polyvinyl butyral being particularly preferred.

[0073] [Electron transport layer] In this disclosure, the electron transport layer 4 must contain a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic insulating resin that is not chemically bonded to the cured product. Alternatively, the electron transport layer 4 must contain a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic resin that is not chemically bonded to the cured product, wherein the mass ratio of conductive portions represented by the formulas (EB6), (EB7), (EB8), (EB9), (EB10), (EB11), (EB12), (EB13), (EB14), (EB15), (EB16), (EB17), (EB18) contained in the resin to the resin is 0.03 or less. Alternatively, the electron transport layer 4 must contain a cured product of a composition containing an organic electron transport compound having polymerizable functional groups, and a thermoplastic resin that is not chemically bonded to the cured product, wherein the volume resistivity of the resin is 10 12 It is necessary to include a resin with a density of Ω·cm or greater.

[0074] Furthermore, in this disclosure, the electron transport layer 4 must be positioned between the second electrode 3 and the photoelectric conversion layer 5.

[0075] The preferred thickness of the electron transport layer 4 is 1 nm at the lower limit and 2000 nm at the upper limit. If the thickness of the electron transport layer 4 is 1 nm or more, holes can be sufficiently blocked, and if it is 2000 nm or less, it will not be a resistance during electron transport, and the photoelectric conversion efficiency will be high. A more preferred lower limit for the thickness is 1 nm, a more preferred upper limit is 1000 nm, an even more preferred lower limit is 1 nm, and an even more preferred upper limit is 500 nm.

[0076] Furthermore, in the present disclosure, from the viewpoint of film compatibility of the electron transport layer 4, a second electron transport layer may be further provided between the electron transport layer 4 and the second electrode 3. The material of the second electron transport layer is not particularly limited, and examples thereof include N-type conductive polymers, N-type low-molecular-weight organic semiconductors, N-type metal oxides, N-type metal sulfides, alkali metal halides, alkali metals, surfactants, and the like. Specific examples include cyano group-containing polyphenylenevinylene, boron-containing polymers, bathocuproine, bathophenanthroline, hydroxyquinolinato aluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, fullerene derivatives, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanine, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, and the like. In particular, tin oxide may be obtained by reacting tin(2) chloride, tin(4) chloride, tin(2) chloride dihydrate, or tin(4) chloride pentahydrate.

[0077] <Organic Electron Transport Compound> Examples of the organic electron transport compound include perylene diimide derivatives, fullerene derivatives, naphthalene diimide derivatives, anthraquinone derivatives, fluorenone derivatives, phenanthrenequinone derivatives, benzimidazoperylene derivatives, benzimidazonaphthalene derivatives, phthalocyanine derivatives, diphenoquinone derivatives, naphthoquinone derivatives, azaacene derivatives, indacenodithiophene derivatives, benzothiadiazole derivatives, triazine derivatives, heteroarene derivatives, quinone derivatives, acridine derivatives, carbazole derivatives, phenanthroline derivatives, dicyanomethylene derivatives, azomethine derivatives, thioxanthone derivatives, pyrimidine derivatives, pyrazine derivatives, pyridine derivatives, imidazole derivatives, indole derivatives, thiophene derivatives, selenophene derivatives, phenazine derivatives, anthraquinonezone derivatives, oxadiazole derivatives, pyrrole derivatives, pyrrolidine derivatives, fluorene derivatives, and the like. Among these, the non-fullerene derivative is preferably a compound selected from phthalocyanine derivatives, triazine derivatives, phenanthroline derivatives, pyrene derivatives, perylenediimide derivatives, naphthalenediimide derivatives, azaacene derivatives and indacenodithiophene derivatives, and more preferably a compound selected from perylenediimide derivatives, naphthalenediimide derivatives, azaacene derivatives and indacenodithiophene derivatives.

[0078] Still more preferably, in the photoelectric conversion element of the present disclosure, the organic electron-transporting compound is at least one compound selected from the compound represented by the following formula (E1), the compound represented by the following formula (E2), the compound represented by the following formula (E3), and the compound represented by the following formula (E4).

Chemical Formula

[0079] The photoelectric conversion element disclosed herein has R in formulas (E1) to (E4) above. 11 ~R 20 , R 21 ~R 26 , R 31 ~R 34 , and R 41 ~R 48 It is more preferable that each of these groups is independently represented by the following formula (2). ―(R a ) m ―(R b ) n ―R c Formula (2) (In equation (2), m and n are independently either 0 or 1.)

[0080] In formula (2), R a R in formula (2) represents an alkylene group having 1 to 10 substituted or unsubstituted carbon atoms, or an arylene group having 6 to 14 substituted or unsubstituted carbon atoms. c or R in equation (2) d They may be connected to each other to form a ring.

[0081] In formula (2), R b represents an oxygen atom, a sulfur atom, or a group represented by the following formula (3). [ka] (In formula (3), R dR represents a hydrogen atom, or an alkyl group having 1 to 4 substituted or unsubstituted carbon atoms. Alternatively, in this case, R in formula (2) a or R in equation (2) c They may be connected together to form a ring.

[0082] In formula (2), R c R represents a hydrogen atom, an alkyl group having 1 to 10 substituted or unsubstituted carbon atoms, an aryl group having 6 to 14 substituted or unsubstituted carbon atoms, or an arylalkyl group having 7 to 18 substituted or unsubstituted carbon atoms. Alternatively, in this case, R in formula (2) a Or R in equation (3) d They may be connected to each other to form a ring.

[0083] The substituents that the alkylene group and the alkyl group may have are a hydroxyl group, a carboxyl group, an amino group, a thiol group, an alkoxy group having 1 to 3 carbon atoms, and an alkoxycarbonyl group having 2 to 4 carbon atoms.

[0084] The substituents that the arylene group, the aryl group, and the arylalkyl group may have are alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, hydroxyalkyl groups having 1 to 3 carbon atoms, carboxyl groups, amino groups, thiol groups, alkoxy groups having 1 to 3 carbon atoms, alkoxycarbonyl groups having 2 to 4 carbon atoms, halogen atoms, cyano groups, and nitro groups.

[0085] However, R 11 ~R 20 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 21 ~R 26 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 31 ~R 34One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 41 ~R 48 One or more of these groups contain a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group.

[0086] Specific examples of organic electron-transporting compounds are given below, but this disclosure is not limited to these examples. [ka] [ka] [ka]

[0087] Furthermore, from the viewpoint of passivation effect, it is preferable that the organic electron-transporting compound contains heteroatoms. It is more preferable that it contains heteroatoms with a number of atoms between 6 and 20, and particularly preferable that it contains heteroatoms with a number of atoms between 8 and 16.

[0088] The content of the electron-transporting compound is preferably 40% to 90% by mass, and more preferably 50% to 80% by mass, relative to the total mass of the electron-transporting layer, from the viewpoint of achieving both electron-transporting performance and smoothness of the electron-transporting layer. In this disclosure, the content can be confirmed by a nuclear magnetic resonance (NMR) spectrometer or a gas chromatograph-mass spectrometer (GC-MS), etc.

[0089] Examples of the method for introducing a polymerizable functional group into an electron-transporting compound include, in addition to the method of directly introducing a polymerizable functional group into a synthesized skeleton, a method of introducing a structure having a functional group that can serve as a polymerizable functional group or a precursor of a polymerizable functional group (for example, a method using a cross-coupling reaction with a palladium catalyst and a base based on a halide of a perylenediimide derivative, a method using a cross-coupling reaction with an FeCl₃ catalyst and a base), a method of using, as a raw material when synthesizing a perylenediimide derivative, a perylenetetracarboxylic dianhydride derivative or a monoamine derivative having a functional group that can serve as a polymerizable functional group or a precursor of a polymerizable functional group, and the like.

[0090] The polymerizable functional group of the organic electron-transporting compound contained in the photoelectric conversion element of the present disclosure is preferably at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a thiol group.

[0091] <Thermoplastic Insulating Resin> Examples of the thermoplastic insulating resin include polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, polycarbonate resin, polyarylate resin, acrylic resin, polymethyl methacrylate resin, polyvinyl acetate resin, polyamide resin, polyphenylene sulfide resin, polyurethane resin, phenol resin, polystyrene resin, epoxy resin, phenoxy resin, polyacetal resin, polyester resin, and the like.

[0092] Among these, in the photoelectric conversion element of the present disclosure, the thermoplastic insulating resin is preferably a resin having a structural unit represented by the following formula (5). Specific examples thereof include polystyrene resin, polymethyl methacrylate resin, and the like.

Chemical Formula

[0093] From the viewpoint of improving durability against high temperatures during heat cycle endurance, the photoelectric conversion element disclosed herein preferably has a glass transition temperature (Tg) of 74°C or higher for the thermoplastic insulating resin.

[0094] In the photoelectric conversion element disclosed herein, from the viewpoint of achieving both conversion efficiency during heat cycle endurance and short-circuit failure resistance, it is preferable that A [mass%], where A is the ratio of the content of thermoplastic insulating resin that is not chemically bonded to the cured product in the electron transport layer relative to the total mass of all solids in the electron transport layer, satisfies the following formula (1). 1≦A≦20 Formula (1) When A is less than 1, the amount of thermoplastic insulating resin that is not chemically bonded to the cured product is insufficient to suppress the occurrence of a short circuit between the perovskite layer and the second electrode, resulting in insufficient resistance to short-circuit failures during heat cycle endurance. On the other hand, when A is greater than 20, the amount of thermoplastic insulating resin that is not chemically bonded to the cured product is excessive, which slows down the electron mobility in the electron transport layer, resulting in a decrease in conversion efficiency during heat cycle endurance.

[0095] <Method for identifying thermoplastic insulating resins that are not chemically bonded to cured products> As described above, a thermoplastic resin that is not chemically bonded to the cured product relating to this disclosure can be understood as a resin that does not contain electron transport sites, or contains extremely few electron transport sites, and the mass ratio of conductive sites to the resin can be defined as 0.03 or less.

[0096] The fact that the photoelectric conversion element of this disclosure has a thermoplastic insulating resin that is not chemically bonded to a cured product can be identified as follows. (1) Obtain a chloroform solution by immersing the electron transport layer of the photoelectric conversion element in chloroform. (2) The molecular weight of the above dissolution is determined by preparative chromatography to confirm whether a polymer (resin) has dissolved. If dissolution is confirmed, it is determined that the solution contains thermoplastic resin that is not chemically bonded to the cured product. (3) If a polymer (resin) has dissolved into the above-mentioned dissolving solution, only the polymer region (resin) shall be recovered. (4) The resin species is estimated from the recovered material using infrared absorption spectroscopy, and the molecular structure of the resin is identified using nuclear magnetic resonance (NMR) or pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS). (5) The molecular structure of the resin identified above is examined to identify the presence or absence of conductive sites in the resin and their molecular structures. (6) Using the information on the molecular structure of the resin and the molecular structure of the conductive part obtained from NMR integral analysis, the ratio of the mass part of the conductive part obtained from NMR integral analysis to the mass part of the resin obtained from NMR integral analysis is determined. (7) If the ratio obtained above is 0.03 or less, the thermoplastic resin that is not chemically bonded with the cured product determined to be included in the photoelectric conversion element of the present disclosure in (2) above is determined to be an insulating resin.

[0097] Specific examples of "conductive parts" in the above identification method include, for example, conductive parts represented by the following formulas (EB6), (EB7), (EB8), (EB9), (EB10), (EB11), (EB12), (EB13), (EB14), (EB15), (EB16), (EB17), and (EB18).

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[0098] In equations (EB6) to (EB18), R 61 ~R 70 R 71 ~R 76 R 81 ~R 84 R 91 ~R 98 R 101 ~R 110 R 111 ~R 118 R 121 ~R 128 R 131 ~R140 , R 141 ~R 146 , R 151 ~R 158 , R 161 ~R 168 , R 171 ~R 180 , and R 181 ~R 190 Each independently represents a functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 substituted or unsubstituted carbon atoms, an aryl group having 6 to 28 substituted or unsubstituted carbon atoms, an arylalkyl group having 7 to 28 substituted or unsubstituted carbon atoms, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a halogen atom, a cyano group, and a nitro group. In this case, R 61 ~R 70 , R 71 ~R 76 , R 81 ~R 84 , R 91 ~R 98 , R 101 ~R 110 , R 111 ~R 118 , R 121 ~R 128 , R 131 ~R 140 , R 141 ~R 146 , R 151 ~R 158 , R 161 ~R 168 , R 171 ~R 180 , and R 181 ~R 190 However, adjacent groups may be linked together to form a ring. 61 ~R 70 One or more of these are chemically bonded to the resin directly or via the substituents, R 71 ~R 76 One or more of these are chemically bonded to the resin directly or via the substituents, R 81 ~R 84 One or more of these are chemically bonded to the resin directly or via the substituents, R 91 ~R 98One or more of these are chemically bonded to the resin directly or via the substituents, R 101 ~R 110 One or more of these are chemically bonded to the resin directly or via the substituents, R 111 ~R 118 One or more of these are chemically bonded to the resin directly or via the substituents, R 121 ~R 128 One or more of these are chemically bonded to the resin directly or via the substituents, R 131 ~R 140 One or more of these are chemically bonded to the resin directly or via the substituents, R 141 ~R 146 One or more of these are chemically bonded to the resin directly or via the substituents, R 151 ~R 158 One or more of these are chemically bonded to the resin directly or via the substituents, R 161 ~R 168 One or more of these are chemically bonded to the resin directly or via the substituents, R 171 ~R 180 One or more of these are chemically bonded to the resin directly or via the substituents, R 181 ~R 190 One or more of these are chemically bonded to the resin directly or via the substituents mentioned above. 101 , Z 111 , Z 121 and Z 131 Each of these independently represents a carbon atom, a nitrogen atom, or an oxygen atom. 101 If it is an oxygen atom, then R 109 and R 110 It does not exist, Z 101 If it is a nitrogen atom, then R 110 It does not exist. Z 111 If it is an oxygen atom, then R 117 and R 118 It does not exist, Z 111 If it is a nitrogen atom, then R 118 It does not exist. Z 121 If it is an oxygen atom, then R 127 and R 128 It does not exist, Z 121 If it is a nitrogen atom, then R 128 It does not exist. Z131 If it is an oxygen atom, then R 139 and R 140 It does not exist, Z 131 If it is a nitrogen atom, then R 140 It does not exist.

[0099] <Method for measuring the volume resistivity of thermoplastic resins that are not chemically bonded to the cured product> Furthermore, as described above, the thermoplastic resin relating to this disclosure is understood to be a resin with high volume resistivity, and the volume resistivity is 10 12 It can be defined as a resin with a density of Ω·cm or greater.

[0100] The photoelectric conversion element of the present disclosure is a thermoplastic resin that is not chemically bonded to a cured product, and the volume resistivity of the resin is 10 12 The presence of a resin with a density of Ω·cm or greater can be confirmed as follows: (1) Obtain a chloroform solution by immersing the electron transport layer of the photoelectric conversion element in chloroform. (2) The molecular weight of the above dissolution is determined by preparative chromatography to confirm whether a polymer (resin) has dissolved. If dissolution is confirmed, it is determined that the solution contains thermoplastic resin that is not chemically bonded to the cured product. (3) If a polymer (resin) has dissolved into the above-mentioned dissolving solution, only the polymer region (resin) shall be recovered. (4) Collect a sufficient amount of the above-mentioned recovered material from multiple elements and heat-cur it. (5) The volume resistivity of the cured material (resin) obtained in (4) above is calculated by observing the output current in response to the voltage applied to the cured material at room temperature using a power supply (Model 236, manufactured by Keithley Corporation) or an impedance analyzer (ModuLab XM MTS, manufactured by Solartron Corporation).

[0101] <Crosslinking agent> The electron transport layer composition may contain a crosslinking agent. Any known material can be used as the crosslinking agent. Specifically, examples include compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981).

[0102] The photoelectric conversion element of the present disclosure preferably contains a composition that includes at least one compound selected from the group consisting of isocyanate compounds, melamine compounds, and guanamine compounds.

[0103] The crosslinking agent is preferably an acid anhydride derivative, a phenol compound, a polyamine compound, an isocyanate compound having an isocyanate group or a blocked isocyanate group, or an amine compound having an N-methylol group or an alkyl etherified N-methylol group. More preferably, it is an isocyanate compound having an isocyanate group or a blocked isocyanate group, or an amine compound having an N-methylol group or an alkyl etherified N-methylol group.

[0104] These crosslinking agents produce many -NH- and -C(=O)- structures after polymerization. These structures form complex hydrogen bonds, which is thought to alleviate the aggregation of organic electron-transporting compounds. Furthermore, when the electron-transporting layer is in contact with the perovskite layer, these structures strongly interact with the perovskite crystal, resulting in high adhesion between layers and mitigating internal stress caused by volume changes in the perovskite crystal due to heat. These effects further suppress interfacial delamination of the electron-transporting layer during heat cycle durability. Isocyanate compounds having 3 to 6 isocyanate groups or blocked isocyanate groups are even more preferable.

[0105] Examples of isocyanate compounds include, but are not limited to, the isocyanate compounds listed below. Furthermore, multiple isocyanate compounds may be used in combination.

[0106] Examples include triisocyanate benzene, triisocyanate methylbenzene, triphenylmethane triisocyanate, lysine triisocyanate, tolylene diisocyanate, biuret modified, biuret-type isocyanate, allophanate modified, and adduct modified with trimethylolpropane or pentaerythritol. A blocked isocyanate group is a group having the structure -NHCOZ1 (where Z1 is a protecting group). Z1 can be any protecting group that can be introduced into an isocyanate group.

[0107] Examples of commercially available isocyanate compounds include isocyanate-based crosslinking agents such as Duranate MFK-60B, SBA-70B, 17B-60P, SBN-70D, SBB-70P (manufactured by Asahi Kasei Corporation), Cosmonate TM-20, TM-50 (manufactured by Mitsui Chemicals, Inc.), and Bronate 1227EV, 1232P, 1902V, 1961V (manufactured by Daiei Sangyo Co., Ltd.).

[0108] Amine compounds having multiple (three or more) N-methylol groups or alkyl etherified N-methylol groups are more preferred. Examples include methylolated melamine, methylolated guanamine, methylolated urea derivatives, methylolated ethyleneurea derivatives, methylolated glycoluryl, compounds in which the methylol moiety is alkyl etherified, and derivatives thereof. Methylolated melamine and methylolated guanamine are even more preferred.

[0109] Examples of commercially available amine compounds include melamine compounds such as Yuban 20SB, 2020, 60R, and 360 (manufactured by Mitsui Chemicals, Inc.), and Nikalac MW-30M, MW-11, and MX-750 (manufactured by Sanwa Chemical Co., Ltd.). Examples of guanamine compounds include Nikalac BL-60 and BX-4000 (manufactured by Sanwa Chemical Co., Ltd.).

[0110] <Thermoplastic resin having polymerizable functional groups> The electron transport layer composition may also contain an electron transport material, a crosslinking agent, and a resin having a polymerizable functional group. Examples of resins having a polymerizable functional group include polyacetal resins, polyvinyl acetal resins, polyolefin resins, polyester resins, polyether resins, and polyamide resins. Preferably, the polymerizable functional group of the resin is at least one functional group selected from the group consisting of hydroxyl groups, carboxyl groups, amino groups, and thiol groups.

[0111] Examples of commercially available resins having polymerizable functional groups include Bekkolite AL-4298-60, AS-019, Polylite OD-X-2420, OD-X-688 (manufactured by DIC Corporation), Esrec BX-1, BM-1, KS-5 (manufactured by Sekisui Chemical Co., Ltd.), Gosenex Z-100, Z-220, LW-100, LW-200 (manufactured by Mitsubishi Chemical Corporation), ARUFON UH-2000, UH-2041, UC-3000, UC-3080 (manufactured by Toagosei Co., Ltd.), and Hyros-X NS-2092, ZS-1417, X-1, X-210, BS-2060 (manufactured by Seikoh PMC Co., Ltd.).

[0112] The weight-average molecular weight of the resin having polymerizable functional groups is more preferably in the range of 5,000 to 400,000. More preferably, it is in the range of 5,000 to 300,000.

[0113] <Other additives> In addition to the polymers described above, the electron transport layer may also contain other organic particles, inorganic particles, leveling agents, etc., to enhance film-forming properties and electrical characteristics. However, the content of these in the electron transport layer is preferably 20% by mass or less, and more preferably 10% by mass or less, relative to the total mass of the electron transport layer. One method for forming an electron transport layer is to form a coating film of an electron transport layer coating solution containing the above-mentioned substance and then dry the coating film. When polymerizing the composition during the drying of the coating film of the electron transport layer coating solution, the polymerization reaction (curing reaction) is accelerated by applying heat or light energy. Examples of solvents used in the electron transport layer coating solution include alcohol-based solvents, sulfoxide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, aromatic hydrocarbon solvents, and the like.

[0114] <Passive layer> A passivation layer may also be provided on top of the electron transport layer 4. The passivation material is not particularly limited and can be an organic salt, an inorganic salt, an ionic liquid, or a resin. The conductivity of the passivation material is not particularly limited and can be either insulating or conductive.

[0115] As the organic salt, a compound composed of at least one cation selected from the group consisting of compounds represented by the above formulas (C1) to (C96) and at least one anion selected from the group consisting of compounds represented by the above formulas (A1) to (A29) is preferred.

[0116] As inorganic salts, compounds composed of at least one cation selected from the group consisting of metal atoms and at least one anion selected from the group consisting of compounds represented by formulas (A1) to (A29) are preferred.

[0117] Examples of metal atoms include copper, silver, zinc, gallium, bismuth, sodium, potassium, lithium, vanadium, manganese, iron, cobalt, nickel, germanium, arsenic, selenium, lead, tin, iridium, platinum, osmium, cesium, barium, rubidium, molybdenum, and ruthenium.

[0118] The material of the ionic liquid is not particularly limited, but a compound composed of at least one cation selected from the group consisting of compounds represented by formulas (ILC1) to (ILC10) and at least one anion selected from the group consisting of compounds represented by formulas (ILA1) to (ILA17) is preferred. 01 ~R 04 , independently represent a hydrogen atom, an optional alkyl group, and an optional aryl group, respectively.

[0119] The resin material is not particularly limited and may have substituents, including polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polystyrene (PS), polyimide (PI), fluororesin (PVDF), polyurethane (PU), silicone resin (PDMS), epoxy resin, nanocomposite resin, PEDOT:PSS, poly(9,9-dioctylfluorene-artenalyl) (PFN), P3HT, poly(fluorene-co- Phenylene (PFP), polyvinylcarbazole (PVK), polythiophene (PTh), polyaniline (PANI), polybithiophene (PBTh), polydioxythiophene (PDT), polyoxyethylene (PEO), polyacrylic acid (PAA), polymethacrylic acid (PMAA), polyfumaric acid (PFA), polysuccinic acid (PSA), polyadipic acid (PAdA), polycaprolactam (PCL), polyisophthalic acid (PIPA), polyterephthalic acid (PT) A) Examples include polynaphthalenedicarboxylic acid (PNA), polyamide-imide (PAI), polysilsesquioxane (POSS), polyphenol resin (PF), polycarbonate (PC), poly(styrene-butadiene) (PSB), polysilyl ether (PSE), poly(ether-imide) (PEI), polyvinylpyrrolidone (PVP), polyacrylic acid ester (PAE), polydimethylaminoethyl methacrylate (PDMAEMA), polytrifluoroethylene (PTFE), polyoxymethylene (POM), polyesterimide (PEI), polyacrylonitrile (PAN), polyvinyl acetal (PVAH), polyolefin ether (PIE), polyacetal (PA), polysulfone (PSU), polyurea urethane (PUU), and polyolefin (PO), with polyvinyl acetal, polyolefin, polymethyl methacrylate, polyurethane, polyvinyl alcohol, and polyvinyl butyral being particularly preferred.

[0120] <Electron injection layer> Furthermore, from the viewpoint of electron injection, an electron injection layer may be provided on the electron transport layer or a second electron transport layer. The material of the electron injection layer is not particularly limited, but bathocuproine, bathophenanthroline, perylenediimide derivatives, and naphthalenediimide derivatives are preferred.

[0121] [Application Examples] Examples of applications of this disclosure include photoelectric converters, mobile devices, and building materials.

[0122] <Photoelectric converter> The photoelectric conversion device disclosed herein comprises a photoelectric conversion element disclosed herein. A photoelectric conversion device can be configured by using multiple photoelectric conversion elements disclosed herein. When multiple photoelectric conversion elements are connected together, such a photoelectric conversion device may also be called a photoelectric conversion cell or a photoelectric conversion module.

[0123] The photoelectric conversion element may be stacked with photoelectric conversion elements having different absorption wavelengths to increase the output voltage. Furthermore, the photoelectric conversion device includes the photoelectric conversion element of this disclosure and an inverter. The inverter may be a converter that converts direct current to alternating current.

[0124] The photoelectric conversion device may have a power storage unit connected to the photoelectric conversion element. The power storage unit is not limited to any device that can store electricity. Examples include secondary batteries using lithium ions, all-solid-state batteries, and electric double-layer capacitors. To provide functions such as maintaining or increasing the amount of incident light, a surface that is resistant to water and dirt, or a function to collect or guide light may be added.

[0125] <Mobile> The mobile body of the present disclosure has the above-described photoelectric conversion element. Figure 2 is a schematic perspective view showing one embodiment of the mobile body equipped with the photoelectric conversion element of the present disclosure. The mobile body 30 has the photoelectric conversion element 31 of the present disclosure and a body 32 equipped with the photoelectric conversion element 31. The photoelectric conversion element 31 is positioned in a location on the body 32 that can receive ambient light.

[0126] If the mobile body 30 is an automobile, it may be placed on the roof. The electrical energy obtained by the photoelectric conversion element 31 may be used to power the mobile body 30 or other electrical equipment. The electrical energy generated from the power of the mobile body 30 may be used to power the photoelectric conversion element 31. If the mobile body 30 is an automobile, the frictional energy generated by the brakes may be converted into electrical energy and used to control the photoelectric conversion element 31.

[0127] The mobile body 30 may be, for example, an automobile, a motorcycle, a railway vehicle, a ship, a satellite, an airplane, or a drone. The structure of the mobile body 32 is not particularly limited, but it is preferably made of a high-strength material.

[0128] <Building materials> The building material of this disclosure has the above-described photoelectric conversion element. Figure 3 is a schematic perspective view showing one embodiment of the building material of this disclosure equipped with the photoelectric conversion element. The building material 40 may be the roof of a building. The building material 40 of this embodiment has the photoelectric conversion element 41 of this disclosure, a protective member 42 for protecting the photoelectric conversion element 41, a heat dissipation member 43, and exterior parts 44a, 44b.

[0129] The building material 40 of this disclosure may have a heat dissipation member 43 with a higher thermal conductivity than the photoelectric conversion element 41. When used on roofs, etc., the temperature of the photoelectric conversion element 41 may rise due to sunlight, which may reduce the photoelectric conversion efficiency. By using the heat dissipation member 43, the decrease in photoelectric conversion efficiency can be reduced. Examples of the heat dissipation member 43 include metals, alloys, liquid metals, liquid resins, etc.

[0130] Furthermore, the building material 40 of this disclosure may have exteriors 44a and 44b. Exteriors 44a and 44b may have different colors or the same color. 44a and 44b may be composed of the same material or different materials. As the exterior, paint or a transparent substrate may be used. It is preferable that the exterior has low light absorption and high heat shielding properties.

[0131] In addition to the above examples of applications, the following are some other examples of applications: Portable devices include calculators, sensors, and small solar panels. Wearable devices include eyeglasses, smartwatches, and portable medical devices. Sheet structures supported by multiple frames include tents, greenhouses, and truck beds. Fixed structures include road panels, floating panels, building materials that utilize the flexibility of the substrate, wall-type building materials, glass-type building materials, and mega solar panels.

[0132] <Manufacturing method for photoelectric conversion elements> A method for manufacturing a photoelectric conversion element according to the present disclosure includes the steps of forming a first electrode, forming a second electrode, forming a photoelectric conversion layer containing a perovskite crystal between the first electrode and the second electrode, and forming an electron transport layer between the photoelectric conversion layer and the second electrode. The following describes each step of the manufacturing process.

[0133] [Steps for forming the first electrode and steps for forming the second electrode] In the process of forming the first electrode and the process of forming the second electrode, an appropriate method can be selected depending on the material of the first electrode and the material of the second electrode, respectively. Examples of such methods include, but are not limited to, sputtering, vacuum deposition, CVD (vapor deposition), and SPD (spray pyrolysis deposition). The materials of the first and second electrodes are as described above. When either or both of the first and second electrodes are transparent electrodes, the thickness of the transparent electrode is preferably 0.03 μm or more and 3 μm or less.

[0134] [Modularization Process] When manufacturing solar cells, cutting processes may be performed between each manufacturing step to form circuits. Examples of cutting processes include mechanical patterning and laser patterning. Furthermore, the element with electrodes formed may be sealed. Examples of sealing methods include sealing with a resin or sealing with a film containing a resin. Examples of materials used for sealing include silazane, silicone rubber, resins having a siloxane skeleton, resins containing fluorine, and glass. Furthermore, from the viewpoint of suppressing adhesion between elements that occurs when winding in a roll-to-roll manner, the surface of the sealed elements may be given a hairline finish.

[0135] [Process for forming the photoelectric conversion layer] The photoelectric conversion layer formation process may include a step of applying a liquid containing the above-mentioned photoelectric conversion layer material. Examples of application methods include spin coating, blade coating, slit die coating, screen printing, bar coating, mold making, print transfer, immersion and pull-up, inkjet, spray, and vacuum deposition. From these options, appropriate choices are made depending on the characteristics of the photoelectric conversion layer to be fabricated, such as thickness control and orientation control. Annealing treatment may be performed under reduced pressure or in an inert atmosphere (nitrogen or argon atmosphere) to remove the solvent or dispersion medium from the liquid containing the material of the applied photoelectric conversion layer. The temperature of the annealing treatment is preferably 40°C to 300°C, and more preferably 50°C to 150°C. Annealing treatment is preferable because it can increase the contact area at the interface between the stacked layers, as the materials constituting each layer penetrate each other, which can increase the short-circuit current.

[0136] [Process for forming the electron transport layer] A preferred method for forming the electron transport layer is to apply a liquid containing the electron transport layer material described above. Examples of application methods include spin coating, blade coating, slit die coating, screen printing, bar coating, molding, print transfer, immersion and pull-up, inkjet, spray, and vacuum deposition. [Examples]

[0137] The present disclosure will be described in more detail below using examples and comparative examples. The present disclosure is not limited in any way by the following examples unless it exceeds the gist of the disclosure. In the following examples, "parts" refers to a mass basis unless otherwise specified.

[0138] (Example 1) [Hole transport layer formation] A 25mm square ITO-coated glass substrate was cleaned, and 3PATAT-3C (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared to a concentration of 0.01 mM in 100 mL of N,N-dimethylformamide (DMF). This solution was then applied to the substrate by spin coating, and the substrate was heated at 110°C for 10 minutes to form a thin-film hole transport layer.

[0139] [Formation of the photoelectric conversion layer] 0.044 g of lead bromide, 0.392 g of formamidium iodide, 1.144 g of lead iodide, 0.0134 g of methylammonium bromide, and 0.0176 g of methylammonium chloride were dissolved in 1384 μL of DMF and 252.4 μL of dimethyl sulfoxide (DMSO) and stirred for 2 hours (Solution 1). Furthermore, 0.036 g of cesium iodide was dissolved in 96.6 μL of DMSO and stirred for 2 hours (Solution 2). Then, the dissolved cesium iodide solution (Solution 2) was added to Solution 1 to prepare the photoelectric conversion layer coating solution. This coating solution was spin-coated onto the hole transport layer using a poor solvent method and heated at 100°C for 10 minutes to obtain {Cs 0.05 (FA 0.86 MA 0.14 ) 0.95} 0.98 Pb(I 0.95 Br 0.05 ) 2.98 A photoelectric conversion layer with a thickness of 600 nm was obtained.

[0140] [Formation of the passivation layer] 2-phenylethylamine hydroiodide (PEAI) was prepared in 2-propanol (IPA) at a concentration of 1 mg / mL. This solution was applied by spin coating to obtain a passivation layer on top of the photoelectric conversion layer.

[0141] [Formation of the electron transport layer] A coating solution for the electron transport layer was prepared using the following procedure and spin-coated onto the photoelectric conversion layer at 2500 rpm. The mixture was then heated at 140°C for 60 minutes to cure the polymerizable functional group compound, forming an electron transport layer approximately 20 nm thick. The coating solution for the electron transport layer was prepared considering the detachable block groups, ensuring that the total mass of the electron transport layer after formation consisted of 5% by mass of thermoplastic insulating resin not chemically bonded to the cured material in the electron transport layer and 60% by mass of organic electron transport compound.

[0142] 6.00 parts of the following compound (PD1) as an organic electron transport compound, 7.18 parts of a blocked isocyanate compound (trade name: SBB-70P, manufactured by Asahi Kasei Corporation) as a crosslinking agent, 0.088 parts of polyolefin resin (trade name: UC-3920, manufactured by Toagosei Co., Ltd.) and 0.088 parts of polyvinyl acetal resin (trade name: KS-5Z, manufactured by Sekisui Chemical Co., Ltd.) as resins, and 0.50 parts of polystyrene resin (PS, manufactured by Sigma-Aldrich, glass transition temperature: Tg=100℃) as a thermoplastic insulating resin without polymerizable functional groups were dissolved in a mixed solvent of 670 parts THF / 330 parts anisole. Subsequently, the mixture was filtered under pressure using an ADVANTEC Teflon® filter (product name: PF020) to obtain a coating solution for the electron transport layer. [ka]

[0143] [Formation of electron injection layer] Vasocuproine (BCP) was prepared in IPA at a concentration of 0.5 mg / mL. This solution was applied to the electron transport layer by spin coating to obtain an electron injection layer. [Formation of the second electrode] On the aforementioned electron transport layer, an area of ​​0.09 cm² 2 Ten Ag electrodes were formed to obtain a photoelectric conversion element.

[0144] [Analysis of compound amounts] The electrode surface of the photoelectric conversion element was stripped off, exposing the electron transport layer surface. This electron transport layer surface was wiped with a cotton swab soaked in solvent and dissolved in heavy DMSO. 1 ¹H-NMR measurements were performed (instrument name: AVANCE3-500, Bruker K.K.). The extracted organic electron-transporting compound was then subjected to mass and structural analysis using GPC, MALDI-TOF-MS, IR, gas chromatography, XPS, EDX, and other elemental analyses to confirm the presence of the compound. Furthermore, the film thickness was confirmed by cutting the photoelectric conversion element, fixing it on an inclined sample stage, and then using a cross-sectional SEM (device name: SmartSEM, manufactured by Carl Zeiss K.K.).

[0145] Table 2 shows the configuration of the electron transport layer of the photoelectric conversion element obtained in Example 1 as described above.

[0146] (Examples 2-34) As shown in Table 2, the photoelectric conversion elements of Examples 2 to 34 were obtained in the same manner as in Example 1, except that the configuration of the electron transport layer was changed.

[0147] (Examples 35-75) As shown in Table 3, photoelectric conversion elements for Examples 35 to 75 were obtained in the same manner as in Example 1, except that the configuration of the electron transport layer was changed.

[0148] (Example 76) A photoelectric conversion element of Example 76 was obtained in the same manner as in Example 1, except that the polystyrene resin used as a thermoplastic insulating resin without polymerizable functional groups was replaced with resin P1 obtained in [Synthesis Example 1] below. The configuration of the electron transport layer of the obtained photoelectric conversion element is shown in Table 3. [Synthesis Example 1] To 2000 parts of dimethylacetamide, 4.0 parts of perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 11.0 parts of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 150 parts of polyetherdiamine (trade name: T2100, manufactured by Koei Chemical Co., Ltd.) were added under a nitrogen atmosphere, and the mixture was refluxed for 10 hours. Then, 1.0 part of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was refluxed for another 5 hours. After dispersion washing with methanol, 93 parts of resin P1 were obtained by heating and drying at 100°C for 5 hours.

[0149] (Example 77) The photoelectric conversion element of Example 77 was obtained in the same manner as in Example 1, except that the polystyrene resin used as a thermoplastic insulating resin without polymerizable functional groups was replaced with resin P2 obtained in [Synthesis Example 2] below. The configuration of the electron transport layer of the obtained photoelectric conversion element is shown in Table 3. [Synthesis Example 2] To 2000 parts of dimethylacetamide, 3.0 parts of perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 parts of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 parts of polyetherdiamine (trade name: T2100, manufactured by Koei Chemical Co., Ltd.) were added under a nitrogen atmosphere, and the mixture was refluxed for 10 hours. Then, 1.0 part of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was refluxed for another 5 hours. After dispersion washing with methanol, 76 parts of resin P2 were obtained by heating and drying at 100°C for 5 hours.

[0150] (Example 78) The photoelectric conversion element of Example 78 was obtained in the same manner as in Example 1, except that the polystyrene resin used as a thermoplastic insulating resin without polymerizable functional groups was changed to resin P3 obtained in [Synthesis Example 3] below. The configuration of the electron transport layer of the obtained photoelectric conversion element is shown in Table 3. [Synthesis Example 3] To 2000 parts of dimethylacetamide, 2.0 parts of perylenetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.0 parts of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 150 parts of polyetherdiamine (trade name: T2100, manufactured by Koei Chemical Co., Ltd.) were added under a nitrogen atmosphere, and the mixture was refluxed for 10 hours. Then, 1.0 part of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was refluxed for another 5 hours. After dispersion washing with methanol, 91 parts of resin P3 were obtained by heating and drying at 100°C for 5 hours.

[0151] (Comparative Examples 1-22) As shown in Table 4, the photoelectric conversion elements of Comparative Examples 1 to 22 were obtained in the same manner as in Example 1, except that the configuration of the electron transport layer was changed.

[0152] The meanings of the notations in Tables 2-4 are as follows: [Organic electron transporting compound] "PD2 / 9 / 10=1 / 2 / 1" is an organic electron-transport compound obtained by mixing the organic electron-transport compounds (PD2), (PD9), and (PD10) in a ratio of (PD2):(PD9):(PD10)=1:2:1. In Comparative Examples 10 and 11, no organic electron-transporting compounds were used. "PDM1" is a perylenediimide derivative represented by the following formula (PDM1), and is an organic electron transport compound that does not have polymerizable functional groups. [ka] "NDM1" is a naphthalenediimide derivative represented by the following formula (NDM1), and is an organic electron transport compound that does not have polymerizable functional groups. [ka] "PCBM" is a fullerene derivative represented by the following formula (PCBM), and is an organic electron transport compound that does not have polymerizable functional groups. [ka]

[0153] [Crosslinking agent] "Yuban 2020" is a melamine compound (product name: Yuban 2020, manufactured by Mitsui Chemicals, Inc.). "Nikkalac BL-60" is a guanamine compound (product name: Nikkalac BL-60, manufactured by Sanwa Chemical Co., Ltd.). • "Phthalic anhydride" means that phthalic anhydride was used as a crosslinking agent. "SBN-70D" is a blocked isocyanate compound (product name: SBN-70D, manufactured by Asahi Kasei Corporation). In Examples 42-49, Examples 59-65, and Comparative Example 11, no crosslinking agent was used.

[0154] [Resin 1] "UC-3920" is a polyolefin resin (product name: UC-3920, manufactured by Toagosei Co., Ltd.) and is a thermoplastic resin having a carboxyl group as a polymerizable functional group. "KS-5Z" is a polyvinyl acetal resin (product name: KS-5Z, manufactured by Sekisui Chemical Co., Ltd.) and is a thermoplastic resin having a hydroxyl group as a polymerizable functional group. In Examples 41, 43-49, 59-65, and Comparative Example 11, thermoplastic resins having polymerizable functional groups were not used.

[0155] [Insulating resin 2] "PCZ-200" is a polycarbonate resin (product name: PCZ-200, manufactured by Mitsubishi Gas Chemical Company, Inc., glass transition temperature: Tg=174℃) and is a thermoplastic insulating resin that does not have polymerizable functional groups. "M-2040" is a polyarylate resin (product name: M-2040, manufactured by Unitika Ltd., glass transition temperature: Tg=220℃), a thermoplastic insulating resin that does not have polymerizable functional groups. "PMMA(70)" is a polymethyl methacrylate resin (PMMA, manufactured by Sigma-Aldrich, glass transition temperature: Tg=70°C), a thermoplastic insulating resin that does not have polymerizable functional groups. "PMMA(100)" is a polymethyl methacrylate resin (PMMA, manufactured by Sigma-Aldrich, glass transition temperature: Tg=100°C), a thermoplastic insulating resin that does not have polymerizable functional groups. "Solvine CN" is a vinyl chloride / vinyl acetate copolymer resin (product name: Solvine CN, manufactured by Nisshin Chemical Industries, Ltd., glass transition temperature: Tg=73℃), and is a thermoplastic insulating resin that does not have polymerizable functional groups. "Solvine C" is a vinyl chloride / vinyl acetate copolymer resin (product name: Solvine C, manufactured by Nisshin Chemical Industries, Ltd., glass transition temperature: Tg=70℃), and is a thermoplastic insulating resin that does not have polymerizable functional groups. "Solvine CL" is a vinyl chloride / vinyl acetate copolymer resin (product name: Solvine CL, manufactured by Nisshin Chemical Co., Ltd., glass transition temperature: Tg=68℃), and is a thermoplastic insulating resin that does not have polymerizable functional groups. "Solvine CLL3" is a vinyl chloride / vinyl acetate copolymer resin (product name: Solvine CLL3, manufactured by Nisshin Chemical Industries, Ltd., glass transition temperature: Tg=66℃), and is a thermoplastic insulating resin that does not have polymerizable functional groups.

[0156] In Comparative Examples 1, 6, 12-16, and 19-22, thermoplastic insulating resins without polymerizable functional groups were not used. "Solvine TAO" is a vinyl chloride / vinyl acetate copolymer resin (product name: Solvine TAO, manufactured by Nisshin Chemical Co., Ltd., glass transition temperature: Tg=76℃), and is a thermoplastic insulating resin having vinyl alcohol as a polymerizable functional group. "Solvine M5" is a vinyl chloride / vinyl acetate copolymer resin (product name: Solvine M5, manufactured by Nisshin Chemical Industries, Ltd., glass transition temperature: Tg=70℃), and is a thermoplastic insulating resin having dicarboxylic acid as a polymerizable functional group. "Solvine TA3" is a vinyl chloride / vinyl acetate copolymer resin (product name: Solvine TA3, manufactured by Nisshin Chemical Co., Ltd., glass transition temperature: Tg=64℃), and is a thermoplastic insulating resin having hydroxyalkyl acrylate as a polymerizable functional group. "BX-1" is a polybutyral resin (product name: BX-1, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: Tg=95℃), and is a thermoplastic insulating resin having a hydroxyl group as a polymerizable functional group.

[0157] [Second electron transport layer] In Example 70, after the formation of the electron transport layer, a second electron transport layer was formed using a fullerene derivative: PCBM. In Example 71, after the electron transport layer was formed, fullerene:C 60 A second electron transport layer was formed using [this method]. In Example 72, Comparative Example 15, Comparative Example 17, Comparative Example 19, and Comparative Example 21, a second electron transport layer was formed using tin oxide (SnO2) after the formation of the electron transport layer. In Example 73, Comparative Example 16, Comparative Example 18, Comparative Example 20, and Comparative Example 22, a second electron transport layer was formed using zinc oxide (ZnO) after the formation of the electron transport layer. In Example 74, a second electron transport layer was formed using zinc-tin oxide (ZTO) after the formation of the electron transport layer. In Example 75, after the formation of the electron transport layer, a second electron transport layer was formed using aluminum-doped zinc oxide (AZO).

[0158] [evaluation] A power supply (Model 236, manufactured by Keithley) was connected between the electrodes of the photoelectric conversion elements fabricated in Examples 1-78 and Comparative Examples 1-22, and an intensity of 100 mW / cm was applied. 2 Using a solar simulator (manufactured by Yamashita Densou Co., Ltd.), a constant amount of light was irradiated, and the initial values ​​of the generated current and voltage were measured to obtain the initial values ​​of the photoelectric conversion efficiency. In addition, five of each photoelectric conversion element were fabricated, and measurements were taken at each of the 10 electrodes on each element. The average of the initial values ​​at a total of 50 locations was taken as the average initial value of that photoelectric conversion element. Next, a 100-hour durability test was conducted in which the temperature of the photoelectric conversion element was controlled by a Peltier element to perform a heat cycle of 5 hours at 85°C and 5 hours at 25°C while blowing nitrogen under 1 sun irradiation. The durability value of the photoelectric conversion efficiency was obtained by measuring it in the same way as the initial value. Also, similar to the initial value, the average of the durability values ​​at a total of 50 locations was taken as the average durability value of the photoelectric conversion element. However, locations with a durability value of less than 1% were judged to have short-circuit failures and were excluded from the calculation of the average value. The conversion efficiency decay rate [%] due to durability was calculated as "Conversion efficiency decay rate [%]" = ("Average initial value" - "Average durability value") / "Average initial value" × 100 [%]. The evaluation results are shown in Tables 2 to 4.

[0159] Furthermore, the percentage of locations with short-circuit failures after durability testing was calculated using the formula: "Percentage of short-circuit failures [%]" = "Number of locations where the photoelectric conversion efficiency after durability testing was less than 1%" / 50 [locations] × 100 [%]. The evaluation results are shown in Tables 2-4. In Comparative Examples 8 and 9 of Table 4, the average initial value was less than 5%, so it was determined that the solar cells were not functioning at the initial stage before durability testing.

[0160] [Table 2]

[0161] [Table 3]

[0162] [Table 4]

[0163] This embodiment includes the following configuration. (Composition 1) A photoelectric conversion element comprising a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, The electron transport layer, A cured product of a composition containing an organic electron transport compound having polymerizable functional groups, A thermoplastic insulating resin that is not chemically bonded to the cured product, Contains A photoelectric conversion element characterized by the following features. (Configuration 2) The photoelectric conversion element according to configuration 1, wherein the cured product of the composition is a cured product of a composition containing the polymerizable functional group-containing organic electron transport compound and a crosslinking agent. (Composition 3) The photoelectric conversion element according to configuration 2, wherein the crosslinking agent contains at least one compound selected from the group consisting of isocyanate compounds, melamine compounds, and guanamine compounds. (Composition 4) The photoelectric conversion element according to configuration 2 or 3, wherein the cured product of the composition is a cured product of a composition containing the organic electron transport compound having the polymerizable functional group, the crosslinking agent, and a thermoplastic resin having the polymerizable functional group. (Composition 5) The photoelectric conversion element according to configuration 4, wherein the thermoplastic resin having the polymerizable functional group further contains a resin having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group. (Composition 6) A photoelectric conversion element according to any one of the configurations 1 to 5, wherein A [mass%] is the ratio of the content of thermoplastic insulating resin in the electron transport layer that is not chemically bonded to the cured product in the electron transport layer to the total mass of the total solids in the electron transport layer, and A satisfies the following formula (1). 1≦A≦20 Formula (1) (Composition 7) The photoelectric conversion element according to any one of the configurations 1 to 6, wherein the organic electron transport compound having the polymerizable functional group comprises at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, and a heteroatom. (Composition 8) The photoelectric conversion element according to any one of the configurations 1 to 7, wherein the organic electron transport compound having the polymerizable functional group is at least one compound selected from the group consisting of the compound represented by the following formula (E1), the compound represented by the following formula (E2), the compound represented by the following formula (E3), and the compound represented by the following formula (E4). [ka] (In formulas (E1) to (E4), R 11 ~R 20 , R 21 ~R 26 , R 31 ~R 34 , and R 41 ~R 48 Each independently represents a functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 substituted or unsubstituted carbon atoms, an aryl group having 6 to 28 substituted or unsubstituted carbon atoms, an arylalkyl group having 7 to 28 substituted or unsubstituted carbon atoms, a hydroxyl group, a carboxyl group, an amino group, a thiol group, a halogen atom, a cyano group, and a nitro group. In this case, R 11 ~R 20 , R 21 ~R 26 , R 31 ~R 34 , and R 41 ~R 48 However, adjacent groups may be linked together to form a ring. 11 ~R 20 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 21 ~R 26 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 31 ~R 34 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 41 ~R 48One or more of these groups contain a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group. (Composition 9) In the above equations (E1) to (E4), R 11 ~R 20 , R 21 ~R 26 , R 31 ~R 34 , and R 41 ~R 48 Each of these is an independent group represented by formula (2) below, the photoelectric conversion element described in configuration 8. ―(R a ) m ―(R b ) n ―R c Formula (2) (In equation (2), m and n are independently either 0 or 1.) In formula (2), R a R in formula (2) represents an alkylene group having 1 to 10 substituted or unsubstituted carbon atoms, or an arylene group having 6 to 14 substituted or unsubstituted carbon atoms. c or R in equation (2) d They may be connected to each other to form a ring. In formula (2), R b represents an oxygen atom, a sulfur atom, or a group represented by the following formula (3). [ka] (In formula (3), R d R represents a hydrogen atom, or an alkyl group having 1 to 4 substituted or unsubstituted carbon atoms. Alternatively, in this case, R in formula (2) a or R in equation (2) c They may be connected together to form a ring. In formula (2), R c R represents a hydrogen atom, an alkyl group having 1 to 10 substituted or unsubstituted carbon atoms, an aryl group having 6 to 14 substituted or unsubstituted carbon atoms, or an arylalkyl group having 7 to 18 substituted or unsubstituted carbon atoms. Alternatively, in this case, R in formula (2) aOr R in equation (3) d They may be connected to each other to form a ring. The substituents that the alkylene group and the alkyl group may have are a hydroxyl group, a carboxyl group, an amino group, a thiol group, an alkoxy group having 1 to 3 carbon atoms, and an alkoxycarbonyl group having 2 to 4 carbon atoms. The substituents that the arylene group, the aryl group, and the arylalkyl group may have are alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, hydroxyalkyl groups having 1 to 3 carbon atoms, carboxyl groups, amino groups, thiol groups, alkoxy groups having 1 to 3 carbon atoms, alkoxycarbonyl groups having 2 to 4 carbon atoms, halogen atoms, cyano groups, and nitro groups. However, R 11 ~R 20 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 21 ~R 26 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 31 ~R 34 One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R 41 ~R 48 One or more of these groups contain a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group. (Composition 10) The photoelectric conversion element according to any one of the claims 1 to 9, wherein the organic electron transport compound having the polymerizable functional group contains heteroatoms with a number of atoms of 6 to 20. (Composition 11) The photoelectric conversion element according to configuration 1, wherein the glass transition temperature of the thermoplastic insulating resin that is not chemically bonded with the cured product is 74°C or higher. (Composition 12) A photoelectric conversion element according to any one of the configurations 1 to 11, wherein the thermoplastic insulating resin, which is not chemically bonded with the cured product, has a structural unit represented by the following formula (5). [ka] (In formula (5), R 51 ~R 54 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a group represented by the following formula (6), or a group represented by the following formula (7). In this case, R 51 ~R 54 However, adjacent groups may connect to each other and jointly form a ring. ―C(=O)―R e Formula (6) ―C(=O)―O―R f Formula (7) In equations (6) and (7), R e and R f Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylalkyl group. (Composition 13) A photoelectric conversion element comprising a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, The electron transport layer, A cured product of a composition containing an organic electron transport compound having polymerizable functional groups, A thermoplastic resin that is not chemically bonded to the cured product, wherein the mass ratio of conductive parts represented by the following formulas (EB6), (EB7), (EB8), (EB9), (EB10), (EB11), (EB12), (EB13), (EB14), (EB15), (EB16), (EB17), (EB18) contained in the resin is 0.03 or less. Contains A photoelectric conversion element characterized by the following features. [ka]

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[0164] 1. Photoelectric conversion element 2 circuit boards 3 Second electrode 4 Electron transport layer 5 Photoelectric conversion layer 6. Hole transport layer 7 First electrode 30 Mobile Units 31, 41 Photoelectric conversion element 32 aircraft 40 Building materials 42 Protective member 43 Heat dissipation components 44a, 44b Exterior

Claims

1. A photoelectric conversion element comprising a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, The electron transport layer, A cured product of a composition containing an organic electron transport compound having polymerizable functional groups, A thermoplastic insulating resin that is not chemically bonded to the cured product, Contains A photoelectric conversion element characterized by the following features.

2. The photoelectric element according to claim 1, wherein the cured product of the composition is a cured product of a composition containing the polymerizable functional group-containing organic electron transport compound and a crosslinking agent.

3. The photoelectric conversion element according to claim 2, wherein the crosslinking agent contains at least one compound selected from the group consisting of isocyanate compounds, melamine compounds, and guanamine compounds.

4. The photoelectric element according to claim 2, wherein the cured product of the composition is a cured product of a composition containing the organic electron transport compound having a polymerizable functional group, the crosslinking agent, and a thermoplastic resin having a polymerizable functional group.

5. The photoelectric conversion element according to claim 4, wherein the thermoplastic resin having the polymerizable functional group further contains a resin having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group.

6. The photoelectric conversion element according to claim 1, wherein when A [mass%] is the ratio of the content of thermoplastic insulating resin in the electron transport layer that is not chemically bonded to the cured product in the electron transport layer to the total mass of all solids in the electron transport layer, A satisfies the following formula (1). 1≦A≦20 Formula (1)

7. The photoelectric element according to claim 1, wherein the organic electron transport compound having the polymerizable functional group contains at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, and a heteroatom.

8. The photoelectric element according to claim 1, wherein the organic electron transport compound having a polymerizable functional group is at least one compound selected from the group consisting of the compound represented by the following formula (E1), the compound represented by the following formula (E2), the compound represented by the following formula (E3), and the compound represented by the following formula (E4). 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 (In formulas (E1) to (E4), R １１ to R ２０ , R ２１ to R ２６ , R ３１ to R ３４ , and R ４１ to R ４８ each independently represent a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 28 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 28 carbon atoms, a hydroxy group, a carboxy group, an amino group, a thiol group, a halogen atom, a cyano group, and a nitro group. At this time, R １１ to R ２０ , R ２１ to R ２６ , R ３１ to R ３４ , and R ４１ to R ４８ may have adjacent groups connected to each other to jointly form a ring. Provided that at least one of R １１ to R ２０ is a group containing a functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a thiol group, at least one of R ２１ to R ２６ is a group containing a functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a thiol group, at least one of R ３１ to R ３４ is a group containing a functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a thiol group, and at least one of R ４１ to R ４８ is a group containing a functional group selected from the group consisting of a hydroxy group, a carboxy group, an amino group, and a thiol group.)

9. In the above formulas (E1) to (E4), R １１ ~R ２０ , R ２１ ~R ２６ , R ３１ ~R ３４ , and R ４１ ~R ４８ The photoelectric conversion element according to claim 8, wherein each of the elements is independently a group represented by the following formula (2). —(R) ａ ) ｍ —(R) ｂ ) ｎ —R ｃ Equation (2) (In equation (2), m and n are independently either 0 or 1.) In formula (2), R ａ R in formula (2) represents an alkylene group having 1 to 10 substituted or unsubstituted carbon atoms, or an arylene group having 6 to 14 substituted or unsubstituted carbon atoms. ｃ or R in formula (2) ｄ They may be connected to each other to form a ring. In formula (2), R ｂ represents an oxygen atom, a sulfur atom, or a group represented by the following formula (3). 【Transformation 5】 (In formula (3), R ｄ R represents a hydrogen atom, or an alkyl group having 1 to 4 substituted or unsubstituted carbon atoms. Alternatively, in this case, R in formula (2) ａ or R in formula (2) ｃ They may be connected to each other to form a ring. In formula (2), R ｃ R represents a hydrogen atom, an alkyl group having 1 to 10 substituted or unsubstituted carbon atoms, an aryl group having 6 to 14 substituted or unsubstituted carbon atoms, or an arylalkyl group having 7 to 18 substituted or unsubstituted carbon atoms. Alternatively, in this case, R in formula (2) ａ or R in formula (3) ｄ They may be connected to each other to form a ring. The substituents that the alkylene group and the alkyl group may have are a hydroxyl group, a carboxyl group, an amino group, a thiol group, an alkoxy group having 1 to 3 carbon atoms, and an alkoxycarbonyl group having 2 to 4 carbon atoms. The substituents that the arylene group, the aryl group, and the arylalkyl group may have are alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, hydroxyalkyl groups having 1 to 3 carbon atoms, carboxyl groups, amino groups, thiol groups, alkoxy groups having 1 to 3 carbon atoms, alkoxycarbonyl groups having 2 to 4 carbon atoms, halogen atoms, cyano groups, and nitro groups. However, R １１ ~R ２０ One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R ２１ ~R ２６ One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R ３１ ~R ３４ One or more of these are groups containing a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group, R ４１ ~R ４８ One or more of these groups contain a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group.

10. The photoelectric conversion element according to claim 1, wherein the organic electron transport compound having the polymerizable functional group contains heteroatoms with a number of atoms of 6 to 20.

11. The photoelectric conversion element according to claim 1, wherein the glass transition temperature of the thermoplastic insulating resin that is not chemically bonded with the cured product is 74°C or higher.

12. The photoelectric conversion element according to claim 1, wherein the thermoplastic insulating resin, which is not chemically bonded with the cured product, has a structural unit represented by the following formula (5). 【Transformation 6】 (In formula (5), R ５１ ~R ５４ Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a group represented by the following formula (6), or a group represented by the following formula (7). In this case, R ５１ ~R ５４ However, adjacent groups may connect to each other and jointly form a ring. ―C (=O) ―R ｅ Equation (6) ―C(=O)―O―R ｆ Equation (7) In equations (6) and (7), R ｅ and R ｆ Each of these independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylalkyl group.

13. A photoelectric conversion element comprising a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, The electron transport layer, A cured product of a composition containing an organic electron transport compound having polymerizable functional groups, A thermoplastic resin that is not chemically bonded to the cured product, wherein the mass ratio of conductive parts represented by the following formulas (EB6), (EB7), (EB8), (EB9), (EB10), (EB11), (EB12), (EB13), (EB14), (EB15), (EB16), (EB17), (EB18) contained in the resin is 0.03 or less. Contains A photoelectric conversion element characterized by the following features. 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 (In Formula (EB6) to Formula (EB18), R ６１ to R ７０ , R ７１ to R ７６ , R ８１ to R ８４ , R ９１ to R ９８ , R １０１ to R １１０ , R １１１ to R １１８ , R １２１ to R １２８ , R １３１ to R １４０ , R １４１ to R １４６ , R １５１ to R １５８ , R １６１ to R １６８ , R １７１ to R １８０ , and R １８１ to R １９０ each independently represent a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 28 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 28 carbon atoms, a hydroxy group, a carboxy group, an amino group, a thiol group, a halogen atom, a cyano group, and a nitro group. At this time, R ６１ to R ７０ , R ７１ to R ７６ , R ８１ to R ８４ , R ９１ to R ９８ , R １０１ to R １１０ , R １１１ to R １１８ , R １２１ to R １２８ , R １３１ to R １４０ , R １４１ to R １４６ , R １５１ to R １５８ , R １６１ to R １６８ , R １７１ to R １８０ , and R １８１ to R １９０ However, adjacent groups may be linked together to form a ring. ６１ ~R ７０ One or more of these are chemically bonded to the resin directly or via the substituents, R ７１ ~R ７６ One or more of these are chemically bonded to the resin directly or via the substituents, R ８１ ~R ８４ One or more of these are chemically bonded to the resin directly or via the substituents, R ９１ ~R ９８ One or more of these are chemically bonded to the resin directly or via the substituents, R １０１ ~R １１０ One or more of these are chemically bonded to the resin directly or via the substituents, R １１１ ~R １１８ One or more of these are chemically bonded to the resin directly or via the substituents, R １２１ ~R １２８ One or more of these are chemically bonded to the resin directly or via the substituents, R １３１ ~R １４０ One or more of these are chemically bonded to the resin directly or via the substituents, R １４１ ~R １４６ One or more of these are chemically bonded to the resin directly or via the substituents, R １５１ ~R １５８ One or more of these are chemically bonded to the resin directly or via the substituents, R １６１ ~R １６８ One or more of these are chemically bonded to the resin directly or via the substituents, R １７１ ~R １８０ One or more of these are chemically bonded to the resin directly or via the substituents, R １８１ ~R １９０ One or more of these are chemically bonded to the resin directly or via the substituents mentioned above. １０１ Z １１１ Z １２１ and Z １３１ Each of these independently represents a carbon atom, a nitrogen atom, or an oxygen atom. １０１ If it is an oxygen atom, then R １０９ and R １１０ It does not exist, Z １０１ If it is a nitrogen atom, then R １１０ It does not exist. Z １１１ If it is an oxygen atom, then R １１７ and R １１８ It does not exist, Z １１１ If it is a nitrogen atom, then R １１８ It does not exist. Z １２１ If it is an oxygen atom, then R １２７ and R １２８ It does not exist, Z １２１ If it is a nitrogen atom, then R １２８ It does not exist. Z １３１ If it is an oxygen atom, then R １３９ and R １４０ It does not exist, Z １３１ If it is a nitrogen atom, then R １４０ It does not exist.

14. A photoelectric conversion element comprising a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal disposed between the first electrode and the second electrode, and an electron transport layer disposed between the second electrode and the photoelectric conversion layer, The electron transport layer, A cured product of a composition containing an organic electron transport compound having polymerizable functional groups, A thermoplastic resin that is not chemically bonded to the cured product, wherein the volume resistivity of the resin is 10 １２ Resins with an Omega-cm or larger value, Contains A photoelectric conversion element characterized by the following features.

15. A photoelectric conversion device comprising a photoelectric conversion element according to any one of claims 1 to 14.

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