JP2016009737A - Method for manufacturing perovskite type solar battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a perovskite type solar battery which is superior to conventional ones in long-term stability and productivity.SOLUTION: A method for manufacturing a perovskite type solar battery including a first electrode having a transparent conductive film substrate and an electron transport layer provided on the transparent conductive film substrate, a porous layer provided on the electron transport layer, a perovskite compound layer provided on the porous layer, a hole transport layer provided on the perovskite compound layer and a second electrode on the hole transport layer comprises: the step of spraying a liquid solution of a halogenated alkylamine and a metal halide on the porous layer, thereby forming a layer of a perovskite compound expressed by the following general formula (1) on the porous layer: XαYβMγ (1)(where X represents a halogen atom, Y represents an alkylamine compound, M includes a metal, the proportion α:β:γ is 3:1:1, and β and γ each represent an integer larger than one).

Description

  The present invention relates to a method for manufacturing a perovskite solar cell and a solar cell.

  In recent years, the importance of solar cells has increased as an alternative energy for fossil fuels and as a countermeasure against global warming. However, current solar cells typified by silicon-based solar cells are expensive at present and are factors that hinder their spread.

Therefore, research and development of various low-cost solar cells are underway, and among them, dye-sensitized solar cells announced by Graetzel et al. Of Lausanne University of Technology in Switzerland are expected to be put into practical use (for example, Patent Document 1: Japanese Patent No. 2664194, Non-Patent Document 1: Nature, 353 (1991) 737, Non-Patent Document 2: J. Am. Chem. Soc., 115 (1993) 6382). This solar cell has a structure in which a porous metal oxide semiconductor is provided on a transparent conductive glass substrate, a dye adsorbed on the surface thereof, an electrolyte having a redox pair, and a counter electrode. Graetzel et al. Significantly improved the photoelectric conversion efficiency by making a metal oxide semiconductor electrode such as titanium oxide porous to increase the surface area, and by adsorbing a ruthenium complex as a dye on a single molecule basis.
Further, since the printing method can be applied to the element manufacturing method, it is expected that the manufacturing cost can be reduced because an expensive manufacturing facility is not required. However, this solar cell contains iodine and a volatile solvent, and has problems such as a decrease in power generation efficiency due to deterioration of the iodine redox system, and volatilization and leakage of the electrolyte.

In order to compensate for this drawback, the following solid-type dye-sensitized solar cells have been announced.
1) Using an inorganic semiconductor (for example, see Non-Patent Document 3: Semicond. Sci. Technol., 10 (1995) 1689, Non-Patent Document 4: Electrochemistry, 70 (2002) 432)
2) A material using a low molecular weight organic hole transport material (for example, Patent Document 2: JP-A-11-144773, Non-Patent Document 5: Synthetic Metals, 9 (1997) 215, Non-Patent Document 6: Nature, 398 ( 1998) 583)
3) Using a conductive polymer (for example, see Patent Document 3: Japanese Patent Laid-Open No. 2000-106223, Non-Patent Document 7: Chem, Lett., (1997) 471)

  In the solar cell described in Non-Patent Document 3, copper iodide is used as a constituent material of the p-type semiconductor layer. It is known that a relatively good photoelectric conversion efficiency immediately after fabrication is halved in a few hours due to deterioration due to an increase in copper iodide crystal grains and the like. Therefore, in the solar cell described in Non-Patent Document 4, the crystallization of copper iodide is suppressed by adding imidazolinium thiocyanate, but this is not sufficient.

  A solid-type dye-sensitized solar cell using the organic hole transport material described in Non-Patent Document 5 has been reported by Hagen et al. And improved by Graetzel et al. (Non-Patent Document 6). In a solid-state dye-sensitized solar cell using a triphenylamine compound described in Patent Document 2, a triphenylamine compound is vacuum-deposited to form a charge transport layer. Therefore, the triphenylamine compound cannot reach the internal pores of the porous semiconductor, and only low conversion efficiency is obtained. In the example described in Non-Patent Document 6, a spiro-type hole transport material is dissolved in an organic solvent, and a composite of nanotitania particles and a hole transport material is obtained using spin coating. However, the optimum value of the nanotitania particle thickness in this solar cell is about 2 μm, which is very thin compared to 10 to 20 μm when using an iodine electrolyte. Therefore, the amount of the dye adsorbed on the titanium oxide is small, and it is difficult to perform sufficient light absorption and carrier generation, and the characteristics when using the electrolytic solution are not achieved. The reason why the film thickness of the nanotitania particles remains at 2 μm is that the penetration of the hole transport material becomes insufficient as the film thickness increases.

  In addition, as a solid-type solar cell using a conductive polymer, Osaka University Yanagida et al. Reported using polypyrrole (see Non-Patent Document 7). Also in these solar cells, the conversion efficiency is low, and the solid-type dye-sensitized solar cell using the polythiophene derivative described in Patent Document 3 uses an electrolytic polymerization method on a porous titanium oxide electrode adsorbing the dye. Although the charge transfer layer is provided, there is a problem that the dye is desorbed from titanium oxide or the dye is decomposed.

In recent years, a perovskite type solar cell that absorbs light and generates electric power has been reported by Miyasaka et al., Toho University of Yokohama (Non-patent Document 8: J. Am. Chem. Soc. 131 (2009) (2009) ) 6050). The perovskite type compound used in this solar cell is formed by mixing halogenated methylamine and lead halide, and has strong absorption in the visible light region. Since this compound is unstable in a solution, when an iodine electrolyte is used, the solar cell characteristics are low. Then, the solar cell which improved conversion efficiency greatly by changing an iodine electrolyte solution into an organic hole transport material was reported (refer nonpatent literature 9: Science, 338 (2012) 643). However, the solar cells reported here are very unstable and as many as 767 solar cells have been fabricated, but the distribution of conversion efficiency is very large.
As described above, none of the solar cells that have been studied so far has been obtained with satisfactory characteristics.

  The subject of this invention is providing the manufacturing method of the perovskite type | mold solar cell which solved such a said problem, was excellent in long-term stability compared with the past, and was excellent also in productivity.

As a result of intensive studies to solve the above problems, it has been found that a method for producing a high-performance perovskite solar cell can be provided, and the present invention has been achieved. The above-described problem is solved by the “method for manufacturing a perovskite solar cell” having the following configuration (1) of the present invention.
(1) “A first electrode provided with an electron transport layer on a transparent conductive film substrate, a porous layer provided on the electron transport layer, a perovskite compound layer provided on the porous layer, and the perovskite compound A method for producing a perovskite solar cell comprising a hole transport layer provided on a layer and a second electrode on the hole transport layer, wherein a solution of a halogenated alkylamine and a metal halide is applied on the porous layer And a step of forming a perovskite compound layer represented by the following general formula (1) on the porous layer.
XαYβMγ General formula (1)
(In the formula, X is a halogen atom, Y is an alkylamine compound, M contains a metal, the ratio of α: β: γ is 3: 1: 1, and β and γ represent integers greater than 1.). "

  As is clear from the following detailed and specific description, according to the method for manufacturing a perovskite solar cell of the present invention, a perovskite solar cell with good characteristics can be obtained by the configuration described in (1) above. Is possible. That is, the excellent effect of providing a perovskite type solar cell that is superior in long-term stability and excellent in productivity as compared with the prior art is exhibited.

1 is a structural diagram of a perovskite solar cell in one embodiment of the present invention. It is a schematic diagram explaining the solvent solubility in the perovskite crystal of the present invention.

  The present invention relates to a “method for manufacturing a perovskite solar cell” having the configuration described in the above (1). This “method for manufacturing a perovskite solar cell” is understood from the following detailed description. As described above, the “perovskite solar cell” of the embodiments described in the following (2) to (12) is also included.

(2) “A first electrode provided with an electron transport layer on a transparent conductive film substrate, a porous layer provided on the electron transport layer, a perovskite compound layer provided on the porous layer, and the perovskite compound In the perovskite solar cell having a hole transport layer provided on the layer and a second electrode on the hole transport layer, the perovskite compound represented by the following general formula (1) is a halogenated alkylamine, a metal halogen, A perovskite solar cell, which is formed by spraying a solution containing a chemical compound in an organic solvent onto the porous layer.
XαYβMγ General formula (1)
(In the formula, X is a halogen atom, Y is an alkylamine compound, M contains a metal, the ratio of α: β: γ is 3: 1: 1, and β and γ represent integers greater than 1.). "
(3) The perovskite compound layer is characterized in that a perovskite layer in which X is a mixture of iodine and other halogen atoms is laminated on the perovskite layer in which X in the general formula (1) is iodine. The perovskite solar cell according to (2) above. "
(4) “Perovskite solar cell according to (2) or (3) above, wherein M in the general formula contains at least lead.”
(5) The perovskite solar cell according to any one of (2) to (4), wherein M in the general formula contains lead and any one of indium, antimony, and tin. . "
(6) In any one of the above (2) to (5), the halogenated alkylamine of Y in the general formula (1) is a halogenated methylamine or a halogenated formamidine. The perovskite solar cell described. "
(7) “The perovskite solar cell according to any one of (2) to (6), wherein the porous layer includes a metal oxide.”
(8) The perovskite solar cell according to any one of (2) to (7), wherein the metal oxide is titanium oxide.
(9) The perovskite solar cell according to any one of (2) to (8), wherein the electron transport layer includes at least one of titanium oxide, niobium oxide, and yttrium oxide.
(10) The perovskite solar cell according to any one of (2) to (9), wherein the hole transport layer contains an oxidizing agent.
As will be understood from the following detailed and specific description, the present invention further includes “perovskite solar cells” according to the embodiments described in the following (11) to (12).
(11) The perovskite solar cell according to any one of (2) to (10), wherein the oxidizing agent is a Co complex compound.
(12) The perovskite solar cell according to any one of (2) to (11), wherein the Co complex compound is a trivalent Co complex.

Hereinafter, the present invention will be described in detail.
The configuration of the perovskite solar cell will be described with reference to FIG.
FIG. 1 is a cross-sectional view of a perovskite solar cell.
In the embodiment shown in FIG. 1, a first electrode 2 (referred to as an electron collector electrode) is provided on a substrate 1, and an electron transport layer 3 and a granular porous layer 4 are sequentially provided. Subsequently, the structure which consists of the perovskite compound layer 5, the hole transport layer 6, and the 2nd electrode 7 (hole current collection electrode) is taken.

<Board>
The substrate 1 used in the present invention needs to maintain a certain hardness, and examples of the substrate 1 that can be used include glass, a transparent plastic plate, a transparent plastic film, and an inorganic transparent crystal.

<Electronic current collecting electrode>
An electrode 2 (hereinafter referred to as an electron collecting electrode) used in the present invention is provided on a substrate 1. The electron current collecting electrode 2 is made of a conductive material or metal that is transparent to visible light, and a known one that is used for a normal photoelectric conversion element, a liquid crystal panel, or the like can be used. For example, indium tin oxide (hereinafter referred to as ITO), fluorine doped tin oxide (hereinafter referred to as FTO), antimony doped tin oxide (hereinafter referred to as ATO), indium zinc oxide, niobium titanium oxide , Graphene, gold, silver, Pt, Ti, Cr, and the like, and these may be used alone or in combination. The thickness of the electron collector electrode is preferably 5 nm to 100 μm, more preferably 50 nm to 10 μm.
Further, a metal lead wire or the like may be used.
Examples of the material of the metal lead wire include metals such as aluminum, copper, silver, gold, platinum, and nickel. For example, the metal lead wire may be provided on the substrate by vapor deposition, sputtering, pressure bonding, or the like, and ITO or FTO may be provided thereon.

<Electron transport layer>
In the dye-sensitized solar cell of the present invention, the electron transport layer 3 made of a semiconductor is formed on the electron collecting electrode 2. Although there is no restriction | limiting in the film thickness of this electron carrying layer 3, 10 nm-1 micrometer are preferable and 20 nm-700 nm are more preferable. The electron transport layer 3 needs to be dense, but “dense” means that the electron transport compound forms a film at a higher density than the packing density of the fine particles in the porous layer 4. .

What is used for the electron transport layer 3 is preferably an electron transporting semiconductor, specifically, a single semiconductor such as silicon or germanium, a compound semiconductor typified by a metal chalcogenide, or a compound having a perovskite structure. Can be mentioned.
Metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, aluminum, magnesium, vanadium, niobium, or tantalum oxide, cadmium, zinc, lead, silver Antimony, bismuth sulfide, cadmium, lead selenide, cadmium telluride and the like.

Other compound semiconductors are preferably phosphides such as zinc, gallium, indium, cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like. As the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like are preferable.
Among these, oxides are preferable, and zinc oxide, tin oxide, titanium oxide, aluminum oxide, niobium oxide, yttrium oxide, and barium titanate are particularly preferable, and they may be used alone or in combination of two or more. The crystal type of these oxides is not particularly limited, and may be single crystal, polycrystal, or amorphous.

The method for producing the electron transport layer 3 is not particularly limited, and examples thereof include a method of forming a thin film in a vacuum and a wet film forming method.
Vacuum deposition includes sputtering, pulsed laser deposition (PLD), ion beam sputtering, ion assist, ion plating, vacuum deposition, atomic layer deposition (ALD), chemical vapor Examples include a growth method (CVD method). Examples of the wet film forming method include production of a thin film by a sol-gel method. In the sol-gel method, a gel is prepared by starting from a solution and undergoing a chemical reaction such as hydrolysis, polymerization or condensation, and then densification is promoted by heat treatment. When this sol-gel method is used, the coating method is not particularly limited and can be performed according to a known method. For example, dip method, spray method, wire bar method, spin coating method, roller coating method, blade coating method, gravure coating method, and wet printing methods such as relief printing, offset, gravure, intaglio printing, rubber printing, screen printing, etc. Can be used. The heat treatment after applying the sol solution is preferably 80 ° C. or higher, and more preferably 100 ° C. or higher.

<Porous layer>
The porous layer 4 may be a single layer or a multilayer. In the case of multiple layers, a dispersion of semiconductor fine particles having different particle diameters can be applied in multiple layers, or different types of semiconductors, and application layers having different compositions of resins and additives can be applied in multiple layers. Multi-layer coating is an effective means when the film thickness is insufficient with a single coating. The thickness of the porous layer is preferably 30 to 1000 nm, and more preferably 100 to 600 nm.

The fine particles used for the porous layer 4 are not particularly limited, and known ones can be used.
Specifically, a single semiconductor such as silicon or germanium, a compound semiconductor typified by a metal chalcogenide, a compound having a perovskite structure, or the like can be given.
Metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, aluminum, magnesium, vanadium, niobium, or tantalum oxide, cadmium, zinc, lead, silver Antimony, bismuth sulfide, cadmium, lead selenide, cadmium telluride and the like.

Other compound semiconductors are preferably phosphides such as zinc, gallium, indium, cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like. As the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like are preferable.
Among these, oxides are preferable, and zinc oxide, tin oxide, titanium oxide, aluminum oxide, niobium oxide, yttrium oxide, and barium titanate are particularly preferable, and they may be used alone or in combination of two or more. The crystal type of these oxides is not particularly limited, and may be single crystal, polycrystal, or amorphous.

  Although there is no restriction | limiting in particular in the size of an oxide fine particle, 1-100 nm is preferable and, as for the average particle diameter of a primary particle, 10-50 nm is more preferable. Further, the efficiency can be improved by the effect of scattering incident light by mixing or laminating oxide fine particles having a larger average particle diameter. In this case, the average particle size of the oxide is preferably 50 to 500 nm.

  As a method for producing the porous layer 4, an immersion method, a spin coating method, a spray method, a dipping method, a roller method, an air knife method, or the like can be used. Further, it may be deposited in a supercritical fluid using carbon dioxide or the like.

When the oxide fine particles are mechanically pulverized or a dispersion is prepared using a mill, the dispersion is formed by dispersing at least the oxide fine particles alone or a mixture of the oxide fine particles and the resin in water or an organic solvent.
As the resin used at this time, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic acid ester, methacrylic acid ester, silicon resin, phenoxy resin, polysulfone resin, polyvinyl butyral resin, polyvinyl formal resin, Examples include polyester resin, cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin, and the like.

  Solvents for dispersing the oxide fine particles include water, methanol, ethanol, isopropyl alcohol, alcohol solvents such as α-terpineol, ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or acetic acid. Ester solvents such as n-butyl, ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl-2-pyrrolidone Amido solvents, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromo Halogenated hydrocarbon solvents such as benzene, iodobenzene or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o Examples thereof include hydrocarbon solvents such as xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or as a mixed solvent of two or more.

  In order to prevent re-aggregation of particles, an oxide fine particle paste obtained by a dispersion of oxide fine particles or a sol-gel method is used. Acids such as hydrochloric acid, nitric acid and acetic acid, polyoxyethylene (10) octylphenyl ether And the like, chelating agents such as acetylacetone, 2-aminoethanol, and ethylenediamine can be added. It is also an effective means to add a thickener for the purpose of improving the film forming property. Examples of the thickener added at this time include polymers such as polyethylene glycol and polyvinyl alcohol, and thickeners such as ethyl cellulose.

Oxide fine particles can be subjected to firing, microwave irradiation, electron beam irradiation, or laser beam irradiation in order to bring the particles into electronic contact with each other after coating and to improve film strength and adhesion to the substrate. preferable. These processes may be performed alone or in combination of two or more.
When firing, the range of the firing temperature is not particularly limited, but if the temperature is raised too much, the resistance of the substrate may be increased or the substrate may be melted, so 30 to 700 ° C is preferable, and 100 to 600 ° C is more preferable. Moreover, although there is no restriction | limiting in particular also in baking time, 10 minutes-10 hours are preferable. Alternatively, chemical plating using an aqueous solution of titanium tetrachloride or a mixed solution with an organic solvent, or electrochemical plating using an aqueous solution of titanium trichloride may be performed. The microwave irradiation may be performed from the porous layer 4 formation side or from the substrate 1 side. Although there is no restriction | limiting in particular in irradiation time, It is preferable to carry out within 1 hour.

A film in which oxide fine particles having a diameter of several tens of nm are stacked by sintering or the like forms a porous state.
This nanoporous structure has a very high surface area, which can be expressed using a roughness factor. This roughness factor is a numerical value representing the actual area inside the porous body relative to the area of the oxide fine particles applied to the substrate. Accordingly, the roughness factor is preferably as large as possible, but is also related to the film thickness of the porous layer 4 and is preferably 20 or more in the present invention.

<Perovskite compounds>
The perovskite compound in the present invention is a composite material of an organic compound and an inorganic compound, and preferably has a layered perovskite structure in which a layer made of a metal halide and a layer in which organic cation molecules are arranged are alternately stacked. It is represented by (1).
XαYβMγ General formula (1)
In the above general formula, X represents a halogen atom, Y represents an alkylamine compound, M represents a mixture of lead and antimony, the ratio of α: β: γ is 3: 1: 1, and β and γ are integers greater than 1. Represents.
Specifically, X can include halogen atoms such as chlorine, bromine and iodine, and these can be used alone or as a mixture. Examples of Y include alkylamine compounds such as methylamine, ethylamine, n-butylamine and formamidine. M represents a metal such as lead, indium, antimony, tin, copper, or bismuth.

  The perovskite compound in the present invention is a one-step precipitation method in which a solution in which a metal halide and a halogenated alkylamine are dissolved or dispersed in a solvent is applied on the porous layer 4 and dried, or a metal halide is dissolved or dissolved. Any of the two-stage precipitation methods in which the dispersed solvent is applied onto the porous layer 4 and dried, and then immersed in a solution in which the halogenated alkylamine is dissolved in the solvent to form the perovskite compound may be used. A two-stage precipitation method is preferred.

  As a method for applying the perovskite compound onto the porous layer 4, spray film formation is used. Spraying is a technique in which fine particles of liquid are scattered by spraying compressed liquid or liquid pressurized with high-pressure gas from a narrow hole in the nozzle and spraying these droplets onto the target substrate. is there. In the case of the two-step precipitation method, after forming the metal halide by spraying, the method of contacting the halogenated alkylamine solution includes dipping method, spin coating method, spray method, dipping method, roller method, air knife method, etc. Existing methods can be used. Further, it may be deposited in a supercritical fluid using carbon dioxide or the like.

  As in the prior art, if a layer is formed by a dynamic coating layer forming method such as typically spin coating, the substrate is melted, and thus a device that is really desired cannot be produced. On the other hand, the present invention adopts a static coating layer forming method, for example, a spray method, as one technical aim of how to laminate the organic / inorganic perovskite compound layer without disturbing its crystal arrangement. By doing so, it is presumed that the performance has been improved because it is possible to laminate without melting the base. In addition, among the various static coating layer forming methods, the spray method can be used to control the evaporation of the solution as soon as it lands. , I guess that the performance has improved.

  As described above in the background art section, it was found that the organic / inorganic perovskite compound targeted by the present invention is unstable with respect to an organic solvent. Therefore, in the present invention, the organic / inorganic perovskite compound layer One of the technical points is to prevent vibration or centrifugal force from being applied to the object to be coated during the formation process (for example, during coating and removal of the solvent).

  That is, as shown in FIG. 2, the organic / inorganic perovskite compound crystal is roughly composed of an octahedron of lead halide in which two pyramids are bonded so that the bottom surface is shared, with the alkylamine moiety as the apex. Embedded in the shell of the cube (however, the six halogen atoms are shared by the six faces of the cube of the shell and the top ridge of the inner octahedron), and the shell ( Since the organic part) is unstable with respect to the solvent, the shell part is easily damaged. The charge transport in the perovskite crystal is directional (in the direction of the arrow in FIG. 2 orthogonal to the two cone-shaped top directions of the internal octahedron, that is, (the 110 direction of the crystal) is the charge transport direction). Therefore, if the shell portion of the perovskite crystal is damaged, the charge transport to the adjacent crystal is hindered. However, in the present invention, it is presumed that such a situation could be avoided as a result.

Further, after the sensitizing dye is mixed with the perovskite compound on the porous layer 4 or the perovskite compound is formed, the sensitizing dye may be adsorbed. The sensitizing dye is not particularly limited as long as it is a compound that is photoexcited by the excitation light used, and specific examples thereof include the following compounds.
The metal complex compounds described in JP 7-500630 A, JP 10-233238 A, JP 2000-26487 A, JP 2000-323191 A, JP 2001-59062 A, etc. 10-93118, JP-A No. 2002-164089, JP-A No. 2004-95450, J. Pat. Phys. Chem. C, 7224, Vol. 111 (2007), etc., JP-A-2004-95450, Chem. Commun. , 4887 (2007), etc., JP-A No. 2003-264010, JP-A No. 2004-63274, JP-A No. 2004-115636, JP-A No. 2004-200068, JP-A No. 2004-235052. J. et al. Am. Chem. Soc. , 12218, Vol. 126 (2004), Chem. Commun. , 3036 (2003), Angew. Chem. Int. Ed. , 1923, Vol. 47 (2008), etc .; Am. Chem. Soc. 16701, Vol. 128 (2006), J.M. Am. Chem. Soc. , 14256, Vol. 128 (2006), JP-A-11-86916, JP-A-11-214730, JP-A-2000-106224, JP-A-2001-76773, JP-A-2003-7359. And the merocyanine dyes described in JP-A-11-214731, JP-A-11-238905, JP-A-2001-52766, JP-A-2001-76775, JP-A-2003-7360, etc. 9-arylxanthene compounds described in JP-A-10-92477, JP-A-11-273754, JP-A-11-273755, JP-A-2003-3273, etc., JP-A-10-93118, Triarylmethane compounds described in Japanese Unexamined Patent Publication No. 2003-31273, JP-A-9- 99744, JP-A No. 10-233238, JP-A No. 11-204821, JP-A No. 11-265738, J. Phys. Chem. , 2342, Vol. 91 (1987), J. MoI. Phys. Chem. B, 6272, Vol. 97 (1993), Electroanaly. Chem. , 31, Vol. 537 (2002), JP-A-2006-032260, J. Pat. Porphyrins Phthalocyanines, 230, Vol. 3 (1999), Angew. Chem. Int. Ed. , 373, Vol. 46 (2007), Langmuir, 5436, Vol. 24 (2008) etc., and the phthalocyanine compound, porphyrin compound, etc. can be mentioned.
Among these, it is particularly preferable to use a metal complex compound, an indoline compound, a thiophene compound, or a porphyrin compound.

<Hole transport layer>
The hole transport layer 6 may be either a liquid electrolyte or a solid hole transport compound, but it is particularly preferable to use a solid hole transport compound.

In the case of a liquid electrolyte, it is preferable to include an electrolyte, a solvent and an additive.
The electrolyte is preferably a metal iodide-iodine combination such as lithium iodide, sodium iodide, potassium iodide, cesium iodide or calcium iodide, tetraalkylammonium iodide, pyridinium iodide or imidazolium iodide. Iodine salts of quaternary ammonium compounds such as iodine-iodine combinations, metal bromides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide or calcium bromide-bromine combinations, tetraalkylammonium bromides or pyridinium bromides, etc. Bromine salt-bromine combinations of quaternary ammonium compounds, metal complexes such as ferrocyanate-ferricyanate or ferrocene-ferricinium ion, sodium polysulfide or alkylthiol-al Sulfur compounds such as disulphide, viologen dye, hydroquinone - quinones or metal complex or nitroxide radical compounds such as cobalt or the like is used.

The electrolyte may be a single combination or a mixture. Further, when an ionic liquid such as imidazolinium iodide is used as the electrolyte, a solvent is not particularly required.
The electrolyte concentration in the electrolytic solution is preferably 0.05 to 20M, and more preferably 0.1 to 15M.

  Solvents used for the electrolyte include carbonate solvents such as ethylene carbonate or propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether solvents such as dioxane, diethyl ether or ethylene glycol dialkyl ether, methanol, ethanol or Alcohol solvents such as polypropylene glycol monoalkyl ether, nitrile solvents such as acetonitrile or benzonitrile, aprotic polar solvents such as dimethyl sulfoxide or sulfolane, and the like are preferable. Moreover, you may use together basic compounds, such as t-butyl pyridine, 2-picoline, and 2, 6- lutidine.

  The electrolyte can also be gelled by techniques such as polymer addition, oil gelling agent addition, polymerization including polyfunctional monomers, and polymer crosslinking reaction.

  Preferable polymers for gelation by polymer addition include, for example, polyacrylonitrile and polyvinylidene fluoride.

  Preferred gelling agents for gelation by adding an oil gelling agent include, for example, dibenzylden-D-sorbitol, cholesterol derivatives, amino acid derivatives, alkylamide derivatives of trans- (1R, 2R) -1,2-cyclohexanediamine, Examples include alkylurea derivatives, N-octyl-D-gluconamidobenzoate, double-headed amino acid derivatives, quaternary ammonium derivatives, and the like.

  Preferred monomers for polymerization with a polyfunctional monomer include, for example, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and the like. Can be mentioned.

Further, esters and amides derived from acrylic acid such as acrylamide or methyl acrylate, α-alkyl acrylic acid, esters derived from maleic acid or fumaric acid such as dimethyl maleate or diethyl fumarate, butadiene or cyclo Dienes such as pentadiene, aromatic vinyl compounds such as styrene, p-chlorostyrene or sodium styrenesulfonate, vinyl esters, acrylonitrile, methacrylonitrile, vinyl compounds having a nitrogen-containing heterocyclic ring, vinyl having a quaternary ammonium salt A monofunctional monomer such as a compound, N-vinylformamide, vinylsulfonic acid, vinylidene fluoride, vinyl alkyl ethers or N-phenylmaleimide may be contained. 0.5-70 mass% is preferable and the polyfunctional monomer which occupies for the monomer whole quantity has more preferable 1.0-50 mass%.
The above-mentioned monomers can be polymerized by radical polymerization. The monomer for gel electrolyte can be radically polymerized by heating, light, electron beam or electrochemical.

  The polymerization initiator used when the crosslinked polymer is formed by heating is 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) or dimethyl-2. An azo initiator such as 2,2′-azobis (2-methylpropionate) or a peroxide initiator such as benzoyl peroxide is preferable.

  The addition amount of these polymerization initiators is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total amount of monomers.

  When the electrolyte is gelled by a polymer crosslinking reaction, it is desirable to use a polymer containing a reactive group necessary for the crosslinking reaction and a crosslinking agent in combination.

  Preferable examples of the crosslinkable reactive group include nitrogen-containing heterocycles such as pyridine, imidazole, thiazole, oxazole, triazole, morpholine, piperidine, piperazine and the like. Preferred examples of the crosslinking agent include bifunctional or higher functional reagents capable of electrophilic reaction with nitrogen atoms such as alkyl halides, halogenated aralkyls, sulfonic acid esters, acid anhydrides, acid chlorides, and isocyanates. .

  The solid hole transport compound may be either an inorganic compound or an organic compound. The inorganic hole transport layer using an inorganic compound is formed inside the electrode by a method such as casting, coating, spin coating, dipping, or electrolytic plating of copper iodide, copper thiocyanide, or the like.

  In the case of an organic compound, a single layer structure made of a single material or a laminated structure made of a plurality of compounds may be used. In the case of a laminated structure, it is preferable to use a polymer material for the hole transport layer in contact with the second electrode 7. This is because the surface of the perovskite compound layer 5 can be further smoothed and the photoelectric conversion characteristics can be improved by using a polymer material having excellent film forming properties.

  As a hole transport material used in a single layer structure used singly, a known hole transport compound is used, and specific examples thereof include an oxadiazole compound shown in Japanese Patent Publication No. 34-5466, A triphenylmethane compound shown in JP-B-45-555, a pyrazoline compound shown in JP-B-52-4188, a hydrazone compound shown in JP-B-55-42380, An oxadiazole compound disclosed in JP-A-56-123544, a tetraarylbenzidine compound disclosed in JP-A-54-58445, or JP-A-58-65440 or JP-A-60. The stilbene compound etc. which are shown by -98437 gazette can be mentioned.

As the polymer material used for the hole transport layer in contact with the second electrode 7 used in the laminated structure, a known hole transport polymer material is used, and specific examples thereof include poly (3-n-hexylthiophene). ), Poly (3-n-octyloxythiophene), poly (9,9′-dioctyl-fluorene-co-bithiophene), poly (3,3 ′ ″-didodecyl-quarterthiophene), poly (3,6- Dioctylthieno [3,2-b] thiophene), poly (2,5-bis (3-decylthiophen-2-yl) thieno [3,2-b] thiophene), poly (3,4-didecylthiophene- Co-thieno [3,2-b] thiophene), poly (3,6-dioctylthieno [3,2-b] thiophene-co-thieno [3,2-b] thiophene), poly (3,6-dio Polythiophene compounds such as tilthieno [3,2-b] thiophene-co-thiophene) or poly (3,6-dioctylthieno [3,2-b] thiophene-co-bithiophene), poly [2-methoxy-5- ( 2-ethylhexyloxy) -1,4-phenylenevinylene], poly [2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylenevinylene] or poly [(2-methoxy-5- ( 2-ethylphenyloxy) -1,4-phenylenevinylene) -co- (4,4′-biphenylene-vinylene)] and the like, poly (9,9′-didodecylfluorenyl-2, 7-diyl), poly [(9,9-dioctyl-2,7-divinylenefluorene) -alt-co- (9,10-anthracene)], poly (9,9-dioctyl-2,7-divinylenefluorene) -alt-co- (4,4′-biphenylene)], poly [(9,9-dioctyl-2,7-divinylenefluorene) -alt- Co- (2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene)] or poly [(9,9-dioctyl-2,7-diyl) -co- (1,4- (2, Polyfluorene compounds such as 5-dihexyloxy) benzene)], poly [2,5-dioctyloxy-1,4-phenylene], poly [2,5-di (2-ethylhexyloxy-1,4-phenylene] and the like A polyphenylene compound, poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (N, N′-diphenyl) -N, N′-di (p-hexylphenyl) -1 , 4-Diamino Nene], poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (N, N′-bis (4-octyloxyphenyl) benzidine-N, N ′-(1, 4-diphenylene)], poly [(N, N′-bis (4-octyloxyphenyl) benzidine-N, N ′-(1,4-diphenylene)]], poly [(N, N′-bis (4- (2-Ethylhexyloxy) phenyl) benzidine-N, N ′-(1,4-diphenylene)], poly [phenylimino-1,4-phenylenevinylene-2,5-dioctyloxy-1,4-phenylenevinylene- 1,4-phenylene], poly [p-tolylimino-1,4-phenylenevinylene-2,5-di (2-ethylhexyloxy) -1,4-phenylenevinylene-1,4-phenylene] or poly [ A polyarylamine compound such as 4- (2-ethylhexyloxy) phenylimino-1,4-biphenylene] or poly [(9,9-dioctylfluorenyl-2,7-diyl) -alt-co- (1, Mentioning polythiadiazole compounds such as 4-benzo (2,1 ′, 3) thiadiazole] or poly (3,4-didecylthiophene-co- (1,4-benzo (2,1 ′, 3) thiadiazole). Can do. Of these, polythiophene compounds and polyarylamine compounds are particularly preferred in consideration of carrier mobility and ionization potential.
Various additives may be added to the inorganic and organic hole transport compounds shown above.

  Examples of the additive include iodine, lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, copper iodide, iron iodide, silver iodide, and other metal iodides, tetraalkyl iodide. Quaternary ammonium salt such as ammonium or pyridinium iodide, metal bromide such as lithium bromide, sodium bromide, potassium bromide, cesium bromide or calcium bromide, quaternary ammonium such as tetraalkylammonium bromide or pyridinium bromide Compound bromine salts, metal chlorides such as copper chloride or silver chloride, metal acetates such as copper acetate, silver acetate or palladium acetate, metal sulfates such as copper sulfate or zinc sulfate, ferrocyanate-ferricyanate Or metal complex such as ferrocene-ferricinium ion, sodium polysulfide Or sulfur compounds such as alkylthiol-alkyldisulfides, viologen dyes, hydroquinones, etc., 1,2-dimethyl-3-n-propylimidazolinium iodide, 1-methyl-3-n-hexylimidazolinium iodide Salt, 1,2-dimethyl-3-ethylimidazolium trifluoromethanesulfonate, 1-methyl-3-butylimidazolium nonafluorobutylsulfonate or 1-methyl-3-ethylimidazolium bis (trifluoromethyl ) Inorganic chemistry such as sulfonylimide, etc. Inorg. Chem. 35 (1996) 1168, basic compounds such as pyridine, 4-t-butylpyridine or benzimidazole, or lithium compounds such as lithium trifluoromethanesulfonylimide or lithium diisopropylimide Etc. It can be.

  Further, for the purpose of improving the conductivity, an oxidizing agent for making a part of the organic hole transport material a radical cation may be added.

  Examples of the oxidizing agent include tris (4-bromophenyl) aminium hexachloroantimonate, silver hexafluoroantimonate, nitrosonium tetrafluorate, silver nitrate, cobalt complex, and the like. Note that it is not necessary for all organic hole transport materials to be oxidized by the addition of an oxidizing agent, and only a part of the hole transporting material needs to be oxidized. Further, the added oxidizing agent may be taken out of the system after the addition or may not be taken out.

  The inorganic and organic hole transport layers are directly formed on the perovskite compound layer 5. The method for producing the organic hole transport layer is not particularly limited, and examples thereof include a method of forming a thin film in a vacuum such as vacuum deposition, a wet film forming method, and the like. In consideration of the manufacturing cost and the like, a wet film forming method is particularly preferable, and a method of applying the film on the perovskite compound layer 5 is preferable.

  When the wet film forming method is used, the coating method is not particularly limited, and can be performed according to a known method. As a coating method, for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or the like can be used. Further, a printing method using a relief plate, offset, gravure, intaglio plate, rubber plate, screen or the like may be used. Moreover, you may form into a film in a supercritical fluid or a subcritical fluid.

  As a supercritical fluid, it exists as a non-aggregating high-density fluid in a temperature and pressure range that exceeds the limit (critical point) at which gas and liquid can coexist, and does not aggregate even when compressed. The fluid is not particularly limited as long as it is in the above state. The supercritical fluid can be appropriately selected according to the purpose by those skilled in the art, but those having a low critical temperature are preferred.

  Supercritical fluids are, for example, carbon monoxide, carbon dioxide, ammonia, nitrogen, water, ercol solvents such as methanol, ethanol or n-butanol, carbonization such as ethane, propane, 2,3-dimethylbutane, benzene or toluene. A hydrogen-based solvent, a halogen-based solvent such as methylene chloride or chlorotrifluoromethane, or an ether-based solvent such as dimethyl ether is preferred.

  Among these, carbon dioxide is particularly preferable because it has a critical pressure of 7.3 MPa and a critical temperature of 31 ° C., so that it can easily create a supercritical state and is nonflammable and easy to handle. These fluids may be used alone or as a mixture of two or more.

  The subcritical fluid is not particularly limited as long as it exists as a high-pressure liquid in a temperature and pressure region near the critical point, and can be appropriately selected by those skilled in the art according to the purpose.

  In addition, the compound mentioned as a supercritical fluid mentioned above can be used conveniently also as a subcritical fluid.

  The critical temperature and critical pressure of the supercritical fluid are not particularly limited and can be appropriately selected by those skilled in the art according to the purpose. The critical temperature is preferably −273 ° C. or higher and 300 ° C. or lower, preferably 0 ° C. or higher. 200 degrees C or less is especially preferable.

  Furthermore, in addition to the above supercritical fluid and subcritical fluid, an organic solvent or an entrainer can be used in combination. By adding an organic solvent and an entrainer, the solubility in the supercritical fluid can be adjusted more easily.

  Such an organic solvent is not particularly limited, and examples thereof include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl formate, ethyl acetate and n-butyl acetate, diisopropyl ether, dimethoxyethane, Ether solvents such as tetrahydrofuran, dioxolane or dioxane, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide or N-methyl-2-pyrrolidone, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, Halogenated hydrocarbon solvents such as trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene or 1-chloronaphthalene Or hydrocarbons such as n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene or cumene System solvents and the like.

  Further, after the inorganic and organic hole transport layer 6 is provided, press treatment may be performed. By applying the press treatment, the inorganic and organic hole transport layer 6 is more closely attached to the perovskite compound layer 5, and it is considered that the photoelectric conversion characteristics are improved.

The press processing method is not particularly limited, and examples thereof include a press molding method using a flat plate represented by an IR tablet shaper, a roll press method using a roller and the like. The pressure for the press treatment is preferably 10 kgf / cm ² or more, more preferably 30 kgf / cm ² or more. The time for the press treatment is not particularly limited, and it is preferably performed within 1 hour. Further, heat may be applied during the pressing process.

  Further, a release material may be sandwiched between the press and the electrode during the above-described press treatment. Examples of the release material include polytetrafluoroethylene, polychlorotrifluoride ethylene, tetrafluoroethylene hexafluoropropylene copolymer, perfluoroalkoxy fluoride resin, polyvinylidene fluoride, ethylene tetrafluoride ethylene copolymer, Examples thereof include fluororesins such as ethylene chlorotrifluoride ethylene copolymer and polyvinyl fluoride.

  A metal oxide may be provided between the inorganic or organic hole transport layer 6 and the second electrode 7 after the pressing process and before the second electrode 7 is provided. Examples of the metal oxide include molybdenum oxide, tungsten oxide, vanadium oxide, nickel oxide, and the like, and molybdenum oxide is particularly preferable.

  The method for providing the metal oxide on the hole transport material is not particularly limited, and examples thereof include a method for forming a thin film in a vacuum such as sputtering and vacuum deposition, and a wet film forming method.

  The wet film forming method is preferably a method in which a paste in which a metal oxide powder or sol is dispersed is prepared and applied onto the hole transport layer.

  When the wet film forming method is used, the coating method is not particularly limited, and can be performed according to a known method. As a coating method, for example, a dipping method, a spray method, a wire bar method, a spin coating method, a roller coating method, a blade coating method, a gravure coating method, or the like can be used. Further, a printing method using a relief plate, offset, gravure, intaglio plate, rubber plate, screen or the like may be used.

  Although the film thickness of a metal oxide is not specifically limited, 0.1-50 nm is preferable and 1-10 nm is more preferable.

<Hall current collector electrode>
Examples of the second electrode 7 (hereinafter referred to as a hole collecting electrode) include metals such as platinum, gold, silver, copper, aluminum, rhodium or indium, carbon compounds such as graphite, fullerene or carbon nanotubes, ITO. And conductive metal oxides such as fluorine-doped tin oxide (hereinafter referred to as FTO) and antimony-doped tin oxide (hereinafter referred to as ATO), and conductive polymers such as polythiophene and polyaniline.

  The film thickness of the hole collector electrode is not particularly limited. The hole collecting electrode may be used alone or in combination of two or more of the above materials.

[Example 1]
(Preparation of electron transport layer)
Titanium tetra-n-propoxide (2 ml), acetic acid (4 ml), ion exchange water (1 ml), and 2-propanol (40 ml) were mixed, spin-coated on an FTO glass substrate, dried at room temperature, and baked at 450 ° C. for 30 minutes in air. Using the same solution again, it was applied on the obtained electrode by spin coating so as to have a film thickness of 100 nm, and baked in air at 450 ° C. for 30 minutes to form a dense electron transport layer.

(Preparation of porous layer)
A Dyesol 18NR-T (titanium oxide paste) was applied by spin coating on the dense electron transport layer using a paste diluted with ethanol, dried in warm air at 120 ° C. for 3 minutes, and then dried in air. Baking at 30 ° C. for 30 minutes formed a porous layer. The film thickness of the porous layer was 308 nm.

(Preparation of perovskite layer)
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.461 g) is dissolved is applied onto the porous titanium oxide electrode using a spray (Tamiya Spray Work HG Compressor Revo). And dried at 100 ° C. for 10 minutes. An isopropyl alcohol solution (concentration 0.038M) in which methyl iodide is dissolved is applied onto the electrode by spin coating and dried, and then an isopropyl alcohol solution (concentration 0.038M in which methyl iodide is dissolved on the electrode). ) Was applied by spin coating and dried repeatedly. Finally, isopropyl alcohol was applied onto this electrode by spin coating and dried to form a perovskite layer. The film thickness of the perovskite layer was 512 nm including the porous electron transport layer.

(Preparation of hole transport layer and hole collecting electrode)
2,2 (7,7 (-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9 (-spirobifluorene))) (50 mM), lithium bis (trifluoromethanesulfonyl) imide (30 mM) A chlorobenzene solution in which 4-t-butylpyridine (200 mM) was dissolved was formed into a film by spin coating and air-dried. On this, gold was formed to a thickness of about 100 nm by vacuum deposition to produce a solar cell element.

(Evaluation of solar cell characteristics)
The photoelectric conversion efficiency of the obtained solar cell under simulated sunlight irradiation (AM1.5, 100 mW / cm ² ) was measured. The simulated solar light was measured by a solar simulator SS-80XIL manufactured by Eiko Seiki Co., Ltd., and the evaluation equipment was measured by a solar cell evaluation system As-510-PV03 manufactured by NF Circuit Design Block. As a result, excellent characteristics of an open circuit voltage = 0.90 V, a short circuit current density of 11.3 mA / cm ² , a form factor = 0.60, and a conversion efficiency = 6.1% were exhibited.

[Example 2]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.

(Preparation of electron transport layer, same as Example 1)
Titanium tetra-n-propoxide (2 ml), acetic acid (4 ml), ion exchange water (1 ml), and 2-propanol (40 ml) were mixed, spin-coated on an FTO glass substrate, dried at room temperature, and baked at 450 ° C. for 30 minutes in air. Using the same solution again, it was applied on the obtained electrode by spin coating so as to have a film thickness of 100 nm, and baked in air at 450 ° C. for 30 minutes to form a dense electron transport layer.

(Preparation of porous layer, as in Example 1)
Using a paste obtained by diluting Diessol 18NR-t (titanium oxide paste) with ethanol, the fine electron transport layer was applied by spin coating, dried in warm air at 120 ° C. for 3 minutes, and then in air. Baking at 30 ° C. for 30 minutes formed a porous layer. The film thickness of the porous layer was 308 nm.

(Preparation of perovskite layer)
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.461 g) and methylamine iodide (0.159 g) were dissolved was sprayed on the porous titanium oxide electrode. It was applied and dried at 100 ° C. for 10 minutes to form a perovskite layer. The film thickness of the perovskite layer was 533 nm.

(Preparation of hole transport layer and hole collecting electrode, same as Example 1)
2,2 (7,7 (-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9 (-spirobifluorene))) (50 mM), lithium bis (trifluoromethanesulfonyl) imide (30 mM) A chlorobenzene solution in which 4-t-butylpyridine (200 mM) was dissolved was formed into a film by spin coating and air-dried. On this, gold was formed to a thickness of about 100 nm by vacuum deposition to produce a solar cell element.
The produced solar cell was evaluated in the same manner as in Example 1. As a result, excellent characteristics of an open circuit voltage = 0.88 V, a short circuit current density of 10.8 mA / cm ² , a form factor = 0.61, and a conversion efficiency = 5.80% were exhibited.

[Example 3]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.461 g) and methylamine iodide (0.159 g) were dissolved was sprayed on the porous titanium oxide electrode. It was applied and dried at 100 ° C. for 10 minutes to form a perovskite layer. The thickness of the perovskite layer was 462 nm including the porous electron transport layer. On this perovskite layer, N, N-dimethylformamide (1. 1) in which lead (II) iodide (0.461 g), methylamine iodide (0.106 g), and methylamine chloride (0.023 g) were dissolved. 0 ml) solution was applied onto the porous titanium oxide electrode by spraying and dried at 100 ° C. for 10 minutes to laminate a perovskite layer having different halogen atom components. The total thickness of the perovskite layer was 539 nm.
The produced solar cell was evaluated in the same manner as in Example 1. As a result, it showed excellent characteristics of an open circuit voltage = 0.93V, a short circuit current density of 13.1 mA / cm ² , a form factor = 0.62, and a conversion efficiency = 7.55%.

[Example 4]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.461 g) and methylamine iodide (0.159 g) were dissolved was sprayed on the porous titanium oxide electrode. It was applied and dried at 100 ° C. for 10 minutes to form a perovskite layer. The thickness of the perovskite layer was 462 nm including the porous electron transport layer. On this perovskite layer, N, N-dimethylformamide (1...) In which lead (II) iodide (0.461 g), methylamine iodide (0.106 g), and methylamine bromide (0.075 g) were dissolved. 0 ml) solution was applied onto the porous titanium oxide electrode by spraying and dried at 100 ° C. for 10 minutes to laminate a perovskite layer having different halogen atom components. The total thickness of the perovskite layer was 539 nm.
The produced solar cell was evaluated in the same manner as in Example 1. As a result, the excellent characteristics of an open circuit voltage = 0.92 V, a short circuit current density of 11.2 mA / cm ² , a form factor = 0.60, and a conversion efficiency = 6.18% were exhibited.

[Example 5]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.415 g) and antimony iodide (III) (0.050 g) are dissolved is sprayed on the porous titanium oxide electrode. And then dried at 100 ° C. for 10 minutes. An isopropyl alcohol solution (concentration 0.038M) in which methyl iodide is dissolved is applied onto the electrode by spin coating and dried, and then an isopropyl alcohol solution (concentration 0.038M in which methyl iodide is dissolved on the electrode). ) Was applied by spin coating and dried repeatedly. Finally, isopropyl alcohol was applied onto this electrode by spin coating and dried to form a perovskite layer. The film thickness of the perovskite layer was 512 nm including the porous electron transport layer. The film thickness of this perovskite layer was 506 nm including the porous electron transport layer.
The produced solar cell was evaluated in the same manner as in Example 1. As a result, excellent characteristics of an open circuit voltage = 0.90 V, a short circuit current density of 12.2 mA / cm ² , a form factor = 0.59, and a conversion efficiency = 6.48% were exhibited.

[Example 6]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.415 g) and indium (III) iodide (0.050 g) are dissolved is sprayed on the porous titanium oxide electrode. And then dried at 100 ° C. for 10 minutes. An isopropyl alcohol solution (concentration 0.038M) in which methyl iodide is dissolved is applied onto the electrode by spin coating and dried, and then an isopropyl alcohol solution (concentration 0.038M in which methyl iodide is dissolved on the electrode). ) Was applied by spin coating and dried repeatedly. Finally, isopropyl alcohol was applied onto this electrode by spin coating and dried to form a perovskite layer. The film thickness of the perovskite layer was 512 nm including the porous electron transport layer. The film thickness of this perovskite layer was 506 nm including the porous electron transport layer. The film thickness of this perovskite layer was 519 nm including the porous electron transport layer. The solar cell produced as described above was evaluated in the same manner as in Example 1. As a result, the excellent characteristics of an open circuit voltage = 0.90 V, a short circuit current density of 11.5 mA / cm ² , a form factor = 0.59, and a conversion efficiency = 6.11% were exhibited.

[Example 7]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.415 g), indium iodide (0.050 g) and methylamine iodide (0.159 g) were dissolved was used as the porous material. A perovskite layer was formed by coating on a titanium oxide electrode using a spray and drying at 100 ° C. for 10 minutes. The thickness of the perovskite layer was 455 nm including the porous electron transport layer. N in which lead (II) iodide (0.415 g), indium iodide (0.050 g), methylamine iodide (0.106 g), and methylamine chloride (0.023 g) were dissolved on the perovskite layer. , N-dimethylformamide (1.0 ml) solution was applied onto the porous titanium oxide electrode by spraying and dried at 100 ° C. for 10 minutes to laminate a perovskite layer having different halogen atom components. The total thickness of the perovskite layer was 522 nm. The solar cell produced as described above was evaluated in the same manner as in Example 3. As a result, the excellent characteristics of an open circuit voltage = 0.92 V, a short circuit current density of 13.8 mA / cm ² , a form factor = 0.60, and a conversion efficiency = 7.62% were exhibited.

[Example 8]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.415 g) and indium (III) iodide (0.050 g) are dissolved is sprayed on the porous titanium oxide electrode. And then dried at 100 ° C. for 10 minutes. N in which lead (II) iodide (0.415 g), indium iodide (0.050 g), methylamine iodide (0.106 g), and methylamine chloride (0.023 g) were dissolved on the perovskite layer. , N-dimethylformamide (1.0 ml) solution was applied onto the porous titanium oxide electrode by spraying and dried at 100 ° C. for 10 minutes to laminate a perovskite layer having different halogen atom components. The total thickness of the perovskite layer was 522 nm. The solar cell produced as described above was evaluated in the same manner as in Example 3. As a result, the excellent characteristics of an open circuit voltage = 0.91 V, a short circuit current density of 13.7 mA / cm ² , a form factor = 0.61, and a conversion efficiency = 7.6% were exhibited.

[Example 9]
A perovskite layer in Example 1 was changed as follows, and a solar cell was fabricated in the same manner as in Example 1 except that.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.415 g) and indium (III) iodide (0.050 g) are dissolved is sprayed on the porous titanium oxide electrode. And then dried at 100 ° C. for 10 minutes. An isopropyl alcohol solution (concentration 0.038M) in which methyl iodide is dissolved is applied onto the electrode by spin coating and dried, and then an isopropyl alcohol solution (concentration 0.038M in which methyl iodide is dissolved on the electrode). ) Was applied by spin coating and dried repeatedly. Finally, isopropyl alcohol was applied onto this electrode by spin coating and dried to form a perovskite layer. On the perovskite layer, an N, N-dimethylformamide (1.0 ml) solution in which lead (II) iodide (0.415 g) and indium (III) iodide (0.050 g) were dissolved was again added to the porous layer. It apply | coated using the spray on the quality titanium oxide electrode, and it dried for 10 minutes at 100 degreeC. An isopropyl alcohol solution (concentration 0.038M) in which methyl iodide is dissolved is applied onto the electrode by spin coating and dried, and then an isopropyl alcohol solution (concentration 0.038M in which methyl iodide is dissolved on the electrode). ) Was applied by spin coating and dried repeatedly. Finally, isopropyl alcohol was applied onto this electrode by spin coating and dried to form a perovskite layer. The total thickness of the perovskite layer was 531 nm. The solar cell produced as described above was evaluated in the same manner as in Example 1. As a result, the excellent characteristics of an open circuit voltage = 0.92 V, a short circuit current density of 12.1 mA / cm ² , a form factor = 0.59, and a conversion efficiency = 6.57% were exhibited.

[Example 10]
A solar cell was fabricated in the same manner as in Example 1 except that the perovskite layer in Example 1 was changed as follows.
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.461 g) was dissolved was applied onto the porous titanium oxide electrode by spraying and dried at 100 ° C. for 10 minutes. . An isopropyl alcohol solution (concentration 0.038M) in which formamidine iodide is dissolved is applied onto the electrode by spin coating and dried, and then an isopropyl alcohol solution (concentration 0.038M in which methylamine iodide is dissolved on the electrode). ) Was applied by spin coating and dried repeatedly. Finally, isopropyl alcohol was applied onto this electrode by spin coating and dried to form a perovskite layer. The thickness of the perovskite layer was 497 nm including the porous electron transport layer. The solar cell produced as described above was evaluated in the same manner as in Example 1. As a result, excellent characteristics of an open circuit voltage = 0.87 V, a short circuit current density of 13.4 mA / cm ² , a form factor = 0.59, and a conversion efficiency = 6.88% were exhibited.

[Example 11]
A solar cell was fabricated in the same manner as in Example 2 except that the porous layer in Example 2 was changed as follows.
Using a solution in which zinc oxide dispersed by CII Kasei Co., Ltd. was dispersed, it was applied onto a dense electron transport layer by spin coating, dried with warm air at 120 ° C. for 3 minutes, then baked at 500 ° C. for 30 minutes in the air, and porous A quality layer was formed. The film thickness of the porous layer was 279 nm. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, the open circuit voltage = 0.73 V, the short circuit current density 9.77 mA / cm ² , the shape factor = 0.56, and the conversion efficiency = 3.99% were exhibited.

[Example 12]
A solar cell was fabricated in the same manner as in Example 2 except that the porous layer in Example 2 was changed as follows.
Using a solution in which tin oxide manufactured by CII Kasei Co., Ltd. was dispersed, it was applied onto a dense electron transport layer by spin coating, dried with warm air at 120 ° C. for 3 minutes, and then baked at 500 ° C. for 30 minutes in the air. A quality layer was formed. The film thickness of the porous layer was 311 nm. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, the open circuit voltage was 0.75 V, the short circuit current density was 8.96 mA / cm ² , the form factor was 0.57, and the conversion efficiency was 3.83%.

[Example 13]
A solar cell was fabricated in the same manner as in Example 2 except that the porous layer in Example 2 was changed as follows.
Using a solution in which aluminum oxide manufactured by CI Kasei Co., Ltd. is dispersed, it is applied onto a dense electron transport layer by spin coating, dried with warm air at 120 ° C. for 3 minutes, and then baked at 500 ° C. for 30 minutes in the air. A quality layer was formed. The film thickness of the porous layer was 304 nm. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, the open circuit voltage = 0.66 V, the short circuit current density 6.12 mA / cm ² , the shape factor = 0.49, and the conversion efficiency = 1.98% were exhibited.

[Example 14]
A solar cell was fabricated in the same manner as in Example 2 except that the porous layer in Example 2 was changed as follows.
Using a solution in which niobium oxide is dispersed, it is applied onto a dense electron transport layer by spin coating, dried in warm air at 120 ° C. for 3 minutes, and then baked in air at 500 ° C. for 30 minutes to form a porous layer did. The film thickness of the porous layer was 288 nm. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, an open circuit voltage = 0.81 V, a short circuit current density of 6.12 mA / cm ² , a form factor = 0.52, and a conversion efficiency = 2.58% were exhibited.

[Example 15]
A solar cell was fabricated in the same manner as in Example 2 except that the porous layer in Example 2 was changed as follows.
Using a solution in which yttrium oxide manufactured by Cai Kasei Co., Ltd. is dispersed, it is applied onto a dense electron transport layer by spin coating, dried with warm air at 120 ° C. for 3 minutes, and then baked at 500 ° C. for 30 minutes in the air. A layer was formed. The film thickness of the porous layer was 293 nm. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, the open circuit voltage = 0.84 V, the short-circuit current density 7.39 mA / cm ² , the form factor = 0.47, and the conversion efficiency = 2.92% were exhibited.

[Example 16]
A solar cell was fabricated in the same manner as in Example 2 except that the porous layer in Example 2 was changed as follows.
Using a solution in which barium titanate is dispersed, a fine electron transport layer is applied by spin coating, dried in warm air at 120 ° C. for 3 minutes, and then fired in air at 500 ° C. for 30 minutes to form a porous layer. Formed. The film thickness of the porous layer was 293 nm. The solar cell produced as described above was evaluated in the same manner as in Example 1. As a result, an open circuit voltage = 0.61V, a short circuit current density of 8.86 mA / cm ² , a form factor = 0.44, and a conversion efficiency = 2.38% were exhibited.

[Example 17]
A solar cell was fabricated in the same manner as in Example 1 except that the electron transport layer in Example 2 was changed as follows.
A dense electron transport layer was formed by providing about 10 nm of niobium oxide on the FTO glass substrate by sputtering. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, the open circuit voltage = 0.91 V, the short-circuit current density 10.9 mA / cm ² , the form factor = 0.62, and the conversion efficiency = 6.15% were exhibited.

[Example 18]
A solar cell was fabricated in the same manner as in Example 2 except that the electron transport layer in Example 2 was changed as follows.
A dense electron transport layer was formed by providing about 10 nm of a mixture (1: 1) of titanium oxide and niobium oxide on a FTO glass substrate by co-sputtering. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, the open circuit voltage = 0.91V, the short circuit current density 11.2 mA / cm ² , the shape factor = 0.61, and the conversion efficiency = 6.22% were exhibited.

[Example 19]
A solar cell was fabricated in the same manner as in Example 2 except that the electron transport layer in Example 2 was changed as follows.
A dense electron transport layer was formed by providing about 2 nm of yttrium oxide on the FTO glass substrate by sputtering. The solar cell produced as described above was evaluated in the same manner as in Example 2. As a result, the open circuit voltage = 0.92V, the short circuit current density 10.9 mA / cm ² , the form factor = 0.61, and the conversion efficiency = 6.12% were exhibited.

[Example 20]
A hole transport layer in Example 2 was changed as follows, and a solar cell was fabricated in the same manner as in Example 2 except that.
2,2 (7,7 (-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9 (-spirobifluorene))) (50 mM), lithium bis (trifluoromethanesulfonyl) imide (30 mM) 4-t-butylpyridine (200 mM), tris (2- (1H-pyrazol-1-yl) -4-tert-butylpyridine) cobalt (III) bis (trifluoromethanesulfonyl) imide (6 mM) A chlorobenzene solution was formed by spin coating and air-dried. As a result, the open circuit voltage = 0.87 V, the short circuit current density 11.5 mA / cm ² , the form factor = 0.64, and the conversion efficiency = 6.4% were exhibited.

[Example 21]
A hole transport layer in Example 2 was changed as follows, and a solar cell was fabricated in the same manner as in Example 2 except that.
2,2 (7,7 (-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9 (-spirobifluorene))) (50 mM), lithium bis (trifluoromethanesulfonyl) imide (30 mM) Spin a chlorobenzene solution in which 4-t-butylpyridine (200 mM), tris (2- (1H-pyrazol-1-yl) -4-tert-butylpyridine) cobalt (III) hexafluorophosphate (6 mM) was dissolved The film was formed with a coat and dried naturally. As a result, the characteristics of an open circuit voltage = 0.88 V, a short circuit current density of 12.1 mA / cm ² , a form factor = 0.62, and a conversion efficiency = 6.6% were exhibited.

[Example 22]
A hole transport layer in Example 2 was changed as follows, and a solar cell was fabricated in the same manner as in Example 2 except that.
2,2 (7,7 (-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9 (-spirobifluorene))) (50 mM), lithium bis (trifluoromethanesulfonyl) imide (30 mM) A chlorobenzene solution in which 4-t-butylpyridine (200 mM), tris (2,2′-bipyridine) cobalt (III) hexafluorophosphate (6 mM) was dissolved was formed by spin coating, and air-dried. As a result, an open circuit voltage = 0.87 V, a short circuit current density of 11.8 mA / cm ² , a form factor = 0.64, and a conversion efficiency = 6.57% were exhibited.

[Example 23]
(Preparation of electron transport layer)
A dense electron transport layer was formed by providing about 10 nm of a mixture (1: 1) of titanium oxide and niobium oxide on a FTO glass substrate by co-sputtering.

(Preparation of porous layer)
Using a paste obtained by diluting Diesol 18NR-T (titanium oxide paste) with ethanol, the fine electron transport layer was applied by spin coating, dried in warm air at 120 ° C. for 3 minutes, and then in air. Baking at 30 ° C. for 30 minutes formed a porous layer. The film thickness of the porous layer was 308 nm.

(Preparation of perovskite layer)
A solution of N, N-dimethylformamide (1.0 ml) in which lead (II) iodide (0.415 g) and antimony iodide (III) (0.050 g) are dissolved is sprayed on the porous titanium oxide electrode. And then dried at 100 ° C. for 10 minutes. An isopropyl alcohol solution (concentration 0.038M) in which methyl iodide is dissolved is applied onto the electrode by spin coating and dried, and then an isopropyl alcohol solution (concentration 0.038M in which methyl iodide is dissolved on the electrode). ) Was applied by spin coating and dried repeatedly. Finally, isopropyl alcohol was applied onto this electrode by spin coating and dried to form a perovskite layer. The film thickness of this perovskite layer was 457 nm including the porous electron transport layer. N in which lead (II) iodide (0.415 g), indium iodide (0.050 g), methylamine iodide (0.106 g), and methylamine chloride (0.023 g) were dissolved on the perovskite layer. , N-dimethylformamide (1.0 ml) solution was applied onto the porous titanium oxide electrode by spraying and dried at 100 ° C. for 10 minutes to laminate a perovskite layer having different halogen atom components. The total thickness of the perovskite layer was 514 nm.

(Preparation of hole transport layer and hole collecting electrode)
2,2 (7,7 (-tetrakis- (N, N-di-p-methoxyphenylamine) 9,9 (-spirobifluorene))) (50 mM), lithium bis (trifluoromethanesulfonyl) imide (30 mM) Spin a chlorobenzene solution in which 4-t-butylpyridine (200 mM), tris (2- (1H-pyrazol-1-yl) -4-tert-butylpyridine) cobalt (III) hexafluorophosphate (6 mM) was dissolved The film was formed with a coat and dried naturally. On this, gold was formed to a thickness of about 100 nm by vacuum deposition to produce a solar cell element.

(Evaluation of solar cell characteristics)
The photoelectric conversion efficiency of the obtained solar cell under pseudo-sunlight irradiation (AM 1.5, 100 mW / cm 2) was measured. The simulated solar light was measured by a solar simulator SS-80XIL manufactured by Eihiro Seiki Co., Ltd., and the evaluation equipment was measured by a solar cell evaluation system As-510-PV03 manufactured by NF Circuit Design Block. As a result, the excellent characteristics of an open circuit voltage = 0.94 V, a short circuit current density of 13.7 mA / cm 2, a form factor = 0.65, and a conversion efficiency = 8.37% were exhibited.

[Comparative Example 1]
A solar cell was produced and evaluated in the same manner as in Example 1 except that the perovskite layer formed by spraying in Example 2 was changed to a perovskite layer formed by spin coating. The thickness of the perovskite layer formed by spin coating was 527 nm including the porous electron transport layer. The characteristics of this solar cell were as follows: open circuit voltage = 0.88 V, short circuit current density 10.6 mA / cm ² , form factor = 0.60, conversion efficiency = 5.60%. Compared with Example 2 produced by the same one-step deposition method, the solar cell of Comparative Example 1 produced by spin coating had lower characteristics.

[Comparative Example 2]
A solar cell was produced and evaluated in the same manner as in Example 1 except that the perovskite layer in the spray in Example 3 was changed to a perovskite layer formed by spin coating. The thickness of the perovskite layer formed by spin coating was 411 nm including the porous electron transport layer. The characteristics of this solar cell were values of open circuit voltage = 0.64 V, short circuit current density 4.7 mA / cm ² , form factor = 0.44, and conversion efficiency = 1.32%. The solar cell of Comparative Example 2 produced by spin coating had lower characteristics than Example 3 where the same perovskite layer was laminated. This is presumed to be because the underlying perovskite layer was melted out once the perovskite layer formed once was laminated on the spin coat.

[Comparative Example 3]
A solar cell was produced and evaluated in the same manner as in Example 1 except that the perovskite layer formed by spraying in Example 1 was changed to a perovskite layer formed by spin coating. The thickness of the perovskite layer formed by spin coating was 496 nm including the porous electron transport layer. The characteristics of the solar cell were as follows: open circuit voltage = 0.84 V, short circuit current density 10.1 mA / cm ² , form factor = 0.60, and conversion efficiency = 0.09%. Compared with Example 1 produced by the same two-step deposition method, the solar cell of Comparative Example 3 produced by spin coating had lower characteristics.

[Comparative Example 4]
A solar cell was produced and evaluated in the same manner as in Example 1 except that the perovskite layer in the spray in Example 8 was changed to a perovskite layer formed by spin coating. The thickness of the perovskite layer formed by spin coating was 442 nm including the porous electron transport layer. The characteristics of the solar cell were as follows: open circuit voltage = 0.61 V, short circuit current density 4.4 mA / cm ² , form factor = 0.49, and conversion efficiency = 1.32%. The solar cell of Comparative Example 4 produced by spin coating had lower characteristics than Example 8 where the same perovskite layer was laminated. This is presumed to be because the underlying perovskite layer was melted out once the perovskite layer formed once was laminated on the spin coat.
Table 1 below summarizes the examples and comparative examples.

  As described above, the perovskite solar cell of the present invention can obtain a solar cell having excellent characteristics in the perovskite layer formed by spraying from the results of Examples 1 and 2, and Examples 3, 4, 7, 8, From the result of 9, it is understood that higher performance can be obtained by laminating by spray film formation. From the results of Examples 5 to 9, it can be seen that better characteristics can be obtained by mixing not only lead but also antimony or indium as a metal. Furthermore, from the result of Example 10, not only halogenated methylamine but also formamidine can obtain good characteristics. From the results of Examples 11 to 16, the oxide used for the porous layer is zinc oxide, Although solar cell characteristics can be obtained with tin oxide, aluminum oxide, niobium oxide, yttrium oxide, and barium titanate, it can be seen that titanium oxide provides the best results. From the results of Examples 17 to 23, it can be seen that higher performance can be obtained by using not only titanium oxide but also niobium oxide, a mixture thereof, or yttrium oxide in the electron transport layer. Furthermore, from the results of Examples 20 to 23, it can be seen that higher performance can be obtained by adding a Co complex to the hole transport layer.

  As mentioned above, although the form which concerns on implementation of this invention was demonstrated, the said content does not limit the content of invention.

1 Substrate 2 First electrode 3 Electron transport layer 4 Porous layer 5 Perovskite layer 6 Hole transport layer 7 Second electrode

Japanese Patent No. 2664194 Japanese Patent Laid-Open No. 11-144773 JP 2000-106223 A WO07 / 100095 publication

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Claims (10)

A first electrode provided with an electron transport layer on a transparent conductive film substrate, a porous layer provided on the electron transport layer, a perovskite compound layer provided on the porous layer, and provided on the perovskite compound layer And a method for producing a perovskite solar cell comprising a second electrode on the hole transport layer, wherein a solution of an alkylamine halide and a metal halide is sprayed on the porous layer. A method for producing a perovskite solar cell, comprising a step of forming a perovskite compound layer represented by the following general formula (1) on the porous layer.
XαYβMγ General formula (1)
(In the formula, X is a halogen atom, Y is an alkylamine compound, M contains a metal, the ratio of α: β: γ is 3: 1: 1, and β and γ represent integers greater than 1.) A first electrode provided with an electron transport layer on a transparent conductive film substrate, a porous layer provided on the electron transport layer, a perovskite compound layer provided on the porous layer, and provided on the perovskite compound layer And a perovskite solar cell having a second electrode on the hole transport layer, wherein the perovskite compound represented by the following general formula (1) contains an alkylamine halide and a metal halide as an organic solvent: A perovskite solar cell, which is formed by spraying the solution contained therein onto the porous layer.
XαYβMγ General formula (1)
(In the formula, X is a halogen atom, Y is an alkylamine compound, M contains a metal, the ratio of α: β: γ is 3: 1: 1, and β and γ represent integers greater than 1.)   The perovskite compound layer, wherein a perovskite layer in which X is a mixture of iodine and other halogen atoms is laminated on a perovskite layer in which X in the general formula (1) is iodine. 2. A perovskite solar cell according to 2.   4. The perovskite solar cell according to claim 2, wherein M in the general formula contains at least lead.   The perovskite solar cell according to any one of claims 2 to 4, wherein M in the general formula contains lead and any one of indium, antimony, and tin.   The perovskite solar cell according to any one of claims 2 to 5, wherein the halogenated alkylamine of Y in the general formula (1) is either a halogenated methylamine or a halogenated formamidine.   The perovskite solar cell according to claim 2, wherein the porous layer contains a metal oxide.   The perovskite solar cell according to any one of claims 2 to 7, wherein the metal oxide is titanium oxide.   The perovskite solar cell according to any one of claims 2 to 8, wherein the electron transport layer contains at least one of titanium oxide, niobium oxide, and yttrium oxide.   The perovskite solar cell according to any one of claims 2 to 9, wherein the hole transport layer contains an oxidizing agent.

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