WO2014196311A1 - Method for producing complex and solution thereof, method for producing light-absorbing layer for solar cell, and method for producing solar cell - Google Patents

Method for producing complex and solution thereof, method for producing light-absorbing layer for solar cell, and method for producing solar cell Download PDF

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WO2014196311A1
WO2014196311A1 PCT/JP2014/062476 JP2014062476W WO2014196311A1 WO 2014196311 A1 WO2014196311 A1 WO 2014196311A1 JP 2014062476 W JP2014062476 W JP 2014062476W WO 2014196311 A1 WO2014196311 A1 WO 2014196311A1
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group
compound
solution
metal
complex
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PCT/JP2014/062476
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French (fr)
Japanese (ja)
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卓矢 大橋
亮正 仲村
啓之 飯田
大 桑原
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東京応化工業株式会社
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Priority to JP2015521351A priority Critical patent/JP6012866B2/en
Priority to CN201480031441.6A priority patent/CN105308760B/en
Publication of WO2014196311A1 publication Critical patent/WO2014196311A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/02557—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H01L21/0256—Selenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03923—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a complex used for forming a light absorption layer of a solar cell, a method for producing the solution, a method for producing a light absorption layer for a solar cell using the complex solution, and production of a solar cell using the complex solution.
  • This application is based on United States provisional application 61/830294 filed in the United States on June 3, 2013 and United States provisional application 61/925621 filed in the United States on January 9, 2014. Insist and use that content here.
  • chalcopyrite solar cells which are thin-film solar cells with high photoelectric conversion efficiency
  • kesterite systems in which rare metals such as indium are replaced with other environmentally friendly metals.
  • Solar cells are attracting particular attention, and research and development are actively underway.
  • a chalcopyrite solar cell is a solar cell formed by forming a light absorption layer made of a chalcopyrite (chalcopyrite) material on a substrate.
  • chalcopyrite-based materials are copper (Cu), indium (In), gallium (Ga), selenium (Se), sulfur (S), and the like, and typical examples of the light absorption layer include Cu.
  • Cu copper
  • In indium
  • Ga gallium
  • Se sulfur
  • typical examples of the light absorption layer include Cu.
  • a kesterite solar cell made of, for example, copper (Cu), zinc (Zn), tin (Sn) selenium (Se) and sulfur (S), which replaces indium, which is a rare metal, has been studied.
  • Typical examples of the layer include Cu 2 ZnSnSe 4 , Cu 2 ZnSnS 4 , Cu 2 ZnSn (S, Se) 4 and the like.
  • FIG. 1 is a schematic cross-sectional view showing an example of a chalcopyrite solar cell or a kesterite solar cell.
  • the chalcopyrite solar cell or the kesterite solar cell includes a first electrode 3, a CIGS or CZTS layer (light absorption layer) 4, a buffer layer 5, an i-ZnO layer 6 and a substrate 2.
  • the second electrode 7 is schematically configured by being stacked in this order.
  • the buffer layer for example, a CdS layer, a ZnS layer, an InS layer, or the like is known.
  • Terminals are joined to the first electrode 3 and the second electrode 7, respectively, and wiring is connected to the terminals.
  • a chalcopyrite-based or kesterite-based solar cell 1 light incident in the direction of arrow A is absorbed by the CIGS or CZTS layer 4 to generate an electromotive force, and a current flows in the direction of arrow B.
  • the surface of the second electrode 7 is protected by being covered with an antireflection film layer 8 made of, for example, an MgF 2 layer.
  • a coating solution is prepared by dissolving elements such as Cu, In, Ga, Se, and S in a specific solvent to prepare a coating solution, which is then applied to a spin coating method, a dipping method, A CIGS layer is formed by applying onto a substrate using a slit casting method or the like and baking.
  • a method of preparing a coating solution a method using hydrazine as a solvent and a method of adding amines as a dissolution accelerator instead of using hydrazine are known (see Patent Documents 1 and 2). .
  • a coating solution is prepared by dissolving elements such as Cu, Zn, Sn, Se, and S in a specific solvent, and this coating solution is prepared by spin coating, dipping, or slit casting. Etc. are applied onto the substrate and baked to form a CZTS layer. (See Patent Document 3).
  • a metal raw material containing at least one of a group IB element and a group III-B element is dissolved in a metal state in a mixed solvent containing a chalcogen element-containing organic compound and a Lewis basic organic compound.
  • a method is also known (see Patent Document 4).
  • zinc chalcogenide compounds such as ZnSe have low solubility in hydrazine, and it has been difficult to prepare a high concentration and uniform zinc complex solution.
  • copper selenide Cu 2 Se
  • Cu 2 Se copper selenide
  • the first aspect of the present invention is a method for producing a complex used for forming a light absorption layer of a solar cell and a solution thereof, which comprises a Group 11 metal, a Group 12 metal, a Group 13 metal, At least one element selected from the group consisting of Group metals, Group 15 elements, Group 11 metal compounds, Group 12 metal compounds, Group 13 metal compounds, Group 14 metal compounds, and Group 15 element-containing compounds or Compound, mercapto group-containing organic compound, sulfide, polysulfide, thiocarbonyl group-containing organic compound, sulfur-containing heterocyclic compound, hydroseleno group-containing organic compound, selenide, polyselenide, selenocarbonyl group-containing organic compound, and selenium-containing heterocyclic compound At least one chalcogen element-containing organic compound selected from the group consisting of: a Lewis basic inorganic compound; Is a complex and a manufacturing method of the solution
  • a method for producing a light absorption layer for a solar cell wherein the complex according to the first aspect and a solution obtained by the method for producing the solution are applied to a substrate and baked. Is the method.
  • a step of forming a first electrode on a substrate, and a solution obtained by the complex according to the first aspect and a method for producing the solution are applied on the first electrode. And baking to form a light absorption layer, forming a buffer layer on the light absorption layer, and forming a second electrode on the buffer layer. It is a manufacturing method of a solar cell.
  • a first aspect of the present invention is a complex used for forming a light absorption layer of a solar cell and a method for producing the complex (hereinafter sometimes simply referred to as “complex (solution) production method”), Group 11 metal, Group 12 metal, Group 13 metal, Group 14 metal, Group 15 element, Group 11 metal compound, Group 12 metal compound, Group 13 metal compound, Group 14 metal compound and Group At least one simple substance or compound selected from the group consisting of group 15 element-containing compounds (hereinafter sometimes collectively referred to as “simple and / or compounds”), mercapto group-containing organic compounds, sulfides, polysulfides, thiocarbonyls Group-containing organic compound, sulfur-containing heterocyclic compound, hydroseleno group-containing organic compound, selenide, polyselenide, selenocarbonyl group-containing organic compound, and selenium-containing complex And obtaining at least one chalcogen element-containing organic compound selected from the group consisting of Formula compound,
  • Examples of the Group 11 metal include a Cu element and an Ag element. Among these, Cu element is particularly preferable.
  • Examples of the Group 12 metal include Zn element and Cd element. Among these, Zn element is particularly preferable.
  • Examples of the Group 13 metal include Al element, Ga element, and In element. Among these, Ga element and In element are particularly preferable.
  • Examples of the Group 14 metal include Si element, Ge element, and Sn element. Among these, Ge element and Sn element are particularly preferable.
  • Examples of the Group 15 element include As element, Sb element, P element, and Bi element. Among these, Sb element is particularly preferable.
  • Examples of the Group 11 metal compound include Cu (OH) 2 , CuS, Cu 2 S, Cu 2 Se, CuSe, Cu 2 Te, CuTe, CuO, Cu 2 O, silver oxide, silver sulfide, and silver selenide.
  • Examples of the Group 12 metal compound include ZnO, zinc hydroxide, ZnS, ZnSe, and ZnTe.
  • Examples of the Group 13 metal compound include In (OH) 3 , indium oxide, indium sulfide, indium selenide, indium telluride, gallium oxide, gallium sulfide, gallium selenide, gallium telluride, boric acid, and boron oxide. Etc.
  • Examples of the Group 14 metal compound include SnS, SnO, SnO 2 , SnS 2 , SnSe, SnTe, germanium oxide, and the like.
  • Examples of the Group 15 element-containing compound include Sb 2 O 3 , phosphoric acid, phosphorous acid, phosphine, arsenic acid, arsenous acid, antimony sulfide, antimony selenide, antimony telluride, and the like.
  • one kind may be used, or two or more kinds may be used in combination.
  • the chalcogen element-containing organic compound is a mercapto group-containing organic compound, sulfide, polysulfide, thiocarbonyl group-containing organic compound, sulfur-containing heterocyclic compound, hydroseleno group-containing organic compound, selenide, polyselenide, or selenocarbonyl group-containing organic compound. It is at least one selected from the group consisting of a compound and a selenium-containing heterocyclic compound.
  • Examples of the mercapto group-containing organic compound include alkylthiol (ethanethiol, propanethiol, etc.), mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thioglycolic acid, thiolactic acid, thiomalic acid, methyl thioglycolate, thioglycol
  • Examples thereof include ethyl acid, ethanedithiol, propanedithiol, butanedithiol, 2,3-dimercapto-1-propanol, meso-2,3-dimercaptosuccinic acid, n-butyl mercaptan, tert-butyl mercaptan and the like.
  • Examples of the sulfide include dibutyl sulfide, ethyl methyl sulfide, diethyl sulfide, thiodiglycol, 2,2′-thiodiglycol, bis (2-hydroxyethyl) disulfide, dithiodiglycolic acid, and 2,2-dithiopropionic acid.
  • Examples of the polysulfide include diheptyl disulfide, diethyl disulfide, methylpropyl disulfide, 2,2′-dithiodiethanol, dithiodiglycolic acid, bis (2-hydroxyethyl) disulfide, dithiodiglycolic acid, 2,2-dithiopropion. An acid etc.
  • thiocarbonyl group-containing organic compounds include thiourea, thioacetamide, dimethylthiourea, trimethylthiourea, ethylenethiourea, thiosemicarbazide, diethylammonium diethyldithiocarbamate, dimethylammonium dimethyldithiocarbamate, tetramethylthiuram monosulfide, and guanylthiourea.
  • sulfur-containing heterocyclic compound include thiophene, 2-amino-5-mercapto-1,3-thiadiazole, bismuthiol and the like.
  • Examples of the hydroseleno group-containing organic compound include benzene selenol and tert-butyl selenol.
  • Examples of the selenide include phenyl selenide and tert-butyl selenide.
  • Examples of the polyselenide include diphenyl diselenide and tert-butyl diselenide.
  • Examples of the selenocarbonyl group-containing organic compound include selenourea and 1,1-dimethyl-2-selenourea.
  • Examples of the selenium-containing heterocyclic compound include selenophene.
  • the chalcogen element-containing organic compound is preferably at least one selected from the group consisting of mercapto group-containing organic compounds, sulfides, polysulfides, thiocarbonyl group-containing organic compounds, and sulfur-containing heterocyclic compounds, and contains mercapto group-containing compounds.
  • mercaptoethanol thioglycolic acid, at least one more preferably selected from the group consisting of alkyl thiols and thioglycerol, propanethiol is especially preferred.
  • the chalcogen element-containing organic compound may be water-soluble.
  • water can be used as a solvent when the simple substance and / or the compound and the chalcogen element-containing organic compound are mixed, thereby further improving the safety of the process.
  • the water-soluble chalcogen element-containing organic compound include mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid, thiomalic acid, thioglycolic acid, thiourea, and thioacetamide.
  • mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thiolactic acid and thioglycerol are particularly preferable.
  • the number of carbon atoms of the chalcogen element-containing organic compound may be 4 or less.
  • the organic compound containing a chalcogen element having 4 or less carbon atoms include propanethiol, mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid, thiomalic acid, thioglycolic acid, thiourea, thioacetamide, and methyl thioglycolate.
  • Ethyl thioglycolate ethanedithiol, propanedithiol, butanedithiol, 2,3-dimercapto-1-propanol, meso-2,3-dimercaptosuccinic acid, ethyl methyl sulfide, diethyl sulfide, thiodiglycol, 2,2 ' -Thiodiglycolic acid, thiolactic acid, diethyl disulfide, methylpropyl disulfide, 2,2'-dithiodiethanol, dithiodiglycolic acid, dimethylthiourea, trimethylthiourea, Chirenchio urea, dimethyl dithiocarbamate dimethyl ammonium and the like.
  • mercaptoethanol and thioglycerol are particularly preferable.
  • the chalcogen element-containing organic compound may be a compound that dissolves 1 g or more in 100 g of water at room temperature (23 ° C.), more preferably a compound that dissolves 5 g or more, and a compound that dissolves 10 g or more. It is particularly preferred that
  • the chalcogen element-containing organic compound may be a chalcogen element-containing organic compound having at least one hydroxy group.
  • the chalcogen element-containing organic compound having at least one hydroxy group include mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid, thiomalic acid, thioglycolic acid, 2,3-dimercapto-1-propanol, meso -2,3-dimercaptosuccinic acid, thiodiglycol, 2,2'-thiodiglycolic acid, 2,2'-dithiodiethanol, dithiodiglycolic acid and the like.
  • mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid and thiomalic acid are preferable, and mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol and thioglycerol are particularly preferable.
  • the chalcogen element-containing organic compound one kind may be used alone, or two or more kinds may be used in combination.
  • the Lewis basic inorganic compound is not particularly limited, and examples thereof include ammonia, hydrazine, NaOH, KOH and the like. Of these, ammonia is preferable.
  • the Lewis basic inorganic compound one kind may be used alone, or two or more kinds may be used in combination.
  • Group 16 elements include O, S, Se, Te, etc., and at least one selected from S and Se is preferable, and Se is particularly preferable.
  • the group 16 element one type may be used alone, or two or more types may be used in combination.
  • an organic solvent in addition to the simple substance and / or compound, the chalcogen-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element, an organic solvent can be added at an arbitrary ratio.
  • organic solvents include dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, tetramethylguanidine, and tetramethylurea.
  • Protic solvents are preferred. Of these, dimethyl sulfoxide is preferable.
  • a solvent having a lower polarity than the Lewis basic inorganic compound (hereinafter sometimes referred to as “poor solvent”) may be added to the reaction solution.
  • the reaction solution can be purified and impurities can be removed.
  • a purification step is not necessarily required in the method for producing a complex (solution) of the present invention. By omitting the purification step, the entire process can be simplified, which is industrially advantageous.
  • the poor solvent is not particularly limited as long as it is a solvent having a lower polarity than the Lewis basic inorganic compound, but acetone and isopropanol are preferable.
  • the poor solvent may be mixed with the simple substance and / or compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the group 16 element, but the simple substance and / or compound and the chalcogen element are contained. It is preferable to mix the organic compound, the Lewis basic inorganic compound, and the Group 16 element after preparing a reaction solution. By preparing a reaction solution and then mixing a poor solvent, the complex as the target product can be precipitated, and impurities such as unreacted chalcogen element-containing organic compounds can be removed as a supernatant.
  • Complexes and impurities can be separated by, for example, centrifugation, filtration, extraction, and the like. Further, after removing impurities as a supernatant, the complex can be further washed with a poor solvent. Impurities can be more reliably removed by performing the cleaning multiple times.
  • the poor solvent one kind may be used alone, or two or more kinds may be used in combination.
  • the reaction solution in the presence of water it is preferable to obtain the reaction solution in the presence of water.
  • the method for obtaining the reaction solution in the presence of water is not particularly limited.
  • a solvent containing water is used as a mixed solvent for each raw material, or a Lewis basic inorganic compound aqueous solution is used as the Lewis basic inorganic compound.
  • the Lewis basic inorganic compound aqueous solution include ammonia water, hydrazine hydrate, NaOH aqueous solution, KOH aqueous solution and the like. Among them, it is preferable to use ammonia water having a concentration of 28% or less. In this case, it is preferable to use a solvent described later, and dimethyl sulfoxide is particularly preferable.
  • the method of mixing a simple substance and / or compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited.
  • each complex solution hereinafter, “ After preparing a “metal precursor solution”, a method of mixing each metal precursor solution (hereinafter referred to as “preparation method (I)”), a method of mixing all raw materials at once (hereinafter referred to as “preparation method (I)”).
  • Preparation method (II) a method of preparing a binary or ternary metal complex solution using at least two Group 11 to Group 15 metals (hereinafter referred to as "Preparation method (III)”).
  • the Cu precursor is obtained, for example, by mixing Cu and / or a Cu compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
  • a Cu compound chalcogen element-containing organic compound, Lewis basic inorganic compound and Group 16 element
  • Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
  • Cu and / or a Cu compound Cu, Cu (OH) 2 , CuS, Cu 2 S, CuO, Cu 2 O, Cu 2 Se, CuSe, Cu 2 Te, and CuTe are preferable, and Cu is more preferable.
  • Cu and / or Cu compound one kind may be used alone, or two or more kinds may be used in combination.
  • the amount of the Group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Cu.
  • the amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, relative to 1 mol of Cu.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, more preferably 2 to 10 moles, and still more preferably 2 to 5 moles relative to 1 mole of Cu.
  • the method of mixing Cu and / or a Cu compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited.
  • a method of stirring after adding Cu and / or a Cu compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, Cu and / or a Cu compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like.
  • a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Cu and / or a Cu compound is added.
  • the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • NMP N-methylpyrrolidone
  • NMF N-methylformamide
  • DMF dimethylformamide
  • tetramethylguanidine tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
  • the amount of the solvent is preferably such that when mixed, the Cu concentration is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, and 0.4 to 1.2 mol / L. L is particularly preferred.
  • the reaction temperature in the preparation of the Cu precursor varies depending on the type of Cu and / or Cu compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc., but safety and Cu complex From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
  • the reaction time in the preparation of the Cu precursor also depends on the type of Cu and / or Cu compound used, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc., stirring time, and reaction temperature. Although it is different, it is usually preferably 1 hour to 1 week, more preferably 1 day to 3 days, still more preferably 1 day to 2 days.
  • the Cu precursor After preparing the Cu precursor, it is preferable to remove impurities by mixing the Cu precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound.
  • a solvent poor solvent
  • isopropyl alcohol is particularly preferable.
  • the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
  • the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, and even more preferably 7 to 20 times that of the Cu precursor.
  • the Zn precursor can be obtained, for example, by mixing Zn and / or a Zn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
  • Zn and / or Zn compounds, chalcogen element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements include the Zn and / or Zn compounds and chalcogens exemplified in the description of the method for producing a metal precursor solution of the present invention.
  • Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
  • Zn and / or Zn compound Zn, ZnO, zinc hydroxide, ZnS, ZnSe, and ZnTe are preferable, and Zn and ZnO are more preferable.
  • Zn and / or Zn compound one kind may be used alone, or two or more kinds may be used in combination.
  • the amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Zn.
  • the amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, with respect to 1 mol of Zn.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, and still more preferably 2 to 5 mol with respect to 1 mol of Zn.
  • a method of mixing Zn and / or a Zn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited.
  • a method of stirring after adding Zn and / or a Zn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, Zn and / or a Zn compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like.
  • a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Zn and / or a Zn compound is added.
  • the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • NMP N-methylpyrrolidone
  • NMF N-methylformamide
  • DMF dimethylformamide
  • tetramethylguanidine tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
  • the amount of the solvent is preferably such that when mixed, the Zn concentration in the Zn precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
  • the reaction temperature varies depending on the type of Zn and / or Zn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
  • the reaction time varies depending on the type of Zn and / or Zn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
  • the Zn precursor After preparing the Zn precursor, it is preferable to remove impurities by mixing the Zn precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound.
  • a solvent poor solvent
  • acetone is particularly preferable.
  • the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
  • the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the Zn precursor.
  • the Sn precursor is obtained, for example, by mixing a Sn and / or Sn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
  • Sn and / or Sn compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element include the Sn and / or Sn compound and chalcogen exemplified in the description of the method for producing the metal precursor solution of the present invention.
  • Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
  • Sn and / or Sn compound Sn, SnS, SnO, SnO 2 , SnS 2 , SnSe, SnTe are preferable, and Sn is more preferable.
  • Sn and / or Sn compound 1 type may be used independently and 2 or more types may be used in combination.
  • the amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Sn.
  • the amount of the chalcogen element-containing organic compound is preferably from 0.1 to 10 mol, more preferably from 0.5 to 10 mol, still more preferably from 0.3 to 1 mol, based on 1 mol of Sn.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, more preferably 2 to 10 moles, and still more preferably 2 to 5 moles per mole of Sn.
  • a method of mixing the Sn and / or Sn compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element is not particularly limited.
  • a method of stirring after adding a Sn and / or Sn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, a Sn and / or Sn compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like.
  • a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Sn and / or Sn compound is added.
  • the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • NMP N-methylpyrrolidone
  • NMF N-methylformamide
  • DMF dimethylformamide
  • tetramethylguanidine tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
  • the amount of the solvent is preferably such that when mixed, the Sn concentration becomes 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, and 0.4 to 1.2 mol / L. L is particularly preferred.
  • the reaction temperature in the preparation of the Sn precursor depends on the type of Sn and / or Sn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc., but safety and Sn complex From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
  • reaction time in the preparation of the Sn precursor varies depending on the type of Sn and / or Sn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
  • the Sn precursor After preparing the Sn precursor, it is preferable to remove impurities by mixing the Sn precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound.
  • a solvent poor solvent
  • acetone is particularly preferable.
  • the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
  • the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the Sn precursor.
  • the In precursor is obtained, for example, by mixing In and / or an In compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
  • In and / or In compounds, chalcogen element-containing organic compounds, Lewis basic inorganic compounds, and Group 16 elements include the In and / or In compounds and chalcogens exemplified in the description of the method for producing a metal precursor solution of the present invention.
  • Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
  • In and / or In compounds In, In (OH) 3 , indium oxide, indium sulfide, indium selenide, and indium telluride are preferable, and In, In (OH) 3 , and indium oxide are more preferable.
  • In and / or In compounds one kind may be used alone, or two or more kinds may be used in combination.
  • the amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of In.
  • the amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, with respect to 1 mol of In.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, and still more preferably 2 to 5 mol with respect to 1 mol of In.
  • a method of mixing In and / or an In compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited.
  • a method of stirring after adding In and / or an In compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, or an In and / or In compound and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like.
  • a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then In and / or an In compound are added.
  • the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • NMP N-methylpyrrolidone
  • NMF N-methylformamide
  • DMF dimethylformamide
  • tetramethylguanidine tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
  • the amount of the solvent is preferably such that when mixed, the In concentration in the In precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
  • the reaction temperature varies depending on the type of In and / or In compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. to be used. From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
  • the reaction time varies depending on the type of In and / or In compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
  • the In precursor After the preparation of the In precursor, it is preferable to remove impurities by mixing the In precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound.
  • a solvent poor solvent
  • acetone is particularly preferable.
  • the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
  • the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the In precursor.
  • Ga precursor The Ga precursor is obtained, for example, by mixing Ga and / or a Ga compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
  • Ga and / or Ga compounds, chalcogen element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements include the Ga and / or Ga compounds and chalcogens exemplified in the description of the method for producing a metal precursor solution of the present invention.
  • Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
  • Ga and / or Ga compounds Ga, gallium oxide, gallium sulfide, gallium selenide, and gallium telluride are preferable, and Ga and gallium oxide are more preferable.
  • Ga and / or Ga compounds one kind may be used alone, or two or more kinds may be used in combination.
  • the amount of the Group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Ga.
  • the amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, relative to 1 mol of Ga.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, still more preferably 2 to 5 mol, relative to 1 mol of Ga.
  • the method of mixing Ga and / or a Ga compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited.
  • a method of stirring after adding Ga and / or Ga compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, and Group 16 element to the solvent, Ga and / or Ga compound, and chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like.
  • a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Ga and / or a Ga compound is added.
  • the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • NMP N-methylpyrrolidone
  • NMF N-methylformamide
  • DMF dimethylformamide
  • tetramethylguanidine tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
  • the amount of the solvent is preferably such that when mixed, the Ga concentration in the Ga precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
  • the reaction temperature varies depending on the type of Ga and / or Ga compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
  • the reaction time varies depending on the type of Ga and / or Ga compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
  • the Ga precursor After the preparation of the Ga precursor, it is preferable to remove impurities by mixing the Ga precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound.
  • a solvent poor solvent
  • acetone is particularly preferable.
  • the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
  • the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, and even more preferably 7 to 20 times that of the Ga precursor.
  • the Sb precursor is obtained, for example, by mixing an Sb and / or Sb compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
  • Sb and / or Sb compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element include the Sb and / or Sb compound and chalcogen exemplified in the description of the method for producing the metal precursor solution of the present invention.
  • Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
  • Sb and / or Sb compound Sb, Sb 2 O 3 , antimony sulfide, antimony selenide, and antimony telluride are preferable, and Sb and Sb 2 O 3 are more preferable.
  • Sb and / or Sb compound one kind may be used alone, or two or more kinds may be used in combination.
  • the amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Sb.
  • the amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, relative to 1 mol of Sb.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, still more preferably 2 to 5 mol, relative to 1 mol of Sb.
  • the method for mixing the Sb and / or Sb compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element is not particularly limited.
  • a method of stirring after adding a Sb and / or Sb compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, a Sb and / or Sb compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like.
  • a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Sb and / or an Sb compound are added.
  • the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • NMP N-methylpyrrolidone
  • NMF N-methylformamide
  • DMF dimethylformamide
  • tetramethylguanidine tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
  • the amount of the solvent is preferably such that when mixed, the Sb concentration in the Sb precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
  • the reaction temperature depends on the type of Sb and / or Sb compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. used, but the safety and Sb complex From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
  • the reaction time varies depending on the type of Sb and / or Sb compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
  • the Sb precursor After the preparation of the Sb precursor, it is preferable to remove impurities by mixing the Sb precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound.
  • a solvent poor solvent
  • acetone is particularly preferable.
  • the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
  • the amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the Sb precursor.
  • the method for mixing the precursors obtained as described above is not particularly limited.
  • a method of stirring after adding each precursor to a solvent a method of adding a solvent after mixing each precursor, drying each precursor under reduced pressure to form a solid complex, and then adding each solid complex to the solvent
  • the method etc. which obtain a complex solution and mix the obtained complex solution are mentioned.
  • the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water;
  • NMP N-methylpyrrolidone
  • NMF N-methylformamide
  • DMF dimethylformamide
  • tetramethylguanidine tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • the solvent one kind may be used alone, or two or more kinds may be used in combination. Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
  • the amount of the solvent is such that the total amount of each metal of Cu, Zn, Sn, and Se, or the solid content concentration remaining when heated at 500 ° C. or higher is 3% or higher. Is preferably 5% or more, more preferably 10% or more.
  • the total amount of each metal of Cu, In, Ga, and Se, or the amount of solid content remaining when heated at 500 ° C. or more is 3% or more.
  • 5% or more is more preferable, and 10% or more is particularly preferable.
  • the simple substance and / or compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element in the preparation method (II) the simple substance and / or the compound exemplified in the description of the method for producing the metal precursor solution of the present invention can be used.
  • a compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element can be used.
  • Preferable examples of each raw material include the same as in the preparation method (I).
  • the amount of the group 16 element is preferably 0.5 to 10 equivalents, more preferably 0.5 to 4 equivalents, and even more preferably 1 to 2 equivalents with respect to 1 mol of the total amount of each metal of Cu, Zn and Sn.
  • the amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 equivalents, more preferably 0.5 to 10 equivalents, and still more preferably 0.3 to 1 equivalents with respect to the metal.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, preferably 2 to 10 moles, more preferably 2 to 5 equivalents.
  • Cu / (In + Ga) 0 in terms of molar ratio of each metal.
  • the amount of the group 16 element is preferably 0.5 to 10 equivalents, more preferably 0.5 to 4 equivalents, and even more preferably 1 to 2 equivalents with respect to 1 mol of the total amount of each metal of Cu, In and Ga.
  • the amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 equivalents, more preferably 0.5 to 10 equivalents, and still more preferably 0.3 to 1 equivalents with respect to the metal.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, preferably 2 to 10 moles, more preferably 2 to 5 moles.
  • a method of mixing each raw material is not particularly limited, and examples thereof include a method of stirring after adding each raw material to a solvent, a method of adding a solvent after mixing each raw material, and the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then a simple substance and / or a compound are added.
  • the solvent examples include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • the amount of the solvent varies depending on the type of each raw material to be used, but it should be prepared so that the solid component concentration is 1 to 30% by weight when the residual component when heated at 500 ° C. by thermogravimetry is defined as the solid component. It is preferably 5 to 20% by weight.
  • the reaction temperature in the preparation method (II) varies depending on the type of each raw material used, but is usually preferably room temperature to 200 ° C., more preferably room temperature to 150 ° C., and more preferably room temperature to 100 ° C. More preferred is ° C.
  • the reaction time in the preparation method (II) varies depending on the types of raw materials used and the stirring time, but is usually preferably 1 hour to 1 week, more preferably 1 day to 3 days, and further preferably 1 day to 2 days.
  • Preparation method (III) As the simple substance and / or compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element in the preparation method (III), the simple substance and / or the compound exemplified in the description of the method for producing the metal precursor solution of the present invention can be used. Alternatively, a compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element can be used. Preferable examples of each raw material include the same as in the preparation method (I).
  • each raw material include the same as in the preparation method (I).
  • the amount of each raw material can be appropriately adjusted depending on the type of each raw material.
  • the coating solution contains a compound represented by the general formula (2) described later
  • Cu element and / or Cu compound, Zn element and / or Zn compound when used for a light absorption layer for CZTS solar cells (when the coating solution contains a compound represented by the general formula (2) described later), Cu element and / or Cu compound, Zn element and / or Zn compound,
  • at least two kinds of Sn elements and / or Sn compounds (hereinafter sometimes collectively referred to as “CZTS metal”) can be used.
  • the amount of Group 16 element is preferably 0.5 to 10 equivalents, more preferably 0.5 to 4 equivalents, and even more preferably 1 to 2 equivalents with respect to 1 mol of the total amount of CZTS metal.
  • the amount of the chalcogen element-containing organic compound is preferably from 0.1 to 10 equivalents, more preferably from 0.5 to 10 equivalents, still more preferably from 0.3 to 1 equivalent, based on 1 mol of the total amount of CZTS metal.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, preferably 2 to 10 mol, more preferably 2 to 5 mol, per 1 mol of the total amount of CZTS metal.
  • the coating solution contains a compound represented by the general formula (1) described later
  • Cu element and / or Cu compound, In element and / or In A compound and at least two kinds of Ga element and / or Ga compound (hereinafter, sometimes collectively referred to as “CIGS metal”) can be used.
  • CIGS metal a compound and at least two kinds of Ga element and / or Ga compound
  • the amount of Group 16 element is preferably 0.5 to 10 moles, more preferably 0.5 to 5 moles, and even more preferably 1 to 3 moles with respect to 1 mole of the total amount of CIGS metal.
  • the amount of the chalcogen element-containing organic compound is preferably 0.05 to 5 mol, more preferably 0.1 to 2 mol, and still more preferably 0.25 to 0.75 mol with respect to the metal.
  • the amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, preferably 1 to 10 moles, more preferably 2 to 6 equivalents.
  • the method of mixing each raw material is not particularly limited, and examples thereof include a method of stirring after adding each raw material to a solvent, and a method of adding a solvent after mixing each raw material. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then a simple substance and / or a compound are added.
  • the solvent examples include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea
  • water examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG).
  • MDG methyl diglycol
  • the amount of the solvent varies depending on the type of each raw material to be used, but it should be prepared so that the solid component concentration is 1 to 30% by weight when the residual component when heated at 500 ° C. by thermogravimetry is defined as the solid component. It is preferably 5 to 20% by weight.
  • the reaction temperature in the preparation method (III) varies depending on the type of each raw material used, but is usually preferably room temperature to 200 ° C., more preferably room temperature to 150 ° C., and more preferably room temperature to 100 ° C. More preferred is ° C.
  • the reaction time in the preparation method (III) varies depending on the types of raw materials used and the stirring time, but is usually preferably 1 hour to 1 week, more preferably 1 day to 3 days, and further preferably 1 day to 2 days.
  • the coating solution for forming a light absorbing layer obtained by the production method of the present invention can be used directly for forming a light absorbing layer, or can be concentrated by vacuum distillation to obtain a concentrated solution.
  • a uniform coating solution for forming a light absorption layer can be obtained by dissolving the concentrated solution in a solvent and diluting it.
  • the solvent include water, dimethyl sulfoxide, hydrazine and the like.
  • the solvent one kind may be used alone, or two or more kinds may be used in combination. Among these, water and dimethyl sulfoxide are preferable.
  • the light absorbing layer forming coating solution obtained by the production method of the present invention is at least one selected from the group consisting of Na, K, Cs, Sb and Bi (hereinafter sometimes collectively referred to as “added metal”). It is also preferred to add.
  • the crystal growth of the light absorption layer can be promoted by adding the additive metal.
  • the added metal may be added after being dissolved in a solution.
  • the Na solution include sodium selenide and those obtained by dissolving selenium in DMSO.
  • the amount of Na added is, for example, preferably from 0.1 to 10 atomic%, more preferably from 0.1 to 2 atomic%, based on the metal molar amount of CZTS when used in a light absorbing layer for CZTS solar cells. Further, for example, when used in a light absorption layer for CIGS solar cells, 0.1 to 10 atomic% is preferable and 0.1 to 2 atomic% is more preferable with respect to the metal molar amount of CIGS.
  • Sb is added to the coating solution for forming a light absorption layer obtained by the production method of the present invention.
  • the amount of Sb added is, for example, preferably 0.1 to 2 atomic%, more preferably 0.1 to 0.5 atomic% with respect to the molar amount of metal in CZTS when used in a light absorbing layer for CZTS solar cells.
  • 0.1 to 2 atomic% is preferable with respect to the metal molar amount of CIGS, preferably 0.1 to 0.5 atomic% with respect to the metal molar amount of CIGS. Is more preferable.
  • the complex or a solution thereof is preferably used for forming a light absorption layer of a chalcopyrite solar cell or a kesterite solar cell.
  • the reaction solution preferably contains a compound represented by the following general formula (1) or (2).
  • A is at least one group 16 element.
  • A is at least one group 16 element, preferably Se and / or S.
  • the method for producing a complex (solution) it is possible to form a light absorption layer in which the content of an organic substance that is a factor inhibiting crystal growth is reduced.
  • the reason why the above effect is obtained is not clear, but is presumed as follows.
  • the chalcogen element-containing organic compound is used in the preparation of the metal precursor solution used for forming the light absorption layer of the solar cell, it is presumed that a metal complex in which the chalcogen element-containing organic compound is coordinated is formed.
  • the group 16 element is mixed together with the chalcogen element-containing organic compound. Therefore, it is estimated that the chalcogen element-containing organic compound acts as a reducing agent for the group 16 element, and the group 16 element is ionized. Since the ionized group 16 element coordinates to the metal to form a metal complex, the amount of the chalcogen element-containing organic compound coordinated to the metal can be reduced.
  • the complex solution obtained by the production method according to the first aspect of the present invention does not contain hydrazine as a coating solvent, the chemical properties (explosiveness, toxicity) of hydrazine are formed when the light absorption layer is formed. ) Is no longer a problem and the safety of the manufacturing process is improved.
  • each metal complex solution can be prepared using one kind of simple substance and / or compound.
  • a binary or ternary metal complex solution can be prepared using two or more kinds of simple substances and / or compounds. Therefore, the composition of the metal complex solution can be freely selected according to the requirements of the light absorption layer to be formed. Thus, it can be expected that the composition of the metal complex solution can be freely selected, so that the arrangement of metals in the light absorption layer can be reliably designed and the structure of the light absorption layer can be reliably controlled.
  • a method for producing a light-absorbing layer for a solar cell wherein a solution obtained by the method for producing a complex (solution) according to the first aspect is applied to a substrate and fired. Is the method.
  • the manufacturing method of the light absorption layer for solar cells of this invention is the same as the process of forming the light absorption layer in the manufacturing method of the solar cell which concerns on the 3rd aspect of this invention.
  • the light absorption layer is preferably for a chalcopyrite solar cell or a kesterite solar cell. In that case, it is preferable that the said light absorption layer contains the compound represented by the said General formula (1) or (2).
  • a step is performed in which a first electrode is formed on a substrate, and a solution obtained by the method for producing a complex (solution) according to the first aspect is applied on the first electrode. And baking to form a light absorption layer, forming a buffer layer on the light absorption layer, and forming a second electrode on the buffer layer. It is a manufacturing method of a solar cell.
  • a method known in the art may be used except for the step of forming a light absorption layer on the first electrode.
  • a Mo layer may be formed by sputtering using nitrogen as a sputtering gas.
  • the buffer layer may be formed as a CdS layer, for example, and may be formed using a chemical bath deposition method, for example.
  • the transparent electrode may be formed using an appropriate material.
  • a metal precursor solution (for light absorption layer formation) obtained by the method for producing a complex (solution) according to the first aspect is formed on the first electrode (substrate).
  • Coating solution is applied.
  • a coating method a spin coating method, a dip coating method, a doctor blade (applicator) method, a curtain / slit casting method, a printing method, a spray method, or the like can be used.
  • the application conditions may be set as appropriate according to the desired film thickness, material concentration, and the like.
  • the substrate is set on a spin coater and a coating solution is applied.
  • the coating conditions at this time may be appropriately set according to the film thickness to be formed.
  • the rotation speed is 300 to 3000 rpm and the film can be formed by maintaining for 10 to 180 seconds.
  • Application can be repeated until a desired film thickness is obtained.
  • it can carry out by immersing a base
  • substrate you may vacuum-dry.
  • Firing conditions can be appropriately set according to the desired film thickness, material type, and the like. For example, it can be a two-stage process in which baking (annealing) is performed in an oven after soft baking (pre-baking) on a hot plate.
  • the temperature of the hot plate is set to 100 to 500 ° C., and soft baking is performed for 1 to 300 seconds, the substrate is cooled to near room temperature, and then coated again. Do. After the desired film thickness is obtained, annealing is performed by raising the inside of the hot plate or oven to 300 to 700 ° C. and holding for 1 to 180 minutes. Thereby, the light absorption layer is cured.
  • each temperature of the said baking shows one condition, and is not restricted to this.
  • the temperature of the hot plate may be increased stepwise, and these heating steps may be performed in an inert gas atmosphere in a glove box.
  • hydrogen sulfide, hydrogen selenide, solid sulfur, and solid selenium may be coexisted in the atmosphere during soft baking and annealing.
  • the solar cell is preferably a chalcopyrite solar cell or a kesterite solar cell.
  • a light absorption layer contains the compound represented by the said General formula (1) or (2).
  • the first complex solution is applied to a substrate, baked to form a first layer, and then a metal different from the first complex solution
  • a second complex solution having a composition can be applied to the first layer and baked to form the second layer.
  • a single light absorption layer having a desired composition or a multilayer light absorption layer having a desired metal composition ratio gradient can be formed.
  • the arrangement of metals in the light absorption layer can be reliably designed and the structure of the light absorption layer can be reliably controlled.
  • the solar cell of this embodiment can be manufactured. And since the solar cell manufactured with the manufacturing method of this embodiment does not contain hydrazine in the coating liquid for light absorption layer formation, the safety
  • preparation method (I), preparation method (II), and preparation method (III) were demonstrated as a preparation method of the coating liquid for light absorption layer formation, this invention is not limited to these.
  • a metal precursor is prepared for some metal components, the prepared metal complex, other metal components, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, a Group 16 element, Other desired components can also be mixed.
  • the preparation method (II) after a part of the raw materials are mixed first, the remaining raw materials can be added.
  • Example 2-1 Zn 1.308 g (20 mmol) Se 2.369 g (30 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ), and 19.425 g of water were mixed and mixed at 23 ° C. After stirring for days, a Zn reaction solution was obtained.
  • Example 2-2 ZnO 1.628 g (20 mmol), Se 2.369 g (30 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and 19.425 g of water were mixed at 23 ° C. After stirring for 3 days, a Zn reaction solution was obtained.
  • Example 3 Sn2.374 g (20 mmol), Se5.527 g (70 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ), and water 15.201 g were mixed at 23 ° C. After stirring for 3 days, an Sn reaction solution was obtained.
  • Example 4-1 In (OH) 3 3.317 g (20 mmol), Se 3.948 g (50 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and water 15.837 g are mixed. After stirring at 23 ° C. for 3 days, an In reaction solution was obtained.
  • Example 4-2 In 2 O 3 5.552 g (20 mmol), Se 3.948 g (50 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and water 15.837 g were mixed. After stirring at 23 ° C. for 3 days, an In reaction solution was obtained.
  • Example 5-1 Ga1.394 g (20 mmol), Se 3.948 g (50 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and 17.759 g of water are mixed at 23 ° C. After stirring for 3 days, a Ga reaction solution was obtained.
  • Example 6-1 Sb1.218 g (10 mmol), Se 1.974 g (25 mmol), thioglycerol 5.408 g (50 mmol), NH 3 28% aqueous solution 3.041 g (50 mmol in terms of NH 3 ) and water 8.359 g were mixed at 23 ° C. After stirring for 3 days, an Sb reaction solution was obtained.
  • Example 6-2 2.916 g (10 mmol) of Sb 2 O 3 , 1.974 g (25 mmol) of Se, 5.408 g (50 mmol) of thioglycerol, 3.041 g of NH 3 28% aqueous solution (50 mmol in terms of NH 3 ) and 8.359 g of water were mixed. After stirring at 23 ° C. for 3 days, an Sb reaction solution was obtained.
  • Example 7 Excess isopropyl alcohol was added to the Cu reaction solution prepared in Example 1 to produce a precipitate, the supernatant was removed after centrifugation (5000 rpm, 10 min), and isopropyl alcohol was added again three times. Further, drying under reduced pressure was performed overnight to obtain powdered solid Cu metal complex 1.
  • Example 8-1 Excess acetone was added to the Zn reaction solution prepared in Example 2-1 to generate a precipitate. After centrifugation (5000 rpm, 10 min), the supernatant was removed, and acetone was added again three times. . Further, drying under reduced pressure was carried out overnight to obtain powdered Zn metal complex 1.
  • Example 8-2 Excess acetone was added to the Zn reaction solution prepared in Example 2-2 to generate a precipitate. After centrifugation (5000 rpm, 10 min), the supernatant was removed, and acetone was added again three times. . Further, drying under reduced pressure was carried out overnight to obtain powdered solid Zn metal complex 2.
  • Example 9 A powdered Sn metal complex 1 was obtained in the same manner as in Example 8-1, except that the Sn precursor solution prepared in Example 3 was used instead of the Zn reaction solution prepared in Example 2-1. It was.
  • Example 10-1 The same procedure as in Example 8-1 was performed except that the In reaction solution prepared in Example 4-1 was used instead of the Zn reaction solution prepared in Example 2-1, and the powdered solid In metal complex 1 was obtained. Obtained.
  • Example 10-2 The same procedure as in Example 8-1 was performed except that the In reaction solution prepared in Example 4-2 was used instead of the Zn reaction solution prepared in Example 2-1, and the powdered solid In metal complex 2 was obtained. Obtained.
  • Example 11-1 The same procedure as in Example 8-1 was carried out except that the Ga reaction solution prepared in Example 5-1 was used instead of the Zn reaction solution prepared in Example 2-1, and the powder solid Ga metal complex 1 was obtained. Obtained.
  • Example 11-2 The same procedure as in Example 8-1 was performed except that the Ga reaction solution prepared in Example 5-2 was used instead of the Zn reaction solution prepared in Example 2-1, and the powdered solid Ga metal complex 2 was obtained. Obtained.
  • Example 12-1 A powdered solid Sb metal complex 1 was prepared in the same manner as in Example 8-1, except that the Sb precursor solution prepared in Example 6-1 was used instead of the Zn reaction solution prepared in Example 2-1. Got.
  • Example 12-2 A powdered solid Sb metal complex 2 was prepared in the same manner as in Example 8-1, except that the Sb precursor solution prepared in Example 6-2 was used instead of the Zn reaction solution prepared in Example 2-1. Got.
  • Example 7 Each metal complex (powder solid) purified in Example 7, Example 8-1, Example 9, Example 10-1, Example 11-1, and Example 12-1 was dissolved in aqua regia and water was added. The ICP measurement was performed after dilution. From the ICP measurement results, the molar ratio of metal, selenium, and sulfur of each metal complex was calculated. Sulfur is derived from thioglycerol. The results are shown in Table 1.
  • the amount of thioglycerol was greater than the amount of selenium in the reaction process, but the final metal complexes were confirmed to have a selenium content greater than that of thioglycerol. This is presumably because thioglycerol acts as a selenium reducing agent and ionized selenium coordinates to the metal in the reaction step of the metal complex.
  • Example 13 Each metal complex obtained in Examples 7 to 12 was subjected to thermogravimetry, and the amount of residue at 500 ° C. was assumed to be solid. Each metal complex obtained in Examples 7 to 12 was dissolved in DMSO so as to have a solid content concentration of 10%, and filtered through a 0.1 um PTFE filter to prepare a metal complex solution (Cu metal complex 1 solution). Zn metal complex 1 solution, Zn metal complex 2 solution, Sn metal complex 1 solution, In metal complex 1 solution, In metal complex 2 solution, Ga metal complex 1 solution, Ga metal complex 2 solution, Sb metal complex 1 solution and Sb Metal complex 2 solution).
  • Example 14 ⁇ Preparation of coating solution for forming light absorption layer> (Example 14)
  • Sn / (Zn + Sn) 0.49 was mixed to prepare a CZTS coating solution.
  • Example 16 ⁇ Formation of light absorption layer> (Example 16)
  • the CZTS coating solution prepared in Example 14 was applied on a Mo-deposited glass substrate, and soft baking was performed at 400 ° C. for 3 minutes. After performing this step 15 times in total, annealing was performed at 580 ° C. for 10 minutes in the presence of a small amount of selenium, thereby producing a CZTS substrate on which a CZTS layer was formed.
  • the CZTS substrate prepared above was observed with an SEM, grain growth of CZTS was confirmed.
  • Example 17 The CIGS coating solution prepared in Example 15 was applied on a Mo-deposited glass substrate, and soft baking was performed at 300 ° C. for 3 minutes. After performing this process 15 times in total, annealing was performed at 540 ° C. for 30 minutes in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed.
  • a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed.
  • Example 18 ⁇ Preparation of coating solution for forming light absorption layer> (Example 18)
  • Example 19 Further, a CIGS coating solution was prepared in the same manner as in Example 18 except that Na 1.0 atomic% was mixed.
  • a CIGS coating solution was prepared with reference to Examples in US Publication No. 2012-0070937.
  • a mixed solvent was prepared by mixing 4.949 g (47.1 mmol) of benzeneselenol and 3.726 g (47.1 mmol) of pyridine.
  • Example 20 The CIGS coating solution prepared in Example 18 was coated on a Mo-deposited glass substrate, and soft-baked at 120 ° C. for 1 minute and 300 ° C. for 3 minutes to form a coating film having a thickness of about 0.3 ⁇ m. After performing this process 5 times in total, annealing was performed at 540 ° C. for 30 minutes in the presence of a small amount of selenium, thereby producing a CIGS substrate on which a CIGS layer was formed.
  • Example 21 A CIGS substrate having a CIGS layer formed thereon was prepared in the same manner as in Example 20 except that the CIGS coating solution prepared in Example 19 was used instead of the CIGS coating solution prepared in Example 18.
  • Comparative Example 2 The CIGS coating solution prepared in Comparative Example 1 was coated on a Mo-deposited glass substrate and soft-baked at 120 ° C. for 1 minute and at 300 ° C. for 3 minutes. Then, the CIGS board
  • Comparative Example 3 The CIGS coating solution prepared in Comparative Example 1 was coated on a Mo-deposited glass substrate and soft-baked at 120 ° C. for 1 minute and at 300 ° C. for 3 minutes. After performing this process twice in total, the CIGS substrate in which the CIGS layer was formed was produced by performing 30 minutes annealing at 540 degreeC in presence of a small amount of selenium.
  • Example 23 2.369 g (30 mmol) of Se, 1.563 g (20 mmol) of 2-mercaptoethanol, 4.866 g of 28 wt% NH 3 aqueous solution (80 mmol in terms of NH 3 ) and 16 g of dimethyl sulfoxide (DMSO) were mixed. Stir at 6 ° C. for 6 hours. Thereafter, 1.38 g (12 mmol) of In and 0.84 g (12 mmol) of Ga were added to the reaction solution, stirred at 23 ° C. for 3 days, filtered through a PTFE 0.45 um filter, and the In—Ga reaction solution was added. Obtained.
  • Example 24 2. 685 g (34 mmol) of Se, 1.117 g (14.3 mmol) of 2-mercaptoethanol, 4.136 g of 28 wt% NH 3 aqueous solution (68 mmol in terms of NH 3 ) and 15 g of dimethyl sulfoxide (DMSO) were mixed. , And stirred at 23 ° C. for 6 hours. Thereafter, 0.279 g (4.25 mmol) of Cu, 0.42 g (4 mmol) of In and 0.46 g (6 mmol) of Ga were added to the reaction solution and stirred at 23 ° C. for 1 day. Thereafter, 0.279 g (4.25 mmol) of Cu was added, stirred at 23 ° C.
  • DMSO dimethyl sulfoxide
  • Example 25 2. 685 g (34 mmol) of Se, 1.117 g (14.3 mmol) of 2-mercaptoethanol, 4.136 g of 28 wt% NH 3 aqueous solution (68 mmol in terms of NH 3 ) and 15 g of dimethyl sulfoxide (DMSO) were mixed. , And stirred at 23 ° C. for 6 hours. Thereafter, 0.279 g (4.25 mmol) of Cu, 0.805 g (7 mmol) of In and 0.21 g (3 mmol) of Ga were added to the reaction solution and stirred at 23 ° C. for 1 day. Thereafter, 0.279 g (4.25 mmol) of Cu was added, stirred at 23 ° C.
  • DMSO dimethyl sulfoxide
  • a light absorption layer was formed using the metal complex coating solution (reaction solution) prepared in Examples 22 and 23.
  • reaction solution metal complex coating solution
  • an In—Ga complex coating solution was coated on a Mo-deposited glass substrate and soft-baked at 350 ° C. for 2 minutes.
  • the first step was repeated 8 times to form an In—Ga complex layer.
  • a Cu complex coating solution was coated on the In—Ga complex layer and soft baked at 350 ° C. for 2 minutes.
  • the second step was repeated 10 times to form a Cu complex layer.
  • the In—Ga complex coating solution was coated on the Cu complex layer and soft baked at 350 ° C. for 2 minutes.
  • the third step was repeated twice.
  • the total number of coating steps in the first step, the second step, and the third step was 20 times.
  • annealing was performed at 590 ° C. for 30 minutes in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed.
  • Example 27 A light absorption layer was formed using the metal complex coating solution (reaction solution) prepared in Examples 24 and 25.
  • the Cu—In—Ga complex coating solution obtained in Example 24 was coated on a Mo-deposited glass substrate and soft baked at 350 ° C. for 2 minutes. The first step was repeated 10 times to form a first Cu—In—Ga complex layer.
  • the Cu—In—Ga complex coating solution obtained in Example 25 was applied on the first Cu—In—Ga complex layer, and soft baking was performed at 350 ° C. for 2 minutes.
  • the second step was repeated 10 times to form a second Cu—In—Ga complex layer on the first Cu—In—Ga complex layer.
  • the total number of coating steps in the first step and the second step was 20 times.
  • annealing was performed at 590 ° C. for 30 minutes in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed.

Abstract

A method for producing a complex to be used in the formation of a light-absorbing layer for a solar cell, and a solution thereof, the method involving obtaining a reaction solution by mixing: one or more types of simplex or compound selected from a group consisting of a group 11 metal, a group 12 metal, a group 13 metal, a group 14 metal, a group 15 element, a group 11 metal compound, a group 12 metal compound, a group 13 metal compound, a group 14 metal compound, and a group-15-element-containing compound; one or more types of a chalcogen-element-containing organic compound selected from a group consisting of a mercapto-group-containing organic compound, a sulfide, a polysulfide, a thiocarbonyl-group-containing organic compound, a sulfur-containing heterocyclic compound, a hydroseleno-group-containing organic compound, a selenide, a polyselenide, a selenocarbonyl-group-containing organic compound, and a selenium-containing heterocyclic compound; a Lewis-base inorganic compound; and a group 16 element.

Description

錯体およびその溶液の製造方法、太陽電池用光吸収層の製造方法および太陽電池の製造方法Method for producing complex and solution thereof, method for producing light absorption layer for solar cell, and method for producing solar cell
　本発明は、太陽電池の光吸収層の形成に用いられる錯体およびその溶液の製造方法、該錯体溶液を用いた太陽電池用光吸収層の製造方法、及び該錯体溶液を用いた太陽電池の製造方法に関する。
　本願は、２０１３年６月３日に米国に出願された、米国仮出願第６１／８３０２９４号及び２０１４年１月９日に米国に出願された、米国仮出願第６１／９２５６２１号に基づき優先権主張し、その内容をここに援用する。 The present invention relates to a complex used for forming a light absorption layer of a solar cell, a method for producing the solution, a method for producing a light absorption layer for a solar cell using the complex solution, and production of a solar cell using the complex solution. Regarding the method.
This application is based on United States provisional application 61/830294 filed in the United States on June 3, 2013 and United States provisional application 61/925621 filed in the United States on January 9, 2014. Insist and use that content here.
　近年、環境への配慮から太陽電池への関心が高まっており、中でも光電変換効率が高い薄膜太陽電池であるカルコパイライト系太陽電池やインジウム等のレアメタルを他の環境に優しい金属に置き換えたケステライト系太陽電池には特に注目が集まっており、現在、研究開発が活発に行われている。 In recent years, interest in solar cells has increased due to environmental considerations. Among them, chalcopyrite solar cells, which are thin-film solar cells with high photoelectric conversion efficiency, and kesterite systems in which rare metals such as indium are replaced with other environmentally friendly metals. Solar cells are attracting particular attention, and research and development are actively underway.
　カルコパイライト系太陽電池は、カルコパイライト系（黄銅鉱系）材料からなる光吸収層を、基板上に成膜して形成される太陽電池である。カルコパイライト系材料の代表的な元素は、銅（Ｃｕ）、インジウム（Ｉｎ）、ガリウム（Ｇａ）、セレン（Ｓｅ）及び硫黄（Ｓ）等であり、光吸収層の代表的なものとして、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ２やＣｕ（Ｉｎ，Ｇａ）（Ｓｅ，Ｓ）２等があり、それぞれＣＩＧＳ、ＣＩＧＳＳ等と略称されている。また、最近ではレアメタルであるインジウムを置き換えた、例えば銅（Ｃｕ）、亜鉛（Ｚｎ）、スズ（Ｓｎ）セレン（Ｓｅ）及び硫黄（Ｓ）からなるケステライト系太陽電池が検討されており、光吸収層の代表的なものとして、Ｃｕ２ＺｎＳｎＳｅ４、Ｃｕ２ＺｎＳｎＳ４、Ｃｕ２ＺｎＳｎ（Ｓ，Ｓｅ）４等がある。 A chalcopyrite solar cell is a solar cell formed by forming a light absorption layer made of a chalcopyrite (chalcopyrite) material on a substrate. Typical elements of chalcopyrite-based materials are copper (Cu), indium (In), gallium (Ga), selenium (Se), sulfur (S), and the like, and typical examples of the light absorption layer include Cu. (in, Ga) Se 2 and Cu (in, Ga) (Se , S) there are 2 or the like, and is abbreviated respectively CIGS, and CIGSS like. Recently, a kesterite solar cell made of, for example, copper (Cu), zinc (Zn), tin (Sn) selenium (Se) and sulfur (S), which replaces indium, which is a rare metal, has been studied. Typical examples of the layer include Cu 2 ZnSnSe 4 , Cu 2 ZnSnS 4 , Cu 2 ZnSn (S, Se) 4 and the like.
　図１は、カルコパイライト系太陽電池又はケステライト系太陽電池の一例を示す断面模式図である。
　図１に示すように、カルコパイライト系太陽電池又はケステライト系太陽電池は、基板２上に第１の電極３、ＣＩＧＳ又はＣＺＴＳ層（光吸収層）４、バッファ層５、ｉ－ＺｎＯ層６及び第２の電極７が、この順序で積層されて概略構成されている。なお、バッファ層としては、例えばＣｄＳ層や、ＺｎＳ層や、ＩｎＳ層等が知られている。 FIG. 1 is a schematic cross-sectional view showing an example of a chalcopyrite solar cell or a kesterite solar cell.
As shown in FIG. 1, the chalcopyrite solar cell or the kesterite solar cell includes a first electrode 3, a CIGS or CZTS layer (light absorption layer) 4, a buffer layer 5, an i-ZnO layer 6 and a substrate 2. The second electrode 7 is schematically configured by being stacked in this order. As the buffer layer, for example, a CdS layer, a ZnS layer, an InS layer, or the like is known.
　第１の電極３と第２の電極７には、それぞれ端子が接合されており、端子には、配線が接続されている。このようなカルコパイライト系又はケステライト系太陽電池１は、矢印Ａの向きに入射された光が、ＣＩＧＳ又はＣＺＴＳ層４で吸収されることにより、起電力が生じ、矢印Ｂの向きに電流が流れる。
　なお、第２の電極７の表面は、例えばＭｇＦ２層からなる反射防止膜層８によって覆われることで保護されている。 Terminals are joined to the first electrode 3 and the second electrode 7, respectively, and wiring is connected to the terminals. In such a chalcopyrite-based or kesterite-based solar cell 1, light incident in the direction of arrow A is absorbed by the CIGS or CZTS layer 4 to generate an electromotive force, and a current flows in the direction of arrow B. .
The surface of the second electrode 7 is protected by being covered with an antireflection film layer 8 made of, for example, an MgF 2 layer.
　ＣＩＧＳ又はＣＺＴＳ層４を成膜する方法としては、真空法や塗布法等の方法が知られている。もっとも、真空法を用いた場合は、装置のスケールアップにつながることから、歩留まりが悪いので、比較的安価に製造することが可能な塗布法の適用が鋭意研究されている。 As a method for forming the CIGS or CZTS layer 4, methods such as a vacuum method and a coating method are known. However, when the vacuum method is used, it leads to scale-up of the apparatus, and thus the yield is poor. Therefore, the application of a coating method that can be manufactured at a relatively low cost has been intensively studied.
　塗布法は、一般に、ＣＩＧＳ層の場合にはＣｕ，Ｉｎ，Ｇａ，Ｓｅ，及びＳ等の元素を特定の溶媒に溶解させて塗布液を調製し、この塗布液をスピンコーティング法、デッピング法やスリットキャスト法等を用いて基板上に塗布し、焼成してＣＩＧＳ層を形成する。
　そして、塗布液を調製する方法としては、溶剤としてヒドラジンを用いる方法と、ヒドラジンを用いない代わりに、溶解促進剤としてアミン類を添加する方法とが知られている（特許文献１及び２参照）。また、ＣＺＴＳ層の場合には、Ｃｕ、Ｚｎ、Ｓｎ、Ｓｅ、及びＳ等の元素を特定の溶媒に溶解させて塗布液を調製し、この塗布液をスピンコーティング法、デッピング法やスリットキャスト法等を用いて基板上に塗布し、焼成してＣＺＴＳ層を形成する。（特許文献３参照）。 In general, in the case of a CIGS layer, a coating solution is prepared by dissolving elements such as Cu, In, Ga, Se, and S in a specific solvent to prepare a coating solution, which is then applied to a spin coating method, a dipping method, A CIGS layer is formed by applying onto a substrate using a slit casting method or the like and baking.
And as a method of preparing a coating solution, a method using hydrazine as a solvent and a method of adding amines as a dissolution accelerator instead of using hydrazine are known (see Patent Documents 1 and 2). . In the case of a CZTS layer, a coating solution is prepared by dissolving elements such as Cu, Zn, Sn, Se, and S in a specific solvent, and this coating solution is prepared by spin coating, dipping, or slit casting. Etc. are applied onto the substrate and baked to form a CZTS layer. (See Patent Document 3).
　また塗布液の調製方法として、カルコゲン元素含有有機化合物およびルイス塩基性有機化合物を含む混合溶媒に、Ｉ－Ｂ族元素およびＩＩＩ－Ｂ族元素の少なくとも一方を含む金属原料を金属の状態で溶解させる方法も知られている（特許文献４参照）。 As a method for preparing the coating solution, a metal raw material containing at least one of a group IB element and a group III-B element is dissolved in a metal state in a mixed solvent containing a chalcogen element-containing organic compound and a Lewis basic organic compound. A method is also known (see Patent Document 4).
米国特許第７０９４６５１号明細書US Pat. No. 7,094,651 米国特許第７５１７７１８号明細書US Pat. No. 7,517,718 米国公開公報２０１１－００９４５５７号US Publication No. 2011-0094557 米国公開公報２０１２－００７０９３７号US Publication No. 2012-0070937
　しかしながら、塗布液を調製する方法として、塗布溶剤にヒドラジンを用いる方法を採用した場合は、ヒドラジンの有する化学特性（爆発性、毒性）の問題から、プロセスの安全性に問題があることが従来から指摘されていた。 However, when a method using hydrazine as a coating solvent is adopted as a method for preparing a coating solution, there has been a problem in the safety of the process because of chemical properties (explosive properties, toxicity) of hydrazine. It was pointed out.
　また、亜鉛カルコゲン化合物（ｚｉｎｃ　ｃｈａｌｃｏｇｅｎｉｄｅ）、例えばＺｎＳｅ等がヒドラジンに対する溶解性が低く、高濃度で均一な亜鉛錯体溶液を調製することが困難であった。また、塗布溶剤にヒドラジンを用いると、塗布液を調製後、２週間程度経過することにより、セレン化銅（Ｃｕ２Ｓｅ）が析出してしまうため、塗布液の保存期間が短いという問題があった。 Also, zinc chalcogenide compounds such as ZnSe have low solubility in hydrazine, and it has been difficult to prepare a high concentration and uniform zinc complex solution. In addition, when hydrazine is used as a coating solvent, copper selenide (Cu 2 Se) is precipitated after about 2 weeks from the preparation of the coating solution, resulting in a short storage period of the coating solution. It was.
　一方、特許文献４の方法では、有機化合物を主成分として用いているため、塗布膜中の有機物含有量が多くなるおそれがある。塗布膜中に有機物が残存すると、光吸収層の結晶成長を阻害する要因となるため、好ましくない。 On the other hand, in the method of Patent Document 4, since an organic compound is used as a main component, the organic matter content in the coating film may increase. If the organic substance remains in the coating film, it becomes a factor that hinders crystal growth of the light absorption layer, which is not preferable.
　このような背景の下、金属を原料として製造可能な、太陽電池の光吸収層の形成に用いられる光吸収層形成用塗布液の製造方法が要望されていたが、有効適切なものは提供されてこなかったのが実情である。 Under such a background, there has been a demand for a method for producing a coating solution for forming a light absorption layer for use in forming a light absorption layer of a solar cell that can be produced using a metal as a raw material, but an effective and appropriate one is provided. It is the actual situation that did not come.
　上記課題を解決するために、本発明は以下の構成を採用した。
　すなわち、本発明の第一の態様は、太陽電池の光吸収層の形成に用いられる錯体およびその溶液の製造方法であって、第１１族金属、第１２族金属、第１３族金属、第１４族金属、第１５族元素、第１１族金属化合物、第１２族金属化合物、第１３族金属化合物、第１４族金属化合物及び第１５族元素含有化合物からなる群より選ばれる少なくとも１種の単体または化合物と、メルカプト基含有有機化合物、スルフィド、ポリスルフィド、チオカルボニル基含有有機化合物、硫黄含有複素環式化合物、ヒドロセレノ基含有有機化合物、セレニド、ポリセレニド、セレノカルボニル基含有有機化合物及びセレン含有複素環式化合物からなる群より選ばれる少なくとも１種のカルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して反応液を得ることを含む錯体およびその溶液の製造方法である。 In order to solve the above problems, the present invention employs the following configuration.
That is, the first aspect of the present invention is a method for producing a complex used for forming a light absorption layer of a solar cell and a solution thereof, which comprises a Group 11 metal, a Group 12 metal, a Group 13 metal, At least one element selected from the group consisting of Group metals, Group 15 elements, Group 11 metal compounds, Group 12 metal compounds, Group 13 metal compounds, Group 14 metal compounds, and Group 15 element-containing compounds or Compound, mercapto group-containing organic compound, sulfide, polysulfide, thiocarbonyl group-containing organic compound, sulfur-containing heterocyclic compound, hydroseleno group-containing organic compound, selenide, polyselenide, selenocarbonyl group-containing organic compound, and selenium-containing heterocyclic compound At least one chalcogen element-containing organic compound selected from the group consisting of: a Lewis basic inorganic compound; Is a complex and a manufacturing method of the solution includes obtaining mixed to the reaction solution and element.
　本発明の第二の態様は、前記第一の態様に係る錯体およびその溶液の製造方法により得られた溶液を、基体に塗布し、焼成することを特徴とする太陽電池用光吸収層の製造方法である。 According to a second aspect of the present invention, there is provided a method for producing a light absorption layer for a solar cell, wherein the complex according to the first aspect and a solution obtained by the method for producing the solution are applied to a substrate and baked. Is the method.
　本発明の第三の態様は、基板上に第１の電極を形成する工程と、前記第１の電極上に、第一の態様に係る錯体およびその溶液の製造方法により得られた溶液を塗布し、焼成して光吸収層を形成する工程と、前記光吸収層上にバッファ層を形成する工程と、前記バッファ層上に第２の電極を形成する工程と、を有することを特徴とする太陽電池の製造方法である。 According to a third aspect of the present invention, a step of forming a first electrode on a substrate, and a solution obtained by the complex according to the first aspect and a method for producing the solution are applied on the first electrode. And baking to form a light absorption layer, forming a buffer layer on the light absorption layer, and forming a second electrode on the buffer layer. It is a manufacturing method of a solar cell.
　本発明によれば、結晶成長を阻害する要因となる有機物の含有量が低減された光吸収層を形成することが出来る。 According to the present invention, it is possible to form a light-absorbing layer in which the content of organic matter that is a factor inhibiting crystal growth is reduced.
カルコパイライト系又はＣＺＴＳ系太陽電池の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of a chalcopyrite type | system | group or a CZTS type solar cell.
　［錯体および溶液の製造方法］
　本発明の第一の態様は、太陽電池の光吸収層の形成に用いられる錯体およびその溶液の製造方法（以下、単に「錯体（溶液）の製造方法」という場合がある。）であって、第１１族金属、第１２族金属、第１３族金属、第１４族金属、第１５族元素、第１１族金属化合物、第１２族金属化合物、第１３族金属化合物、第１４族金属化合物及び第１５族元素含有化合物からなる群より選ばれる少なくとも１種の単体または化合物（以下、まとめて「単体および／または化合物」という場合がある。）と、メルカプト基含有有機化合物、スルフィド、ポリスルフィド、チオカルボニル基含有有機化合物、硫黄含有複素環式化合物、ヒドロセレノ基含有有機化合物、セレニド、ポリセレニド、セレノカルボニル基含有有機化合物及びセレン含有複素環式化合物からなる群より選ばれる少なくとも１種のカルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して反応液を得ることを含む。 [Production method of complex and solution]
A first aspect of the present invention is a complex used for forming a light absorption layer of a solar cell and a method for producing the complex (hereinafter sometimes simply referred to as “complex (solution) production method”), Group 11 metal, Group 12 metal, Group 13 metal, Group 14 metal, Group 15 element, Group 11 metal compound, Group 12 metal compound, Group 13 metal compound, Group 14 metal compound and Group At least one simple substance or compound selected from the group consisting of group 15 element-containing compounds (hereinafter sometimes collectively referred to as “simple and / or compounds”), mercapto group-containing organic compounds, sulfides, polysulfides, thiocarbonyls Group-containing organic compound, sulfur-containing heterocyclic compound, hydroseleno group-containing organic compound, selenide, polyselenide, selenocarbonyl group-containing organic compound, and selenium-containing complex And obtaining at least one chalcogen element-containing organic compound selected from the group consisting of Formula compound, a Lewis basic inorganic compound, mixing the reaction solution and a Group 16 element.
　前記第１１族金属としては、例えば、Ｃｕ元素、およびＡｇ元素等が挙げられる。これらの中でも、Ｃｕ元素が特に好ましい。
　前記第１２族金属としては、例えば、Ｚｎ元素、およびＣｄ元素等が挙げられる。これらの中でも、Ｚｎ元素が特に好ましい。
　前記第１３族金属としては、例えば、Ａｌ元素、Ｇａ元素、およびＩｎ元素等が挙げられる。これらの中でも、Ｇａ元素およびＩｎ元素が特に好ましい。
　前記第１４族金属としては、例えば、Ｓｉ元素、Ｇｅ元素、およびＳｎ元素等が挙げられる。これらの中でも、Ｇｅ元素およびＳｎ元素が特に好ましい。
　前記第１５族元素としては、例えば、Ａｓ元素、Ｓｂ元素、Ｐ元素、およびＢｉ元素等が挙げられる。これらの中でも、Ｓｂ元素が特に好ましい。 Examples of the Group 11 metal include a Cu element and an Ag element. Among these, Cu element is particularly preferable.
Examples of the Group 12 metal include Zn element and Cd element. Among these, Zn element is particularly preferable.
Examples of the Group 13 metal include Al element, Ga element, and In element. Among these, Ga element and In element are particularly preferable.
Examples of the Group 14 metal include Si element, Ge element, and Sn element. Among these, Ge element and Sn element are particularly preferable.
Examples of the Group 15 element include As element, Sb element, P element, and Bi element. Among these, Sb element is particularly preferable.
　前記第１１族金属化合物としては、例えば、Ｃｕ（ＯＨ）２、ＣｕＳ、Ｃｕ２Ｓ、Ｃｕ２Ｓｅ、ＣｕＳｅ、Ｃｕ２Ｔｅ、ＣｕＴｅ、ＣｕＯ、Ｃｕ２Ｏ、酸化銀、硫化銀、セレン化銀等が挙げられる
　前記第１２族金属化合物としては、例えば、ＺｎＯ、水酸化亜鉛、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ等が挙げられる。
　前記第１３族金属化合物としては、例えば、Ｉｎ（ＯＨ）３、酸化インジウム、硫化インジウム、セレン化インジウム、テルル化インジウム、酸化ガリウム、硫化ガリウム、セレン化ガリウム、テルル化ガリウム、ホウ酸、酸化ホウ素等が挙げられる。
　前記第１４族金属化合物としては、例えば、ＳｎＳ、ＳｎＯ、ＳｎＯ２、ＳｎＳ２、ＳｎＳｅ、ＳｎＴｅ、酸化ゲルマニウム等が挙げられる。
　　前記第１５族元素含有化合物としては、例えば、Ｓｂ２Ｏ３、リン酸、亜リン酸、ホスフィン、砒酸、亜砒酸、硫化アンチモン、セレン化アンチモン、テルル化アンチモン等が挙げられる。 Examples of the Group 11 metal compound include Cu (OH) 2 , CuS, Cu 2 S, Cu 2 Se, CuSe, Cu 2 Te, CuTe, CuO, Cu 2 O, silver oxide, silver sulfide, and silver selenide. Examples of the Group 12 metal compound include ZnO, zinc hydroxide, ZnS, ZnSe, and ZnTe.
Examples of the Group 13 metal compound include In (OH) 3 , indium oxide, indium sulfide, indium selenide, indium telluride, gallium oxide, gallium sulfide, gallium selenide, gallium telluride, boric acid, and boron oxide. Etc.
Examples of the Group 14 metal compound include SnS, SnO, SnO 2 , SnS 2 , SnSe, SnTe, germanium oxide, and the like.
Examples of the Group 15 element-containing compound include Sb 2 O 3 , phosphoric acid, phosphorous acid, phosphine, arsenic acid, arsenous acid, antimony sulfide, antimony selenide, antimony telluride, and the like.
　単体および／または化合物としては、１種を用いてもよく、２種以上を組み合わせて用いてもよい。 As the simple substance and / or compound, one kind may be used, or two or more kinds may be used in combination.
　本発明において、カルコゲン元素含有有機化合物は、メルカプト基含有有機化合物、スルフィド、ポリスルフィド、チオカルボニル基含有有機化合物、硫黄含有複素環式化合物、ヒドロセレノ基含有有機化合物、セレニド、ポリセレニド、セレノカルボニル基含有有機化合物及びセレン含有複素環式化合物からなる群より選ばれる少なくとも１種である。 In the present invention, the chalcogen element-containing organic compound is a mercapto group-containing organic compound, sulfide, polysulfide, thiocarbonyl group-containing organic compound, sulfur-containing heterocyclic compound, hydroseleno group-containing organic compound, selenide, polyselenide, or selenocarbonyl group-containing organic compound. It is at least one selected from the group consisting of a compound and a selenium-containing heterocyclic compound.
　メルカプト基含有有機化合物としては、例えばアルキルチオール（エタンチオール、プロパンチオール等）、メルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール、チオグリセロール、チオグリコール酸、チオ乳酸、チオリンゴ酸、チオグリコール酸メチル、チオグリコール酸エチル、エタンジチオール、プロパンジチオール、ブタンジチオール、２，３－ジメルカプト－１－プロパノール、ｍｅｓｏ－２，３－ジメルカプトこはく酸、ｎブチルメルカプタン、ｔｅｒｔ－ブチルメルカプタン等が挙げられる。
　スルフィドとしては、例えばジブチルスルフィド、エチルメチルスルフィド、ジエチルスルフィド、チオジグリコール、２，２’－チオジグリコール、ビス（２－ヒドロキシエチル）ジサルファイド、ジチオジグリコール酸、２，２－ジチオプロピオン酸等が挙げられる。
　ポリスルフィドとしては、例えばジヘプチルジスルフィド、ジエチルジスルフィド、メチルプロピルジスルフィド、２，２’－ジチオジエタノール、ジチオジグリコール酸、ビス（２－ヒドロキシエチル）ジサルファイド、ジチオジグリコール酸、２，２－ジチオプロピオン酸等が挙げられる。
　チオカルボニル基含有有機化合物としては、チオ尿素、チオアセトアミド、ジメチルチオ尿素、トリメチルチオ尿素、エチレンチオ尿素、チオセミカルバジド、ジエチルジチオカルバミン酸ジエチルアンモニウム、ジメチルジチオカルバミン酸ジメチルアンモニウム、テトラメチルチウラムモノスルフィド、グアニルチオ尿素等が挙げられる。
　硫黄含有複素環式化合物としては、チオフェン、２－アミノ－５－メルカプト－１，３－チアジアゾール、ビスムチオール等が挙げられる。
　ヒドロセレノ基含有有機化合物としては、ベンゼンセレノール、ｔｅｒｔ－ブチルセレノール等が挙げられる。
　セレニドとしては、フェニルセレニド、ｔｅｒｔ－ブチルセレニド等が挙げられる。
　ポリセレニドとしては、ジフェニルジセレニド、ｔｅｒｔ－ブチルジセレニド等が挙げられる。
　セレノカルボニル基含有有機化合物としては、セレノウレア、１，１－ジメチルー２－セレノウレア等が挙げられる。
　セレン含有複素環式化合物としては、セレノフェン等が挙げられる。 Examples of the mercapto group-containing organic compound include alkylthiol (ethanethiol, propanethiol, etc.), mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thioglycolic acid, thiolactic acid, thiomalic acid, methyl thioglycolate, thioglycol Examples thereof include ethyl acid, ethanedithiol, propanedithiol, butanedithiol, 2,3-dimercapto-1-propanol, meso-2,3-dimercaptosuccinic acid, n-butyl mercaptan, tert-butyl mercaptan and the like.
Examples of the sulfide include dibutyl sulfide, ethyl methyl sulfide, diethyl sulfide, thiodiglycol, 2,2′-thiodiglycol, bis (2-hydroxyethyl) disulfide, dithiodiglycolic acid, and 2,2-dithiopropionic acid. Etc.
Examples of the polysulfide include diheptyl disulfide, diethyl disulfide, methylpropyl disulfide, 2,2′-dithiodiethanol, dithiodiglycolic acid, bis (2-hydroxyethyl) disulfide, dithiodiglycolic acid, 2,2-dithiopropion. An acid etc. are mentioned.
Examples of thiocarbonyl group-containing organic compounds include thiourea, thioacetamide, dimethylthiourea, trimethylthiourea, ethylenethiourea, thiosemicarbazide, diethylammonium diethyldithiocarbamate, dimethylammonium dimethyldithiocarbamate, tetramethylthiuram monosulfide, and guanylthiourea. Can be mentioned.
Examples of the sulfur-containing heterocyclic compound include thiophene, 2-amino-5-mercapto-1,3-thiadiazole, bismuthiol and the like.
Examples of the hydroseleno group-containing organic compound include benzene selenol and tert-butyl selenol.
Examples of the selenide include phenyl selenide and tert-butyl selenide.
Examples of the polyselenide include diphenyl diselenide and tert-butyl diselenide.
Examples of the selenocarbonyl group-containing organic compound include selenourea and 1,1-dimethyl-2-selenourea.
Examples of the selenium-containing heterocyclic compound include selenophene.
　本発明において、カルコゲン元素含有有機化合物としては、メルカプト基含有有機化合物、スルフィド、ポリスルフィド、チオカルボニル基含有有機化合物及び硫黄含有複素環式化合物からなる群より選ばれる少なくとも１種が好ましく、メルカプト基含有有機化合物及びチオカルボニル基含有有機化合物からなる群より選ばれる少なくとも１種がより好ましく、チオグリコール酸、メルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール、チオグリセロール、チオ乳酸、チオリンゴ酸、ｔｅｒｔ－ブチルメルカプタン、ジエチルジチオカルバミン酸ジエチルアンモニウム、ジメチルジチオカルバミン酸ジメチルアンモニウム及びプロパンチオールからなる群より選ばれる少なくとも１種が更に好ましく、塗布膜の焼成時に除去し易く、光吸収層に残存しないという観点から、メルカプトエタノール、チオグリコール酸、アルキルチオール及びチオグリセロールからなる群より選ばれる少なくとも１種が更に好ましく、プロパンチオールが特に好ましい。 In the present invention, the chalcogen element-containing organic compound is preferably at least one selected from the group consisting of mercapto group-containing organic compounds, sulfides, polysulfides, thiocarbonyl group-containing organic compounds, and sulfur-containing heterocyclic compounds, and contains mercapto group-containing compounds. More preferably, at least one selected from the group consisting of an organic compound and a thiocarbonyl group-containing organic compound, thioglycolic acid, mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid, thiomalic acid, tert-butyl mercaptan, More preferably, at least one selected from the group consisting of diethylammonium diethyldithiocarbamate, dimethylammonium dimethyldithiocarbamate and propanethiol is used. Easily removed during sintering, from the standpoint of not remain in the light-absorbing layer, mercaptoethanol, thioglycolic acid, at least one more preferably selected from the group consisting of alkyl thiols and thioglycerol, propanethiol is especially preferred.
　本発明において、カルコゲン元素含有有機化合物は水溶性であってもよい。水溶性のカルコゲン元素含有有機化合物を用いることにより、単体及び／又は化合物とカルコゲン元素含有有機化合物とを混合する際に溶媒として水を用いることが出来るので、プロセスの安全性がより高まる。
　水溶性のカルコゲン元素含有有機化合物としては、例えばメルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール、チオグリセロール、チオ乳酸、チオリンゴ酸、チオグリコール酸、チオ尿素、チオアセトアミド等が挙げられる。これらの中でも、メルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール、チオ乳酸及びチオグリセロールが特に好ましい。 In the present invention, the chalcogen element-containing organic compound may be water-soluble. By using a water-soluble chalcogen element-containing organic compound, water can be used as a solvent when the simple substance and / or the compound and the chalcogen element-containing organic compound are mixed, thereby further improving the safety of the process.
Examples of the water-soluble chalcogen element-containing organic compound include mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid, thiomalic acid, thioglycolic acid, thiourea, and thioacetamide. Among these, mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thiolactic acid and thioglycerol are particularly preferable.
　本発明において、カルコゲン元素含有有機化合物の炭素数は４以下であってもよい。炭素数４以下のカルコゲン元素含有有機化合物としては、例えばプロパンチオール、メルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール、チオグリセロール、チオ乳酸、チオリンゴ酸、チオグリコール酸、チオ尿素、チオアセトアミド、チオグリコール酸メチル、チオグリコール酸エチル、エタンジチオール、プロパンジチオール、ブタンジチオール、２，３－ジメルカプト－１－プロパノール、ｍｅｓｏ－２，３－ジメルカプトこはく酸、エチルメチルスルフィド、ジエチルスルフィド、チオジグリコール、２，２’－チオジグリコール酸、チオ乳酸、ジエチルジスルフィド、メチルプロピルジスルフィド、２，２’－ジチオジエタノール、ジチオジグリコール酸、ジメチルチオ尿素、トリメチルチオ尿素、エチレンチオ尿素、ジメチルジチオカルバミン酸ジメチルアンモニウム等が挙げられる。中でも、メルカプトエタノール及びチオグリセロールが特に好ましい。 In the present invention, the number of carbon atoms of the chalcogen element-containing organic compound may be 4 or less. Examples of the organic compound containing a chalcogen element having 4 or less carbon atoms include propanethiol, mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid, thiomalic acid, thioglycolic acid, thiourea, thioacetamide, and methyl thioglycolate. , Ethyl thioglycolate, ethanedithiol, propanedithiol, butanedithiol, 2,3-dimercapto-1-propanol, meso-2,3-dimercaptosuccinic acid, ethyl methyl sulfide, diethyl sulfide, thiodiglycol, 2,2 ' -Thiodiglycolic acid, thiolactic acid, diethyl disulfide, methylpropyl disulfide, 2,2'-dithiodiethanol, dithiodiglycolic acid, dimethylthiourea, trimethylthiourea, Chirenchio urea, dimethyl dithiocarbamate dimethyl ammonium and the like. Among these, mercaptoethanol and thioglycerol are particularly preferable.
　本発明において、カルコゲン元素含有有機化合物は、室温（２３℃）の水１００ｇに対して１ｇ以上溶解する化合物であってもよく、５ｇ以上溶解する化合物であることがより好ましく、１０ｇ以上溶解する化合物であることが特に好ましい。 In the present invention, the chalcogen element-containing organic compound may be a compound that dissolves 1 g or more in 100 g of water at room temperature (23 ° C.), more preferably a compound that dissolves 5 g or more, and a compound that dissolves 10 g or more. It is particularly preferred that
　本発明において、カルコゲン元素含有有機化合物は、少なくとも１つのヒドロキシ基を有するカルコゲン元素含有有機化合物であってもよい。
　少なくとも１つのヒドロキシ基を有するカルコゲン元素含有有機化合物としては、例えばメルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール、チオグリセロール、チオ乳酸、チオリンゴ酸、チオグリコール酸、２，３－ジメルカプト－１－プロパノール、ｍｅｓｏ－２，３－ジメルカプトこはく酸、チオジグリコール、２，２’－チオジグリコール酸、２，２’－ジチオジエタノール、ジチオジグリコール酸等が挙げられる。これらの中でも、メルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール、チオグリセロール、チオ乳酸及びチオリンゴ酸が好ましく、メルカプトエタノール、メルカプトプロパノール、メルカプトエトキシエタノール及びチオグリセロールが特に好ましい。 In the present invention, the chalcogen element-containing organic compound may be a chalcogen element-containing organic compound having at least one hydroxy group.
Examples of the chalcogen element-containing organic compound having at least one hydroxy group include mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid, thiomalic acid, thioglycolic acid, 2,3-dimercapto-1-propanol, meso -2,3-dimercaptosuccinic acid, thiodiglycol, 2,2'-thiodiglycolic acid, 2,2'-dithiodiethanol, dithiodiglycolic acid and the like. Among these, mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol, thioglycerol, thiolactic acid and thiomalic acid are preferable, and mercaptoethanol, mercaptopropanol, mercaptoethoxyethanol and thioglycerol are particularly preferable.
　本発明において、カルコゲン元素含有有機化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the present invention, as the chalcogen element-containing organic compound, one kind may be used alone, or two or more kinds may be used in combination.
　本発明において、ルイス塩基性無機化合物は特に限定されないが、アンモニア、ヒドラジン、ＮａＯＨ、ＫＯＨ等が挙げられる。中でも、アンモニアが好ましい。
　ルイス塩基性無機化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the present invention, the Lewis basic inorganic compound is not particularly limited, and examples thereof include ammonia, hydrazine, NaOH, KOH and the like. Of these, ammonia is preferable.
As the Lewis basic inorganic compound, one kind may be used alone, or two or more kinds may be used in combination.
　本発明において、第１６族元素としては、Ｏ、Ｓ、Ｓｅ、Ｔｅ等が挙げられ、Ｓ、Ｓｅから選ばれる少なくとも１種が好ましく、Ｓｅが特に好ましい。
　第１６族元素としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 In the present invention, Group 16 elements include O, S, Se, Te, etc., and at least one selected from S and Se is preferable, and Se is particularly preferable.
As the group 16 element, one type may be used alone, or two or more types may be used in combination.
　本発明において、前記単体および／または化合物、カルコゲン含有有機化合物、ルイス塩基性無機化合物及び第１６族元素に加えて、有機溶媒を任意の割合で添加することができる。有機溶媒としては、ジメチルスルホキシド、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルホルムアミド、Ｎ－メチルアセトアミド、テトラメチルグアニンジン、テトラメチル尿素などの極性の非プロトン性溶媒が好ましい。中でも、ジメチルスルホキシドが好ましい。 In the present invention, in addition to the simple substance and / or compound, the chalcogen-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element, an organic solvent can be added at an arbitrary ratio. Examples of organic solvents include dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, tetramethylguanidine, and tetramethylurea. Protic solvents are preferred. Of these, dimethyl sulfoxide is preferable.
　本発明の錯体（溶液）の製造方法においては、前記反応液に前記ルイス塩基性無機化合物よりも極性の低い溶媒（以下、「貧溶媒」という場合がある。）を加えてもよい。貧溶媒を加えることにより、前記反応液を精製することができ、不純物を取り除くことできる。しかしながら、本発明の錯体（溶液）の製造方法においては、そのような精製工程は必ずしも必要ない。精製工程を省略することにより、全体のプロセスを簡略化でき、工業的に有利である。 In the method for producing a complex (solution) of the present invention, a solvent having a lower polarity than the Lewis basic inorganic compound (hereinafter sometimes referred to as “poor solvent”) may be added to the reaction solution. By adding a poor solvent, the reaction solution can be purified and impurities can be removed. However, such a purification step is not necessarily required in the method for producing a complex (solution) of the present invention. By omitting the purification step, the entire process can be simplified, which is industrially advantageous.
　前記貧溶媒としては、前記ルイス塩基性無機化合物よりも極性の低い溶媒であれば特に限定されないが、アセトン、イソプロパノールが好ましい。
　前記貧溶媒は、前記単体および／または化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素と共に混合してもよいが、前記単体および／または化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して反応液を調製した後に混合することが好ましい。反応液を調製した後に貧溶媒を混合することにより、目的物である錯体を沈殿させ、未反応カルコゲン元素含有有機化合物等の不純物を上清として除去できる。錯体と不純物は、例えば遠心分離、ろ過、抽出等で分離できる。
　また、不純物を上清として除去した後に、更に貧溶媒で錯体を洗浄できる。洗浄を複数回行うことにより、より確実に不純物を除去することができる。
　貧溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The poor solvent is not particularly limited as long as it is a solvent having a lower polarity than the Lewis basic inorganic compound, but acetone and isopropanol are preferable.
The poor solvent may be mixed with the simple substance and / or compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the group 16 element, but the simple substance and / or compound and the chalcogen element are contained. It is preferable to mix the organic compound, the Lewis basic inorganic compound, and the Group 16 element after preparing a reaction solution. By preparing a reaction solution and then mixing a poor solvent, the complex as the target product can be precipitated, and impurities such as unreacted chalcogen element-containing organic compounds can be removed as a supernatant. Complexes and impurities can be separated by, for example, centrifugation, filtration, extraction, and the like.
Further, after removing impurities as a supernatant, the complex can be further washed with a poor solvent. Impurities can be more reliably removed by performing the cleaning multiple times.
As the poor solvent, one kind may be used alone, or two or more kinds may be used in combination.
　本発明の錯体（溶液）の製造方法においては、水の存在下で前記反応液を得ることが好ましい。水の存在下で前記反応液を得る方法としては特に限定されないが、例えば各原料の混合溶媒として水を含む溶媒を用いることや、前記ルイス塩基性無機化合物としてルイス塩基性無機化合物水溶液を用いることが好ましい。前記ルイス塩基性無機化合物水溶液としては、アンモニア水、ヒドラジン水和物、ＮａＯＨ水溶液、ＫＯＨ水溶液等が挙げられ、中でも濃度２８％以下のアンモニア水を用いることが好ましい。この場合、後述する溶媒を用いることが好ましく、特にジメチルスルホキシドが好ましい。 In the method for producing a complex (solution) of the present invention, it is preferable to obtain the reaction solution in the presence of water. The method for obtaining the reaction solution in the presence of water is not particularly limited. For example, a solvent containing water is used as a mixed solvent for each raw material, or a Lewis basic inorganic compound aqueous solution is used as the Lewis basic inorganic compound. Is preferred. Examples of the Lewis basic inorganic compound aqueous solution include ammonia water, hydrazine hydrate, NaOH aqueous solution, KOH aqueous solution and the like. Among them, it is preferable to use ammonia water having a concentration of 28% or less. In this case, it is preferable to use a solvent described later, and dimethyl sulfoxide is particularly preferable.
　本発明の錯体（溶液）の製造方法において、単体および／または化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合する方法は特に限定されない。例えば、ＣＺＴＳ系又はＣＩＧＳ系太陽電池の光吸収層の形成に用いられる光吸収層形成用塗布液を調製する場合など、複数種類の単体および／または化合物を用いる場合、各錯体溶液（以下、「金属前駆体溶液」という場合がある）を調製した後に、各金属前駆体溶液を混合する方法（以下、「調製方法（Ｉ）」という。）、全ての原料を一括に混合する方法（以下、「調製方法（ＩＩ）」という。）、少なくとも２種の第１１族～第１５族金属を用いて二元または三元金属錯体溶液を調製する方法（以下、「調製方法（ＩＩＩ）」という。）等が挙げられる。 In the method for producing a complex (solution) of the present invention, the method of mixing a simple substance and / or compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited. For example, when a plurality of types of simple substances and / or compounds are used, such as when preparing a coating solution for forming a light absorption layer used for forming a light absorption layer of a CZTS or CIGS solar cell, each complex solution (hereinafter, “ After preparing a “metal precursor solution”, a method of mixing each metal precursor solution (hereinafter referred to as “preparation method (I)”), a method of mixing all raw materials at once (hereinafter referred to as “preparation method (I)”). "Preparation method (II)"), a method of preparing a binary or ternary metal complex solution using at least two Group 11 to Group 15 metals (hereinafter referred to as "Preparation method (III)"). ) And the like.
＜調製方法（Ｉ）＞
（Ｃｕ前駆体）
　Ｃｕ前駆体は、例えばＣｕ及び／又はＣｕ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合することにより得られる。
　Ｃｕ及び／又はＣｕ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記Ｃｕ及び／又はＣｕ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　Ｃｕ及び／又はＣｕ化合物としては、Ｃｕ、Ｃｕ（ＯＨ）２、ＣｕＳ、Ｃｕ２Ｓ、ＣｕＯ、Ｃｕ２Ｏ、Ｃｕ２Ｓｅ、ＣｕＳｅ、Ｃｕ２Ｔｅ、ＣｕＴｅが好ましく、Ｃｕがより好ましい。
　Ｃｕ及び／又はＣｕ化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 <Preparation method (I)>
(Cu precursor)
The Cu precursor is obtained, for example, by mixing Cu and / or a Cu compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
As Cu and / or Cu compound, chalcogen element-containing organic compound, Lewis basic inorganic compound and Group 16 element, the Cu and / or Cu compound, chalcogen exemplified in the description of the method for producing a metal precursor solution of the present invention Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
As Cu and / or a Cu compound, Cu, Cu (OH) 2 , CuS, Cu 2 S, CuO, Cu 2 O, Cu 2 Se, CuSe, Cu 2 Te, and CuTe are preferable, and Cu is more preferable.
As Cu and / or Cu compound, one kind may be used alone, or two or more kinds may be used in combination.
　第１６族元素の量は、Ｃｕ１モルに対し、０．５～１０モルが好ましく、０．５～４モルがより好ましく、１～２モルが更に好ましい。カルコゲン元素含有有機化合物の量はＣｕ１モルに対し、０．１～１０モルが好ましく、０．５～１０モルがより好ましく、０．３～１モルが更に好ましい。
　ルイス塩基性無機化合物の量は、Ｃｕ１モルに対し、１～２０モルが好ましく、２～１０モルがより好ましく、２～５モルが更に好ましい。 The amount of the Group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Cu. The amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, relative to 1 mol of Cu.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, more preferably 2 to 10 moles, and still more preferably 2 to 5 moles relative to 1 mole of Cu.
　Ｃｕ及び／又はＣｕ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合する方法は特に限定されない。例えば、Ｃｕ及び／又はＣｕ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加した後に撹拌する方法や、Ｃｕ及び／又はＣｕ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して得た反応液に溶媒を添加する方法や、反応液に前記貧溶媒を添加して得た錯体に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いでＣｕ及び／又はＣｕ化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、混合した際にＣｕ濃度が０．１ｍｏｌ／Ｌ～２．０ｍｏｌ／Ｌになる量が好ましく、０．２～１．５ｍｏｌ／Ｌがより好ましく、０．４～１．２ｍｏｌ／Ｌが特に好ましい。 The method of mixing Cu and / or a Cu compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited. For example, a method of stirring after adding Cu and / or a Cu compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, Cu and / or a Cu compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Cu and / or a Cu compound is added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent is preferably such that when mixed, the Cu concentration is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, and 0.4 to 1.2 mol / L. L is particularly preferred.
　Ｃｕ前駆体の調製における反応温度は、使用するＣｕ及び／又はＣｕ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類によっても異なるが、安全性やＣｕ錯体の安定性の観点から、通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 The reaction temperature in the preparation of the Cu precursor varies depending on the type of Cu and / or Cu compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc., but safety and Cu complex From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
　また、Ｃｕ前駆体の調製における反応時間は、使用するＣｕ及び／又はＣｕ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類、撹拌時間、反応温度によっても異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 The reaction time in the preparation of the Cu precursor also depends on the type of Cu and / or Cu compound used, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc., stirring time, and reaction temperature. Although it is different, it is usually preferably 1 hour to 1 week, more preferably 1 day to 3 days, still more preferably 1 day to 2 days.
　Ｃｕ前駆体の調製後、Ｃｕ前駆体に前記ルイス塩基性無機化合物よりも極性の低い溶媒（貧溶媒）を混合して不純物を除去することが好ましい。貧溶媒としては特にイソプロピルアルコールが好ましい。また、貧溶媒の混合は複数回行うことが好ましく、具体的には１回～５回行うことが好ましい。
　貧溶媒の量は、Ｃｕ前駆体に対して２～２０倍が好ましく、５～２０倍がより好ましく、７～２０倍が更に好ましい。 After preparing the Cu precursor, it is preferable to remove impurities by mixing the Cu precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound. As the poor solvent, isopropyl alcohol is particularly preferable. Further, the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
The amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, and even more preferably 7 to 20 times that of the Cu precursor.
（Ｚｎ前駆体）
　Ｚｎ前駆体は、例えばＺｎ及び／又はＺｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合することにより得られる。
　Ｚｎ及び／又はＺｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記Ｚｎ及び／又はＺｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　Ｚｎ及び／又はＺｎ化合物としては、Ｚｎ、ＺｎＯ、水酸化亜鉛、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅが好ましく、ＺｎおよびＺｎＯがより好ましい。
　Ｚｎ及び／又はＺｎ化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (Zn precursor)
The Zn precursor can be obtained, for example, by mixing Zn and / or a Zn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
Examples of Zn and / or Zn compounds, chalcogen element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements include the Zn and / or Zn compounds and chalcogens exemplified in the description of the method for producing a metal precursor solution of the present invention. Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
As the Zn and / or Zn compound, Zn, ZnO, zinc hydroxide, ZnS, ZnSe, and ZnTe are preferable, and Zn and ZnO are more preferable.
As Zn and / or Zn compound, one kind may be used alone, or two or more kinds may be used in combination.
　第１６族元素の量は、Ｚｎ１モルに対し、０．５～１０モルが好ましく、０．５～４モルがより好ましく、１～２モルが更に好ましい。カルコゲン元素含有有機化合物の量はＺｎ１モルに対し、０．１～１０モルが好ましく、０．５～１０モルがより好ましく、０．３～１モルが更に好ましい。
　ルイス塩基性無機化合物の量は、Ｚｎ１モルに対し、１～２０モルが好ましく、２～１０モルがより好ましく、２～５モルが更に好ましい。 The amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Zn. The amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, with respect to 1 mol of Zn.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, and still more preferably 2 to 5 mol with respect to 1 mol of Zn.
　Ｚｎ及び／又はＺｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合する方法は特に限定されない。例えば、Ｚｎ及び／又はＺｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加した後に撹拌する方法や、Ｚｎ及び／又はＺｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して得た反応液に溶媒を添加する方法や、反応液に前記貧溶媒を添加して得た錯体に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いでＺｎ及び／又はＺｎ化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、混合した際にＺｎ前駆体中のＺｎ濃度が０．１ｍｏｌ／Ｌ～２．０ｍｏｌ／Ｌになる量が好ましく、０．２～１．５ｍｏｌ／Ｌがより好ましく、０．４～１．２ｍｏｌ／Ｌが特に好ましい。 A method of mixing Zn and / or a Zn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited. For example, a method of stirring after adding Zn and / or a Zn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, Zn and / or a Zn compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Zn and / or a Zn compound is added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent is preferably such that when mixed, the Zn concentration in the Zn precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
　Ｚｎ前駆体の調製において、反応温度は使用するＺｎ及び／又はＺｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類によっても異なるが、安全性やＺｎ錯体の安定性の観点から、通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 In the preparation of the Zn precursor, the reaction temperature varies depending on the type of Zn and / or Zn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
　また、Ｚｎ前駆体の調製において、反応時間は使用するＺｎ及び／又はＺｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類、撹拌時間によっても異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 In the preparation of the Zn precursor, the reaction time varies depending on the type of Zn and / or Zn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
　Ｚｎ前駆体の調製後、Ｚｎ前駆体に前記ルイス塩基性無機化合物よりも極性の低い溶媒（貧溶媒）を混合して不純物を除去することが好ましい。貧溶媒としては特にアセトンが好ましい。また、貧溶媒の混合は複数回行うことが好ましく、具体的には１回～５回行うことが好ましい。
　貧溶媒の量は、Ｚｎ前駆体に対して２～２０倍が好ましく、５～２０倍がより好ましく、７～２０倍が更に好ましい。 After preparing the Zn precursor, it is preferable to remove impurities by mixing the Zn precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound. As the poor solvent, acetone is particularly preferable. Further, the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
The amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the Zn precursor.
（Ｓｎ前駆体）
　Ｓｎ前駆体は、例えばＳｎ及び／又はＳｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合することにより得られる。
　Ｓｎ及び／又はＳｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記Ｓｎ及び／又はＳｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　Ｓｎ及び／又はＳｎ化合物としては、Ｓｎ、ＳｎＳ、ＳｎＯ、ＳｎＯ２、ＳｎＳ２、ＳｎＳｅ、ＳｎＴｅが好ましく、Ｓｎがより好ましい。
　Ｓｎ及び／又はＳｎ化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (Sn precursor)
The Sn precursor is obtained, for example, by mixing a Sn and / or Sn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
Examples of the Sn and / or Sn compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element include the Sn and / or Sn compound and chalcogen exemplified in the description of the method for producing the metal precursor solution of the present invention. Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
As the Sn and / or Sn compound, Sn, SnS, SnO, SnO 2 , SnS 2 , SnSe, SnTe are preferable, and Sn is more preferable.
As Sn and / or Sn compound, 1 type may be used independently and 2 or more types may be used in combination.
　第１６族元素の量は、Ｓｎ１モルに対し、０．５～１０モルが好ましく、０．５～４モルがより好ましく、１～２モルが更に好ましい。カルコゲン元素含有有機化合物の量はＳｎ１モルに対し、０．１～１０モルが好ましく、０．５～１０モルがより好ましく、０．３～１モルが更に好ましい。
　ルイス塩基性無機化合物の量は、Ｓｎ１モルに対し、１～２０モルが好ましく、２～１０モルがより好ましく、２～５モルが更に好ましい。 The amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Sn. The amount of the chalcogen element-containing organic compound is preferably from 0.1 to 10 mol, more preferably from 0.5 to 10 mol, still more preferably from 0.3 to 1 mol, based on 1 mol of Sn.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, more preferably 2 to 10 moles, and still more preferably 2 to 5 moles per mole of Sn.
　Ｓｎ及び／又はＳｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合する方法は特に限定されない。例えば、Ｓｎ及び／又はＳｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加した後に撹拌する方法や、Ｓｎ及び／又はＳｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して得た反応液に溶媒を添加する方法や、反応液に前記貧溶媒を添加して得た錯体に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いでＳｎ及び／又はＳｎ化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、混合した際にＳｎ濃度が０．１ｍｏｌ／Ｌ～２．０ｍｏｌ／Ｌになる量が好ましく、０．２～１．５ｍｏｌ／Ｌがより好ましく、０．４～１．２ｍｏｌ／Ｌが特に好ましい。 A method of mixing the Sn and / or Sn compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element is not particularly limited. For example, a method of stirring after adding a Sn and / or Sn compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, a Sn and / or Sn compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Sn and / or Sn compound is added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent is preferably such that when mixed, the Sn concentration becomes 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, and 0.4 to 1.2 mol / L. L is particularly preferred.
　Ｓｎ前駆体の調製における反応温度は、使用するＳｎ及び／又はＳｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類によっても異なるが、安全性やＳｎ錯体の安定性の観点から、通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 The reaction temperature in the preparation of the Sn precursor depends on the type of Sn and / or Sn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc., but safety and Sn complex From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
　また、Ｓｎ前駆体の調製における反応時間は、使用するＳｎ及び／又はＳｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類、撹拌時間によっても異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 In addition, the reaction time in the preparation of the Sn precursor varies depending on the type of Sn and / or Sn compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
　Ｓｎ前駆体の調製後、Ｓｎ前駆体に前記ルイス塩基性無機化合物よりも極性の低い溶媒（貧溶媒）を混合して不純物を除去することが好ましい。貧溶媒としては特にアセトンが好ましい。また、貧溶媒の混合は複数回行うことが好ましく、具体的には１回～５回行うことが好ましい。
　貧溶媒の量は、Ｓｎ前駆体に対して２～２０倍が好ましく、５～２０倍がより好ましく、７～２０倍が更に好ましい。 After preparing the Sn precursor, it is preferable to remove impurities by mixing the Sn precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound. As the poor solvent, acetone is particularly preferable. Further, the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
The amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the Sn precursor.
（Ｉｎ前駆体）
　Ｉｎ前駆体は、例えばＩｎ及び／又はＩｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合することにより得られる。
　Ｉｎ及び／又はＩｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記Ｉｎ及び／又はＩｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　Ｉｎ及び／又はＩｎ化合物としては、Ｉｎ、Ｉｎ（ＯＨ）３、酸化インジウム、硫化インジウム、セレン化インジウム、テルル化インジウムが好ましく、Ｉｎ、Ｉｎ（ＯＨ）３、酸化インジウムがより好ましい。
　Ｉｎ及び／又はＩｎ化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (In precursor)
The In precursor is obtained, for example, by mixing In and / or an In compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
Examples of In and / or In compounds, chalcogen element-containing organic compounds, Lewis basic inorganic compounds, and Group 16 elements include the In and / or In compounds and chalcogens exemplified in the description of the method for producing a metal precursor solution of the present invention. Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
As In and / or In compounds, In, In (OH) 3 , indium oxide, indium sulfide, indium selenide, and indium telluride are preferable, and In, In (OH) 3 , and indium oxide are more preferable.
As In and / or In compounds, one kind may be used alone, or two or more kinds may be used in combination.
　第１６族元素の量は、Ｉｎ１モルに対し、０．５～１０モルが好ましく、０．５～４モルがより好ましく、１～２モルが更に好ましい。カルコゲン元素含有有機化合物の量はＩｎ１モルに対し、０．１～１０モルが好ましく、０．５～１０モルがより好ましく、０．３～１モルが更に好ましい。
　ルイス塩基性無機化合物の量は、Ｉｎ１モルに対し、１～２０モルが好ましく、２～１０モルがより好ましく、２～５モルが更に好ましい。 The amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of In. The amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, with respect to 1 mol of In.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, and still more preferably 2 to 5 mol with respect to 1 mol of In.
　Ｉｎ及び／又はＩｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合する方法は特に限定されない。例えば、Ｉｎ及び／又はＩｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加した後に撹拌する方法や、Ｉｎ及び／又はＩｎ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して得た反応液に溶媒を添加する方法や、反応液に前記貧溶媒を添加して得た錯体に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いでＩｎ及び／又はＩｎ化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、混合した際にＩｎ前駆体中のＩｎ濃度が０．１ｍｏｌ／Ｌ～２．０ｍｏｌ／Ｌになる量が好ましく、０．２～１．５ｍｏｌ／Ｌがより好ましく、０．４～１．２ｍｏｌ／Ｌが特に好ましい。 A method of mixing In and / or an In compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited. For example, a method of stirring after adding In and / or an In compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, or an In and / or In compound and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then In and / or an In compound are added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent is preferably such that when mixed, the In concentration in the In precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
　Ｉｎ前駆体の調製において、反応温度は使用するＩｎ及び／又はＩｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類によっても異なるが、安全性やＩｎ錯体の安定性の観点から、通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 In the preparation of the In precursor, the reaction temperature varies depending on the type of In and / or In compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. to be used. From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
　また、Ｉｎ前駆体の調製において、反応時間は使用するＩｎ及び／又はＩｎ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類、撹拌時間によっても異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 In the preparation of the In precursor, the reaction time varies depending on the type of In and / or In compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
　Ｉｎ前駆体の調製後、Ｉｎ前駆体に前記ルイス塩基性無機化合物よりも極性の低い溶媒（貧溶媒）を混合して不純物を除去することが好ましい。貧溶媒としては特にアセトンが好ましい。また、貧溶媒の混合は複数回行うことが好ましく、具体的には１回～５回行うことが好ましい。
　貧溶媒の量は、Ｉｎ前駆体に対して２～２０倍が好ましく、５～２０倍がより好ましく、７～２０倍が更に好ましい。 After the preparation of the In precursor, it is preferable to remove impurities by mixing the In precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound. As the poor solvent, acetone is particularly preferable. Further, the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
The amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the In precursor.
（Ｇａ前駆体）
　Ｇａ前駆体は、例えばＧａ及び／又はＧａ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合することにより得られる。
　Ｇａ及び／又はＧａ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記Ｇａ及び／又はＧａ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　Ｇａ及び／又はＧａ化合物としては、Ｇａ、酸化ガリウム、硫化ガリウム、セレン化ガリウム、テルル化ガリウムが好ましく、Ｇａ、酸化ガリウムがより好ましい。
　Ｇａ及び／又はＧａ化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (Ga precursor)
The Ga precursor is obtained, for example, by mixing Ga and / or a Ga compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
Examples of Ga and / or Ga compounds, chalcogen element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements include the Ga and / or Ga compounds and chalcogens exemplified in the description of the method for producing a metal precursor solution of the present invention. Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
As Ga and / or Ga compounds, Ga, gallium oxide, gallium sulfide, gallium selenide, and gallium telluride are preferable, and Ga and gallium oxide are more preferable.
As Ga and / or Ga compounds, one kind may be used alone, or two or more kinds may be used in combination.
　第１６族元素の量は、Ｇａ１モルに対し、０．５～１０モルが好ましく、０．５～４モルがより好ましく、１～２モルが更に好ましい。カルコゲン元素含有有機化合物の量はＧａ１モルに対し、０．１～１０モルが好ましく、０．５～１０モルがより好ましく、０．３～１モルが更に好ましい。
　ルイス塩基性無機化合物の量は、Ｇａ１モルに対し、１～２０モルが好ましく、２～１０モルがより好ましく、２～５モルが更に好ましい。 The amount of the Group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Ga. The amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, relative to 1 mol of Ga.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, still more preferably 2 to 5 mol, relative to 1 mol of Ga.
　Ｇａ及び／又はＧａ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合する方法は特に限定されない。例えば、Ｇａ及び／又はＧａ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加した後に撹拌する方法や、Ｇａ及び／又はＧａ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して得た反応液に溶媒を添加する方法や、反応液に前記貧溶媒を添加して得た錯体に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いでＧａ及び／又はＧａ化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、混合した際にＧａ前駆体中のＧａ濃度が０．１ｍｏｌ／Ｌ～２．０ｍｏｌ／Ｌになる量が好ましく、０．２～１．５ｍｏｌ／Ｌがより好ましく、０．４～１．２ｍｏｌ／Ｌが特に好ましい。 The method of mixing Ga and / or a Ga compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element is not particularly limited. For example, a method of stirring after adding Ga and / or Ga compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, and Group 16 element to the solvent, Ga and / or Ga compound, and chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Ga and / or a Ga compound is added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent is preferably such that when mixed, the Ga concentration in the Ga precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
　Ｇａ前駆体の調製において、反応温度は使用するＧａ及び／又はＧａ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類によっても異なるが、安全性やＧａ錯体の安定性の観点から、通常通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 In the preparation of the Ga precursor, the reaction temperature varies depending on the type of Ga and / or Ga compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
　また、Ｇａ前駆体の調製において、反応時間は使用するＧａ及び／又はＧａ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類、撹拌時間によっても異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 Further, in the preparation of Ga precursor, the reaction time varies depending on the type of Ga and / or Ga compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
　Ｇａ前駆体の調製後、Ｇａ前駆体に前記ルイス塩基性無機化合物よりも極性の低い溶媒（貧溶媒）を混合して不純物を除去することが好ましい。貧溶媒としては特にアセトンが好ましい。また、貧溶媒の混合は複数回行うことが好ましく、具体的には１回～５回行うことが好ましい。
　貧溶媒の量は、Ｇａ前駆体に対して２～２０倍が好ましく、５～２０倍がより好ましく、７～２０倍が更に好ましい。 After the preparation of the Ga precursor, it is preferable to remove impurities by mixing the Ga precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound. As the poor solvent, acetone is particularly preferable. Further, the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
The amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, and even more preferably 7 to 20 times that of the Ga precursor.
（Ｓｂ前駆体）
　Ｓｂ前駆体は、例えばＳｂ及び／又はＳｂ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合することにより得られる。
　Ｓｂ及び／又はＳｂ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記Ｓｂ及び／又はＳｂ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　Ｓｂ及び／又はＳｂ化合物としては、Ｓｂ、Ｓｂ２Ｏ３、硫化アンチモン、セレン化アンチモン、テルル化アンチモンが好ましく、Ｓｂ、Ｓｂ２Ｏ３がより好ましい。
　Ｓｂ及び／又はＳｂ化合物としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 (Sb precursor)
The Sb precursor is obtained, for example, by mixing an Sb and / or Sb compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element.
Examples of the Sb and / or Sb compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element include the Sb and / or Sb compound and chalcogen exemplified in the description of the method for producing the metal precursor solution of the present invention. Element-containing organic compounds, Lewis basic inorganic compounds and Group 16 elements can be used.
As the Sb and / or Sb compound, Sb, Sb 2 O 3 , antimony sulfide, antimony selenide, and antimony telluride are preferable, and Sb and Sb 2 O 3 are more preferable.
As the Sb and / or Sb compound, one kind may be used alone, or two or more kinds may be used in combination.
　第１６族元素の量は、Ｓｂ１モルに対し、０．５～１０モルが好ましく、０．５～４モルがより好ましく、１～２モルが更に好ましい。カルコゲン元素含有有機化合物の量はＳｂ１モルに対し、０．１～１０モルが好ましく、０．５～１０モルがより好ましく、０．３～１モルが更に好ましい。
　ルイス塩基性無機化合物の量は、Ｓｂ１モルに対し、１～２０モルが好ましく、２～１０モルがより好ましく、２～５モルが更に好ましい。 The amount of the group 16 element is preferably 0.5 to 10 mol, more preferably 0.5 to 4 mol, and still more preferably 1 to 2 mol with respect to 1 mol of Sb. The amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 mol, more preferably 0.5 to 10 mol, and still more preferably 0.3 to 1 mol, relative to 1 mol of Sb.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, more preferably 2 to 10 mol, still more preferably 2 to 5 mol, relative to 1 mol of Sb.
　Ｓｂ及び／又はＳｂ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合する方法は特に限定されない。例えば、Ｓｂ及び／又はＳｂ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加した後に撹拌する方法や、Ｓｂ及び／又はＳｂ化合物と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して得た反応液に溶媒を添加する方法や、反応液に前記貧溶媒を添加して得た錯体に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いでＳｂ及び／又はＳｂ化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、混合した際にＳｂ前駆体中のＳｂ濃度が０．１ｍｏｌ／Ｌ～２．０ｍｏｌ／Ｌになる量が好ましく、０．２～１．５ｍｏｌ／Ｌがより好ましく、０．４～１．２ｍｏｌ／Ｌが特に好ましい。 The method for mixing the Sb and / or Sb compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element is not particularly limited. For example, a method of stirring after adding a Sb and / or Sb compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element to a solvent, a Sb and / or Sb compound, and a chalcogen element A method of adding a solvent to a reaction solution obtained by mixing a contained organic compound, a Lewis basic inorganic compound, and a Group 16 element, or adding a solvent to a complex obtained by adding the poor solvent to the reaction solution And the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then Sb and / or an Sb compound are added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent is preferably such that when mixed, the Sb concentration in the Sb precursor is 0.1 mol / L to 2.0 mol / L, more preferably 0.2 to 1.5 mol / L, 0.4 -1.2 mol / L is particularly preferred.
　Ｓｂ前駆体の調製において、反応温度は使用するＳｂ及び／又はＳｂ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類によっても異なるが、安全性やＳｂ錯体の安定性の観点から、通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 In the preparation of the Sb precursor, the reaction temperature depends on the type of Sb and / or Sb compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, etc. used, but the safety and Sb complex From the viewpoint of stability, the temperature is usually preferably from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, and further preferably from room temperature to 100 ° C.
　また、Ｓｂ前駆体の調製において、反応時間は使用するＳｂ及び／又はＳｂ化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物、第１６族元素、溶媒等の種類、撹拌時間によっても異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 In the preparation of the Sb precursor, the reaction time varies depending on the type of Sb and / or Sb compound, chalcogen element-containing organic compound, Lewis basic inorganic compound, Group 16 element, solvent, and the like used, and the stirring time. Usually, 1 hour to 1 week is preferable, 1 day to 3 days is more preferable, and 1 day to 2 days is still more preferable.
　Ｓｂ前駆体の調製後、Ｓｂ前駆体に前記ルイス塩基性無機化合物よりも極性の低い溶媒（貧溶媒）を混合して不純物を除去することが好ましい。貧溶媒としては特にアセトンが好ましい。また、貧溶媒の混合は複数回行うことが好ましく、具体的には１回～５回行うことが好ましい。
　貧溶媒の量は、Ｓｂ前駆体に対して２～２０倍が好ましく、５～２０倍がより好ましく、７～２０倍が更に好ましい。 After the preparation of the Sb precursor, it is preferable to remove impurities by mixing the Sb precursor with a solvent (poor solvent) having a polarity lower than that of the Lewis basic inorganic compound. As the poor solvent, acetone is particularly preferable. Further, the mixing of the poor solvent is preferably performed a plurality of times, and specifically, it is preferably performed once to 5 times.
The amount of the poor solvent is preferably 2 to 20 times, more preferably 5 to 20 times, still more preferably 7 to 20 times that of the Sb precursor.
　上記のように得られた各前駆体を混合する方法は特に限定されない。例えば、各前駆体を溶媒に添加した後に撹拌する方法、各前駆体を混合した後に溶媒を添加する方法、各前駆体を減圧乾燥して固体錯体とした後に各固体錯体を溶媒に添加して錯体溶液を得て、得られた錯体溶液を混合する方法等が挙げられる。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、例えばＣＺＴＳ系太陽電池用の光吸収層に用いる場合、Ｃｕ、Ｚｎ、Ｓｎ、Ｓｅ各金属の合計量または、５００℃以上で加熱した際に残る固形分濃度が３％以上になる量が好ましく、５％以上がより好ましく、１０％以上が特に好ましい。
　また、例えばＣＩＧＳ系太陽電池用の光吸収層に用いる場合、Ｃｕ、Ｉｎ、Ｇａ、Ｓｅ各金属の合計量または、５００℃以上で加熱した際に残る固形分濃度が３％以上になる量が好ましく、５％以上がより好ましく、１０％以上が特に好ましい。 The method for mixing the precursors obtained as described above is not particularly limited. For example, a method of stirring after adding each precursor to a solvent, a method of adding a solvent after mixing each precursor, drying each precursor under reduced pressure to form a solid complex, and then adding each solid complex to the solvent The method etc. which obtain a complex solution and mix the obtained complex solution are mentioned.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
For example, when used in a light absorbing layer for CZTS solar cells, the amount of the solvent is such that the total amount of each metal of Cu, Zn, Sn, and Se, or the solid content concentration remaining when heated at 500 ° C. or higher is 3% or higher. Is preferably 5% or more, more preferably 10% or more.
For example, when used for a light absorption layer for CIGS solar cells, the total amount of each metal of Cu, In, Ga, and Se, or the amount of solid content remaining when heated at 500 ° C. or more is 3% or more. Preferably, 5% or more is more preferable, and 10% or more is particularly preferable.
＜調製方法（ＩＩ）＞
　調製方法（ＩＩ）における単体及び／又は化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記単体及び／又は化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　各原料の好ましい例としては、前記調製方法（Ｉ）と同様のものが挙げられる。 <Preparation method (II)>
As the simple substance and / or compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element in the preparation method (II), the simple substance and / or the compound exemplified in the description of the method for producing the metal precursor solution of the present invention can be used. Alternatively, a compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element can be used.
Preferable examples of each raw material include the same as in the preparation method (I).
　各原料の量は、各原料の種類によって適宜調整することができる。例えばＣＺＴＳ系太陽電池用の光吸収層に用いる場合（塗布液が後述する一般式（２）で表される化合物を含む場合）、各金属のモル比で、Ｃｕ／（Ｚｎ＋Ｓｎ）＝０．５～１．０、Ｚｎ／（Ｚｎ＋Ｓｎ）＝０．４～０．６、Ｓｎ／（Ｚｎ＋Ｓｎ）＝０．４～０．６の範囲となるように調製することが好ましい。
　Ｃｕ、Ｚｎ、Ｓｎ各金属の合計量１モルに対し、第１６族元素の量は０．５～１０当量が好ましく、０．５～４当量がより好ましく、１～２当量が更に好ましい。カルコゲン元素含有有機化合物の量は、金属に対して０．１～１０当量が好ましく、０．５～１０当量がより好ましく、０．３～１当量が更に好ましい。
　ルイス塩基性無機化合物の量は、１～２０モルであることが好ましく、好ましくは２～１０モルがより好ましく、２～５当量が更に好ましい。
　また、例えばＣＩＧＳ系太陽電池用の光吸収層に用いる場合（塗布液が後述する一般式（１）で表される化合物を含む場合）、各金属のモル比で、Ｃｕ／（Ｉｎ＋Ｇａ）＝０．５～１．０、Ｉｎ／（Ｉｎ＋Ｇａ）＝０．０～１．０、Ｇａ／（Ｉｎ＋Ｇａ）＝０．０～１．０の範囲となるように調製することが好ましい。
　Ｃｕ、Ｉｎ、Ｇａ各金属の合計量１モルに対し、第１６族元素の量は０．５～１０当量が好ましく、０．５～４当量がより好ましく、１～２当量が更に好ましい。カルコゲン元素含有有機化合物の量は、金属に対して０．１～１０当量が好ましく、０．５～１０当量がより好ましく、０．３～１当量が更に好ましい。
　ルイス塩基性無機化合物の量は、１～２０モルであることが好ましく、好ましくは２～１０モルがより好ましく、２～５モルが更に好ましい。 The amount of each raw material can be appropriately adjusted depending on the type of each raw material. For example, when used for a light absorption layer for a CZTS solar cell (when the coating solution contains a compound represented by the general formula (2) described later), Cu / (Zn + Sn) = 0.5 in terms of the molar ratio of each metal. It is preferable to prepare such that the range is 1.0, Zn / (Zn + Sn) = 0.4 to 0.6, and Sn / (Zn + Sn) = 0.4 to 0.6.
The amount of the group 16 element is preferably 0.5 to 10 equivalents, more preferably 0.5 to 4 equivalents, and even more preferably 1 to 2 equivalents with respect to 1 mol of the total amount of each metal of Cu, Zn and Sn. The amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 equivalents, more preferably 0.5 to 10 equivalents, and still more preferably 0.3 to 1 equivalents with respect to the metal.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, preferably 2 to 10 moles, more preferably 2 to 5 equivalents.
For example, when used for a light absorption layer for CIGS solar cells (when the coating solution contains a compound represented by the general formula (1) described later), Cu / (In + Ga) = 0 in terms of molar ratio of each metal. It is preferable to prepare them in the ranges of 0.5 to 1.0, In / (In + Ga) = 0.0 to 1.0, and Ga / (In + Ga) = 0.0 to 1.0.
The amount of the group 16 element is preferably 0.5 to 10 equivalents, more preferably 0.5 to 4 equivalents, and even more preferably 1 to 2 equivalents with respect to 1 mol of the total amount of each metal of Cu, In and Ga. The amount of the chalcogen element-containing organic compound is preferably 0.1 to 10 equivalents, more preferably 0.5 to 10 equivalents, and still more preferably 0.3 to 1 equivalents with respect to the metal.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, preferably 2 to 10 moles, more preferably 2 to 5 moles.
　調製方法（ＩＩ）において、各原料を混合する方法は特に限定されないが、例えば各原料を溶媒に添加した後に撹拌する方法や、各原料を混合した後に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いで単体及び／又は化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、使用する各原料の種類によって異なるが、熱重量測定で５００℃で加熱したときの残渣成分を固形分としたとき、固形分濃度が１～３０重量％になるよう調製することが好ましく、５～２０重量％がより好ましい。 In the preparation method (II), a method of mixing each raw material is not particularly limited, and examples thereof include a method of stirring after adding each raw material to a solvent, a method of adding a solvent after mixing each raw material, and the like. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then a simple substance and / or a compound are added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent varies depending on the type of each raw material to be used, but it should be prepared so that the solid component concentration is 1 to 30% by weight when the residual component when heated at 500 ° C. by thermogravimetry is defined as the solid component. It is preferably 5 to 20% by weight.
　調製方法（ＩＩ）における反応温度は、使用する各原料の種類によって異なるが、安全性や錯体の安定性の観点から、通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 The reaction temperature in the preparation method (II) varies depending on the type of each raw material used, but is usually preferably room temperature to 200 ° C., more preferably room temperature to 150 ° C., and more preferably room temperature to 100 ° C. More preferred is ° C.
　調製方法（ＩＩ）における反応時間は、使用する各原料の種類、撹拌時間によって異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 The reaction time in the preparation method (II) varies depending on the types of raw materials used and the stirring time, but is usually preferably 1 hour to 1 week, more preferably 1 day to 3 days, and further preferably 1 day to 2 days.
＜調製方法（ＩＩＩ）＞
　調製方法（ＩＩＩ）における単体及び／又は化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素としては、本発明の金属前駆体溶液の製造方法の説明において例示した前記単体及び／又は化合物、カルコゲン元素含有有機化合物、ルイス塩基性無機化合物ならびに第１６族元素を用いることができる。
　各原料の好ましい例としては、前記調製方法（Ｉ）と同様のものが挙げられる。 <Preparation method (III)>
As the simple substance and / or compound, the chalcogen element-containing organic compound, the Lewis basic inorganic compound, and the Group 16 element in the preparation method (III), the simple substance and / or the compound exemplified in the description of the method for producing the metal precursor solution of the present invention can be used. Alternatively, a compound, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element can be used.
Preferable examples of each raw material include the same as in the preparation method (I).
　調製方法（ＩＩＩ）において、例えば、少なくとも２種の第１１族～第１５族金属と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合することにより、二元又は三元金属錯体溶液を得ることが出来る。
　各原料の好ましい例としては、前記調製方法（Ｉ）と同様のものが挙げられる。 In the preparation method (III), for example, by mixing at least two Group 11 to Group 15 metals, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element, Alternatively, a ternary metal complex solution can be obtained.
Preferable examples of each raw material include the same as in the preparation method (I).
　各原料の量は、各原料の種類によって適宜調整することができる。例えばＣＺＴＳ系太陽電池用の光吸収層に用いる場合（塗布液が後述する一般式（２）で表される化合物を含む場合）、Ｃｕ元素及び／又はＣｕ化合物、Ｚｎ元素及び／又はＺｎ化合物、並びにＳｎ元素及び／又はＳｎ化合物の少なくとも２種（以下、まとめて「ＣＺＴＳ金属」という場合がある。）を用いることが出来る。この場合、各金属のモル比が後述する一般式（２）で規定される範囲内となるように塗布液を調製することが好ましい。
　ＣＺＴＳ金属の合計量１モルに対し、第１６族元素の量は０．５～１０当量が好ましく、０．５～４当量がより好ましく、１～２当量が更に好ましい。カルコゲン元素含有有機化合物の量は、ＣＺＴＳ金属の合計量１モルに対し、０．１～１０当量が好ましく、０．５～１０当量がより好ましく、０．３～１当量が更に好ましい。
　ルイス塩基性無機化合物の量は、ＣＺＴＳ金属の合計量１モルに対し、１～２０モルであることが好ましく、好ましくは２～１０モルがより好ましく、２～５モルが更に好ましい。
　また、例えばＣＩＧＳ系太陽電池用の光吸収層に用いる場合（塗布液が後述する一般式（１）で表される化合物を含む場合）、Ｃｕ元素及び／又はＣｕ化合物、Ｉｎ元素及び／又はＩｎ化合物、並びにＧａ元素及び／又はＧａ化合物の少なくとも２種（以下、まとめて「ＣＩＧＳ金属」という場合がある。）を用いることが出来る。この場合、各金属のモル比が後述する一般式（１）で規定される範囲内となるように塗布液を調製することが好ましい。
　ＣＩＧＳ金属の合計量１モルに対し、第１６族元素の量は０．５～１０モルが好ましく、０．５～５モルがより好ましく、１～３モルが更に好ましい。カルコゲン元素含有有機化合物の量は、金属に対して０．０５～５モルが好ましく、０．１～２モルがより好ましく、０．２５～０．７５モルが更に好ましい。
　ルイス塩基性無機化合物の量は、１～２０モルであることが好ましく、好ましくは１～１０モルがより好ましく、２～６当量が更に好ましい。 The amount of each raw material can be appropriately adjusted depending on the type of each raw material. For example, when used for a light absorption layer for CZTS solar cells (when the coating solution contains a compound represented by the general formula (2) described later), Cu element and / or Cu compound, Zn element and / or Zn compound, In addition, at least two kinds of Sn elements and / or Sn compounds (hereinafter sometimes collectively referred to as “CZTS metal”) can be used. In this case, it is preferable to prepare the coating solution so that the molar ratio of each metal is within the range defined by the general formula (2) described later.
The amount of Group 16 element is preferably 0.5 to 10 equivalents, more preferably 0.5 to 4 equivalents, and even more preferably 1 to 2 equivalents with respect to 1 mol of the total amount of CZTS metal. The amount of the chalcogen element-containing organic compound is preferably from 0.1 to 10 equivalents, more preferably from 0.5 to 10 equivalents, still more preferably from 0.3 to 1 equivalent, based on 1 mol of the total amount of CZTS metal.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 mol, preferably 2 to 10 mol, more preferably 2 to 5 mol, per 1 mol of the total amount of CZTS metal.
For example, when used for a light absorption layer for a CIGS solar cell (when the coating solution contains a compound represented by the general formula (1) described later), Cu element and / or Cu compound, In element and / or In A compound and at least two kinds of Ga element and / or Ga compound (hereinafter, sometimes collectively referred to as “CIGS metal”) can be used. In this case, it is preferable to prepare the coating solution so that the molar ratio of each metal is within the range defined by the general formula (1) described later.
The amount of Group 16 element is preferably 0.5 to 10 moles, more preferably 0.5 to 5 moles, and even more preferably 1 to 3 moles with respect to 1 mole of the total amount of CIGS metal. The amount of the chalcogen element-containing organic compound is preferably 0.05 to 5 mol, more preferably 0.1 to 2 mol, and still more preferably 0.25 to 0.75 mol with respect to the metal.
The amount of the Lewis basic inorganic compound is preferably 1 to 20 moles, preferably 1 to 10 moles, more preferably 2 to 6 equivalents.
　調製方法（ＩＩＩ）において、各原料を混合する方法は特に限定されないが、例えば各原料を溶媒に添加した後に撹拌する方法や、各原料を混合した後に溶媒を添加する方法等が挙げられる。また、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを溶媒に添加して撹拌し、次いで単体及び／又は化合物を添加する方法も好ましい。
　前記溶媒としては、例えばジメチルスルホキシド、Ｎ－メチルピロリドン（ＮＭＰ）、Ｎ－メチルホルムアミド（ＮＭＦ）、ジメチルホルムアミド（ＤＭＦ）、テトラメチルグアニンジン、テトラメチル尿素等の非プロトン性の極性溶剤；水；エタノール、メチルジグリコール（ＭＤＧ）等の水溶性の高いアルコールまたはグリコールエーテル等が挙げられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　これらの中でも、ジメチルスルホキシド、水、又はジメチルスルホキシドと水との組み合わせが好ましい。
　溶媒の量は、使用する各原料の種類によって異なるが、熱重量測定で５００℃で加熱したときの残渣成分を固形分としたとき、固形分濃度が１～３０重量％になるよう調製することが好ましく、５～２０重量％がより好ましい。 In preparation method (III), the method of mixing each raw material is not particularly limited, and examples thereof include a method of stirring after adding each raw material to a solvent, and a method of adding a solvent after mixing each raw material. Also preferred is a method in which a chalcogen element-containing organic compound, a Lewis basic inorganic compound, and a Group 16 element are added to a solvent and stirred, and then a simple substance and / or a compound are added.
Examples of the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone (NMP), N-methylformamide (NMF), dimethylformamide (DMF), tetramethylguanidine, tetramethylurea; water; Examples thereof include highly water-soluble alcohols or glycol ethers such as ethanol and methyl diglycol (MDG). As the solvent, one kind may be used alone, or two or more kinds may be used in combination.
Among these, dimethyl sulfoxide, water, or a combination of dimethyl sulfoxide and water is preferable.
The amount of the solvent varies depending on the type of each raw material to be used, but it should be prepared so that the solid component concentration is 1 to 30% by weight when the residual component when heated at 500 ° C. by thermogravimetry is defined as the solid component. It is preferably 5 to 20% by weight.
　調製方法（ＩＩＩ）における反応温度は、使用する各原料の種類によって異なるが、安全性や錯体の安定性の観点から、通常室温～２００℃が好ましく、室温～１５０℃がより好ましく、室温～１００℃が更に好ましい。 The reaction temperature in the preparation method (III) varies depending on the type of each raw material used, but is usually preferably room temperature to 200 ° C., more preferably room temperature to 150 ° C., and more preferably room temperature to 100 ° C. More preferred is ° C.
　調製方法（ＩＩＩ）における反応時間は、使用する各原料の種類、撹拌時間によって異なるが、通常１時間～１週間が好ましく、１日～３日がより好ましく、１日～２日が更に好ましい。 The reaction time in the preparation method (III) varies depending on the types of raw materials used and the stirring time, but is usually preferably 1 hour to 1 week, more preferably 1 day to 3 days, and further preferably 1 day to 2 days.
　本発明の製造方法により得られた光吸収層形成用塗布液は、直接光吸収層形成に用いることができるし、減圧蒸留により濃縮して濃縮液とすることも可能である。光吸収層形成用塗布液を濃縮することにより、未反応ルイス塩基性無機化合物、溶媒、水、未反応カルコゲン元素含有有機化合物等を除去することができる。
　更に、上記濃縮液を溶媒に溶解して希釈することにより、均一な光吸収層形成用塗布液を得ることができる。前記溶媒としては、水、ジメチルスルホキシド、ヒドラジン等があげられる。溶媒としては、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらの中でも水及びジメチルスルホキシドが好ましい。 The coating solution for forming a light absorbing layer obtained by the production method of the present invention can be used directly for forming a light absorbing layer, or can be concentrated by vacuum distillation to obtain a concentrated solution. By concentrating the coating solution for forming the light absorption layer, unreacted Lewis basic inorganic compound, solvent, water, unreacted chalcogen element-containing organic compound and the like can be removed.
Furthermore, a uniform coating solution for forming a light absorption layer can be obtained by dissolving the concentrated solution in a solvent and diluting it. Examples of the solvent include water, dimethyl sulfoxide, hydrazine and the like. As the solvent, one kind may be used alone, or two or more kinds may be used in combination. Among these, water and dimethyl sulfoxide are preferable.
　また、本発明の製造方法により得られた光吸収層形成用塗布液は、Ｎａ、Ｋ、Ｃｓ、Ｓｂ及びＢｉからなる群より選ばれる少なくとも１種（以下、まとめて「添加金属」という場合がある。）を添加することも好ましい。添加金属を添加することにより、光吸収層の結晶成長を促進することができる。また、添加金属は溶液に溶解して添加してもよい。
　Ｎａ液をとしては、セレン化ナトリウム、セレンをＤＭＳＯに溶解したもの等が挙げられる。
　Ｎａの添加量は、例えばＣＺＴＳ系太陽電池用の光吸収層に用いる場合、ＣＺＴＳの金属モル量に対して０．１～１０ａｔｏｍｉｃ％が好ましく、０．１～２ａｔｏｍｉｃ％が更に好ましい。
　また、例えばＣＩＧＳ系太陽電池用の光吸収層に用いる場合、ＣＩＧＳの金属モル量に対して、０．１～１０ａｔｏｍｉｃ％が好ましく、０．１～２ａｔｏｍｉｃ％が更に好ましい。 In addition, the light absorbing layer forming coating solution obtained by the production method of the present invention is at least one selected from the group consisting of Na, K, Cs, Sb and Bi (hereinafter sometimes collectively referred to as “added metal”). It is also preferred to add. The crystal growth of the light absorption layer can be promoted by adding the additive metal. Further, the added metal may be added after being dissolved in a solution.
Examples of the Na solution include sodium selenide and those obtained by dissolving selenium in DMSO.
The amount of Na added is, for example, preferably from 0.1 to 10 atomic%, more preferably from 0.1 to 2 atomic%, based on the metal molar amount of CZTS when used in a light absorbing layer for CZTS solar cells.
Further, for example, when used in a light absorption layer for CIGS solar cells, 0.1 to 10 atomic% is preferable and 0.1 to 2 atomic% is more preferable with respect to the metal molar amount of CIGS.
　また、本発明の製造方法により得られた光吸収層形成用塗布液は、Ｓｂを添加することも好ましい。
　Ｓｂの添加量は、例えばＣＺＴＳ系太陽電池用の光吸収層に用いる場合、ＣＺＴＳの金属モル量に対して０．１～２ａｔｏｍｉｃ％が好ましく、０．１～０．５ａｔｏｍｉｃ％がより好ましい。
　また、例えばＣＩＧＳ系太陽電池用の光吸収層に用いる場合、ＣＩＧＳの金属モル量に対して、ＣＩＧＳの金属モル量に対して０．１～２ａｔｏｍｉｃ％が好ましく、０．１～０．５ａｔｏｍｉｃ％がより好ましい。 Moreover, it is also preferable that Sb is added to the coating solution for forming a light absorption layer obtained by the production method of the present invention.
The amount of Sb added is, for example, preferably 0.1 to 2 atomic%, more preferably 0.1 to 0.5 atomic% with respect to the molar amount of metal in CZTS when used in a light absorbing layer for CZTS solar cells.
For example, when used for a light absorption layer for a CIGS solar cell, 0.1 to 2 atomic% is preferable with respect to the metal molar amount of CIGS, preferably 0.1 to 0.5 atomic% with respect to the metal molar amount of CIGS. Is more preferable.
　本発明の錯体（溶液）の製造方法において、錯体またはその溶液は、カルコパイライト系太陽電池又はケステライト系太陽電池の光吸収層の形成に用いられることが好ましい。この場合、前記反応液は、下記一般式（１）又は（２）で表される化合物を含有することが好ましい。 In the method for producing a complex (solution) of the present invention, the complex or a solution thereof is preferably used for forming a light absorption layer of a chalcopyrite solar cell or a kesterite solar cell. In this case, the reaction solution preferably contains a compound represented by the following general formula (1) or (2).
Figure JPOXMLDOC01-appb-C000004
 ［式中、０≦ｗ≦１、０≦ｘ≦１、０≦ｙ≦１、０＜ｚ≦１、Ａは少なくとも１種の１６族元素である。
Figure JPOXMLDOC01-appb-C000004
 [Wherein, 0 ≦ w ≦ 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 <z ≦ 1, and A is at least one group 16 element.
Figure JPOXMLDOC01-appb-C000005
 ［式中、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦１、及び－１≦ｄ≦１である。］
Figure JPOXMLDOC01-appb-C000005
 [Where 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 1, and −1 ≦ d ≦ 1. ]
　前記一般式（１）中、０≦ｗ≦１、好ましくは０．７５≦ｗ≦１である。０≦ｘ≦１、好ましくは０．１≦ｘ≦０．５である。０≦ｙ≦１である。０＜ｚ≦１である。Ａは少なくとも１種の１６族元素であり、好ましくはＳｅ及び／又はＳである。
　前記一般式（２）中、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦１、及び－１≦ｄ≦１である。 In the general formula (1), 0 ≦ w ≦ 1, preferably 0.75 ≦ w ≦ 1. 0 ≦ x ≦ 1, preferably 0.1 ≦ x ≦ 0.5. 0 ≦ y ≦ 1. 0 <z ≦ 1. A is at least one group 16 element, preferably Se and / or S.
In the general formula (2), 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 1, and −1 ≦ d ≦ 1.
　本発明の第一の態様に係る錯体（溶液）の製造方法によれば、結晶成長を阻害する要因となる有機物の含有量が低減された光吸収層を形成することが出来る。
　上記効果が得られる理由は明らかではないが、以下のように推測される。太陽電池の光吸収層の形成に用いられる金属前駆体溶液の調製においてカルコゲン元素含有有機化合物を用いた場合、カルコゲン元素含有有機化合物が配位した金属錯体が形成されると推測される。そのため、光吸収層をカルコゲン元素含有有機化合物単体の沸点以上の温度に加熱した場合であっても、カルコゲン元素含有有機化合物が一部光吸収層に残留してしまい、結晶成長を阻害する要因となる。
　これに対し、本発明においては、カルコゲン元素含有有機化合物と共に第１６族元素を混合する。そのため、カルコゲン元素含有有機化合物は第１６族元素の還元剤として作用し、第１６族元素はイオン化されると推測される。イオン化された第１６族元素は金属に配位して金属錯体を形成するので、金属に配位するカルコゲン元素含有有機化合物の量を低減させることが出来る。その結果、結晶成長を阻害する要因となる有機物の含有量が低減された光吸収層を形成することが出来ると推測される。
　また、本発明の第一の態様に係る製造方法により得られた錯体溶液は、塗布溶剤としてヒドラジンが含まれていないので、光吸収層を形成する際に、ヒドラジンの化学特性（爆発性、毒性）が問題とならなくなり、製造プロセスの安全性が向上する。 According to the method for producing a complex (solution) according to the first aspect of the present invention, it is possible to form a light absorption layer in which the content of an organic substance that is a factor inhibiting crystal growth is reduced.
The reason why the above effect is obtained is not clear, but is presumed as follows. When the chalcogen element-containing organic compound is used in the preparation of the metal precursor solution used for forming the light absorption layer of the solar cell, it is presumed that a metal complex in which the chalcogen element-containing organic compound is coordinated is formed. Therefore, even when the light absorption layer is heated to a temperature equal to or higher than the boiling point of the chalcogen element-containing organic compound alone, part of the chalcogen element-containing organic compound remains in the light absorption layer, which is a factor that inhibits crystal growth. Become.
In contrast, in the present invention, the group 16 element is mixed together with the chalcogen element-containing organic compound. Therefore, it is estimated that the chalcogen element-containing organic compound acts as a reducing agent for the group 16 element, and the group 16 element is ionized. Since the ionized group 16 element coordinates to the metal to form a metal complex, the amount of the chalcogen element-containing organic compound coordinated to the metal can be reduced. As a result, it is presumed that a light absorption layer in which the content of organic substances that cause crystal growth inhibition is reduced can be formed.
Further, since the complex solution obtained by the production method according to the first aspect of the present invention does not contain hydrazine as a coating solvent, the chemical properties (explosiveness, toxicity) of hydrazine are formed when the light absorption layer is formed. ) Is no longer a problem and the safety of the manufacturing process is improved.
　また、本発明の錯体（溶液）の製造方法において、１種の単体および／または化合物を用いて各金属錯体溶液を調製することができる。あるいは、２種以上の単体および／または化合物を用いて二元または三元金属錯体溶液を調製することもできる。従って、形成する光吸収層の要求に応じ、金属錯体溶液の組成を自由に選択することができる。このように金属錯体溶液の組成を自由に選択できることにより、光吸収層における金属の配列を確実にデザインでき、光吸収層の構造を確実に制御できることが期待される。 In the method for producing a complex (solution) of the present invention, each metal complex solution can be prepared using one kind of simple substance and / or compound. Alternatively, a binary or ternary metal complex solution can be prepared using two or more kinds of simple substances and / or compounds. Therefore, the composition of the metal complex solution can be freely selected according to the requirements of the light absorption layer to be formed. Thus, it can be expected that the composition of the metal complex solution can be freely selected, so that the arrangement of metals in the light absorption layer can be reliably designed and the structure of the light absorption layer can be reliably controlled.
　［太陽電池用光吸収層の製造方法］
　本発明の第二の態様は、前記第一の態様に係る錯体（溶液）の製造方法により得られた溶液を、基体に塗布し、焼成することを特徴とする太陽電池用光吸収層の製造方法である。
　本発明の太陽電池用光吸収層の製造方法は、本発明の第三の態様に係る太陽電池の製造方法における光吸収層を形成する工程と同様である。 [Method for producing light absorption layer for solar cell]
According to a second aspect of the present invention, there is provided a method for producing a light-absorbing layer for a solar cell, wherein a solution obtained by the method for producing a complex (solution) according to the first aspect is applied to a substrate and fired. Is the method.
The manufacturing method of the light absorption layer for solar cells of this invention is the same as the process of forming the light absorption layer in the manufacturing method of the solar cell which concerns on the 3rd aspect of this invention.
　本発明の太陽電池用光吸収層の製造方法において、光吸収層はカルコパイライト系太陽電池用又はケステライト系太陽電池用であることが好ましい。その場合、前記光吸収層は、前記一般式（１）又は（２）で表される化合物を含むことが好ましい。 In the method for producing a light absorption layer for a solar cell of the present invention, the light absorption layer is preferably for a chalcopyrite solar cell or a kesterite solar cell. In that case, it is preferable that the said light absorption layer contains the compound represented by the said General formula (1) or (2).
　［太陽電池の製造方法］
　本発明の第三の態様は、基板上に第１の電極を形成する工程と、前記第１の電極上に、第一の態様に係る錯体（溶液）の製造方法により得られた溶液を塗布し、焼成して光吸収層を形成する工程と、前記光吸収層上にバッファ層を形成する工程と、前記バッファ層上に第２の電極を形成する工程と、を有することを特徴とする太陽電池の製造方法である。 [Method for manufacturing solar cell]
In a third aspect of the present invention, a step is performed in which a first electrode is formed on a substrate, and a solution obtained by the method for producing a complex (solution) according to the first aspect is applied on the first electrode. And baking to form a light absorption layer, forming a buffer layer on the light absorption layer, and forming a second electrode on the buffer layer. It is a manufacturing method of a solar cell.
　本発明の太陽電池の製造方法において、第１の電極上に光吸収層を形成する工程以外は、従来から知られている適宜の方法を用いて形成すればよい。例えば、基板上に第１の電極を形成する際は、窒素をスパッタガスとして、スパッタ法によって例えばＭｏ層を成膜すればよい。また、バッファ層は、例えばＣｄＳ層として形成すればよく、例えば、ケミカルバスデポション法を用いて成膜すればよい。また、第２の電極を形成する際は、適宜の材料を用いて透明電極として成膜すればよい。 In the method for manufacturing a solar cell of the present invention, a method known in the art may be used except for the step of forming a light absorption layer on the first electrode. For example, when forming the first electrode on the substrate, for example, a Mo layer may be formed by sputtering using nitrogen as a sputtering gas. The buffer layer may be formed as a CdS layer, for example, and may be formed using a chemical bath deposition method, for example. Further, when the second electrode is formed, the transparent electrode may be formed using an appropriate material.
　光吸収層を形成する際には、まず、第１の電極（基体）上に、前記第一の態様に係る錯体（溶液）の製造方法により得られた金属前駆体溶液（光吸収層形成用塗布液）を塗布する。塗布の方法としてはスピンコート法、ディップコート法、ドクターブレード（アプリケーター）法、カーテン／スリットキャスト法、印刷法、スプレー法等を用いることができる。
　塗布条件は、所望の膜厚、材料の濃度などに応じて適宜設定すればよい。 When forming the light absorption layer, first, a metal precursor solution (for light absorption layer formation) obtained by the method for producing a complex (solution) according to the first aspect is formed on the first electrode (substrate). (Coating solution) is applied. As a coating method, a spin coating method, a dip coating method, a doctor blade (applicator) method, a curtain / slit casting method, a printing method, a spray method, or the like can be used.
The application conditions may be set as appropriate according to the desired film thickness, material concentration, and the like.
　例えば、スピンコーティング法を用いる場合には、基体をスピンコーターにセットし、塗布液を塗布する。この際の塗布条件は、形成しようとする膜厚に応じて適宜設定すればよく、例えば回転速度は、３００～３０００ｒｐｍで、１０～１８０秒間維持することにより形成することができる。塗布は所望の膜厚が得られるまで、繰り返し行うことができる。
　また、ディップ法を用いる場合には、塗布液が入った容器中に、基体を浸漬させることにより行うことができ、浸漬回数は１回でもよいし、複数回行ってもよい。
　なお、基体上に光吸収層形成用塗布液を塗布した後に、真空乾燥を行っても構わない。 For example, when the spin coating method is used, the substrate is set on a spin coater and a coating solution is applied. The coating conditions at this time may be appropriately set according to the film thickness to be formed. For example, the rotation speed is 300 to 3000 rpm and the film can be formed by maintaining for 10 to 180 seconds. Application can be repeated until a desired film thickness is obtained.
Moreover, when using a dip method, it can carry out by immersing a base | substrate in the container containing a coating liquid, and the frequency | count of immersion may be 1 time and may be performed in multiple times.
In addition, after apply | coating the coating liquid for light absorption layer formation on a base | substrate, you may vacuum-dry.
　次に、基体上に塗布液を塗布した後は、基体を焼成して光吸収層を形成する。
　焼成条件は、所望の膜厚、材料の種類などに応じて適宜設定することができる。例えば、ホットプレート上でソフトベーク（前焼成）を行った後に、オーブン中で焼成（アニーリング）を行う２段階工程とすることができる。 Next, after coating the coating solution on the substrate, the substrate is baked to form a light absorption layer.
Firing conditions can be appropriately set according to the desired film thickness, material type, and the like. For example, it can be a two-stage process in which baking (annealing) is performed in an oven after soft baking (pre-baking) on a hot plate.
　この場合、例えば、ホットプレート上に、基体を配置して保持した後、ホットプレートの温度を１００～５００℃として１～３００秒ソフトベークを行い、基体を室温付近まで冷却した後、再び塗布を行う。所望の膜厚が得られた後、ホットプレートまたはオーブン内部をを３００～７００℃に上昇させて１～１８０分間保持することでアニーリングを行う。
これにより、光吸収層が硬化される。 In this case, for example, after placing and holding the substrate on a hot plate, the temperature of the hot plate is set to 100 to 500 ° C., and soft baking is performed for 1 to 300 seconds, the substrate is cooled to near room temperature, and then coated again. Do. After the desired film thickness is obtained, annealing is performed by raising the inside of the hot plate or oven to 300 to 700 ° C. and holding for 1 to 180 minutes.
Thereby, the light absorption layer is cured.
　なお、上記焼成の各温度は、一条件を示したものであり、これに限られるものではない。例えば、ホットプレートの温度は段階的に上げてもよいし、これらの加熱工程はグローブボックス中の不活性ガス雰囲気下で行ってもよい。また、硫化水素、セレン化水素、固体硫黄、固体セレンをソフトベイク、アニール時に雰囲気中に共存させてもよい。 In addition, each temperature of the said baking shows one condition, and is not restricted to this. For example, the temperature of the hot plate may be increased stepwise, and these heating steps may be performed in an inert gas atmosphere in a glove box. Further, hydrogen sulfide, hydrogen selenide, solid sulfur, and solid selenium may be coexisted in the atmosphere during soft baking and annealing.
　本発明の太陽電池の製造方法において、太陽電池はカルコパイライト系太陽電池又はケステライト系太陽電池であることが好ましい。その場合、光吸収層は、前記一般式（１）又は（２）で表される化合物を含むことが好ましい。 In the method for producing a solar cell of the present invention, the solar cell is preferably a chalcopyrite solar cell or a kesterite solar cell. In that case, it is preferable that a light absorption layer contains the compound represented by the said General formula (1) or (2).
　前記調製方法（ＩＩＩ）により調製した２以上の金属錯体溶液を用いる場合、第１の錯体溶液を基体に塗布し、ベークして第１層を形成し、次いで第１の錯体溶液とは異なる金属組成を有する第２の錯体溶液を第１層に塗布し、ベークして第２層を形成できる。その後、第１層及び第２層をアニールすることにより、所望の組成を有する単一の光吸収層又は所望の金属組成比勾配を有する多層光吸収層を形成することができる。この場合、光吸収層における金属の配列を確実にデザインでき、光吸収層の構造を確実に制御できることが期待される。 When two or more metal complex solutions prepared by the preparation method (III) are used, the first complex solution is applied to a substrate, baked to form a first layer, and then a metal different from the first complex solution A second complex solution having a composition can be applied to the first layer and baked to form the second layer. Thereafter, by annealing the first layer and the second layer, a single light absorption layer having a desired composition or a multilayer light absorption layer having a desired metal composition ratio gradient can be formed. In this case, it is expected that the arrangement of metals in the light absorption layer can be reliably designed and the structure of the light absorption layer can be reliably controlled.
　以上のようにして、本実施形態の太陽電池を製造することができる。そして、本実施形態の製造方法によって製造された太陽電池は、光吸収層形成用塗布液にヒドラジンが含まれていないので、プロセスの安全性が向上する。 As described above, the solar cell of this embodiment can be manufactured. And since the solar cell manufactured with the manufacturing method of this embodiment does not contain hydrazine in the coating liquid for light absorption layer formation, the safety | security of a process improves.
　以上、本発明を実施形態に基づき説明したが、本発明は、上記実施形態に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能であることは言うまでもない。
　上記実施形態では、光吸収層形成用塗布液の調製方法として、調製方法（Ｉ）、調製方法（ＩＩ）及び調製方法（ＩＩＩ）について説明したが、本発明はこれらに限定されるものではない。例えば、一部の金属成分については金属前駆体を調製しておき、調製した金属錯体と、他の金属成分と、カルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素と、その他所望の成分とを混合することもできる。また、例えば調製方法（ＩＩ）において、一部の原料を先に混合した後に、残りの原料を添加することもできる。 As mentioned above, although this invention was demonstrated based on embodiment, it cannot be overemphasized that this invention can be variously changed in the range which is not limited to the said embodiment and does not deviate from the summary.
In the said embodiment, although preparation method (I), preparation method (II), and preparation method (III) were demonstrated as a preparation method of the coating liquid for light absorption layer formation, this invention is not limited to these. . For example, a metal precursor is prepared for some metal components, the prepared metal complex, other metal components, a chalcogen element-containing organic compound, a Lewis basic inorganic compound, a Group 16 element, Other desired components can also be mixed. Further, for example, in the preparation method (II), after a part of the raw materials are mixed first, the remaining raw materials can be added.
　次に、実施例により本発明をさらに詳細に説明するが、本発明はこれらの例によって限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
　＜反応液の調製＞
　（実施例１）
　Ｃｕ１．３１１ｇ（２０ｍｍｏｌ）、Ｓｅ６．３１７ｇ（８０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）及びジメチルスルホキシド（ＤＭＳＯ）２５．４７４ｇを混合し、２３℃で３日間撹拌後Ｃｕ反応液を得た。 <Preparation of reaction solution>
(Example 1)
Cu 1.311 g (20 mmol), Se 6.317 g (80 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and dimethyl sulfoxide (DMSO) 25.474 g were mixed. After stirring at 23 ° C. for 3 days, a Cu reaction solution was obtained.
　（実施例２－１）
　Ｚｎ１．３０８ｇ（２０ｍｍｏｌ）Ｓｅ２．３６９ｇ（３０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）及び水１９．４２５ｇを混合し、２３℃で３日間撹拌後、Ｚｎ反応液を得た。 Example 2-1
Zn 1.308 g (20 mmol) Se 2.369 g (30 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ), and 19.425 g of water were mixed and mixed at 23 ° C. After stirring for days, a Zn reaction solution was obtained.
　（実施例２－２）
　ＺｎＯ１．６２８ｇ（２０ｍｍｏｌ）、Ｓｅ２．３６９ｇ（３０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）及び水１９．４２５ｇを混合し、２３℃で３日間撹拌後、Ｚｎ反応液を得た。 (Example 2-2)
ZnO 1.628 g (20 mmol), Se 2.369 g (30 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and 19.425 g of water were mixed at 23 ° C. After stirring for 3 days, a Zn reaction solution was obtained.
　（実施例３）
　Ｓｎ２．３７４ｇ（２０ｍｍｏｌ）、Ｓｅ５．５２７ｇ（７０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）、水１５．２０１ｇを混合し、２３℃で３日間撹拌後に、Ｓｎ反応液を得た。 (Example 3)
Sn2.374 g (20 mmol), Se5.527 g (70 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ), and water 15.201 g were mixed at 23 ° C. After stirring for 3 days, an Sn reaction solution was obtained.
　（実施例４－１）
　Ｉｎ（ＯＨ）３３．３１７ｇ（２０ｍｍｏｌ）、Ｓｅ３．９４８ｇ（５０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）及び水１５．８３７ｇを混合し、２３℃で３日間撹拌後、Ｉｎ反応液を得た。 Example 4-1
In (OH) 3 3.317 g (20 mmol), Se 3.948 g (50 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and water 15.837 g are mixed. After stirring at 23 ° C. for 3 days, an In reaction solution was obtained.
　（実施例４－２）
　Ｉｎ２Ｏ３５．５５２ｇ（２０ｍｍｏｌ）、Ｓｅ３．９４８ｇ（５０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）及び水１５．８３７ｇを混合し、２３℃で３日間撹拌後、Ｉｎ反応液を得た。 (Example 4-2)
In 2 O 3 5.552 g (20 mmol), Se 3.948 g (50 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and water 15.837 g were mixed. After stirring at 23 ° C. for 3 days, an In reaction solution was obtained.
　（実施例５－１）
　Ｇａ１．３９４ｇ（２０ｍｍｏｌ）、Ｓｅ３．９４８ｇ（５０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）及び水１７．７５９ｇを混合し、２３℃で３日間撹拌後、Ｇａ反応液を得た。 Example 5-1
Ga1.394 g (20 mmol), Se 3.948 g (50 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and 17.759 g of water are mixed at 23 ° C. After stirring for 3 days, a Ga reaction solution was obtained.
　（実施例５－２）
　Ｇａ２Ｏ３３．７４９ｇ（２０ｍｍｏｌ）、Ｓｅ３．９４８ｇ（５０ｍｍｏｌ）、チオグリセロール１０．８１６ｇ（１００ｍｍｏｌ）、ＮＨ３２８％水溶液６．０８２ｇ（ＮＨ３換算で１００ｍｍｏｌ）及び水１７．７５９ｇを混合し、２３℃で３日間撹拌後、Ｇａ反応液を得た。 (Example 5-2)
Ga 2 O 3 3.749 g (20 mmol), Se 3.948 g (50 mmol), thioglycerol 10.816 g (100 mmol), NH 3 28% aqueous solution 6.082 g (100 mmol in terms of NH 3 ) and 17.759 g of water were mixed. After stirring at 23 ° C. for 3 days, a Ga reaction solution was obtained.
　（実施例６－１）
　Ｓｂ１．２１８ｇ（１０ｍｍｏｌ）、Ｓｅ１．９７４ｇ（２５ｍｍｏｌ）、チオグリセロール５．４０８ｇ（５０ｍｍｏｌ）、ＮＨ３２８％水溶液３．０４１ｇ（ＮＨ３換算で５０ｍｍｏｌ）及び水８．３５９ｇを混合し、２３℃で３日間撹拌後、Ｓｂ反応液を得た。 Example 6-1
Sb1.218 g (10 mmol), Se 1.974 g (25 mmol), thioglycerol 5.408 g (50 mmol), NH 3 28% aqueous solution 3.041 g (50 mmol in terms of NH 3 ) and water 8.359 g were mixed at 23 ° C. After stirring for 3 days, an Sb reaction solution was obtained.
　（実施例６－２）
　Ｓｂ２Ｏ３２．９１６ｇ（１０ｍｍｏｌ）、Ｓｅ１．９７４ｇ（２５ｍｍｏｌ）、チオグリセロール５．４０８ｇ（５０ｍｍｏｌ）、ＮＨ３２８％水溶液３．０４１ｇ（ＮＨ３換算で５０ｍｍｏｌ）及び水８．３５９ｇを混合し、２３℃で３日間攪拌後、Ｓｂ反応液を得た。 (Example 6-2)
2.916 g (10 mmol) of Sb 2 O 3 , 1.974 g (25 mmol) of Se, 5.408 g (50 mmol) of thioglycerol, 3.041 g of NH 3 28% aqueous solution (50 mmol in terms of NH 3 ) and 8.359 g of water were mixed. After stirring at 23 ° C. for 3 days, an Sb reaction solution was obtained.
　＜反応液の精製＞
　（実施例７）
　実施例１で調製したＣｕ反応液に過剰のイソプロピルアルコールを添加して沈殿物を生成し、遠心分離（５０００ｒｐｍ、１０ｍｉｎ）後に上澄み液を取り除き、再度イソプロピルアルコールを添加する工程を３回行った。さらに減圧乾燥を一晩行い、粉末固体のＣｕ金属錯体１を得た。 <Purification of reaction solution>
(Example 7)
Excess isopropyl alcohol was added to the Cu reaction solution prepared in Example 1 to produce a precipitate, the supernatant was removed after centrifugation (5000 rpm, 10 min), and isopropyl alcohol was added again three times. Further, drying under reduced pressure was performed overnight to obtain powdered solid Cu metal complex 1.
　（実施例８－１）
　実施例２－１で調製したＺｎ反応液に過剰のアセトンを添加することで沈殿物を生成し、遠心分離（５０００ｒｐｍ，１０ｍｉｎ）後に上澄み液を取り除き、再度アセトンを添加する工程を３回行った。さらに減圧乾燥を一晩行い、粉末固体のＺｎ金属錯体１を得た。 Example 8-1
Excess acetone was added to the Zn reaction solution prepared in Example 2-1 to generate a precipitate. After centrifugation (5000 rpm, 10 min), the supernatant was removed, and acetone was added again three times. . Further, drying under reduced pressure was carried out overnight to obtain powdered Zn metal complex 1.
　（実施例８－２）
　実施例２－２で調製したＺｎ反応液に過剰のアセトンを添加することで沈殿物を生成し、遠心分離（５０００ｒｐｍ，１０ｍｉｎ）後に上澄み液を取り除き、再度アセトンを添加する工程を３回行った。さらに減圧乾燥を一晩行い、粉末固体のＺｎ金属錯体２を得た。 (Example 8-2)
Excess acetone was added to the Zn reaction solution prepared in Example 2-2 to generate a precipitate. After centrifugation (5000 rpm, 10 min), the supernatant was removed, and acetone was added again three times. . Further, drying under reduced pressure was carried out overnight to obtain powdered solid Zn metal complex 2.
　（実施例９）
　実施例２－１で調製したＺｎ反応液の替わりに実施例３で調製したＳｎ前駆体溶液を用いた以外は実施例８－１と同様の操作を行い、粉末固体のＳｎ金属錯体１を得た。 Example 9
A powdered Sn metal complex 1 was obtained in the same manner as in Example 8-1, except that the Sn precursor solution prepared in Example 3 was used instead of the Zn reaction solution prepared in Example 2-1. It was.
　（実施例１０－１）
　実施例２－１で調製したＺｎ反応液の替わりに実施例４－１で調製したＩｎ反応液を用いた以外は実施例８－１と同様の操作を行い、粉末固体のＩｎ金属錯体１を得た。 (Example 10-1)
The same procedure as in Example 8-1 was performed except that the In reaction solution prepared in Example 4-1 was used instead of the Zn reaction solution prepared in Example 2-1, and the powdered solid In metal complex 1 was obtained. Obtained.
　（実施例１０－２）
　実施例２－１で調製したＺｎ反応液の替わりに実施例４－２で調製したＩｎ反応液を用いた以外は実施例８－１と同様の操作を行い、粉末固体のＩｎ金属錯体２を得た。 (Example 10-2)
The same procedure as in Example 8-1 was performed except that the In reaction solution prepared in Example 4-2 was used instead of the Zn reaction solution prepared in Example 2-1, and the powdered solid In metal complex 2 was obtained. Obtained.
　（実施例１１－１）
　実施例２－１で調製したＺｎ反応液の替わりに実施例５－１で調製したＧａ反応液を用いた以外は実施例８－１と同様の操作を行い、粉末固体のＧａ金属錯体１を得た。 (Example 11-1)
The same procedure as in Example 8-1 was carried out except that the Ga reaction solution prepared in Example 5-1 was used instead of the Zn reaction solution prepared in Example 2-1, and the powder solid Ga metal complex 1 was obtained. Obtained.
　（実施例１１－２）
　実施例２－１で調製したＺｎ反応液の替わりに実施例５－２で調製したＧａ反応液を用いた以外は実施例８－１と同様の操作を行い、粉末固体のＧａ金属錯体２を得た。 (Example 11-2)
The same procedure as in Example 8-1 was performed except that the Ga reaction solution prepared in Example 5-2 was used instead of the Zn reaction solution prepared in Example 2-1, and the powdered solid Ga metal complex 2 was obtained. Obtained.
　（実施例１２－１）
　実施例２－１で調製したＺｎ反応液の替わりに実施例６－１で調製したＳｂ前駆体溶液を用いた以外は実施例８－１と同様の操作を行い、粉末固体のＳｂ金属錯体１を得た。 (Example 12-1)
A powdered solid Sb metal complex 1 was prepared in the same manner as in Example 8-1, except that the Sb precursor solution prepared in Example 6-1 was used instead of the Zn reaction solution prepared in Example 2-1. Got.
　（実施例１２－２）
　実施例２－１で調製したＺｎ反応液の替わりに実施例６－２で調製したＳｂ前駆体溶液を用いた以外は実施例８－１と同様の操作を行い、粉末固体のＳｂ金属錯体２を得た。 (Example 12-2)
A powdered solid Sb metal complex 2 was prepared in the same manner as in Example 8-1, except that the Sb precursor solution prepared in Example 6-2 was used instead of the Zn reaction solution prepared in Example 2-1. Got.
　［ＩＣＰ測定］
　実施例７、実施例８－１、実施例９、実施例１０－１、実施例１１－１、及び実施例１２－１で精製した各金属錯体（粉末固体）を王水に溶解し、水で希釈後ＩＣＰ測定を行った。ＩＣＰ測定結果から各金属錯体の金属、セレン、硫黄のモル比を計算した。なお、硫黄はチオグリセロールに由来する。結果を表１に示す。 [ICP measurement]
Each metal complex (powder solid) purified in Example 7, Example 8-1, Example 9, Example 10-1, Example 11-1, and Example 12-1 was dissolved in aqua regia and water was added. The ICP measurement was performed after dilution. From the ICP measurement results, the molar ratio of metal, selenium, and sulfur of each metal complex was calculated. Sulfur is derived from thioglycerol. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　いずれの金属錯体も、反応工程ではチオグリセロールの量がセレンの量より大きいが、最終的に得られた金属錯体はいずれもセレンの含有量がチオグリセロールの含有量より大きいことが確認された
　これは、金属錯体の反応工程において、チオグリセロールがセレンの還元剤として作用し、イオン化セレンが金属に配位するためと推測される。 In any reaction, the amount of thioglycerol was greater than the amount of selenium in the reaction process, but the final metal complexes were confirmed to have a selenium content greater than that of thioglycerol. This is presumably because thioglycerol acts as a selenium reducing agent and ionized selenium coordinates to the metal in the reaction step of the metal complex.
　＜金属錯体溶液の調製＞
　（実施例１３）
　実施例７～１２で得られた各金属錯体の熱重量測定を行い、５００℃時点の残渣量を固形分と仮定した。
　実施例７～１２で得られた各金属錯体をそれぞれ固形分濃度１０％になるようにＤＭＳＯに溶解し、０．１ｕｍ　ＰＴＦＥフィルタでろ過して金属錯体溶液をそれぞれ調製した（Ｃｕ金属錯体１溶液、Ｚｎ金属錯体１溶液、Ｚｎ金属錯体２溶液、Ｓｎ金属錯体１溶液、Ｉｎ金属錯体１溶液、Ｉｎ金属錯体２溶液、Ｇａ金属錯体１溶液、Ｇａ金属錯体２溶液、Ｓｂ金属錯体１溶液及びＳｂ金属錯体２溶液）。 <Preparation of metal complex solution>
(Example 13)
Each metal complex obtained in Examples 7 to 12 was subjected to thermogravimetry, and the amount of residue at 500 ° C. was assumed to be solid.
Each metal complex obtained in Examples 7 to 12 was dissolved in DMSO so as to have a solid content concentration of 10%, and filtered through a 0.1 um PTFE filter to prepare a metal complex solution (Cu metal complex 1 solution). Zn metal complex 1 solution, Zn metal complex 2 solution, Sn metal complex 1 solution, In metal complex 1 solution, In metal complex 2 solution, Ga metal complex 1 solution, Ga metal complex 2 solution, Sb metal complex 1 solution and Sb Metal complex 2 solution).
　＜光吸収層形成用塗布液の調製＞
　（実施例１４）
　実施例１３で作成したＣｕ金属錯体１溶液と、Ｚｎ金属錯体１溶液と、Ｓｎ金属錯体１溶液とを、金属比率がＣｕ／（Ｚｎ＋Ｓｎ）＝０．７８、Ｚｎ／（Ｚｎ＋Ｓｎ）＝０．５１、Ｓｎ／（Ｚｎ＋Ｓｎ）＝０．４９になるよう混合し、ＣＺＴＳ塗布液を調製した。 <Preparation of coating solution for forming light absorption layer>
(Example 14)
The metal ratio of Cu / (Zn + Sn) = 0.78 and Zn / (Zn + Sn) = 0.51 in the Cu metal complex 1 solution, Zn metal complex 1 solution, and Sn metal complex 1 solution prepared in Example 13. , Sn / (Zn + Sn) = 0.49 was mixed to prepare a CZTS coating solution.
　（実施例１５）
　実施例１３で作成したＣｕ金属錯体１溶液と、Ｉｎ金属錯体１溶液と、Ｇａ金属錯体１溶液とを、金属比率がＣｕ／（Ｉｎ＋Ｇａ）＝０．９２、Ｉｎ／（Ｉｎ＋Ｇａ）＝０．７２、Ｇａ／（Ｉｎ＋Ｇａ）＝０．２８になるよう混合した。
　さらに、実施例１３で作成したＳｂ金属錯体１溶液をＳｂ／（Ｃｕ＋Ｉｎ＋Ｇａ）＝０．００５（５ａｔｏｍｉｃ％）になるよう混合し、ＣＩＧＳ塗布液を調製した。 (Example 15)
In the Cu metal complex 1 solution, the In metal complex 1 solution, and the Ga metal complex 1 solution prepared in Example 13, the metal ratios are Cu / (In + Ga) = 0.92, In / (In + Ga) = 0.72. , Ga / (In + Ga) = 0.28.
Further, the Sb metal complex 1 solution prepared in Example 13 was mixed so that Sb / (Cu + In + Ga) = 0.005 (5 atomic%) to prepare a CIGS coating solution.
　＜光吸収層の形成＞
　（実施例１６）
　実施例１４で調製したＣＺＴＳ塗布液をＭｏ蒸着したガラス基板上に塗布し、４００℃で３分間のソフトベイクを行った。この工程を合計１５回行った後、少量のセレン存在下で、５８０℃で１０分間アニーリングを行うことにより、ＣＺＴＳ層が成膜されたＣＺＴＳ基板を作成した。
　上記で作成したＣＺＴＳ基板をＳＥＭで観察したところ、ＣＺＴＳのグレイン成長が確認された。
　更に、上記で作成したＣＺＴＳ基板をＸＲＤ測定したところ、２θ＝約２７゜、４５゜および５３～５４゜にそれぞれ、ＣＺＴＳの（１１２）面、（２２０）／（２０４）面、（３１２）／（１１６）面に相当する強いピークが確認された。これらはスパッタ法（Ｒ．　Ａ．　Ｗｉｂｏｗｏ　ｅｔ　ａｌ．，　Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｙｓｉｃｓ　ａｎｄ　Ｃｈｅｍｉｓｔｒｙ　ｏｆ　Ｓｏｌｉｄｓ，　６８，　１９０８－１９１３　（２００７））や同時蒸着法（Ｇ．　Ｓ．　Ｂａｂｕ　ｅｔ　ａｌ，　Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｙｓｉｃｓ　Ｄ：　Ａｐｐｌｉｅｄ　Ｐｈｙｓｉｃｓ，　４１，　２０５３０５　（２００８）およびＧ．　Ｓ．　Ｂａｂｕ　ｅｔ　ａｌ，　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ，　２３，　０８５０２３　（２００８））などの真空法にて報告されているＸＲＤ測定結果と良い一致を示すことから、ＣＺＴＳ膜の生成を確認した。 <Formation of light absorption layer>
(Example 16)
The CZTS coating solution prepared in Example 14 was applied on a Mo-deposited glass substrate, and soft baking was performed at 400 ° C. for 3 minutes. After performing this step 15 times in total, annealing was performed at 580 ° C. for 10 minutes in the presence of a small amount of selenium, thereby producing a CZTS substrate on which a CZTS layer was formed.
When the CZTS substrate prepared above was observed with an SEM, grain growth of CZTS was confirmed.
Further, when the CZTS substrate prepared above was measured by XRD, 2θ = about 27 °, 45 ° and 53-54 °, respectively, the (112) plane, (220) / (204) plane, (312) / A strong peak corresponding to the (116) plane was confirmed. These include sputtering (R. A. Wibowo et al., Journal of Physics and Chemistry of Solids, 68, 1908-1913 (2007)) and co-evaporation (G. S. Buba et al. Physics, 41, 205305 (2008) and GS Babu et al, Semiconductor Science and Technology, 23, 085023 (2008)), etc., show good agreement with the results of XRD measurement. Formation of a CZTS film was confirmed.
　（実施例１７）
　実施例１５で作成したＣＩＧＳ塗布液をＭｏ蒸着したガラス基板上に塗布し、３００℃で３分間のソフトベイクを行った。この工程を合計１５回行った後、少量のセレン存在下で、５４０℃で３０分間アニーリングを行うことにより、ＣＩＧＳ層が成膜されたＣＩＧＳ基板を作成した。
　上記で作成したＣＩＧＳ基板をＳＥＭで観察したところ、ＣＩＧＳのグレイン成長が確認された。
　更に、上記で作成したＣＩＧＳ基板をＸＲＤ測定したところ、２θ＝約２７゜、４５゜および５２～５３゜にそれぞれ、ＣＩＧＳの（１１２）面、（２２０）／（２０４）面、（３１２）／（１１６）面に相当する強いピークが確認された。これらは既存のＣＩＧＳ膜の結果（Ｓｏｕｉｌａｈ，　Ｍ．　，　Ｌａｆｏｎｄ，　Ａ．　，　Ｇｕｉｌｌｏｔ　Ｄｅｕｄｏｎ，　Ｃ．　，　Ｈａｒｅｌ，　Ｓ．　，　　Ｅｖａｉｎ，　Ｍ．　Ｊ．Ｓｏｌｉｄ　Ｓｔａｔｅ　Ｃｈｅｍ．　１８３　（２０１０）　２２７４）と良い一致を示すことから、ＣＩＧＳ膜の生成を確認した。 (Example 17)
The CIGS coating solution prepared in Example 15 was applied on a Mo-deposited glass substrate, and soft baking was performed at 300 ° C. for 3 minutes. After performing this process 15 times in total, annealing was performed at 540 ° C. for 30 minutes in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed.
When the CIGS substrate created above was observed with an SEM, the grain growth of CIGS was confirmed.
Further, when the CIGS substrate prepared above was measured by XRD, the CIGS (112) plane, (220) / (204) plane, (312) / 3 ° were 2θ = about 27 °, 45 ° and 52-53 °, respectively. A strong peak corresponding to the (116) plane was confirmed. These are the results of existing CIGS films (Souilah, M., Lafondo, A., Guillot Deudon, C., Harel, S., Evain, M. J. Solid State Chem. 183 (2010) 2274). As shown, the generation of the CIGS film was confirmed.
　＜光吸収層形成用塗布液の調製＞
　（実施例１８）
実施例１３で作成したＣｕ金属錯体１溶液と、Ｉｎ金属錯体１溶液と、Ｇａ金属錯体１溶液とを、金属比率がＣｕ／（Ｉｎ＋Ｇａ）＝０．９２、Ｉｎ／（Ｉｎ＋Ｇａ）＝０．７２、Ｇａ／（Ｉｎ＋Ｇａ）＝０．２８になるよう混合した。 <Preparation of coating solution for forming light absorption layer>
(Example 18)
In the Cu metal complex 1 solution, the In metal complex 1 solution, and the Ga metal complex 1 solution prepared in Example 13, the metal ratios are Cu / (In + Ga) = 0.92, In / (In + Ga) = 0.72. , Ga / (In + Ga) = 0.28.
　（実施例１９）
　更にＮａ１．０ａｔｏｍｉｃ％を混合したこと以外は実施例１８と同様にしてＣＩＧＳ塗布液を調製した。 (Example 19)
Further, a CIGS coating solution was prepared in the same manner as in Example 18 except that Na 1.0 atomic% was mixed.
　（比較例１）
　米国公開公報２０１２－００７０９３７号の実施例を参照してＣＩＧＳ塗布液を調製した。ベンゼンセレノール４．９４９ｇ（４７．１ｍｍｏｌ）とピリジン３．７２６ｇ（４７．１ｍｍｏｌ）とを混合して混合溶媒を調製した。この混合溶媒に、固形分濃度１４％、金属比率がＣｕ／（Ｉｎ＋Ｇａ）＝０．７８、Ｉｎ／（Ｉｎ＋Ｇａ）＝０．６０、Ｇａ／（Ｉｎ＋Ｇａ）＝０．４０となるように、Ｃｕ０．２３０ｇ（３．６１９ｍｍｏｌ）と、Ｉｎ０．３２０ｇ　（２．７８７ｍｍｏｌ）と、Ｇａ０．１３０ｇ（１．８６５ｍｍｏｌ）と、Ｓｅ０．７２０ｇ（９．１１９ｍｍｏｌ）とを混合し、室温で２週間撹拌した。
　得られた溶液の上澄み液の金属比率をＩＣＰで確認したところ、Ｃｕ／（Ｉｎ＋Ｇａ）＝０．９３、Ｉｎ／（Ｉｎ＋Ｇａ）＝０．６２、Ｇａ／（Ｉｎ＋Ｇａ）＝０．３８であった。 (Comparative Example 1)
A CIGS coating solution was prepared with reference to Examples in US Publication No. 2012-0070937. A mixed solvent was prepared by mixing 4.949 g (47.1 mmol) of benzeneselenol and 3.726 g (47.1 mmol) of pyridine. In this mixed solvent, Cu 0 .. so that the solid content concentration was 14%, the metal ratio was Cu / (In + Ga) = 0.78, In / (In + Ga) = 0.60, and Ga / (In + Ga) = 0.40. 230 g (3.619 mmol), In 0.320 g (2.787 mmol), Ga 0.130 g (1.865 mmol), and Se 0.720 g (9.119 mmol) were mixed and stirred at room temperature for 2 weeks.
When the metal ratio of the supernatant of the obtained solution was confirmed by ICP, it was Cu / (In + Ga) = 0.93, In / (In + Ga) = 0.62, and Ga / (In + Ga) = 0.38.
　＜光吸収層の形成＞
　（実施例２０）
　実施例１８で調製したＣＩＧＳ塗布液をＭｏ蒸着したガラス基板上に塗布し、１２０℃で１分間、３００℃で３分間ソフトベイクを行って膜厚約０．３μｍの塗布膜を形成した。この工程を合計５回行った後、少量のセレン存在下で、５４０℃で３０分間アニーリングを行うことにより、ＣＩＧＳ層が成膜されたＣＩＧＳ基板を作成した。 <Formation of light absorption layer>
(Example 20)
The CIGS coating solution prepared in Example 18 was coated on a Mo-deposited glass substrate, and soft-baked at 120 ° C. for 1 minute and 300 ° C. for 3 minutes to form a coating film having a thickness of about 0.3 μm. After performing this process 5 times in total, annealing was performed at 540 ° C. for 30 minutes in the presence of a small amount of selenium, thereby producing a CIGS substrate on which a CIGS layer was formed.
　（実施例２１）
　実施例１８で調製したＣＩＧＳ塗布液の替わりに実施例１９で調製したＣＩＧＳ塗布液を用いた以外は実施例２０と同様にＣＩＧＳ層が成膜されたＣＩＧＳ基板を作成した。 (Example 21)
A CIGS substrate having a CIGS layer formed thereon was prepared in the same manner as in Example 20 except that the CIGS coating solution prepared in Example 19 was used instead of the CIGS coating solution prepared in Example 18.
　（比較例２）
　比較例１で調製したＣＩＧＳ塗布液をＭｏ蒸着したガラス基板上に塗布し、１２０℃で１分間、３００℃で３分間ソフトベイクを行った。その後、少量のセレン存在下で、５４０℃で３０分間アニーリングを行うことにより、ＣＩＧＳ層が成膜されたＣＩＧＳ基板を作成した。 (Comparative Example 2)
The CIGS coating solution prepared in Comparative Example 1 was coated on a Mo-deposited glass substrate and soft-baked at 120 ° C. for 1 minute and at 300 ° C. for 3 minutes. Then, the CIGS board | substrate with which the CIGS layer was formed was created by performing annealing for 30 minutes at 540 degreeC in the presence of a small amount of selenium.
　（比較例３）
　比較例１で調製したＣＩＧＳ塗布液をＭｏ蒸着したガラス基板上に塗布し、１２０℃で１分間、３００℃で３分間ソフトベイクを行った。この工程を合計２回行った後、少量のセレン存在下で、５４０℃で３０分間アニーリングを行うことにより、ＣＩＧＳ層が成膜されたＣＩＧＳ基板を作成した。 (Comparative Example 3)
The CIGS coating solution prepared in Comparative Example 1 was coated on a Mo-deposited glass substrate and soft-baked at 120 ° C. for 1 minute and at 300 ° C. for 3 minutes. After performing this process twice in total, the CIGS substrate in which the CIGS layer was formed was produced by performing 30 minutes annealing at 540 degreeC in presence of a small amount of selenium.
　［ＸＲＤ測定］
　実施例２０～２１、比較例２～３で作成したＣＩＧＳ基板をＸＲＤ測定したところ、実施例２０～２１のＣＩＧＳ基板では、ＣＩＧＳの（１１２）面に相当するピークの強度が比較例２～３のＣＩＧＳ基板よりも強いことが確認された。実施例２０及び比較例２についてのＸＲＤ測定における膜厚、積分強度、半値幅を表２に示す。 [XRD measurement]
When the CIGS substrates prepared in Examples 20 to 21 and Comparative Examples 2 to 3 were subjected to XRD measurement, in the CIGS substrates of Examples 20 to 21, the peak intensity corresponding to the (112) plane of CIGS was in Comparative Examples 2 to 3. It was confirmed that it was stronger than the CIGS substrate. Table 2 shows the film thickness, integrated intensity, and full width at half maximum in XRD measurement for Example 20 and Comparative Example 2.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　［ラマン分光測定］
　実施例２０～２１、比較例２～３で作成したＣＩＧＳ基板について、ラマンスペクトルのアモルファス炭素ピークから有機物残存量を見積もったところ、実施例２０～２１のＣＩＧＳ基板では、有機物残存量が比較例２～３のＣＩＧＳ基板よりも少ないことが確認された。 [Raman spectroscopy measurement]
For the CIGS substrates prepared in Examples 20 to 21 and Comparative Examples 2 to 3, the remaining amount of organic substance was estimated from the amorphous carbon peak of the Raman spectrum. As a result, the remaining amount of organic substance in the CIGS substrates of Examples 20 to 21 was Comparative Example 2. It was confirmed that it was less than the CIGS substrate of ~ 3.
　＜反応液の調製（金属錯体塗布液）＞
　（実施例２２）
　３．１５８ｇ（４０ｍｍｏｌ）のＳｅ、１．５６３ｇ（２０ｍｍｏｌ）の２－メルカプトエタノール、３．０４１ｇの２８ｗｔ％ＮＨ３水溶液（ＮＨ３換算で５０ｍｍｏｌ）及び２２ｇのジメチルスルホキシド（ＤＭＳＯ）を混合し、２３℃で６時間撹拌した。その後、１．３１１ｇ（２０ｍｍｏｌ）のＣｕを反応液に添加し、２３℃で１日撹拌し、ＰＴＦＥ　０．４５ｕｍフィルターでろ過を行い、Ｃｕ反応液を得た。 <Preparation of reaction solution (metal complex coating solution)>
(Example 22)
3. 158 g (40 mmol) of Se, 1.563 g (20 mmol) of 2-mercaptoethanol, 3.041 g of 28 wt% NH 3 aqueous solution (50 mmol in terms of NH 3 ) and 22 g of dimethyl sulfoxide (DMSO) were mixed. Stir at 6 ° C. for 6 hours. Thereafter, 1.311 g (20 mmol) of Cu was added to the reaction solution, stirred at 23 ° C. for 1 day, and filtered through a PTFE 0.45 um filter to obtain a Cu reaction solution.
　（実施例２３）
　２．３６９ｇ（３０ｍｍｏｌ）のＳｅ、１．５６３ｇ（２０ｍｍｏｌ）の２－メルカプトエタノール、４．８６６ｇの２８ｗｔ％ＮＨ３水溶液（ＮＨ３換算で８０ｍｍｏｌ）及び１６ｇのジメチルスルホキシド（ＤＭＳＯ）を混合し、２３℃で６時間撹拌した。その後、１．３８ｇ（１２ｍｍｏｌ）のＩｎ及び０．８４ｇ（１２ｍｍｏｌ）のＧａを反応液に添加し、２３℃で３日撹拌し、ＰＴＦＥ　０．４５ｕｍフィルターでろ過を行い、Ｉｎ－Ｇａ反応液を得た。 (Example 23)
2.369 g (30 mmol) of Se, 1.563 g (20 mmol) of 2-mercaptoethanol, 4.866 g of 28 wt% NH 3 aqueous solution (80 mmol in terms of NH 3 ) and 16 g of dimethyl sulfoxide (DMSO) were mixed. Stir at 6 ° C. for 6 hours. Thereafter, 1.38 g (12 mmol) of In and 0.84 g (12 mmol) of Ga were added to the reaction solution, stirred at 23 ° C. for 3 days, filtered through a PTFE 0.45 um filter, and the In—Ga reaction solution was added. Obtained.
　（実施例２４）
　２．６８５ｇ（３４ｍｍｏｌ）のＳｅ、１．１１７ｇ（１４．３ｍｍｏｌ）の２－メルカプトエタノール、４．１３６ｇの２８ｗｔ％ＮＨ３水溶液（ＮＨ３換算で６８ｍｍｏｌ）及び１５ｇのジメチルスルホキシド（ＤＭＳＯ）を混合し、２３℃で６時間撹拌した。その後、０．２７９ｇ（４．２５ｍｍｏｌ）のＣｕ、０．４２ｇ（４ｍｍｏｌ）のＩｎ及び０．４６ｇ（６ｍｍｏｌ）のＧａを反応液に添加し、２３℃で１日撹拌した。その後、０．２７９ｇ（４．２５ｍｍｏｌ）のＣｕを添加し、２３℃で６時間、７０℃で１日の順で撹拌し、ＰＴＦＥ０．４５ｕｍフィルターでろ過を行い、金属比Ｃｕ／（Ｉｎ＋Ｇａ）＝０．８５、Ｉｎ／（Ｉｎ＋Ｇａ）＝０．４０、Ｇａ／（Ｉｎ＋Ｇａ）＝０．６０のＣｕ－Ｉｎ－Ｇａ反応液を得た。 (Example 24)
2. 685 g (34 mmol) of Se, 1.117 g (14.3 mmol) of 2-mercaptoethanol, 4.136 g of 28 wt% NH 3 aqueous solution (68 mmol in terms of NH 3 ) and 15 g of dimethyl sulfoxide (DMSO) were mixed. , And stirred at 23 ° C. for 6 hours. Thereafter, 0.279 g (4.25 mmol) of Cu, 0.42 g (4 mmol) of In and 0.46 g (6 mmol) of Ga were added to the reaction solution and stirred at 23 ° C. for 1 day. Thereafter, 0.279 g (4.25 mmol) of Cu was added, stirred at 23 ° C. for 6 hours and then at 70 ° C. for 1 day, filtered through a PTFE 0.45 um filter, and the metal ratio Cu / (In + Ga) = A Cu—In—Ga reaction solution with 0.85, In / (In + Ga) = 0.40, and Ga / (In + Ga) = 0.60 was obtained.
　（実施例２５）
　２．６８５ｇ（３４ｍｍｏｌ）のＳｅ、１．１１７ｇ（１４．３ｍｍｏｌ）の２－メルカプトエタノール、４．１３６ｇの２８ｗｔ％ＮＨ３水溶液（ＮＨ３換算で６８ｍｍｏｌ）及び１５ｇのジメチルスルホキシド（ＤＭＳＯ）を混合し、２３℃で６時間撹拌した。その後、０．２７９ｇ（４．２５ｍｍｏｌ）のＣｕ、０．８０５ｇ（７ｍｍｏｌ）のＩｎ及び０．２１ｇ（３ｍｍｏｌ）のＧａを反応液に添加し、２３℃で１日撹拌した。その後、０．２７９ｇ（４．２５ｍｍｏｌ）のＣｕを添加し、２３℃で６時間、７０℃で１日の順で撹拌し、ＰＴＦＥ０．４５ｕｍフィルターでろ過を行い、金属比Ｃｕ／（Ｉｎ＋Ｇａ）＝０．８５、Ｉｎ／（Ｉｎ＋Ｇａ）＝０．７０、Ｇａ／（Ｉｎ＋Ｇａ）＝０．３０のＣｕ－Ｉｎ－Ｇａ反応液を得た。 (Example 25)
2. 685 g (34 mmol) of Se, 1.117 g (14.3 mmol) of 2-mercaptoethanol, 4.136 g of 28 wt% NH 3 aqueous solution (68 mmol in terms of NH 3 ) and 15 g of dimethyl sulfoxide (DMSO) were mixed. , And stirred at 23 ° C. for 6 hours. Thereafter, 0.279 g (4.25 mmol) of Cu, 0.805 g (7 mmol) of In and 0.21 g (3 mmol) of Ga were added to the reaction solution and stirred at 23 ° C. for 1 day. Thereafter, 0.279 g (4.25 mmol) of Cu was added, stirred at 23 ° C. for 6 hours and then at 70 ° C. for 1 day, filtered through a PTFE 0.45 um filter, and the metal ratio Cu / (In + Ga) = A Cu—In—Ga reaction solution with 0.85, In / (In + Ga) = 0.70, and Ga / (In + Ga) = 0.30 was obtained.
　［ＩＣＰ測定］
　実施例２２～２５で得られた各反応液（金属錯体）を王水に溶解し、水で希釈後ＩＣＰ測定を行った。ＩＣＰ測定結果から各金属錯体の金属及びセレンのモル比を計算した。結果を表３に示す。 [ICP measurement]
Each reaction solution (metal complex) obtained in Examples 22 to 25 was dissolved in aqua regia, diluted with water, and then subjected to ICP measurement. From the ICP measurement results, the molar ratio of metal and selenium of each metal complex was calculated. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　＜光吸収層の形成＞
　（実施例２６）
　実施例２２及び２３で調製した金属錯体塗布液（反応液）を用いて光吸収層を形成した。第１の工程において、Ｉｎ－Ｇａ錯体塗布液をＭｏ蒸着したガラス基板上に塗布し、３５０℃で２分間ソフトベイクを行った。第１の工程を８回繰り返し、Ｉｎ－Ｇａ錯体層を形成した。第２の工程において、Ｃｕ錯体塗布液をＩｎ－Ｇａ錯体層の上に塗布し、３５０℃で２分間ソフトベイクを行った。第２の工程を１０回繰り返し、Ｃｕ錯体層を形成した。第３の工程において、Ｉｎ－Ｇａ錯体塗布液をＣｕ錯体層の上に塗布し、３５０℃で２分間ソフトベイクを行った。第３の工程を２回繰り返した。第１の工程、第２の工程及び第３の工程における合計塗布工程数は２０回であった。次いで、少量のセレン存在下で、５９０℃で３０分間アニーリングを行うことにより、ＣＩＧＳ層が成膜されたＣＩＧＳ基板を作成した。 <Formation of light absorption layer>
(Example 26)
A light absorption layer was formed using the metal complex coating solution (reaction solution) prepared in Examples 22 and 23. In the first step, an In—Ga complex coating solution was coated on a Mo-deposited glass substrate and soft-baked at 350 ° C. for 2 minutes. The first step was repeated 8 times to form an In—Ga complex layer. In the second step, a Cu complex coating solution was coated on the In—Ga complex layer and soft baked at 350 ° C. for 2 minutes. The second step was repeated 10 times to form a Cu complex layer. In the third step, the In—Ga complex coating solution was coated on the Cu complex layer and soft baked at 350 ° C. for 2 minutes. The third step was repeated twice. The total number of coating steps in the first step, the second step, and the third step was 20 times. Next, annealing was performed at 590 ° C. for 30 minutes in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed.
　（実施例２７）
　実施例２４及び２５で調製した金属錯体塗布液（反応液）を用いて光吸収層を形成した。第１の工程において、実施例２４で得られたＣｕ－Ｉｎ－Ｇａ錯体塗布液をＭｏ蒸着したガラス基板上に塗布し、３５０℃で２分間ソフトベイクを行った。第１の工程を１０回繰り返し、第１のＣｕ－Ｉｎ－Ｇａ錯体層を形成した。第２の工程において、実施例２５で得られたＣｕ－Ｉｎ－Ｇａ錯体塗布液を第１のＣｕ－Ｉｎ－Ｇａ錯体層の上に塗布し、３５０℃で２分間ソフトベイクを行った。第２の工程を１０回繰り返し、第１のＣｕ－Ｉｎ－Ｇａ錯体層の上に第２のＣｕ－Ｉｎ－Ｇａ錯体層を形成した。第１の工程及び第２の工程における合計塗布工程数は２０回であった。次いで、少量のセレン存在下で、５９０℃で３０分間アニーリングを行うことにより、ＣＩＧＳ層が成膜されたＣＩＧＳ基板を作成した。　　　 (Example 27)
A light absorption layer was formed using the metal complex coating solution (reaction solution) prepared in Examples 24 and 25. In the first step, the Cu—In—Ga complex coating solution obtained in Example 24 was coated on a Mo-deposited glass substrate and soft baked at 350 ° C. for 2 minutes. The first step was repeated 10 times to form a first Cu—In—Ga complex layer. In the second step, the Cu—In—Ga complex coating solution obtained in Example 25 was applied on the first Cu—In—Ga complex layer, and soft baking was performed at 350 ° C. for 2 minutes. The second step was repeated 10 times to form a second Cu—In—Ga complex layer on the first Cu—In—Ga complex layer. The total number of coating steps in the first step and the second step was 20 times. Next, annealing was performed at 590 ° C. for 30 minutes in the presence of a small amount of selenium to produce a CIGS substrate on which a CIGS layer was formed.
　以上、本発明の好ましい実施例を説明したが、本発明はこれら実施例に限定されることはない。本発明の趣旨を逸脱しない範囲で、構成の付加、省略、置換、およびその他の変更が可能である。本発明は前述した説明によって限定されることはなく、添付のクレームの範囲によってのみ限定される。 The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention. The present invention is not limited by the above description, but only by the scope of the appended claims.

Claims (20)

  1. 　太陽電池の光吸収層の形成に用いられる錯体およびその溶液の製造方法であって、
    　第１１族金属、第１２族金属、第１３族金属、第１４族金属、第１５族元素、第１１族金属化合物、第１２族金属化合物、第１３族金属化合物、第１４族金属化合物及び第１５族元素含有化合物からなる群より選ばれる少なくとも１種の単体または化合物と、メルカプト基含有有機化合物、スルフィド、ポリスルフィド、チオカルボニル基含有有機化合物、硫黄含有複素環式化合物、ヒドロセレノ基含有有機化合物、セレニド、ポリセレニド、セレノカルボニル基含有有機化合物及びセレン含有複素環式化合物からなる群より選ばれる少なくとも１種のカルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して反応液を得ることを含む錯体およびその溶液の製造方法。     A method for producing a complex used for forming a light absorption layer of a solar cell and a solution thereof,
    Group 11 metal, Group 12 metal, Group 13 metal, Group 14 metal, Group 15 element, Group 11 metal compound, Group 12 metal compound, Group 13 metal compound, Group 14 metal compound and Group At least one element or compound selected from the group consisting of Group 15 element-containing compounds, mercapto group-containing organic compounds, sulfides, polysulfides, thiocarbonyl group-containing organic compounds, sulfur-containing heterocyclic compounds, hydroseleno group-containing organic compounds, A mixture of at least one chalcogen element-containing organic compound selected from the group consisting of selenide, polyselenide, selenocarbonyl group-containing organic compound and selenium-containing heterocyclic compound, a Lewis basic inorganic compound, and a Group 16 element A complex comprising obtaining a reaction solution and a method for producing the solution.
  2. 　前記太陽電池がカルコパイライト系太陽電池又はケステライト系太陽電池である請求項１に記載の錯体およびその溶液の製造方法。 The method for producing a complex and a solution thereof according to claim 1, wherein the solar cell is a chalcopyrite solar cell or a kesterite solar cell.
  3. 　前記反応液が、下記一般式（１）又は（２）で表される化合物を含有する請求項２に記載の錯体およびその溶液の製造方法。
    Figure JPOXMLDOC01-appb-C000001
     ［式中、０≦ｗ≦１、０≦ｘ≦１、０≦ｙ≦１、０＜ｚ≦１、Ａは少なくとも１種の１６族元素、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦１、及び－１≦ｄ≦１である。］     The complex according to claim 2, wherein the reaction solution contains a compound represented by the following general formula (1) or (2) and a method for producing the solution.
    Figure JPOXMLDOC01-appb-C000001
     [Wherein, 0 ≦ w ≦ 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 <z ≦ 1, A is at least one group 16 element, 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 1 and −1 ≦ d ≦ 1. ]
  4. 　第１１族金属、第１２族金属、第１３族金属、第１４族金属、第１５族元素、第１１族金属化合物、第１２族金属化合物、第１３族金属化合物、第１４族金属化合物及び第１５族元素含有化合物からなる群より選ばれる少なくとも２種の単体または化合物と、メルカプト基含有有機化合物、スルフィド、ポリスルフィド、チオカルボニル基含有有機化合物、硫黄含有複素環式化合物、ヒドロセレノ基含有有機化合物、セレニド、ポリセレニド、セレノカルボニル基含有有機化合物及びセレン含有複素環式化合物からなる群より選ばれる少なくとも１種のカルコゲン元素含有有機化合物と、ルイス塩基性無機化合物と、第１６族元素とを混合して反応液を得ることを含む請求項１～３のいずれか一項に記載の錯体およびその溶液の製造方法。 Group 11 metal, Group 12 metal, Group 13 metal, Group 14 metal, Group 15 element, Group 11 metal compound, Group 12 metal compound, Group 13 metal compound, Group 14 metal compound and Group At least two simple substances or compounds selected from the group consisting of Group 15 element-containing compounds, mercapto group-containing organic compounds, sulfides, polysulfides, thiocarbonyl group-containing organic compounds, sulfur-containing heterocyclic compounds, hydroseleno group-containing organic compounds, A mixture of at least one chalcogen element-containing organic compound selected from the group consisting of selenide, polyselenide, selenocarbonyl group-containing organic compound and selenium-containing heterocyclic compound, a Lewis basic inorganic compound, and a Group 16 element The complex according to any one of claims 1 to 3, which comprises obtaining a reaction solution, and a method for producing the solution.
  5. 　前記１６族元素が、Ｓ、Ｓｅから選ばれる少なくとも１種である請求項１～４のいずれか一項に記載の錯体およびその溶液の製造方法。 The method for producing a complex and a solution thereof according to any one of claims 1 to 4, wherein the group 16 element is at least one selected from S and Se.
  6. 　水の存在下で前記反応液を得る請求項１～５のいずれか一項に記載の錯体およびその溶液の製造方法。 The method for producing a complex and a solution thereof according to any one of claims 1 to 5, wherein the reaction solution is obtained in the presence of water.
  7. 　前記カルコゲン元素含有有機化合物がメルカプト基含有有機化合物、スルフィド、ポリスルフィド、チオカルボニル基含有有機化合物及び硫黄含有複素環式化合物からなる群より選ばれる少なくとも１種である請求項１～６のいずれか一項に記載の錯体およびその溶液の製造方法。 7. The chalcogen element-containing organic compound is at least one selected from the group consisting of mercapto group-containing organic compounds, sulfides, polysulfides, thiocarbonyl group-containing organic compounds, and sulfur-containing heterocyclic compounds. A method for producing the complex according to the item and a solution thereof.
  8. 　前記カルコゲン元素含有有機化合物がメルカプトエタノール、チオグリコール酸、アルキルチオールおよびチオグリセロールからなる群より選ばれる少なくとも１種である請求項１～７のいずれか一項に記載の錯体およびその溶液の製造方法。 The complex and the method for producing a solution thereof according to any one of claims 1 to 7, wherein the chalcogen element-containing organic compound is at least one selected from the group consisting of mercaptoethanol, thioglycolic acid, alkylthiol and thioglycerol. .
  9. 　前記ルイス塩基性無機化合物がアンモニアである請求項１～８のいずれか一項に記載の錯体およびその溶液の製造方法。 The method for producing a complex and a solution thereof according to any one of claims 1 to 8, wherein the Lewis basic inorganic compound is ammonia.
  10. 　　更にＮａ、Ｋ、Ｃｓ、Ｓｂ及びＢｉからなる群より選ばれる少なくとも１種を添加することを含む請求項１～９のいずれか一項に記載の錯体およびその溶液の製造方法。 The method for producing a complex and a solution thereof according to any one of claims 1 to 9, further comprising adding at least one selected from the group consisting of Na, K, Cs, Sb and Bi.
  11. 　請求項１～１０のいずれか一項に記載の錯体およびその溶液の製造方法により得られた溶液を、基体に塗布し、焼成することを特徴とする太陽電池用光吸収層の製造方法。 A method for producing a light-absorbing layer for a solar cell, comprising applying a solution obtained by the method of producing a complex according to any one of claims 1 to 10 and a solution thereof to a substrate and baking the substrate.
  12. 　前記太陽電池がカルコパイライト系太陽電池又はケステライト系太陽電池である請求項１１に記載の太陽電池用光吸収層の製造方法。 The method for producing a light absorption layer for a solar cell according to claim 11, wherein the solar cell is a chalcopyrite solar cell or a kesterite solar cell.
  13. 　前記光吸収層が、下記一般式（１）又は（２）で表される化合物を含有する請求項１２に記載の太陽電池用光吸収層の製造方法。
    Figure JPOXMLDOC01-appb-C000002
     ［式中、０≦ｗ≦１、０≦ｘ≦１、０≦ｙ≦１、０＜ｚ≦１、Ａは少なくとも１種の１６族元素、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦１、及び－１≦ｄ≦１である。］     The manufacturing method of the light absorption layer for solar cells of Claim 12 in which the said light absorption layer contains the compound represented by the following general formula (1) or (2).
    Figure JPOXMLDOC01-appb-C000002
     [Wherein, 0 ≦ w ≦ 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 <z ≦ 1, A is at least one group 16 element, 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 1 and −1 ≦ d ≦ 1. ]
  14. 　請求項１～１０のいずれか一項に記載の錯体およびその溶液の製造方法により得られた第１の錯体溶液を、基体に塗布し、焼成して第１層を形成し、
    　請求項１～１０のいずれか一項に記載の錯体およびその溶液の製造方法により得られた第２の錯体溶液を前記第１層に塗布し、焼成することを含み、
    　前記第１の錯体溶液および前記第２の錯体溶液が異なる金属組成を有する請求項１１～１３のいずれか一項に記載の太陽電池用光吸収層の製造方法。     The first complex solution obtained by the complex according to any one of claims 1 to 10 and the method for producing the solution thereof is applied to a substrate and baked to form a first layer,
    Applying the second complex solution obtained by the complex according to any one of claims 1 to 10 and the method for producing the solution to the first layer and baking the complex solution.
    The method for producing a solar cell light-absorbing layer according to any one of claims 11 to 13, wherein the first complex solution and the second complex solution have different metal compositions.
  15. 　請求項１～１０のいずれか一項に記載の錯体およびその溶液の製造方法により得られた第１の錯体溶液を、基体に塗布し、焼成して第１層を形成し、
    　請求項１～１０のいずれか一項に記載の錯体およびその溶液の製造方法により得られた第２の錯体溶液を前記第１層に塗布し、焼成することを含み、
    　前記第１の錯体溶液および前記第２の錯体溶液がそれぞれ第１１族金属、第１２族金属、第１３族金属、第１４族金属、第１５族元素、第１１族金属化合物、第１２族金属化合物、第１３族金属化合物、第１４族金属化合物及び第１５族元素含有化合物からなる群より選ばれる少なくとも２種の単体または化合物を含み、
    　前記第１の錯体溶液および前記第２の錯体溶液が同じ金属組成および異なる金属比率を有する請求項１１～１３のいずれか一項に記載の太陽電池用光吸収層の製造方法。     The first complex solution obtained by the complex according to any one of claims 1 to 10 and the method for producing the solution thereof is applied to a substrate and baked to form a first layer,
    Applying the second complex solution obtained by the complex according to any one of claims 1 to 10 and the method for producing the solution to the first layer and baking the complex solution.
    The first complex solution and the second complex solution are respectively Group 11 metal, Group 12 metal, Group 13 metal, Group 14 metal, Group 15 element, Group 11 metal compound, Group 12 metal. Including at least two kinds of simple substances or compounds selected from the group consisting of a compound, a Group 13 metal compound, a Group 14 metal compound and a Group 15 element-containing compound,
    The method for producing a solar cell light absorption layer according to any one of claims 11 to 13, wherein the first complex solution and the second complex solution have the same metal composition and different metal ratios.
  16. 　基板上に第１の電極を形成する工程と、
    　前記第１の電極上に、請求項１～１０のいずれか一項に記載の錯体およびその溶液の製造方法により得られた溶液を塗布し、焼成して光吸収層を形成する工程と、
    　前記光吸収層上にバッファ層を形成する工程と、
    　前記バッファ層上に第２の電極を形成する工程と、を有することを特徴とする太陽電池の製造方法。     Forming a first electrode on a substrate;
    Applying a solution obtained by the method of producing a complex according to any one of claims 1 to 10 and a solution thereof on the first electrode, and baking to form a light absorption layer;
    Forming a buffer layer on the light absorbing layer;
    And a step of forming a second electrode on the buffer layer.
  17. 　前記太陽電池がカルコパイライト系太陽電池又はケステライト系太陽電池である請求項１６に記載の太陽電池の製造方法。 The method for manufacturing a solar cell according to claim 16, wherein the solar cell is a chalcopyrite solar cell or a kesterite solar cell.
  18. 　前記反応液が、下記一般式（１）又は（２）で表される化合物を含有する請求項１７に記載の太陽電池の製造方法。
    Figure JPOXMLDOC01-appb-C000003
     ［式中、０≦ｗ≦１、０≦ｘ≦１、０≦ｙ≦１、０＜ｚ≦１、Ａは少なくとも１種の１６族元素、０≦ａ≦１、０≦ｂ≦１、０≦ｃ≦１、及び－１≦ｄ≦１である。］     The method for producing a solar cell according to claim 17, wherein the reaction solution contains a compound represented by the following general formula (1) or (2).
    Figure JPOXMLDOC01-appb-C000003
     [Wherein, 0 ≦ w ≦ 1, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 <z ≦ 1, A is at least one group 16 element, 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, 0 ≦ c ≦ 1 and −1 ≦ d ≦ 1. ]
  19. 　前記光吸収層が、請求項１４に記載の太陽電池用光吸収層の製造方法によって形成される請求項１６～１８のいずれか一項に記載の太陽電池の製造方法。 The method for manufacturing a solar cell according to any one of claims 16 to 18, wherein the light absorption layer is formed by the method for manufacturing a light absorption layer for a solar cell according to claim 14.
  20. 　前記光吸収層が、請求項１５に記載の太陽電池用光吸収層の製造方法によって形成される請求項１６～１８のいずれか一項に記載の太陽電池の製造方法。 The method for manufacturing a solar cell according to any one of claims 16 to 18, wherein the light absorption layer is formed by the method for manufacturing a light absorption layer for a solar cell according to claim 15.
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