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

Abstract

The present invention provides a composition that has improved dispersion stability and that improves the photoelectric conversion efficiency of a photoelectric conversion element in which the composition is used.　This photoelectric conversion element has a first electrode, a second electrode, and a photoelectric conversion layer that is disposed between the first electrode and the second electrode and that contains a crystal having a perovskite structure. The photoelectric conversion element is characterized by having a charge transport layer that is disposed between the photoelectric conversion layer and the first electrode and that is in contact with the first electrode, and is characterized in that: the charge transport layer contains an insulating resin, a calixarene compound, and particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugated and bonded; and the first electrode is a carbon electrode.

Description

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

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

[0002] In order to solve the problems 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 hydropower. Among these, interest is growing in solar cells that directly convert sunlight into electrical energy. Here, a solar cell refers to a cell that generates current and voltage by utilizing the photovoltaic effect, in which light energy from sunlight is absorbed and electrons and holes are generated.

[0003] Currently, n-p 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 solar power generation. However, these require high-temperature processing steps and the materials themselves are expensive, resulting in high costs per unit of power. Furthermore, there are also supply issues due to the limited 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 using a sheet-like substrate using a so-called roll-to-roll method, which is expected to reduce costs. However, further improvements in power generation efficiency and durability are desired for the practical use of organic solar cells. In particular, perovskite solar cells, which have crystals with a perovskite structure as a photoelectric conversion layer, have excellent photoelectric conversion characteristics and are therefore being developed for practical use. For example, Patent Document 1 describes a technology in which the hole transport layer contains an organic semiconductor and an insulating polymer compound with a glass transition temperature of 100°C or higher, thereby making it difficult for the hole transport layer to peel off from the electrode. Furthermore, Patent Document 2 describes a technology in which the charge transport layer contains a phthalocyanine compound and an aromatic ring compound having a hydroxyl group other than the phthalocyanine compound, thereby suppressing a decrease in conversion efficiency during long-term continuous use.

[0005] JP 2018-170382 A JP 2024-60579 A

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

[0007] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a photoelectric conversion element that has improved photoelectric conversion efficiency when a carbon electrode is used.

[0008] The above object can be achieved by the present invention, which provides 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, wherein 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 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 the first electrode is a carbon electrode.

[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.

[0010] 1 is a schematic cross-sectional view in a thickness direction of a first embodiment of the photoelectric conversion element of the present invention; FIG. 2 is a perspective view schematically showing an embodiment of a moving body including the photoelectric conversion element of the present invention; and FIG. 3 is a perspective view schematically showing an embodiment of a building material including the photoelectric conversion element of the present invention.

[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, wherein 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 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-described 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 thought to be as follows.

[0013] The particles of the cyclic conjugated compound in which multiple pyrrole rings are covalently bonded are formed as a charge transport material to form a film, which exhibits high hole transport ability. However, when combined with a carbon electrode, the exchange of charges with the electrode is insufficient, resulting in a decrease in photoelectric conversion efficiency. Furthermore, previous studies by the present inventors suggested that the addition of a calixarene compound could increase the electronic interaction with the carbon electrode and reduce the series resistance of the film. However, it was found that the number of calixarene compound molecules arranged near the electrode was insufficient, limiting the increase in photoelectric conversion efficiency.

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

[0015] In the present invention, the particles of a 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, such as Ga, Cu, Ti, Zn, Si, V, Pb, Pt, Co, Sn, Mg, Fe, Al, or Mn. A metal phthalocyanine compound having a metal element at the center is preferred. Among these, a gallium phthalocyanine compound having Ga as the central element or a titanyl phthalocyanine compound having Ti as the central metal is preferred. A hydroxygallium phthalocyanine compound is more preferred. These charge transport particles can more efficiently transport 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. Furthermore, it is preferable that the glass transition temperature of the insulating resin is 95°C or lower. Within this range, the insulating resin can easily come into close contact with the charge transport material, resulting in a more effective charge distribution. The glass transition temperature can be determined by differential scanning calorimetry (DSC).

[0017] In the present invention, the insulating resin is preferably a polyvinyl acetal resin or a polyvinyl butyral resin, which can easily come into close contact with the charge transport material (particles of a cyclic conjugated compound in which multiple pyrrole rings are conjugated), thereby forming 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]. (In the formula [A], R １ ~R ５ are independently in each repeating unit and independently for every n repeating units, R １ represents a hydrogen atom or an alkyl group, and R ２ represents a substituted or unsubstituted alkylene group, and 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.

[0019] The above R １ ~R ５ Examples of the alkyl group mentioned above 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 facilitate improving 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 every n repeating units. ２ is preferably a methylene group, an ethylene group, or a trimethylene group, independently for every 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 these, 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).

[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 using inexpensive and simple materials and a simple manufacturing method.

[0027] As explained above, the effects of the present invention can be achieved by the synergistic effects of the various components.

[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 those 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 with clear boundaries or a flat, thin-film layer, but also to a layer with a gradually changing concentration gradient of contained elements, or to a layer that can form a complex, intricate structure together with other layers. Elemental analysis of a layer can be performed, for example, by performing TOF-SIMS / FE-TEM / EDS line analysis 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 that layer.

[0030] 1 is a cross-sectional view schematically illustrating the 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 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 through 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 the 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 component will be described below.

[0032] [Photoelectric Conversion Element] The photoelectric conversion element of the present invention comprises a first electrode, a second electrode, a photoelectric conversion layer containing a perovskite crystal structure disposed between the first electrode and the second electrode, and a charge transport layer between the photoelectric conversion layer and the first electrode, wherein 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, and the first electrode is a carbon electrode. Furthermore, to improve photoelectric conversion efficiency, the photoelectric conversion elements may be stacked in a tandem configuration. The photoelectric conversion elements to be stacked are not limited to a specific type of photoelectric conversion element, and may include perovskite solar cells using perovskite crystals in the photoelectric conversion layer, silicon solar cells, CIGS solar cells, and the like.

[0033] Methods for forming each layer, including the photoelectric conversion layer and the charge transport layer, of the photoelectric conversion element of the present invention include coating methods and vapor deposition methods. Examples of coating methods 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 involves preparing a coating solution for each layer, which will be described later, applying the solution in the desired layer order, and drying the solution. A desired method can be selected from these film formation methods depending on 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 electrodes, 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 electrodes 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, for example, 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] [Electrodes] 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 conventionally known materials 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, and Al / Al ２ O ３ Examples of transparent electrode materials include CuI, ITO (indium tin oxide), and SnO. ２ Examples of the conductive transparent material include AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc oxide), FTO (fluorine-doped tin oxide), and ATO (antimony-doped tin oxide), as well as conductive transparent polymers. These materials may be used alone or in combination of two or more. The first electrode 7 and the second electrode 3 may be such that at least one electrode on the light incident side is a transparent electrode, and the other electrode may be a transparent electrode or may double as a reflective layer formed of a light-reflective material, or may be a transparent electrode with a reflective layer on the side opposite 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 that is disposed between a first electrode and a second electrode and contains a crystal with a perovskite structure. The photoelectric conversion layer 5 has a crystal with a perovskite structure. The crystal with a perovskite structure used in the present invention is preferably represented by the following general formula [1]:

[0039] ABX ３ [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 general formula [1], for example, in the case of an organic molecule, C ｐ N ｍ H ｎ (where p, m, and n are all positive integers) 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] If the constituent cation A is too large to fit within a crystal with a three-dimensional perovskite structure, the resulting crystal will be a two-dimensional perovskite structure, a 2.5-dimensional perovskite structure crystal having both two-dimensional and three-dimensional properties, a bilayer crystal of a three-dimensional and two-dimensional perovskite structure, or a crystal with a mixed three-dimensional and two-dimensional perovskite structure, all of which function as a photoelectric conversion layer. A bilayer crystal of a three-dimensional and two-dimensional perovskite structure refers to a crystal in which crystals with a three-dimensional and two-dimensional perovskite structure are stacked as independent, separate layers, while a mixed three-dimensional and two-dimensional perovskite refers to a crystal with a structure in which regions or domains of both two-dimensional or 2.5-dimensional layered and three-dimensional perovskite structure crystals are mixed.

[0043] The crystal of the two-dimensional perovskite or 2.5-dimensional perovskite structure is preferably represented by the following general formulas [2] to [4], where n is a positive integer: R' ２ A 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, isobutylammonium, 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, guanidium, propylammonium, propargylamine, alkylammonium, cyclohexylmethylammonium, 4-(aminomethyl)piperidinium, piperidinium, pyrrolidinium, cyclohexylammonium, 4-furan ... 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, or iodine. These halogen atoms may be used alone or in combination of two or more. Among these, halogen atoms are preferred because the inclusion of halogen in the structure makes the perovskite structure crystal more soluble in organic solvents, enabling application to inexpensive printing methods, etc. Furthermore, iodine is more preferred because it narrows the energy band gap of the perovskite structure crystal.

[0047] Specifically, 3D perovskite, 2D perovskite, and mixed 3D / 2D perovskite are MAPbI ３ and FAPbCl ３ , FAPbI ３ , 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 , (FAPbI ３ ) ０．９５ (MAPbBr３ ) ０．０５ 、(FAPbI ３ ) ０．８５ (MAPbBr ３ ) ０．１５ 、CsPbI ３ 、CsPbBr ３ 、Cs ｘ (MA) １－ｘ PbI ３ 、Csx(FA) １－ｘ PbI ３ 、MA ｘ (FA) １－ｘ PbI ３ 、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 、(PEA) ２ (MA) ２ Pb ３ I １０ 、(PTA) ２ (MA) ４ Pb ５ I １６ 、(PEA) ２ (MA) ４ Pb ５ I １６ 、(ThMA) ２ (MA) ２ Pb ３ I １０ 、(3BBA) ２ (MA) ２ Pb ３ I １０ 、(ThMA) ２ (FA) ４ Pb ５ I １６ 、(pF-PEA) ２ (FA ０．３ MA ０．７ )４ Pb ５ I １６ 、(PDMA)FA ２ Pb ３ I １０ 、(3AMPY)(MA) ３ Pb ４ I １３ 、(PDMA)MA ５ Pb ６ I １９ 、(PDMA)MA ３ Pb ４ I １３ 、(TTDMA)MA ３ Pb ４ I １３ 、(TTDMA)MA ４ Pb ５ I １６ 、(BA ０．９ PEA ０．１ ) ２ MA ４ Pb ５ I １６ 、(BA ０．９ PEA ０．１ ) ２ MA ３ Pb ４ I １３ 、(4FPEA) ２ MA ３ Pb ４ I １３ 、(4FPEA) ２ MA ４ Pb ５ I １６ (BA) ２ MA ２ Pb ３ I １０ 、(BA) ２ MA ３ Pb ４ I １３ 、(TEA) ２ MA ２ Pb ３ I １０ 、(BA) ２ MA ４ Pb ５ I １６ 、(BA) ２ MA ３ Pb ４ I １３ 、CsSnBr ３ 、CsSnI３ , F.A. ０．７５ MA ０．２５ Sn ０．９５ Ge ０．０５ I ３ , FAMASnGeI ３ , FASnBr ３ , FASnI ３ , M.A. ２ Sn ３ I ８ , MASnBr ３ , MASnGeI ３ , MASnI ３ is preferred. Depending on the purpose, the A site, B site, or X site in the above general formula may be adjusted to be insufficient or excessive, and the combination of x1 to x5 may be changed depending on the purpose. Combinations of x1 to x5 are, 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 also be included as a material for forming perovskite crystals.

[0048]

[0049] 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, "BA" represents butylammonium, and "TEA" represents 2-thiophenethylammonium.

[0050] The perovskite crystal 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 such a structure allows the orientation of the octahedra in the crystal lattice to be easily changed, thereby increasing the mobility of electrons in the perovskite crystal 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. A crystalline semiconductor refers to a semiconductor from which a scattering peak can be detected by measuring an X-ray scattering intensity distribution. When the organic-inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic-inorganic perovskite compound increases, improving the photoelectric conversion efficiency of the photoelectric conversion element.

[0052] Furthermore, the photoelectric conversion layer according to the present invention may contain materials other than the crystals of 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. A thickness of 5 nm or more allows sufficient absorption of light, and a thickness of 2000 nm or less allows generated charges to be transported to each electrode. A more preferred lower limit is 50 nm or more, a more preferred upper limit is 1200 nm, an even more preferred lower limit is 100 nm, and an 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 the photoelectric conversion layer and the 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 which 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 cyclic conjugated compound particles 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 solvents 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 and 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 for the electron transport layer 4 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, etc. Specific examples thereof include cyano group-containing polyphenylene vinylene, boron-containing polymers, bathocuproine, bathophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compounds, benzimidazole compounds, naphthalene tetracarboxylic 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(2) chloride, tin(4) chloride, tin(2) chloride dihydrate, or tin(4) chloride pentahydrate.

[0060] The thickness of the electron transport layer 4 is preferably 1 nm or more in lower limit and 2000 nm or more in upper limit. When the thickness of the electron transport layer 4 is 1 nm or more, holes can be sufficiently blocked, and when the thickness is 2000 nm or less, the layer is less likely to act as a resistance during electron transport, resulting in high photoelectric conversion efficiency. The thickness is more preferably 3 nm or less in lower limit and 1000 nm or less in upper limit, and even more preferably 5 nm or less in lower limit and 500 nm or more in 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 coating liquid for the charge transport layer using a paint shaker, and the particle size can be reduced by extending the dispersion time. Furthermore, the particle size can be further reduced by centrifuging the coating liquid for the charge transport layer.

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

[0063] [Photoelectric Conversion Device] The photoelectric conversion device of the present invention includes the photoelectric conversion element described above. A photoelectric conversion device can be constructed by using multiple photoelectric conversion elements of the present invention. When multiple 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 with different absorption wavelengths to increase the output voltage. The photoelectric conversion device also includes 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 include a power storage unit connected to the photoelectric conversion element. The power storage unit is not limited as long as it can store electricity. Examples include secondary batteries using lithium ions, all-solid-state batteries, and electric double-layer capacitors. To impart functionality such as maintaining or increasing the amount of incident light, a surface layer that is resistant to water and dirt, or a function to collect or guide light, may be added.

[0064] [Mobile object] The mobile object of the present invention has the photoelectric conversion element described above. FIG. 2 is a perspective view schematically showing one embodiment of a mobile object equipped with the photoelectric conversion element of the present invention. The mobile object 30 has a photoelectric conversion element 31 of the present invention and a body 32 equipped with the photoelectric conversion element 31. The photoelectric conversion element 31 is disposed in a position on the body 32 where it can receive external light. If the mobile object 30 is an automobile, it may be disposed on the roof. The electrical energy obtained by the photoelectric conversion element 31 may power the mobile object 30 or may power other electrical equipment. Electrical energy generated from the power of the mobile object 30 may be used to power the photoelectric conversion element 31. If the mobile object 30 is an automobile, frictional energy generated by braking may be converted into electrical energy and used to control the photoelectric conversion element 31.

[0065] The mobile object 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 mobile object 30 is not particularly limited, but it is preferably made of a high-strength material.

[0066] [Building Material] The building material of the present invention has the photoelectric conversion element described above. Fig. 3 is a perspective view schematically showing one 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 exterior coverings 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, sunlight may increase the temperature of the photoelectric conversion element 41, potentially reducing the photoelectric conversion efficiency. The use of the heat dissipation member 43 can reduce the reduction in photoelectric conversion efficiency. Examples of the heat dissipation member 43 include a metal, an alloy, a liquid metal, and a liquid resin.

[0068] The building material 40 of the present invention may also have exterior coatings 44a and 44b. The exterior coatings 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 coating. A material with low light absorption and high heat insulation properties is preferred.

[0069] In addition to the above application examples, other 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, 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.

[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 Particles 1 Step (1) Under a nitrogen flow atmosphere, 5.46 parts of orthophthalonitrile and 45 parts of α-chloronaphthalene were added to a reaction vessel, and the mixture was heated to 30°C and maintained at this temperature. Next, 3.75 parts of gallium trichloride was added at this temperature (30°C). The water concentration of the mixed solution at the time of addition was 150 ppm. The mixture was then heated to 200°C. Next, under a nitrogen flow atmosphere, the mixture was reacted at 200°C for 4.5 hours, cooled, and when the temperature reached 150°C, the product was filtered. The resulting filtrate was dispersed and washed using N,N-dimethylformamide at 140°C for 2 hours, and then filtered. The resulting filtrate was washed with methanol and dried to obtain chlorogallium phthalocyanine particles in a yield of 71%.

[0072] Step (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, and the solution was dropped into 620 parts of ice water under stirring to reprecipitate, followed by vacuum filtration using a filter press. No. 5C (manufactured by Advantec Co., Ltd.) was used as the filter. The obtained wet cake (filtrate) was dispersed and washed with 2% aqueous ammonia 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 filtered three times using a filter press. Finally, freeze-drying was performed to obtain hydroxygallium phthalocyanine particles (hydrated hydroxygallium phthalocyanine particles) with a solids content of 23% by mass in 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 Nippon Biocon) to obtain hydroxygallium phthalocyanine (OHGaPc) particles (crystals) with a water content of 1.0 mass % or less.

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

[0074] <Preparation of Resin Solution 1> Resin solution 1 was obtained by dissolving 1.0 g of polyvinyl butyral (trade name: BM-2, manufactured by Sekisui Chemical Co., Ltd., glass transition temperature 71° C.) in 19 g of 2-propanol with stirring for 24 hours.

[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% aqueous dispersion, manufactured by Alfa Aesar) was applied thereon by spin coating, 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 onto the electron transport layer by a poor solvent method, resulting in a Cs ０．０５ (FA ０．８３ MA ０．１７ ) ０．９５ Pb(I ０．８３ Br ０．１７ ) ３ A photoelectric conversion layer having a thickness of 600 nm was formed.

[0077] [Formation of Charge Transport Layer] 0.1 g of the particles 1 and 0.01 g of a mixture of the calixarene compounds represented by the formulas [C-1] to [C-4] 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® zirconia beads, 0.3 mm) were encapsulated in this mixture, and the mixture was dispersed in a paint shaker (manufactured by Toyo Seiki Seisaku-sho). 0.2 g of resin solution 1 was then added, and the dispersion was again conducted in a paint shaker for 6 hours to prepare charge transport layer solution 1. Charge transport layer solution 1 was spin-coated onto the photoelectric conversion layer to form a 160 nm thick charge transport layer.

[0078] [Formation of First Electrode] A carbon paste (trade 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 first electrode having an area of ​​0.09 cm 2 . ２ Electrodes of this type were formed at 10 locations to obtain a photoelectric conversion element.

[0079] [Analysis of Compound Amount] 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 or the like soaked in a solvent, dissolved in heavy water sulfuric acid, and subjected to 1H-NMR measurement (apparatus: AVANCE3-500, manufactured by BRUKER). The peeled charge transport layer components were subjected to mass and structural analysis using elemental analysis such as GPC, MALDI-TOF-MS, IR, gas chromatography, XPS, and EDX to confirm the presence of the compound. The film thickness was also confirmed by cutting the photoelectric conversion element, fixing it to an inclined sample stage, and then using a cross-sectional SEM (apparatus: SmartSEM, manufactured by Carl Zeiss K.K.).

[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 A thin film layer having a thickness of 20 nm was formed between the charge transport layer and the photoelectric conversion layer by dissolving 2.49 mg of 2-phenethylethylamine hydroiodide in 1 mL of 2-propanol to prepare a solution for the thin film layer, and spin-coating this solution for the thin film layer on the photoelectric conversion layer.Other than that, a photoelectric conversion element was obtained in the same manner as in Example 1.

[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 As the particles of the cyclic conjugated compound in which a plurality of pyrrole rings are conjugated, particles 1 were prepared using silicon phthalocyanine dichloride (SiPcCl ２ A photoelectric conversion element is obtained in the same manner as in Example 1, except that the photoelectric conversion element is made into granules.

[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 conjugated.

[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 to prepare 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 (trade 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 was 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 was used as the calixarene compound.

[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 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, phenol is used instead of the calixarene compound.

[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 A photoelectric conversion element was obtained in the same manner as in Example 1, except that in forming the charge transport layer, a charge transport layer solution 2 was used, which was 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.

[0107] [Evaluation] A power supply (manufactured by Keithley, Model 236) was connected between the electrodes of the photoelectric conversion element prepared in Example 1, and an intensity of 114 mW / cm ２ The photoelectric conversion efficiency was measured by irradiating a constant amount of light using a solar simulator (manufactured by Yamashita Denso Co., Ltd.) and measuring the generated current and voltage. Furthermore, 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]

[0110] The present invention is not limited to the above-described embodiments, and various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, the following claims are appended to apprise the public of the scope of the present invention.

[0111] This application is related to Japanese Patent Application No. 2023-184761 filed on October 27, 2023, Japanese Patent Application No. 2023-184756 filed on October 27, 2023, Japanese Patent Application No. 2023-184750 filed on October 27, 2023, Japanese Patent Application No. 2023-216294 filed on December 21, 2023, Japanese Patent Application No. 2023-216296 filed on December 21, 2023, and Japanese Patent Application No. 2023-21629 filed on December 21, 2023. 9, Japanese Patent Application No. 2024-022244 filed on February 16, 2024, Japanese Patent Application No. 2024-022251 filed on February 16, 2024, Japanese Patent Application No. 2024-022246 filed on February 16, 2024, Japanese Patent Application No. 2024-177318 filed on October 9, 2024, and Japanese Patent Application No. 2024-186701 filed on October 23, 2024. Priority is claimed based on the Japanese Patent Application No. 2024-177318 filed on October 9, 2024, and the entire contents of which are incorporated herein by reference.

[0112] REFERENCE SIGNS LIST 1 Photoelectric conversion element 2 Substrate 3 Second electrode 4 Electron transport layer 5 Photoelectric conversion layer 6 Charge transport layer 7 First electrode 30 Mobile body 31, 41 Photoelectric conversion element 32 Airframe 40 Building material 42 Protective member 43 Heat dissipation member 44a, 44b Exterior

Claims

1. 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, wherein 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 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.

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

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 any one of claims 1 to 5, wherein the calixarene compound is represented by the following formula [A]: (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 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]:

8. The photoelectric conversion element according to any one of claims 1 to 7, wherein the insulating resin has a glass transition temperature of 95°C or lower.

9. The photoelectric conversion element according to any one of claims 1 to 8, wherein the insulating resin is a polyvinyl acetal resin or a polyvinyl butyral resin.

10. The photoelectric conversion element according to any one of claims 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.

11. The photoelectric conversion element according to any one of claims 1 to 10, 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 any one of claims 1 to 11, 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 manufacturing 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 of a perovskite structure; forming the charge transport layer including particles of a cyclic conjugated compound in which a plurality of pyrrole rings are conjugatedly bonded, a calixarene compound, and an insulating resin; and forming the electrodes by applying a coating liquid, in this order.

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