WO2014196311A1 - 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 - Google Patents

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 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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English (en)
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 CN201480031441.6A priority Critical patent/CN105308760B/zh
Priority to JP2015521351A priority patent/JP6012866B2/ja
Publication of WO2014196311A1 publication Critical patent/WO2014196311A1/ja

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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 potential barriers
    • 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 potential barriers 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 potential barriers 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.

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WO2014017644A1 (ja) * 2012-07-26 2014-01-30 東京応化工業株式会社 光吸収層形成用塗布液の製造方法

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