Photoelectric conversion element, photoelectric conversion device, and method for manufacturing photoelectric conversion element

Abstract

To provide a composition that is improved in dispersion stability and improves the photoelectric conversion efficiency of a photoelectric conversion element using the composition.SOLUTION: A photoelectric conversion element has a first electrode, a second electrode, and a photoelectric conversion layer arranged between the first electrode and the second electrode and including a crystal of a perovskite structure. The photoelectric conversion element has a charge transport layer arranged between the photoelectric conversion layer and the first electrode and in contact with the first electrode. The charge transport layer has particles of an annular conjugated compound in which a plurality of pyrrole rings are conjugated and bonded, a calixarene compound, and insulating resin. The first electrode is a carbon electrode.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] In order to solve the problem of fossil energy depletion and the global environmental problems caused by the use of fossil energy, active research is being conducted on renewable and clean alternative energy sources such as solar energy, wind power, and hydroelectric power. Among them, interest in solar cells that directly convert sunlight into electrical energy is increasing. Here, a solar cell refers to a cell that generates a current and voltage by utilizing the photovoltaic effect in which light energy from sunlight is absorbed and electrons and holes are generated.

[0003] Currently, np diode type silicon (Si) single crystal-based solar cells with a light energy conversion efficiency of over 20% are widely known and are actually used for photovoltaic power generation. However, these require high-temperature processing and the materials themselves are expensive, so they have the problem of high cost per unit of power. In addition, there are problems with supply in terms of silicon resources.

[0004] 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 by the so-called roll-to-roll method using a sheet-like substrate, which is expected to reduce costs. However, further improvement in power generation efficiency and durability is desired for practical use of organic solar cells. In particular, perovskite-type solar cells having a crystal of a perovskite structure as a photoelectric conversion layer have excellent photoelectric conversion characteristics, so their development is being advanced toward practical use of solar cells. For example, Patent Document 1 describes a technology in which the hole transport layer contains an organic semiconductor and an insulating polymer compound having a glass transition point of 100°C or higher, thereby making it difficult for the hole transport layer and the electrode to peel off. Patent Document 2 also describes a technology in which the charge transport layer contains a phthalocyanine compound and an aromatic ring compound having a hydroxyl group different from the phthalocyanine compound, thereby suppressing a decrease in conversion efficiency during long-term continuous use. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-170382 A [Patent Document 2] JP 2024-60579 A Summary of the Invention [Problem to be solved by the invention]

[0006] According to the studies of the present inventors, it has been found that in the photoelectric conversion elements described in Patent Documents 1 and 2, there is room for improvement in the photoelectric conversion efficiency when a carbon electrode is used.

[0007] SUMMARY OF THE PRESENT EMBODIMENTS Accordingly, an object of the present invention is to provide a photoelectric conversion element having improved photoelectric conversion efficiency when a carbon electrode is used. [Means for solving the problem]

[0008] The above object can be achieved by the present invention. A first electrode; A second electrode; a photoelectric conversion layer including a crystal having a perovskite structure, the photoelectric conversion layer being disposed between the first electrode and the second electrode; A photoelectric conversion element having the photoelectric conversion element has a charge transport layer disposed between the photoelectric conversion layer and the first electrode and in contact with the first electrode; the charge transport layer comprises particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin; The photoelectric conversion element is characterized in that the first electrode is a carbon electrode. Effect of the Invention

[0009] According to the present invention, it is possible to provide a photoelectric conversion element in which the photoelectric conversion efficiency is improved when a carbon electrode is used. [Brief description of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view in a thickness direction of a first embodiment of a photoelectric conversion element of the present invention. [Diagram 2] 1 is a perspective view showing a schematic diagram of an embodiment of a moving body including a photoelectric conversion element of the present invention; [Diagram 3] FIG. 1 is a perspective view illustrating a schematic diagram of one embodiment of a building material including a photoelectric conversion element of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The photoelectric conversion element of the present invention is a photoelectric conversion element having a first electrode, a second electrode, and a photoelectric conversion layer containing crystals of a perovskite structure and disposed between the first electrode and the second electrode, the photoelectric conversion element having a charge transport layer disposed between the photoelectric conversion layer and the first electrode and in contact with the first electrode, the charge transport layer having particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin, and the first electrode is a carbon electrode.

[0012] As a result of investigations, the present inventors have found that the above-mentioned configuration results in a photoelectric conversion element having excellent conversion efficiency. Although the details of why a photoelectric conversion element having excellent conversion efficiency can be obtained in the present invention are not clear, it is believed to be for the following reason.

[0013] By forming a film of particles of the cyclic conjugated compound in which a plurality of pyrrole rings are covalently bonded as a charge transport material, a high hole transport ability is exhibited, but when combined with a carbon electrode, the exchange of charges with the electrode is insufficient, and the photoelectric conversion efficiency may decrease. In addition, the inventors' previous studies suggested that the addition of a calixarene compound may increase the electronic interaction with the carbon electrode and reduce the series resistance of the film, but it was found that the number of molecules of the calixarene compound arranged near the electrode was insufficient, and the increase in the photoelectric conversion efficiency was limited.

[0014] On the other hand, by adding a calixarene compound and an insulating resin, the calixarene compound is dispersed into molecules through interaction with the resin while the resin ensures leakage resistance, allowing the compound to be appropriately positioned in the charge transport layer and enabling sufficient interaction with the carbon electrode, which is believed to contribute to an increase in conversion efficiency.

[0015] In the present invention, the particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugated and contained in the charge transport layer are more preferably particles of a phthalocyanine compound. The phthalocyanine compound may have a central element, and examples of the central element include Ga, Cu, Ti, Zn, Si, V, Pb, Pt, Co, Sn, Mg, Fe, Al, Mn, etc., and a metal phthalocyanine compound having a metal element at the center is preferred. Among them, a gallium phthalocyanine compound whose central element is Ga or a titanyl phthalocyanine compound whose central metal is Ti is preferred. A hydroxygallium phthalocyanine compound is more preferred. The charge transporting particles can more efficiently transport the charges generated in the photoelectric conversion layer.

[0016] In the present invention, specific examples of the insulating resin contained in the charge transport layer include polyacetal resin, acrylic resin, polyarylate resin, polycarbonate resin, polyvinyl acetate resin, polyester resin, polyamide resin, polyurethane resin, and polystyrene resin. The glass transition temperature of the insulating resin is preferably 95° C. or lower. Within this range, it is easy to come into close contact with the charge transport material, and a more effective charge distribution can be formed. The glass transition temperature can be determined by a differential scanning calorimeter (DSC).

[0017] In the present invention, the insulating resin is preferably a polyvinyl acetal resin or a polyvinyl butyral resin, which is easily in close contact with the charge transport material (particles of a cyclic conjugated compound in which multiple pyrrole rings are conjugated), and can form a more effective charge distribution.

[0018] In the present invention, the calixarene compound contained in the charge transport layer is specifically represented by the following formula [A]. [ka] (In the formula [A], R 1 ~R 5 R 1 represents a hydrogen atom or an alkyl group, R 2 represents a substituted or unsubstituted alkylene group, R 3 ~R 5 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted -Y-Ar group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and at least one of them is a substituted or unsubstituted -Y-Ar group. -Y- in the -Y-Ar group represents -CH=N-, -CH=CH-, or -N=N-, and Ar represents a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. n is an integer of 3 to 20.

[0019] Above R 1 ~R5 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0020] R 3 ~R 5 Examples of the aromatic hydrocarbons mentioned above include benzene, naphthalene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene.

[0021] Also, R 3 ~R 5 Examples of the heterocycles mentioned above include furan, thiophene, pyridine, indole, benzothiazole, carbazole, benzocarbazole, acridone, dibenzothiophene, benzoxazole, benzotriazole, oxathiazole, thiazole, phenazine, cinnoline, and benzocinnoline.

[0022] Also, R 2 ~R 5 Examples of the substituent that the alkyl group, phenylazo group, aromatic hydrocarbon group, and heterocycle mentioned above may have include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; alkoxy groups such as a methoxy group and an ethoxy group; dialkylamino groups such as a dimethylamino group and a diethylamino group; alkoxycarbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group; halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; a hydroxy group, a nitro group, a cyano group, and a halomethyl group.

[0023] In the aromatic ring compound having a calixarene structure represented by the above formula [A], in terms of molecular size, in order to easily improve dispersion stability, it is preferable that n is 4 or more and 8 or less, and the molecular weight is 10,000 or less.

[0024] In the present invention, R 1 is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group for each of the n repeating units. 2is preferably a methylene group, an ethylene group, or a trimethylene group, independently for each of the n repeating units. 3 , R 5 is a hydrogen atom, R 4 is preferably a nitrophenylazo group or a dinitrophenylazo group, independently for every n repeating units.

[0025] Among them, specific examples of calixarene compounds that are particularly preferably used in the present invention are listed below. In the present invention, the dispersant preferably contains at least one selected from the group consisting of a compound represented by the following formula [C-1], a compound represented by the following formula [C-2], a compound represented by the following formula [C-3], and a compound represented by the following formula [C-4], and more preferably contains all four (a mixture). [ka] [ka] [ka] [ka]

[0026] In the present invention, the first electrode is a carbon electrode, and preferably contains at least one of carbon black, graphite, and carbon nanotubes. By using a carbon electrode, an electrode for a photoelectric conversion element having excellent conversion efficiency can be provided by using inexpensive and simple materials and a manufacturing method.

[0027] As explained above, the respective components exert a synergistic effect on each other, thereby making it possible to achieve the effects of the present invention.

[0028] The present invention will be described in detail below with reference to preferred embodiments. The present invention is not limited to the following embodiments, and any modifications or improvements to the following embodiments based on the ordinary knowledge of a person skilled in the art without departing from the spirit of the present invention are also included in the scope of the present invention.

[0029] In this specification, the term "layer" refers not only to a layer having a clear boundary or a flat thin-film layer, but also to a layer having a concentration gradient in which the contained elements change gradually, or to a layer that can form a complex structure together with other layers. Elemental analysis of a layer can be performed, for example, by performing TOF-SIMS / FE-TEM / EDS line analysis measurement of a cross section of a photoelectric conversion element to confirm the element distribution of a specific element. Analysis of each layer may be performed by peeling and removing the completed photoelectric conversion element to expose the layer to be analyzed. In the present invention, the volume ratio is quantified by using the area ratio of the exposed surface or cross section as the volume ratio of the layer.

[0030] 1 is a cross-sectional view showing a schematic configuration of one embodiment of a photoelectric conversion element of the present invention. The photoelectric conversion element 1 has a second electrode 3, an electron transport layer 4, a photoelectric conversion layer 5, a charge transport layer 6, and a first electrode 7 on a substrate 2. One of the first electrode 7 and the second electrode 3 is an anode and the other is a cathode, and a current can be extracted by connecting the first electrode 7 and the second electrode 3 to an external circuit.

[0031] The photoelectric conversion layer 5 is excited by light incident through the substrate 2, the second electrode 3, and the electron transport layer 4, or the first electrode 7 and the charge transport layer 6, and generates electrons or holes. That is, the photoelectric conversion layer 5 generates a current between the first electrode 7 and the second electrode 3. The electron transport layer 4 is a layer disposed between the photoelectric conversion layer 5 and two electrodes (the second electrode 3 and the first electrode 7), and may not be formed in some cases. A configuration in which a plurality of electron transport layers 4 and photoelectric conversion layers 5 are stacked may be used. Such a configuration may also be called a tandem structure. Each member will be described below.

[0032] [Photoelectric conversion element] The photoelectric conversion element of the present invention has a first electrode, a second electrode, a photoelectric conversion layer containing a crystal of a perovskite structure arranged between the first electrode and the second electrode, and a charge transport layer between the photoelectric conversion layer and the first electrode, the charge transport layer having particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugated, a calixarene compound and an insulating resin, and the first electrode is a carbon electrode. In addition, in order to improve the photoelectric conversion efficiency, the photoelectric conversion elements may be stacked in a tandem type. The photoelectric conversion elements to be stacked are not limited to the type of photoelectric conversion element, and may include a perovskite solar cell using a perovskite crystal in the photoelectric conversion layer, a silicon solar cell, a CIGS solar cell, etc.

[0033] The photoelectric conversion layer of the photoelectric conversion element of the present invention and each layer including the charge transport layer can be formed by coating or vapor deposition. Examples of the coating method include dip 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 is a method in which the coating liquid for each layer described later is prepared, coated in the desired layer order, and dried. A desired method can be selected from these film formation methods according to each layer.

[0034] The present invention relates to a method for manufacturing a photoelectric conversion element having a photoelectric conversion layer, a charge transport layer, and an electrode, the method comprising, in this order, a step of forming the photoelectric conversion layer containing crystals of a perovskite structure, a step of forming the charge transport layer containing particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin, and a step of forming the electrode by applying a coating liquid.

[0035] According to the manufacturing method of the present invention, by producing an electrode using a coating liquid, a photoelectric conversion element having improved photoelectric conversion efficiency can be produced inexpensively and simply.

[0036] Each layer will be described below. 〔substrate〕 The photoelectric conversion element 1 of the present invention may include a substrate 2, examples of which include a transparent glass substrate such as soda-lime glass or alkali-free glass, a ceramic substrate, a transparent plastic substrate, etc. When light is taken in from the first electrode 7 side, an opaque material can be used for the substrate 2, and when light is taken in from the second electrode 3 side, the substrate 2 is made of a transparent material.

[0037] 〔electrode〕 The photoelectric conversion element of the present invention has a first electrode and a second electrode. The first electrode is a carbon electrode, and preferably has at least one selected from the group consisting of carbon black, graphite, and carbon nanotubes. The material of the second electrode 3 is not particularly limited, and a conventionally known material can be used. For example, metals such as gold, silver, titanium, and copper, sodium, sodium-potassium alloy, lithium, magnesium, carbon, carbon nanotubes, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / Al2O3 mixture, and Al / LiF mixture can be mentioned. Examples of transparent electrode materials include conductive transparent materials such as CuI, ITO (indium tin oxide), SnO2, AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc oxide), FTO (fluorine-doped tin oxide), and ATO (antimony-doped tin oxide), conductive transparent polymers, etc. These materials may be used alone, or two or more of them may be used in combination. At least one of the first electrode 7 and the second electrode 3 on the light incident side is a transparent electrode, and the other may be a transparent electrode or may also serve as a reflective layer formed of a light-reflective material, or may be a transparent electrode provided with a reflective layer on the side opposite to the light incident side. When the first electrode 7 is on the light incident 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.

[0038] [Photoelectric Conversion Layer] The photoelectric conversion element of the present invention has a photoelectric conversion layer including a crystal having a perovskite structure, which is disposed between a first electrode and a second electrode. The photoelectric conversion layer 5 has a crystal having a perovskite structure. The crystal having a perovskite structure used in the present invention is preferably represented by the following general formula [1].

[0039] ABX3[1] In the above general formula [1], A is a monovalent cation of an organic molecule or a metal atom, B is a divalent metal cation, and X is a monovalent halide anion.

[0040] As A in the above general formula [1], for example, in the case of an organic molecule, C p N m H n (wherein p, m, and n are all positive integers) are preferred. Specific examples include methylammonium and formamidium.

[0041] The metal atom is not particularly limited, but lithium, cesium, sodium, potassium, and rubidium are preferred. These organic molecules or metal atoms may be used alone or in combination of two or more.

[0042] When the constituent A cations are too large to fit within the 3D perovskite crystal, they form 2D perovskite crystals, 2.5D perovskite crystals with both 2D and 3D properties, bilayer crystals of 3D and 2D perovskite structures, or mixed 3D and 2D perovskite crystals, all of which function as photoelectric conversion layers. A bilayer 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 and 2D perovskite refers to a crystal with a structure in which both regions or domains of 2D or 2.5D layered and 3D perovskite crystals are mixed.

[0043] The crystals having a two-dimensional perovskite or 2.5-dimensional perovskite structure are preferably represented by the following general formulas [2] to [4], where n is a positive integer. R'2A n-1 B n X 3n+1 [2] R''A n-1 B n X 3n+1 [3] R'''A n B n X 3n+1 [4] In the above general formulas, [2] forms an RP (Ruddlesden-Popper) type perovskite structure, [3] forms a DJ (Dion-Jacobson) type perovskite structure, and [4] forms an ACI (Alternating cations in the interlayer) type perovskite structure.

[0044] R', R'', and R''' in the above general formulas [2] to [4] are organic molecules or metal cations which may have a substituent, and specific examples thereof include ethylammonium, propylammonium, n-butylammonium, n-hexylammonium, n-octylammonium, 1,6-hexadiammonium, iso-butylammonium, 3-(nonafluoro-tert-butyloxy)propylamine, 1,3-propanediammonium, 1,5-pentamethylenediamine, octyldiammonium, 2,2-(ethylenedioxy)bis(ethylammonium), 5-aminovaleric acid, 4-tert-butylammonium, N,N'-dimethylethylene-1,2-diammonium, 2,2,3,3,3-pentafluoropropylammonium, guanidinium, propylammonium, propargylamine, alkylammonium, cyclohexylmethylammonium, 4-(aminomethyl)piperidinium, piperidinium, pyrrolidinium, cyclohexylammonium, 4-fluoropropylammonium, ethylammonium, ethylammonium, propylammonium, propargylamine, alkylammonium, cyclohexylmethylammonium, 4-(aminomethyl)piperidinium, piperidinium, pyrrolidinium, cyclohexylammonium, 4-fluoropropylammonium, propylammonium, propylammonium, propargylamine, alkylammonium, cyclohexylmethylammonium, 4-(aminomethyl)piperidinium, propylammonium, pyrrolidinium, cyclohexylammonium, 4-fluoropropylammonium, ... Preferred are fluorophenethylammonium, 4-fluorophenethylammonium, trifluoromethylbenzylammonium, pentafluorobenzylammonium, pentafluorophenylethylammonium, 4-methoxyphenethylammonium, imidazolium, pyridinium, 3-thiophenemethylammonium, 2-thiopheneethylammonium, 2-thiopheneformamidium, 2-thiophenemethylammonium, 1-naphthylmethylammonium, 2-naphthylmethylammonium, phenethylammonium, phenylammonium, benzylammonium, 2,5-thiophenedimethylammonium, phenylpropylammonium, 1,4-phenylenedimethanamine, 3-phenyl-2-propene-1-ammonium, phenylbutylammonium, 4-tert-butyl-benzylammonium, 3-(aminomethyl)piperidinium, and 4-(aminomethyl)piperidinium.

[0045] In the above general formulas [1] to [4], B is a metal atom, such as 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, and bismuth are preferred from the viewpoint of electron orbital overlap. These metal atoms may be used alone or in combination of two or more.

[0046] X in the above general formulas [1] to [4] is a halogen atom, such as chlorine, bromine, and iodine. These halogen atoms may be used alone or in combination of two or more. Among them, halogen atoms are preferred because the perovskite crystals are easily soluble in organic solvents by containing halogen in the structure, making it possible to apply the perovskite crystals to inexpensive printing methods and the like. Furthermore, iodine is more preferred because the energy band gap of the perovskite crystals is narrowed.

[0047] Specifically, 3D perovskites, 2D perovskites, and mixed 3D / 2D perovskites are MAPbI3, FAPbCl3, FAPbI3, 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、Csx(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 、(pF-AND)2(FA 0.3 MA 0.7 )4Pb5I 16 、(PDMA)FA2Pb3I 10 、(3AMPY)(MA)3Pb4I 13 、(PDMA)MA5Pb6I 19 、(PDMA)MA3Pb4I 13 、(TTDMA)MA3Pb4I 13 、(TTDMA)MA4Pb5I 16 ,(THAT 0.9 AND 0.1 )2MA4Pb5I 16 ,(THAT 0.9 AND 0.1 )2MA3Pb4I 13 、(4FPEA)2MA3Pb4I 13 、(4FPEA)2MA4Pb5I 16 (BA)2MA2Pb3I 10, (BA)2MA3Pb4I 13 , (TEA)2MA2Pb3I 10 , (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. The A site, B site, and X site in the above general formula may be adjusted to be under- or over-adjusted depending on the purpose, and the combination of x1 to x5 may be changed depending on the purpose. The combination of x1 to x5 is, for example, as shown in Table 1. 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 be included as a material for forming perovskite crystals.

[0048] [Table 1]

[0049] In the above specific examples, "MA" stands for methylammonium, "FA" stands for formamidinium, "PEA" stands for phenethylammonium, "PTA" stands for phenyltriethylammonium, "ThMA" stands for 2-thiophenemethylammonium, "3BBA" stands for 3-bromobenzylammonium, "3AMPY" stands for 3-(aminomethyl)pyridine, "PDMA" stands for 1,4-phenylenedimethaneammonium, "TTDMA" stands for thieno[3,2-b]thiophene-2.5-diyldimethaneammonium, "4FPEA" stands for 4-fluorophenethylammonium, "BA" stands for butylammonium, and "TEA" stands for 2-thiophenethylammonium.

[0050] The crystal with the perovskite structure preferably has a cubic structure in which a metal atom B is located at the body center, an organic molecule A at each vertex, and a halogen atom X at the face center. Although the details are not clear, it is presumed that the presence of such a structure makes it easy to change the orientation of the octahedron in the crystal lattice, thereby increasing the mobility of electrons in the crystal with the perovskite structure and improving the photoelectric conversion efficiency of the photoelectric conversion element.

[0051] The organic-inorganic perovskite compound used in the present invention is preferably a crystalline semiconductor. The crystalline semiconductor means a semiconductor in which the scattering peak can be detected by measuring the X-ray scattering intensity distribution. By using the organic-inorganic perovskite compound as a crystalline semiconductor, the mobility of electrons in the organic-inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the photoelectric conversion element is improved.

[0052] Furthermore, the photoelectric conversion layer according to the present invention may contain materials other than the crystals having the organic-inorganic perovskite structure, as long as the photoelectric conversion efficiency and charge transport properties are not impaired.

[0053] The thickness of the photoelectric conversion layer according to the present invention is preferably 5 nm or more and 2000 nm or less. If the thickness is 5 nm or more, light can be sufficiently absorbed, and if the thickness is 2000 nm or less, the generated charge can be transported to each electrode. The more preferred lower limit is 50 nm or more, the more preferred upper limit is 1200 nm, the even more preferred lower limit is 100 nm, and the even more preferred upper limit is 1000 nm.

[0054] [Charge transport layer] In the photoelectric conversion element of the present invention, a charge transport layer is disposed between a photoelectric conversion layer and a first electrode, and the charge transport layer is formed of particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin. The respective items of the particles of the cyclic conjugated compound, the calixarene compound, the insulating resin, etc. are as described above.

[0055] In the present invention, the charge transport layer contains particles of a cyclic conjugated compound that is a P-type semiconductor and an insulating resin, and the mass content of the particles of the cyclic conjugated compound in the charge transport layer is preferably 5 to 30 times the mass content of the insulating resin in the charge transport layer. 8 The mass content of the particles of the cyclic conjugated compound in the charge transport layer is preferably 2 to 20 times the mass content of the calixarene compound in the charge transport layer.

[0056] The thickness of the charge transport layer is preferably from 1 nm to 1000 nm, more preferably from 5 nm to 500 nm, and particularly preferably from 10 nm to 200 nm.

[0057] The charge transport layer can be formed by preparing a coating solution for the charge transport layer containing the above-mentioned materials and solvent, forming this coating film on the photoelectric conversion layer, and drying it. Examples of the solvent used in the coating solution include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. Among these solvents, alcohol-based solvents or aromatic hydrocarbon-based solvents are preferred.

[0058] [Electron transport layer] In the photoelectric conversion element of the present invention, as shown in FIG. 1, an electron transport layer 4 may be disposed between the second electrode 3 and the photoelectric conversion layer 5.

[0059] The material of the electron transport layer 4 is not particularly limited, and examples thereof include N-type conductive polymers, N-type low-molecular organic semiconductors, N-type metal oxides, N-type metal sulfides, alkali metal halides, alkali metals, surfactants, etc. Specific examples thereof include cyano group-containing polyphenylene vinylene, boron-containing polymers, bathocuproine, bathophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, fullerene compounds, perylene derivatives, phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, etc. In particular, tin oxide may be obtained by reacting tin chloride (2), tin chloride (4), tin chloride (2) dihydrate, or tin chloride (4) pentahydrate.

[0060] The thickness of the electron transport layer 4 is preferably 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 blocked sufficiently, and if it is 2000 nm or less, it is unlikely to become a resistance during electron transport, and the photoelectric conversion efficiency is high. The thickness is more preferably 3 nm at the lower limit and 1000 nm at the upper limit, and even more preferably 5 nm at the lower limit and 500 nm at the upper limit.

[0061] [Control of particle size of cyclic conjugated compound particles] The particle size of the cyclic conjugated compound particles can be changed by dispersing the charge transport layer coating liquid with a paint shaker, and the particle size can be reduced by extending the dispersion time, and the particle size can be further reduced by centrifuging the charge transport layer coating liquid.

[0062] <Application Examples> Application examples of the present invention include photoelectric conversion devices, moving objects, and building materials.

[0063] [Photoelectric conversion device] The photoelectric conversion device of the present invention has the above-mentioned photoelectric conversion element. A photoelectric conversion device can be constructed by using a plurality of photoelectric conversion elements of the present invention. When a plurality of photoelectric conversion elements are connected, the photoelectric conversion device can also be called a photoelectric conversion cell or a photoelectric conversion module. The photoelectric conversion element may be a stack of photoelectric conversion elements having different absorption wavelengths in order to increase the output voltage. The photoelectric conversion device may have the photoelectric conversion element of the present invention and an inverter. The inverter may be a converter that converts direct current to alternating current. The photoelectric conversion device may have a storage unit connected to the photoelectric conversion element. The storage unit is not limited as long as it can store electricity. For example, a secondary battery using lithium ions or the like, an all-solid-state battery, an electric double layer capacitor, etc. may be mentioned. In order to impart a function such as maintaining or increasing the amount of incident light, a surface layer that is resistant to water and dirt, or a function of collecting or guiding light may be added.

[0064] [Mobile object] The moving body of the present invention has the above-mentioned photoelectric conversion element. FIG. 2 is a perspective view showing an embodiment of a moving body equipped with the photoelectric conversion element of the present invention. The moving body 30 has the photoelectric conversion element 31 of the present invention and a vehicle 32 equipped with the photoelectric conversion element 31. The photoelectric conversion element 31 is arranged at a position where the vehicle 32 can receive external light. If the moving body 30 is an automobile, it may be arranged on the roof. The electric energy obtained by the photoelectric conversion element 31 may be used as the power of the moving body 30 or as the power of other electric devices. The electric energy generated from the power of the moving body 30 may be used to power the photoelectric conversion element 31. If the moving body 30 is an automobile, frictional energy generated by braking may be converted into electric energy and used to control the photoelectric conversion element 31.

[0065] The moving body 30 may be, for example, an automobile, a motorcycle, a railroad vehicle, a ship, an artificial satellite, an airplane, or a flying object including a drone. The configuration of the body 32 of the moving body 30 is not particularly limited, but it is preferable that the body 32 be made of a high-strength material.

[0066] [Building materials] The building material of the present invention has the above-mentioned photoelectric conversion element. Fig. 3 is a perspective view showing an embodiment of a building material including the photoelectric conversion element of the present invention. 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 the present invention, a protective member 42 that protects the photoelectric conversion element 41, a heat dissipation member 43, and exteriors 44a and 44b.

[0067] The building material 40 of the present invention may have a heat dissipation member 43 having a higher thermal conductivity than the photoelectric conversion element 41. When used on a roof or the like, the temperature of the photoelectric conversion element 41 may increase due to sunlight, and the photoelectric conversion efficiency may decrease. The use of the heat dissipation member 43 can reduce the decrease in photoelectric conversion efficiency. Examples of the heat dissipation member 43 include metal, alloy, liquid metal, and liquid resin.

[0068] Furthermore, the building material 40 of the present invention may have exteriors 44a and 44b. The exteriors 44a and 44b may emit different colors or may be the same. 44a and 44b may be made of the same material or different materials. Paint or a transparent substrate may be used as the exterior. A material with low light absorption and high heat insulation is preferable.

[0069] In addition to the above application examples, other application examples include the following: Portable devices, such as calculators, sensors, and small solar panels. Wearable devices, such as eyeglass-type terminals, wristwatch-type terminals, and portable medical equipment. Sheet structures supported by multiple frames, such as tents, vinyl greenhouses, and truck beds. Fixed structures, such as road panels, floating panels, building materials that take advantage of the flexibility of the substrate, wall-type building materials, glass-type building materials, and mega solar panels. EXAMPLES

[0070] The present invention will be described in more detail below using examples and comparative examples. The present invention is not limited to the following examples without departing from the gist of the present invention. In the following description of the examples, "parts" are by mass unless otherwise specified.

[0071] Example 1 Preparation of particle 1 Process (1) In a nitrogen flow atmosphere, 5.46 parts of orthophthalonitrile and 45 parts of α-chloronaphthalene were put into a reaction vessel, and then heated to a temperature of 30°C and maintained at this temperature. Next, 3.75 parts of gallium trichloride were put in at this temperature (30°C). The water concentration of the mixed liquid at the time of putting in was 150 ppm. Then, the temperature was raised to 200°C. Next, under a nitrogen flow atmosphere, the reaction was carried out at a temperature of 200°C for 4.5 hours, and then cooled. When the temperature reached 150°C, the product was filtered. The obtained filtrate was dispersed and washed using N,N-dimethylformamide at a temperature of 140°C for 2 hours, and then filtered. The obtained filtrate was washed with methanol and then dried to obtain chlorogallium phthalocyanine particles with a yield of 71%.

[0072] Process (2) 4.65 parts of the chlorogallium phthalocyanine particles were dissolved in 139.5 parts of concentrated sulfuric acid at a temperature of 10° C., dropped into 620 parts of ice water under stirring to reprecipitate, and filtered under reduced pressure using a filter press. At this time, No. 5C (manufactured by Advantec Co., Ltd.) was used as the filter. The obtained wet cake (filtrate) was dispersed and washed with 2% ammonia water for 30 minutes, and then filtered using a filter press. Next, the obtained wet cake (filtrate) was dispersed and washed with ion-exchanged water, and then filtration using a filter press was repeated three times. Finally, freeze-drying was performed to obtain hydroxygallium phthalocyanine particles (hydrated hydroxygallium phthalocyanine particles) with a solid content of 23% by mass at a yield of 71%. The hydroxygallium phthalocyanine particles were dried in a Hyper Dry dryer (product name: HD-06R, frequency (oscillation frequency): 2455 MHz ± 15 MHz, manufactured by Japan Biocon) to obtain hydroxygallium phthalocyanine (OHGaPc) particles (crystals) with a moisture content of 1.0 mass% or less.

[0073] Process (3) Five parts of the hydroxygallium phthalocyanine particles were mixed with 5 parts of N-methylformamide solvent, and the mixture was dispersed for 6 hours using a sand mill (TSG-1 / 4G-4U, manufactured by Igarashi Machinery Manufacturing (now Imex), disk diameter 70 mm, number of disks 5) containing 5 parts of glass beads, filtered, and dried to obtain Particle 1 (specific gravity 1.6).

[0074] Preparation of resin solution 1 1.0 g of polyvinyl butyral (product name: BM-2, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature 71° C.) was dissolved in 19 g of 2-propanol with stirring for 24 hours to obtain resin solution 1.

[0075] [Formation of Electron Transport Layer] A square ITO-coated glass substrate with sides of 25 mm was cleaned, and a 5-fold diluted tin oxide (2) colloidal solution (15% water dispersion, manufactured by Alfa Aesar) was spin-coated onto it, followed by heating at 150°C for 30 minutes to form a thin-film electron transport layer with a thickness of 16 nm.

[0076] [Formation of photoelectric conversion layer] 0.487 g of lead bromide, 1.034 g of formamidium iodide, 2.903 g of lead iodide, and 0.139 g of methylammonium bromide were dissolved in 4.25 g of N,N-dimethylformamide and 1.216 g of dimethyl sulfoxide, and the mixture was stirred for 1 hour (solution 1). Furthermore, 0.100 g of cesium iodide was dissolved in 0.285 g of dimethyl sulfoxide, and the mixture was stirred for 1 hour (solution 2). The dissolved cesium iodide solution (solution 2) was then added to solution 1 to prepare a photoelectric conversion layer coating solution. This coating solution was spin-coated on the electron transport layer using the poor solvent method, resulting in the formation of a photoelectric conversion layer containing Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 Pb(I 0.83 Br 0.17 A photoelectric conversion layer having a thickness of 600 nm was formed from the photoelectric conversion layer 3.

[0077] [Formation of Charge Transport Layer] 0.1 g of the particles 1 and 0.01 g of the mixture of the compounds represented by the formulas [C-1] to [C-4] as calixarene compounds were mixed with 10.6 g of 2-propanol. The mass ratio was [C-1]:[C-2]:[C-3]:[C-4]=1:1:1:1. 11 g of beads (zirconia beads, Treceram (registered trademark) zirconia beads, 0.3 mm) were enclosed in this mixture, and dispersion was performed using a paint shaker (manufactured by Toyo Seiki) for 7 hours. Then, 0.2 g of resin solution 1 was added, and dispersion was performed using a paint shaker again for 6 hours to prepare a charge transport layer solution 1. This charge transport layer solution 1 was spin-coated on the photoelectric conversion layer to form a charge transport layer having a thickness of 160 nm.

[0078] [Formation of the first electrode] A carbon paste (product name: JELCON CH-8, manufactured by Jujo Chemical Co., Ltd.) was applied onto the charge transport layer, and then heated at 120°C for 15 minutes to form a layer with an area of ​​0.09 cm. 2 Electrodes were formed in ten places to obtain a photoelectric conversion element.

[0079] [Analysis of compound amounts] The electrode surface of the photoelectric conversion element was peeled off to expose the charge transport layer surface. This charge transport layer surface was wiped with a cotton swab soaked in a solvent, dissolved in heavy water sulfuric acid, and 1H-NMR measurement (apparatus: AVANCE3-500, manufactured by BRUKER) was performed. In addition, the peeled off charge transport layer components were subjected to mass and structure analysis by elemental analysis such as GPC, MALDI-TOF-MS, IR, gas chromatography, XPS, and EDX to confirm the presence of compounds. The film thickness was confirmed by cutting the photoelectric conversion element, fixing it to an inclined sample stage, and then observing the cross-section with a SEM (apparatus: Carl Zeiss, SmartSEM).

[0080] Example 2 A photoelectric conversion element is obtained in the same manner as in Example 1, except that the polyvinyl butyral is changed to polyvinyl butyral (product name: BL-5Z, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: 67° C.).

[0081] Example 3 Between the charge transport layer and the photoelectric conversion layer, 2.49 mg of 2-phenethylethylamine hydroiodide is dissolved in 1 mL of 2-propanol to prepare a solution for the thin film layer, and the solution for the thin film layer is spin-coated on the photoelectric conversion layer to form a thin film layer having a thickness of 20 nm. A photoelectric conversion element is obtained in the same manner as in Example 1 except for the above.

[0082] Example 4 A photoelectric conversion element is obtained in the same manner as in Example 1, except that particles 1 are chlorogallium phthalocyanine (ClGaPc) particles as the particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded.

[0083] Example 5 A photoelectric conversion element is obtained in the same manner as in Example 1, except that particles 1 are copper phthalocyanine (CuPc) particles as the particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded.

[0084] Example 6 A photoelectric conversion element is obtained in the same manner as in Example 1, except that particles 1 are titanyl phthalocyanine (TiOPc) particles as the particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded.

[0085] Example 7 A photoelectric conversion element is obtained in the same manner as in Example 1, except that particles 1 are zinc phthalocyanine (ZnPc) particles as the particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded.

[0086] Example 8 A photoelectric conversion element is obtained in the same manner as in Example 1, except that particles 1 are silicon phthalocyanine dichloride (SiPcCl2) particles as the particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded.

[0087] Example 9 A photoelectric conversion element is obtained in the same manner as in Example 1, except that particles 1 are tetraphenylporphyrin (TPP) particles as particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded.

[0088] Example 10 A photoelectric conversion element is obtained in the same manner as in Example 1, except that 0.07 g of the resin solution 1 is used in preparing the charge transport layer solution.

[0089] Example 11 A photoelectric conversion element is obtained in the same manner as in Example 1, except that 0.4 g of the resin solution 1 is used in preparing the charge transport layer solution.

[0090] Example 12 A photoelectric conversion element is obtained in the same manner as in Example 1, except that 0.005 g of the calixarene compound is used in preparing the charge transport layer solution.

[0091] Example 13 A photoelectric conversion element is obtained in the same manner as in Example 1, except that 0.05 g of the calixarene compound is used in preparing the charge transport layer solution.

[0092] Example 14 A photoelectric conversion element is obtained in the same manner as in Example 1, except that 0.06 g of the resin solution 1 is used in preparing the charge transport layer solution.

[0093] Example 15 A photoelectric conversion element is obtained in the same manner as in Example 1, except that 1.0 g of the resin solution 1 is used in preparing the charge transport layer solution.

[0094] Example 16 A photoelectric conversion element is obtained in the same manner as in Example 1, except that 0.004 g of the calixarene compound is used in preparing the charge transport layer solution.

[0095] (Example 17) A photoelectric conversion element is obtained in the same manner as in Example 1, except that 0.1 g of the calixarene compound is used in preparing the charge transport layer solution.

[0096] (Example 18) A photoelectric conversion element is obtained in the same manner as in Example 1, except that the polyvinyl butyral is changed to polyvinyl butyral (product name: BX-1, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: 95° C.).

[0097] (Example 19) A photoelectric conversion element is obtained in the same manner as in Example 1, except that the polyvinyl butyral is replaced with polyvinyl acetal (product name: KS-1, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: 107° C.).

[0098] (Example 20) A photoelectric conversion element is obtained in the same manner as in Example 1, except that the polyvinyl butyral is replaced with polymethyl methacrylate (PMMA, manufactured by Sigma-Aldrich, glass transition temperature 70° C.).

[0099] Example 21 A photoelectric conversion element is obtained in the same manner as in Example 1, except that a mixture of compounds represented by the following formulas [C-5] and [C-6] in a mass ratio of 1:1 is used as the calixarene compound. [ka] [ka]

[0100] Example 22 A photoelectric conversion element is obtained in the same manner as in Example 1, except that a boron-doped diamond electrode formed by plasma CVD is used as the carbon electrode.

[0101] Comparative Example 1 A photoelectric conversion element was obtained in the same manner as in Example 1, except that the calixarene compound and the resin solution 1 were not used in forming the charge transport layer.

[0102] Comparative Example 2 A photoelectric conversion element is obtained in the same manner as in Example 1, except that the calixarene compound is not used in forming the charge transport layer.

[0103] Comparative Example 3 A photoelectric conversion element is obtained in the same manner as in Example 1, except that resin solution 1 is not used in forming the charge transport layer.

[0104] Comparative Example 4 A photoelectric conversion element is obtained in the same manner as in Example 1, except that in forming the charge transport layer, the calixarene compound is replaced with phenol.

[0105] Comparative Example 5 A photoelectric conversion element is obtained in the same manner as in Example 1, except that in preparing the resin solution 1, polyvinyl butyral is replaced with poly(3-hexylthiophene-2,5-diyl) (P3HT, manufactured by Sigma-Aldrich).

[0106] Comparative Example 6 In forming the charge transport layer, a photoelectric conversion element is obtained in the same manner as in Example 1, except that a charge transport layer solution 2 prepared by dissolving 79.91 mg of Spiro-OMeTAD as a charge transport material, 34 μL of t-butylpyridine, 10 mg of bis(trifluoromethylsulfonyl)imide silver salt, and 0.9 mg of norbornene resin (trade name: TOPAS6013, manufactured by Polyplastics Co., Ltd., glass transition temperature: 130° C.) as an insulating resin in 1 mL of chlorobenzene is used.

[0107] [evaluation] A power supply (KEITHLEY, Model 236) was connected between the electrodes of the photoelectric conversion element prepared in Example 1, and the intensity was 114 mW / cm 2 The photoelectric conversion efficiency was measured by irradiating a certain amount of light using a solar simulator (manufactured by Yamashita Denso Co., Ltd.) and measuring the generated current and voltage. In addition, measurements were taken at 10 electrodes for each photoelectric conversion element, and the average value was used as the representative value for that photoelectric conversion element. The results are shown in Table 2.

[0108] In Table 2, the photoelectric conversion efficiency in Example 1 is set to 1, and the ratio to this is shown as the conversion efficiency of each photoelectric conversion element.

[0109] [Table 2]

[0110] The disclosure of this embodiment includes the following configurations and methods. [Configuration 1] A first electrode; A second electrode; a photoelectric conversion layer including a crystal having a perovskite structure, the photoelectric conversion layer being disposed between the first electrode and the second electrode; A photoelectric conversion element having the photoelectric conversion element has a charge transport layer disposed between the photoelectric conversion layer and the first electrode and in contact with the first electrode; the charge transport layer comprises particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin; A photoelectric conversion element, wherein the first electrode is a carbon electrode. [Configuration 2] 3. The photoelectric conversion element according to configuration 2, wherein the cyclic conjugated compound is a phthalocyanine compound. [Configuration 3] 3. The photoelectric conversion element according to configuration 2, wherein the phthalocyanine compound is a metal phthalocyanine compound having a metal element at the center. [Configuration 4] The photoelectric conversion element according to configuration 3, wherein the metal phthalocyanine compound is a gallium phthalocyanine compound. [Configuration 5] 6. The photoelectric conversion element according to configuration 5, wherein the gallium phthalocyanine compound is a hydroxygallium phthalocyanine compound. [Configuration 6] 6. The photoelectric conversion element according to any one of configurations 1 to 5, wherein the calixarene compound is represented by the following formula [A]: [ka] (In the formula [A], R 1 ~R 5R 1 represents a hydrogen atom or an alkyl group, R 2 represents a substituted or unsubstituted alkylene group, R 3 ~R 5 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted -Y-Ar group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and at least one of them is a substituted or unsubstituted -Y-Ar group. -Y- in the -Y-Ar group represents -CH=N-, -CH=CH-, or -N=N-, and Ar represents a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. n is an integer of 3 to 20. [Configuration 7] A photoelectric conversion element according to configuration 6, wherein the calixarene compound of formula [A] includes at least one selected from the group consisting of compounds represented by the following formulas [C-1], [C-2], [C-3] and [C-4]. [ka] [ka] [ka] [ka] [Configuration 8] 8. The photoelectric conversion element according to any one of configurations 1 to 7, wherein the insulating resin has a glass transition temperature of 95° C. or lower. [Configuration 9] 9. The photoelectric conversion element according to any one of configurations 1 to 8, wherein the insulating resin is a polyvinyl acetal resin or a polyvinyl butyral resin. [Configuration 10] 10. The photoelectric conversion element according to any one of configurations 1 to 9, wherein the mass content of the cyclic conjugated compound particles in the charge transport layer is 5 to 30 times the mass content of the insulating resin in the charge transport layer. [Configuration 11] 11. The photoelectric conversion element according to any one of configurations 1 to 10, wherein the mass content of the cyclic conjugated compound particles in the charge transport layer is 2 to 20 times the mass content of the calixarene compound in the charge transport layer. [Configuration 12] 12. The photoelectric conversion element according to any one of configurations 1 to 11, wherein the carbon electrode comprises at least one selected from the group consisting of carbon black, graphite, and carbon nanotubes. [Configuration 13] 13. A photoelectric conversion device comprising the photoelectric conversion element according to any one of configurations 1 to 12. [Method 1] A method for producing a photoelectric conversion element having a photoelectric conversion layer, a charge transport layer, and an electrode, comprising the steps of: forming the photoelectric conversion layer including crystals having a perovskite structure; forming the charge transport layer having particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin; forming the electrode by applying a coating liquid; A method for manufacturing a photoelectric conversion element. [Explanation of symbols]

[0111] 1 Photoelectric conversion element 2. Board 3 Second electrode 4 Electron transport layer 5 Photoelectric conversion layer 6 Charge transport layer 7 First electrode 30 Mobile 31, 41 Photoelectric conversion element 32 Aircraft 40 Building materials 42 Protective materials 43 Heat dissipation materials 44a, 44b Exterior

Claims

1. A first electrode; A second electrode; a photoelectric conversion layer including a crystal having a perovskite structure, the photoelectric conversion layer being disposed between the first electrode and the second electrode; A photoelectric conversion element having the photoelectric conversion element has a charge transport layer disposed between the photoelectric conversion layer and the first electrode and in contact with the first electrode; the charge transport layer comprises particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin; A photoelectric conversion element, wherein the first electrode is a carbon electrode.

2. The photoelectric conversion element according to claim 1 , wherein the cyclic conjugated compound is a phthalocyanine compound.

3. 3. The photoelectric conversion element according to claim 2, wherein the phthalocyanine compound is a metal phthalocyanine compound having a metal element at the center.

4. The photoelectric conversion element according to claim 3 , wherein the metal phthalocyanine compound is a gallium phthalocyanine compound.

5. The photoelectric conversion element according to claim 4 , wherein the gallium phthalocyanine compound is a hydroxygallium phthalocyanine compound.

6. The photoelectric conversion element according to claim 1 , wherein the calixarene compound is represented by the following formula [A]: 【Chemistry 1】 (In the formula [A], R １ ~R ５ R １ represents a hydrogen atom or an alkyl group; R ２ represents a substituted or unsubstituted alkylene group; R ３ ~R ５ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted -Y-Ar group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group, and at least one is a substituted or unsubstituted -Y-Ar group. -Y- in the -Y-Ar group represents -CH=N-, -CH=CH-, or -N=N-, and Ar is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. n is an integer of 3 or more and 20 or less.

7. The photoelectric conversion element according to claim 6, wherein the calixarene compound of the formula [A] includes at least one selected from the group consisting of compounds represented by the following formulas [C-1], [C-2], [C-3] and [C-4]. 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】

8. 2. The photoelectric conversion element according to claim 1, wherein the insulating resin has a glass transition temperature of 95° C. or lower.

9. The photoelectric conversion element according to claim 1 , wherein the insulating resin is a polyvinyl acetal resin or a polyvinyl butyral resin.

10. 2 . The photoelectric conversion element according to claim 1 , wherein a mass content of the cyclic conjugated compound particles in the charge transport layer is 5 to 30 times a mass content of the insulating resin in the charge transport layer.

11. 2. The photoelectric conversion element according to claim 1, wherein the mass content of the cyclic conjugated compound particles in the charge transport layer is from 2 to 20 times the mass content of the calixarene compound in the charge transport layer.

12. The photoelectric conversion element according to claim 1 , wherein the carbon electrode comprises at least one selected from the group consisting of carbon black, graphite, and carbon nanotubes.

13. A photoelectric conversion device comprising the photoelectric conversion element according to any one of claims 1 to 12.

14. A method for producing a photoelectric conversion element having a photoelectric conversion layer, a charge transport layer, and an electrode, comprising the steps of: forming the photoelectric conversion layer including crystals having a perovskite structure; forming the charge transport layer having particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin; forming the electrode by applying a coating liquid; A method for manufacturing a photoelectric conversion element.

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