JP2011042537A - Chalcogen compound powder, chalcogen compound paste, and process for producing chalcogen compound powder - Google Patents

Chalcogen compound powder, chalcogen compound paste, and process for producing chalcogen compound powder Download PDF

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JP2011042537A
JP2011042537A JP2009192460A JP2009192460A JP2011042537A JP 2011042537 A JP2011042537 A JP 2011042537A JP 2009192460 A JP2009192460 A JP 2009192460A JP 2009192460 A JP2009192460 A JP 2009192460A JP 2011042537 A JP2011042537 A JP 2011042537A
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chalcogen compound
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chalcogen
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JP2011042537A5 (en
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Yuichi Ishikawa
石川雄一
Tsuyoshi Fujino
藤野剛聡
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Dowa Holdings Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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    • H01L31/0256—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 the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
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Abstract

<P>PROBLEM TO BE SOLVED: To solve such problems that one of the processes for obtaining a filmy crystal of a chalcogen compound comprises forming a metal film composed of Cu, In, and Ga and treating the film with Se, this process, however, has difficulties in the uniformity of the film obtained and the productivity, the use of a process producing nano particles containing Cu, In, Ga, and Se at a low cost gives a highly uniform filmy crystal of a chalcogen compound, but the filmy crystal has too high a resistance to meet properties required for use in solar cells and the like, because the chalcogen compound obtained by this process contains a large amount of carbon. <P>SOLUTION: The chalcogen compound powder is expressed by the formula: Cu<SB>a</SB>In<SB>b</SB>Ga<SB>1-b</SB>Se<SB>c</SB>S<SB>d</SB>(wherein, 0.65≤a≤1.2; 0≤b≤1; 1.9≤C+d≤2.4), and has an average particle size (D50) of not less than 5 nm and less than 0.5 μm and a carbon content of not larger than 0.2 mass%. The process for producing the chalcogen compound powder includes a step to obtain a chalcogen compound by heating a metal source containing copper and indium having an average primary particle size of not larger than 0.3 μm and at least one kind selected from the group consisting of selenium, selenium compounds, sulfur and sulfur compounds at a temperature of not lower than 200°C and not higher than 400°C in a reducing gas and a step to pulverize the chalcogen compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、薄膜太陽電池の光吸収層、蛍光体、ペルチェ素子用の電極膜の形成等に用いられるカルコゲン系元素を含んだカルコゲン化合物粉、カルコゲン化合物ペースト及びカルコゲン化合物粉の製造方法に関し、特に、低コストで危険性が少なく、更に、このカルコゲン化合物粉を用いたカルコゲン化合物ペーストを塗布、焼成して形成した膜の電気抵抗を低くすることができるカルコゲン化合物粉、カルコゲン化合物ペースト及びカルコゲン化合物粉の製造方法に関する。   The present invention relates to a method for producing a chalcogen compound powder, a chalcogen compound paste and a chalcogen compound powder containing a chalcogen-based element used for forming a light absorbing layer of a thin film solar cell, a phosphor, an electrode film for a Peltier element, and the like. The chalcogen compound powder, the chalcogen compound paste, and the chalcogen compound powder that can reduce the electrical resistance of the film formed by applying and baking the chalcogen compound paste using the chalcogen compound powder. It relates to the manufacturing method.

カルコゲン系元素を含んだカルコゲン化合物粉のうち、銅（Ｃｕ）およびインジウム（Ｉｎ）およびセレン（Ｓｅ）を含むＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物のナノ粒子（ナノ結晶）は、薄膜化して太陽電池を製造する用途として期待されている。薄膜を形成する方法として、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物のナノ粒子（ナノ結晶）を含むペーストを基板上に塗布し焼成することができる。ここで、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）と表記した場合の（Ｇａ）、（Ｓ）は、ガリウム（Ｇａ）および硫黄（Ｓ）を含まなくてもよいことを示す（以下同様）。   Among the chalcogen compound powders containing chalcogen-based elements, Cu (In) (Ga) .Se. (S) compound nanoparticles (nanocrystals) containing copper (Cu) and indium (In) and selenium (Se) are: It is expected to be used as a thin film to manufacture solar cells. As a method for forming a thin film, a paste containing nanoparticles (nanocrystals) of a Cu • In • (Ga) • Se • (S) compound can be applied onto a substrate and fired. Here, (Ga) and (S) in the notation of Cu · In · (Ga) · Se · (S) indicate that gallium (Ga) and sulfur (S) need not be included (hereinafter referred to as “Ga” and “S”). The same).

Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物の粉末を得る方法として、Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金溶湯を鋳造して得られたインゴットを粉砕して、Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金の粉末を製造する方法が知られている。（例えば特許文献１参照。）。   As a method for obtaining a powder of Cu • In • (Ga) • Se • (S) compound, an ingot obtained by casting a Cu—In—Ga—Se quaternary alloy molten metal is pulverized, and Cu—In— A method for producing a Ga-Se quaternary alloy powder is known. (For example, refer to Patent Document 1).

また、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ化合物の粉末の製造方法として、原料となるＣｕ、Ｉｎ、Ｓｅ等を遊星ボールミルを用いたメカのケミカルプロセスを経ることにより得る方法がある。   Further, as a method for producing a powder of Cu • In • (Ga) • Se compound, there is a method of obtaining Cu, In, Se, or the like as a raw material through a mechanical chemical process using a planetary ball mill.

また、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ化合物粉末の製造方法として、本発明者らは、金属の複合水酸化物粉末とＳｅを高沸点有機溶媒中で加熱することにより得る方法を開発し、出願済みである（特願２００９−００９２４１号明細書）。   In addition, as a method for producing a Cu · In · (Ga) · Se compound powder, the present inventors have developed a method of obtaining a metal composite hydroxide powder and Se by heating them in a high boiling organic solvent, An application has been filed (Japanese Patent Application No. 2009-009241).

さらに、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ化合物の粉末の製造方法として、本発明者らは、溶媒中に金属化合物とＳｅ（Ｓ）を添加して加熱する方法を開発して、出願している。この方法の製造方法によれば、結晶性が高く、平均粒径が８０ｎｍ以下である、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ化合物のナノ粒子（ナノ結晶）を得ることが可能となった（特願２００９−１４１３２２号明細書）。   Furthermore, as a method for producing a powder of Cu • In • (Ga) • Se compound, the present inventors have developed and filed a method of heating by adding a metal compound and Se (S) in a solvent. Yes. According to the production method of this method, it is possible to obtain nanoparticles (nanocrystals) of Cu · In · (Ga) · Se compound having high crystallinity and an average particle size of 80 nm or less (special characteristics). Application No. 2009-141322).

特開２００８−１６３３６７号公報JP 2008-163367 A

上記の特許文献１の方法で得られるＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金の粉末の粒径は、１００メッシュアンダー程度であり、平均粒径数μｍ以下の粉末を得ることができない。また遊星ボールミルを用いたメカのケミカルプロセスを経ることにより得る方法では、平均粒径が０．５μｍ以下の粉末は得られていない。   The particle diameter of the Cu—In—Ga—Se quaternary alloy powder obtained by the method of Patent Document 1 is about 100 mesh under, and a powder having an average particle diameter of several μm or less cannot be obtained. Further, in a method obtained by a mechanical chemical process using a planetary ball mill, a powder having an average particle size of 0.5 μm or less has not been obtained.

既述の如くＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物の粉末は、これをペースト化して基板上に塗布し、焼成することで太陽電池用途の薄膜を得ることができる。しかし、平均粒径が０．５μｍ超のＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物の粉末を含むペーストは、平均粒径が大きいことにより、焼成の熱処理の温度が６００℃程度では、十分に粒子間の焼結が進まない。このため、空隙が多数存在する膜となり、導電性が低くなることや、空隙の存在が太陽電池の短絡の原因になる等の課題があった。   As described above, the Cu · In · (Ga) · Se · (S) compound powder can be made into a paste, applied onto a substrate, and fired to obtain a thin film for solar cell use. However, the paste containing Cu · In · (Ga) · Se · (S) compound powder having an average particle size of more than 0.5 μm has a large average particle size, so that the heat treatment temperature of firing is about 600 ° C. Sintering between particles does not proceed sufficiently. For this reason, it became a film | membrane with many space | gap, and there existed problems, such as electrical conductivity becoming low and the presence of a space | gap causing a short circuit of a solar cell.

また、特願２００９−００９２４１号明細書に開示の方法で得られたカルコゲン化合物粉末は、平均粒径は１００ｎｍ以下と非常に小さいが、有機物を５質量％以上含有しており、この粉末をペースト化して焼成して得られる薄膜の導電性が低い（抵抗が高い）ことが判明した。太陽電池用薄膜としては、薄膜の電気抵抗が十分低いことが必要であり、この課題を解決する必要があった。   Further, the chalcogen compound powder obtained by the method disclosed in the specification of Japanese Patent Application No. 2009-009241 has a very small average particle size of 100 nm or less, but contains 5% by mass or more of organic substances. It turned out that the electroconductivity of the thin film obtained by making it and baking is low (resistance is high). As a thin film for solar cells, it is necessary that the electric resistance of the thin film is sufficiently low, and it is necessary to solve this problem.

さらに特願２００９−１４１３２２号明細書に開示の方法では、合成時に有機溶媒を使用する必要があり、得られた粉末の有機物含有量は０．３％以上であり、これでも太陽電池用薄膜としては電気抵抗が高い問題があった。   Furthermore, in the method disclosed in Japanese Patent Application No. 2009-141322, it is necessary to use an organic solvent at the time of synthesis, and the organic matter content of the obtained powder is 0.3% or more. Had the problem of high electrical resistance.

このように、従来の方法では、 平均粒径が０．５μｍ未満であり、粉末中の有機物（炭素（Ｃ））含有量が０．２質量％以下であるＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ化合物粉末は得られていなかった。   Thus, in the conventional method, Cu · In · (Ga) · Se having an average particle size of less than 0.5 μm and an organic substance (carbon (C)) content of 0.2% by mass or less in the powder. Compound powder was not obtained.

本発明は、係る課題に鑑みてなされたものであり、第１に、一般式ＣｕａＩｎｂＧａ1-ｂＳｅｃＳｄ（0.65≦ａ≦1.2、0≦b≦1、1.9≦C＋d≦2.4）で表され、平均粒径（Ｄ５０）が５ｎｍ以上、０．５μｍ未満で、炭素量が０．２質量％以下であることを特徴とするカルコゲン化合物粉を提供することにより解決するものである。 The present invention has been made in view of the problem according to the first, the general formula Cu a In b Ga 1-b Se c S d (0.65 ≦ a ≦ 1.2,0 ≦ b ≦ 1,1.9 ≦ C + d ≦ The problem is solved by providing a chalcogen compound powder represented by 2.4) having an average particle size (D50) of 5 nm or more and less than 0.5 μm and a carbon content of 0.2% by mass or less. is there.

また、前記炭素量が０．１質量％未満であることを特徴とするものである。   The carbon content is less than 0.1% by mass.

第２に、請求項１に記載のカルコゲン化合物粉と分散媒を含有することを特徴とするカルコゲン化合物ペーストを提供することにより解決するものである。   Second, the problem is solved by providing a chalcogen compound paste comprising the chalcogen compound powder according to claim 1 and a dispersion medium.

また、前記分散媒がアルコールであることを特徴とするものである。   Further, the dispersion medium is alcohol.

また、前記ペースト中の前記カルコゲン化合物粉の含有量が２０質量％〜８０質量％であることを特徴とするものである。   Moreover, content of the said chalcogen compound powder in the said paste is 20 mass%-80 mass%, It is characterized by the above-mentioned.

第３に、平均１次粒径が０．３μｍ以下の銅およびインジウムを含む金属源と、セレン、セレン化合物、硫黄、硫黄化合物の群より選択された１種以上とを、還元性ガス中で、２００℃以上、４００℃以下に加熱し、カルコゲン化合物を生成する工程と、前記カルコゲン化合物を粉砕する工程と、を具備することにより解決するものである。   Third, in a reducing gas, a metal source containing copper and indium having an average primary particle size of 0.3 μm or less, and at least one selected from the group of selenium, selenium compounds, sulfur, and sulfur compounds It solves by comprising the process of heating 200 degreeC or more and 400 degrees C or less and producing | generating a chalcogen compound, and the process of grind | pulverizing the said chalcogen compound.

また、前記金属源は、金属水酸化物粉末であることを特徴とするものである。   Further, the metal source is a metal hydroxide powder.

また、前記金属源は、金属酸化物粉末または金属水酸化物と酸化物の混合物であることを特徴とするものである。   The metal source is a metal oxide powder or a mixture of a metal hydroxide and an oxide.

また、前記金属源は、ガリウムを含むことを特徴とするものである。   Further, the metal source contains gallium.

また、前記還元性ガスは水素ガス、または水素と不活性ガスの混合ガスのいずれかであることを特徴とするものである。   Further, the reducing gas is either hydrogen gas or a mixed gas of hydrogen and inert gas.

また、前記還元性ガス中で２２０℃以上に加熱することを特徴とするものである。   Moreover, it heats to 220 degreeC or more in the said reducing gas, It is characterized by the above-mentioned.

また、前記還元性ガスは水素化セレンまたは水素化硫黄を含むことを特徴とするものである。   The reducing gas contains selenium hydride or sulfur hydride.

また、前記金属源を水素化セレンまたは水素化硫黄を含む前記還元性ガス中で２２０℃以上に加熱することを特徴とするものである。   Further, the metal source is heated to 220 ° C. or higher in the reducing gas containing selenium hydride or sulfur hydride.

第１に、本実施形態によれば、平均粒径（Ｄ５０）が０．５μｍ未満であり、粉末中の有機物（Ｃ）含有量が０．２％以下であるカルコゲン化合物（Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物）粉及びカルコゲン化合物ペーストを提供できる。   First, according to the present embodiment, a chalcogen compound (Cu • In • (Cu • In • () having an average particle size (D50) of less than 0.5 μm and an organic matter (C) content of 0.2% or less in the powder. Ga) · Se · (S) compound) powder and chalcogen compound paste can be provided.

このカルコゲン化合物粉を含むペーストを塗布し、焼成することで、導電性が高く（電気抵抗が低く）、空隙の少ないカルコゲン化合物の薄膜を得ることができる。   By applying and baking the paste containing the chalcogen compound powder, a thin film of the chalcogen compound having high conductivity (low electrical resistance) and few voids can be obtained.

第２に、本実施形態の製造方法によれば、カルコゲン化合物粉を含むペーストを塗布し、焼成するという低コストかつ危険性の少ない方法で、太陽電池に用いて好適な高品質のカルコゲン化合物の薄膜を得ることができる。   Secondly, according to the manufacturing method of the present embodiment, a high-quality chalcogen compound suitable for use in solar cells can be obtained by applying a paste containing a chalcogen compound powder and firing the paste at a low cost and with a low risk. A thin film can be obtained.

本発明の実施形態の製造方法を説明するフロー図である。It is a flowchart explaining the manufacturing method of embodiment of this invention. 本発明の実施例１における反応済み粉末のＴＥＭ写真である。It is a TEM photograph of the reacted powder in Example 1 of the present invention. 本発明の実施例１による試料の状態を評価した結果である。It is the result of having evaluated the state of the sample by Example 1 of this invention. 本発明の実施例１による粒度分布である。It is a particle size distribution by Example 1 of this invention. 本発明の実施例１によるカルコゲン化合物粉の蛍光Ｘ線による分析の結果である。It is a result of the analysis by the fluorescent X ray of the chalcogen compound powder by Example 1 of this invention. 本発明の実施例１によるカルコゲン化合物粉のＸ線回折結果を示すグラフである。It is a graph which shows the X-ray-diffraction result of the chalcogen compound powder by Example 1 of this invention. 本発明の比較例１による試料の状態を評価した結果である。It is the result of evaluating the state of the sample by the comparative example 1 of this invention. 本発明の比較例１によるカルコゲン化合物粉のＸ線回折結果を示すグラフである。It is a graph which shows the X-ray-diffraction result of the chalcogen compound powder by the comparative example 1 of this invention. 本発明の実施例１および比較例１に含有される炭素量の測定結果である。It is a measurement result of the amount of carbon contained in Example 1 and comparative example 1 of the present invention. 本発明の実施例１および比較例１のカルコゲン化合物薄膜のシート抵抗の測定結果である。It is a measurement result of the sheet resistance of the chalcogen compound thin film of Example 1 and Comparative Example 1 of the present invention. 本発明の実施例１および比較例１について、炭素量のＳＥＭ−ＥＳＤ評価結果である。It is a SEM-ESD evaluation result of carbon amount about Example 1 and comparative example 1 of the present invention. 本発明の実施例１および比較例１のカルコゲン化合物薄膜の断面のＳＥＭ写真である。It is a SEM photograph of the section of the chalcogen compound thin film of Example 1 and comparative example 1 of the present invention.

以下、本発明の実施形態を、図１から図１２を参照して詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 to 12.

本実施形態のカルコゲン化合物粉は銅（Ｃｕ）、インジウム（Ｉｎ）、セレン（Ｓｅ）を含み、あるいは、Ｃｕ、Ｉｎ、硫黄（Ｓ）を含み、一般式ＣｕａＩｎｂＧａ1-ｂＳｅｃＳｄ（0.65≦ａ≦1.2、0≦b≦1、1.9≦C＋d≦2.4）で表され、平均粒径（Ｄ５０）が０．５μｍ未満であり、粉末中の炭素（Ｃ）量が０．２％以下の化合物である。 The chalcogen compound powder of this embodiment contains copper (Cu), indium (In), and selenium (Se), or contains Cu, In, and sulfur (S), and has a general formula Cu a In b Ga 1-b Se c. S d (0.65 ≦ a ≦ 1.2, 0 ≦ b ≦ 1, 1.9 ≦ C + d ≦ 2.4), the average particle size (D50) is less than 0.5 μm, and the amount of carbon (C) in the powder is 0.00. 2% or less of the compound.

また、本実施形態のカルコゲン化合物とは、金属元素の１種以上とセレン（Ｓｅ）、硫黄（Ｓ）から選択される元素の１種以上を構成元素とする化合物をいう。   In addition, the chalcogen compound of the present embodiment refers to a compound having one or more metal elements and one or more elements selected from selenium (Se) and sulfur (S) as constituent elements.

図１は、本実施形態のカルコゲン化合物粉、カルコゲン化合物ペーストおよびカルコゲン化合物薄膜を得るための製造方法の一例を説明するフロー図である。   FIG. 1 is a flowchart for explaining an example of a manufacturing method for obtaining a chalcogen compound powder, a chalcogen compound paste, and a chalcogen compound thin film according to this embodiment.

まず、図１（Ａ）を参照して、本実施形態のカルコゲン化合物結晶粉の製造方法を説明する。本実施形態のカルコゲン化合物結晶粉の製造方法は、銅およびインジウムを含む金属源と、カルコゲン源（セレン、セレン化合物、硫黄、硫黄化合物の群より選択された１種以上）とを、還元性ガス中で２００℃以上、４００℃以下に加熱し、カルコゲン化合物を生成する工程と、前記工程で得られたカルコゲン化合物を粉砕する工程と、を有する。   First, with reference to FIG. 1 (A), the manufacturing method of the chalcogen compound crystal powder of this embodiment is demonstrated. The manufacturing method of the chalcogen compound crystal powder of this embodiment comprises a metal source containing copper and indium and a chalcogen source (one or more selected from the group of selenium, selenium compound, sulfur and sulfur compound) as a reducing gas. Among them, there are a step of heating to 200 ° C. or more and 400 ° C. or less to produce a chalcogen compound, and a step of pulverizing the chalcogen compound obtained in the step.

この方法により、平均粒径（Ｄ５０）が０．５μｍ未満で、粉末中の炭素量が０．２％以下のカルコゲン化合物粉（Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉）を得ることができる。   By this method, a chalcogen compound powder (Cu • In • (Ga) • Se • (S) compound powder) having an average particle size (D50) of less than 0.5 μm and a carbon content in the powder of 0.2% or less is obtained. Obtainable.

尚、本実施形態では、カルコゲン化合物粉として、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉を例に説明するが、Ｃｕ・Ｉｎ・（Ｇａ）・（Ｓｅ）・Ｓ化合物粉でも同様に実施することができる。   In this embodiment, Cu · In · (Ga) · Se · (S) compound powder will be described as an example of the chalcogen compound powder, but Cu · In · (Ga) · (Se) · S compound powder may be used. It can be implemented similarly.

原料となる金属源は、銅およびインジウムの複合水酸化物または、銅、インジウムおよびガリウムの複合水酸化物の粉末である。複合水酸化物粉末は、複合水酸化物を構成する金属の塩を溶媒に溶解し、アルカリを添加して生成することができる。複合水酸化物粉末は、平均１次粒径が０．３μｍ以下とすることが、平均粒径（Ｄ５０）が０．５μｍ未満であるＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉を得るために必要である。なお２次粒径は、大きくてもよい。   The metal source used as a raw material is a composite hydroxide of copper and indium or a powder of composite hydroxide of copper, indium and gallium. The composite hydroxide powder can be produced by dissolving a metal salt constituting the composite hydroxide in a solvent and adding an alkali. The composite hydroxide powder has an average primary particle size of 0.3 μm or less, and a Cu • In • (Ga) • Se • (S) compound powder having an average particle size (D50) of less than 0.5 μm. Is necessary to get. The secondary particle size may be large.

金属源は、金属酸化物粉末または、酸化物若しくは、金属水酸化物と酸化物の混合物である。水酸化物の粉末を加熱(脱水)して、酸化物の粉末としてもよいし、水酸化物の一部のみが酸化物になった形態の粉末としてもよいが、後の工程で、還元するので水酸化物がより好ましい。   The metal source is a metal oxide powder or an oxide or a mixture of a metal hydroxide and an oxide. The hydroxide powder may be heated (dehydrated) to form an oxide powder or a powder in which only a part of the hydroxide is converted into an oxide, but it is reduced in a later step. Therefore, hydroxide is more preferable.

そして、金属塩（銅塩およびインジウム塩、必要に応じてガリウム塩）の混合物を出発原料とする場合には、前記金属塩を溶媒に溶解し、アルカリを添加して前記金属塩に含まれる金属の複合水酸化物を沈殿させた後に、デカンテーションや遠心沈降、ろ過等を行い、必要に応じて水洗し、乾燥して複合水酸化物の金属化合物粉末を得る。または複合水酸化物を酸化（脱水）して複合酸化物の金属化合物粉末を得る。各金属塩は混合物として溶媒に溶解してもよいし、各金属塩を混合せず順次溶媒に溶解してもよい。   When a mixture of metal salts (a copper salt and an indium salt, and optionally a gallium salt) is used as a starting material, the metal salt is dissolved in a solvent, an alkali is added, and the metal contained in the metal salt After the composite hydroxide is precipitated, decantation, centrifugal sedimentation, filtration and the like are performed, washed with water as necessary, and dried to obtain a metal compound powder of the composite hydroxide. Alternatively, the composite hydroxide is oxidized (dehydrated) to obtain a metal compound powder of the composite oxide. Each metal salt may be dissolved in a solvent as a mixture, or may be sequentially dissolved in a solvent without mixing each metal salt.

以下の例では、金属塩を出発原料とし、複合水酸化物又は複合酸化物を生成して、カルコゲン化合物を得る場合を例に説明するが、複合水酸化物の金属化合物粉末や、複合酸化物の金属化合物粉末を出発原料とすることもできる。また、Ｇａを含むカルコゲン化合物を得る場合には、金属塩として、ガリウム塩を加えればよい。   In the following examples, the case where a metal salt is used as a starting material and a chalcogen compound is obtained by producing a composite hydroxide or composite oxide will be described as an example. These metal compound powders can also be used as starting materials. Further, when obtaining a chalcogen compound containing Ga, a gallium salt may be added as a metal salt.

まず、Ｃｕ塩およびＩｎ塩を溶媒に溶解させる。溶媒としては水を使用することができる。その後、アルカリを添加することにより中和して金属水酸化物を生成する。詳細には、アンモニア水溶液、水酸化ナトリウム、水酸化カリウム、またはアミノ基を持つアルカリ性有機化合物によって金属水酸化物として沈殿させる。   First, Cu salt and In salt are dissolved in a solvent. Water can be used as the solvent. Then, it neutralizes by adding an alkali and produces | generates a metal hydroxide. Specifically, it is precipitated as a metal hydroxide by an aqueous ammonia solution, sodium hydroxide, potassium hydroxide, or an alkaline organic compound having an amino group.

この際、得ようとするカルコゲン化合物が複数の金属元素を含有する化合物であるので、金属塩の構成として、前記カルコゲン化合物と同じ金属元素比を有する金属水酸化物の沈殿を得るために、少なくともＣｕとＩｎの金属塩を用いて金属水酸化物の生成をおこなう。具体的に例えば、ＣｕＩｎＳｅ２を製造する場合には、ＣｕとＩｎの原子比が１：１になるように、銅塩とインジウム塩を原料として用い、金属水酸化物を生成する。 At this time, since the chalcogen compound to be obtained is a compound containing a plurality of metal elements, at least in order to obtain a precipitate of metal hydroxide having the same metal element ratio as the chalcogen compound as the metal salt composition, Metal hydroxide is generated using a metal salt of Cu and In. Specifically, for example, when manufacturing CuInSe 2 , a metal hydroxide is generated using a copper salt and an indium salt as raw materials so that the atomic ratio of Cu and In is 1: 1.

これらの金属水酸化物を含むスラリーを遠心脱水機、高速遠心沈降管、またはフィルタープレス、ヌッチェ等により反応副産物を含んだ溶媒を一度除去して、水やエタノール等の溶媒に再分散して、更に溶媒を除去するという操作を繰り返し、洗浄を行う。洗浄は、残液（ろ液）の導電率が１０−１Ｓｍ−１以下になるまで繰り返すことが望ましい。特にアルカリ金属は残留すると揮発しないために不純物元素として残ることになるので問題となる可能性がある。 The slurry containing these metal hydroxides is removed once with a centrifugal dehydrator, a high-speed centrifugal settling tube, or a filter press, Nutsche, etc., and re-dispersed in a solvent such as water or ethanol, Further, the operation of removing the solvent is repeated to perform washing. It is desirable to repeat the washing until the conductivity of the residual liquid (filtrate) becomes 10 −1 Sm −1 or less. In particular, if alkali metal remains, it does not volatilize and therefore remains as an impurity element, which may cause a problem.

洗浄を行うことにより反応不純物を除去できる。本実施形態の中和におけるｐＨの終了点はアルカリ性であることが好ましい。そのｐＨは特に限定されるものではないが、例えば１０以上でも良い。また、水洗によるろ液の導電率が低いほど良いが、ｐＨが中性に近付くと金属水酸化物自体が溶出するために組成が変わるので、前記ろ液のｐＨは、７．５以上に維持することが望ましい。   Reaction impurities can be removed by washing. The end point of the pH in the neutralization in this embodiment is preferably alkaline. The pH is not particularly limited, but may be 10 or more, for example. Moreover, the lower the conductivity of the filtrate by washing with water, the better. However, when the pH approaches neutral, the metal hydroxide itself elutes and the composition changes, so the pH of the filtrate is maintained at 7.5 or higher. It is desirable to do.

後述するカルコゲン化反応の金属源としては、前記洗浄後の水酸化物を固液分離して得た溶媒を含有するケーキから下記の方法で得た水酸化物または酸化物のいずれかまたはこれらの混合物を使用することができる。   As a metal source for the chalcogenation reaction described later, either a hydroxide or an oxide obtained by the following method from a cake containing a solvent obtained by solid-liquid separation of the washed hydroxide, or these oxides. Mixtures can be used.

前記洗浄後固液分離をおこなうことにより得た金属水酸化物（ケーキ）を例えば空気雰囲気下で７０℃から９０℃で乾燥させ、複合水酸化物の粉末（金属化合物粉末）を得ることができる。この際、乾燥温度は、特に限定されず、真空乾燥にすることにより乾燥温度を下げることが出来る。また乾燥温度は２００℃以上であっても良い。これにより、平均１次粒径が０．３μｍ以下の複合水酸化物粉末を得ることができる。   The metal hydroxide (cake) obtained by performing solid-liquid separation after the washing can be dried at, for example, 70 ° C. to 90 ° C. in an air atmosphere to obtain a composite hydroxide powder (metal compound powder). . At this time, the drying temperature is not particularly limited, and the drying temperature can be lowered by vacuum drying. The drying temperature may be 200 ° C. or higher. Thereby, a composite hydroxide powder having an average primary particle size of 0.3 μm or less can be obtained.

また、上記の複合水酸化物を加熱し、酸化して複合酸化物の粉末（金属化合物粉末）を生成してもよく、この場合、複合水酸化物の一部を酸化物とすることも全部を酸化物とすることもできる。   The composite hydroxide may be heated and oxidized to produce a composite oxide powder (metal compound powder). In this case, a part of the composite hydroxide may be converted into an oxide. Can also be an oxide.

以下、複合水酸化物粉末（金属水酸化物粉末）を用いる場合を例に説明する。   Hereinafter, the case where a composite hydroxide powder (metal hydroxide powder) is used will be described as an example.

平均１次粒径が小さい（０．３μｍ以下）複合水酸化物粉末を、固体のＳe（得ようとするカルコゲン化合物粉末にＳが含まれる場合には、固体のＳも使用）と混合し、還元性ガス中で、２２０℃以上に加熱することにより、カルコゲン化合物（Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物）を得る。   A composite hydroxide powder having a small average primary particle size (0.3 μm or less) is mixed with solid Se (when the chalcogen compound powder to be obtained contains S, solid S is also used), A chalcogen compound (Cu • In • (Ga) • Se • (S) compound) is obtained by heating to 220 ° C. or higher in a reducing gas.

前記加熱温度は、高すぎると焼結が進み、粉砕しても平均粒径が大きい状態のままとなることがあり、４００℃以下が好ましく、粉砕により所望の平均粒径であるＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉を容易に得るためには、３５０℃以下が更に好ましく、３００℃以下が一層好ましい。固体のＳｅ（Ｓ）は、平均粒径１０μｍ以下の粉末であることが好ましい。平均粒径を１０μｍ以下とすることにより、均一な組成のカルコゲン化合物粉をより容易に得ることができる。セレン化合物として例えば、セレン化水素（Ｈ２Ｓｅ）、硫黄化合物として、硫化水素（Ｈ２Ｓ）を還元性ガスに添加することもできる。 If the heating temperature is too high, the sintering proceeds, and even if pulverized, the average particle size may remain large, preferably 400 ° C. or lower, and Cu · In · In order to easily obtain the (Ga) · Se · (S) compound powder, 350 ° C or lower is more preferable, and 300 ° C or lower is more preferable. Solid Se (S) is preferably a powder having an average particle size of 10 μm or less. By setting the average particle size to 10 μm or less, a chalcogen compound powder having a uniform composition can be obtained more easily. For example, hydrogen selenide (H 2 Se) as a selenium compound and hydrogen sulfide (H 2 S) as a sulfur compound can be added to the reducing gas.

前記複合水酸化物粉末の平均１次粒径は、より小さい方が、平均粒径の小さいＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉末を得る上で有利であり、前記平均１次粒径は０．１μｍ以下が、更に好ましく、５０ｎｍ以下が一層好ましい。前記平均１次粒径の下限は特にないが、１ｎｍ以下とすることは難しい。前記平均１次粒径は、複合水酸化物粉末のＴＥＭまたはＳＥＭ写真上で、粒子１００個以上の粒径を測定し、その平均値を計算することにより求められる。前記の平均１次粒径に関する記載内容は、金属源に複合酸化物を含む場合でも、同様である。   A smaller average primary particle size of the composite hydroxide powder is advantageous for obtaining a Cu · In · (Ga) · Se · (S) compound powder having a smaller average particle size. The next particle size is preferably 0.1 μm or less, and more preferably 50 nm or less. There is no particular lower limit to the average primary particle size, but it is difficult to make it 1 nm or less. The average primary particle size is obtained by measuring the particle size of 100 or more particles on a TEM or SEM photograph of the composite hydroxide powder and calculating the average value. The description regarding the average primary particle size is the same even when the metal source contains a composite oxide.

このカルコゲン化合物を粉砕することにより、平均粒径（Ｄ５０）が０．５μｍ未満であり、粉末中の有機物（カーボン)含有量が０．２％未満であるＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉末を得ることができる。   By pulverizing this chalcogen compound, Cu · In · (Ga) · Se · with an average particle size (D50) of less than 0.5 μm and an organic matter (carbon) content of the powder of less than 0.2%. (S) A compound powder can be obtained.

還元性ガスは、水素ガス、水素と不活性ガスの混合ガス、およびこれらに、水素化セレン（Ｈ２Ｓｅ）、及び／または水素化硫黄（Ｈ２Ｓ）を混合したガスを使用することができる。還元性ガスに水素化セレン、及び／または水素化硫黄を混合すれば、上記の複合水酸化物粉末と混合するＳｅ（Ｓｅ化合物）／Ｓ(Ｓ化合物)は不要であるが、気体で還元性ガスに含ませることでＳｅ／Ｓのロスが増えるので、金属水酸化物と固体のＳｅ（Ｓｅ化合物）／Ｓ(Ｓ化合物)を混合することが好ましい。還元性ガスの流量は、水素ガスとして、処理をする金属化合物１ｇ当り、０．００２Ｌ／ｍｉｎ〜０．２Ｌ／ｍｉｎ（０℃換算）とすることができる。 As the reducing gas, hydrogen gas, a mixed gas of hydrogen and an inert gas, and a gas obtained by mixing selenium hydride (H 2 Se) and / or sulfur hydride (H 2 S) may be used. it can. If selenium hydride and / or sulfur hydride are mixed in the reducing gas, Se (Se compound) / S (S compound) to be mixed with the above composite hydroxide powder is unnecessary, but it is gas and is reducible. Since the loss of Se / S increases when it is included in the gas, it is preferable to mix a metal hydroxide and solid Se (Se compound) / S (S compound). The flow rate of the reducing gas can be 0.002 L / min to 0.2 L / min (converted to 0 ° C.) per 1 g of the metal compound to be treated as hydrogen gas.

粉砕方法は、特に限定されないが、ボールミル、振動ミル等が好適に利用できる。本実施形態の製造方法では、粉砕の対象物が、平均１次粒径が０．５μｍ以下の粒子の一部のみが互いに焼結したような形態であるため、既存のボールミル、振動ミルで処理することにより、平均粒径（Ｄ５０）が０．５μｍ未満のＣｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉を得ることができる。得られた化合物粉をペースト化し、塗布・焼成して膜を形成する際の焼成温度が低くても、導電性が高く良質な膜を得ることを可能にする観点から、Ｃｕ・Ｉｎ・（Ｇａ）・Ｓｅ・（Ｓ）化合物粉の平均粒径（Ｄ５０）は小さい方が好ましく、０．３μｍ以下がより好ましく、０．２μｍ以下が更に好ましく、０．１μｍ以下が一層好ましい。また、本願製法では、平均粒径（Ｄ５０）５ｎｍ未満の粒子を得ることは困難である。   The pulverization method is not particularly limited, but a ball mill, a vibration mill, or the like can be suitably used. In the manufacturing method of the present embodiment, the object to be crushed is in a form in which only some of the particles having an average primary particle size of 0.5 μm or less are sintered together. By doing so, Cu * In * (Ga) * Se * (S) compound powder whose average particle diameter (D50) is less than 0.5 micrometer can be obtained. From the viewpoint of making it possible to obtain a high-conductivity and high-quality film even if the baking temperature when forming the film by pasting the obtained compound powder and applying and baking to form a film is low, Cu · In · (Ga ) · Se · (S) The compound powder preferably has a smaller average particle diameter (D50), more preferably 0.3 μm or less, still more preferably 0.2 μm or less, and even more preferably 0.1 μm or less. In addition, it is difficult to obtain particles having an average particle size (D50) of less than 5 nm by the present production method.

本実施形態で得られるカルコゲン化合物粉は、Ｘ線回折のピーク強度比（目的とするカルコゲン化合物のピーク強度のうち最も高いピーク高さを、それ以外の物質によるピークのうち最も高いピーク高さで割った値）が５以上であり、目的とする組成を有する結晶からなる粒子を高濃度で含む。このカルコゲン化合物粉（一般式ＣｕａＩｎｂＧａ1-ｂＳｅｃＳｄ（0.65≦ａ≦1.2、0≦b≦1、1.9≦C＋d≦2.4））を使用して成膜することにより、成膜した膜の特性向上が期待できる。 The chalcogen compound powder obtained in the present embodiment has an X-ray diffraction peak intensity ratio (the highest peak height among the peak intensities of the target chalcogen compound is the highest peak height among the peaks of other substances). (Divided value) is 5 or more, and particles composed of crystals having the target composition are included at a high concentration. By film formation using this chalcogen compound powder (formula Cu a In b Ga 1-b Se c S d (0.65 ≦ a ≦ 1.2,0 ≦ b ≦ 1,1.9 ≦ C + d ≦ 2.4)), growth The improvement of the characteristics of the film formed can be expected.

また、カルコゲン反応時に添加するカルコゲン源の量は、余剰に添加しすぎても不経済なので、固体のカルコゲン源を使用する場合、当量の１倍〜１．５倍を添加するのが好ましい。   Moreover, since the amount of chalcogen source added during the chalcogen reaction is uneconomical even if it is added excessively, it is preferable to add 1 to 1.5 times the equivalent when using a solid chalcogen source.

本実施形態では以下、「過剰に添加」、と記載した場合には、当量の１倍超、１．５倍以下の量を添加すること意味する。   In the present embodiment, hereinafter, “addition in excess” means adding an amount of more than 1 time and not more than 1.5 times the equivalent.

次に、図１（Ｂ）および図１（Ｃ）を参照して、本実施形態のカルコゲン化合物ペーストおよびそれらの製造方法を説明する。さらに、ペーストを塗布・焼成して得られる膜の評価方法について説明する。   Next, with reference to FIG. 1 (B) and FIG. 1 (C), the chalcogen compound paste of this embodiment and the manufacturing method thereof will be described. Furthermore, the evaluation method of the film | membrane obtained by apply | coating and baking a paste is demonstrated.

図１（Ｂ）の如く、上記で作成したカルコゲン化合物粉を、分散媒とを混合する。分散媒としては、アルコール（多価アルコールを含む）等の液体を用いることができ、Ｃ３までのアルコールが好適である。例えば、メタノール、エタノール、イソプロパノールなどである。また、カルコゲン化合物ペースト中のカルコゲン化合物粉の含有量は、２０質量％〜８０質量％とすることが好ましい。２０質量％未満では、塗布時のパターン形成に不具合が生じることがあり、８０質量％超ではペーストの粘度が高くなりすぎる場合がある。これらを攪拌しながら混合し、カルコゲン化合物ペーストを生成する。尚、本実施形態のカルコゲン化合物ペーストは、分散媒中にカルコゲン化合物粉が分散した状態のものをいう。   As shown in FIG. 1B, the chalcogen compound powder prepared above is mixed with a dispersion medium. As the dispersion medium, liquid such as alcohol (including polyhydric alcohol) can be used, and alcohols up to C3 are preferable. For example, methanol, ethanol, isopropanol and the like. Moreover, it is preferable that content of the chalcogen compound powder in a chalcogen compound paste shall be 20 mass%-80 mass%. If it is less than 20% by mass, there may be a problem in pattern formation at the time of application, and if it exceeds 80% by mass, the viscosity of the paste may become too high. These are mixed with stirring to produce a chalcogen compound paste. The chalcogen compound paste of the present embodiment refers to a state in which the chalcogen compound powder is dispersed in a dispersion medium.

次に、図１（Ｃ）の如く、得られたカルコゲン化合物ペーストを塗布し、乾燥する。その後、例えばアルゴン（Ａｒ）雰囲気中で焼成を行い、カルコゲン化合物薄膜を形成する。本実施形態では、分散媒としてイソプロパノールを使用したカルコゲン化合物ペーストを塗布・焼成して得たカルコゲン化合物膜のシート抵抗を測定した。   Next, as shown in FIG. 1C, the obtained chalcogen compound paste is applied and dried. Thereafter, for example, baking is performed in an argon (Ar) atmosphere to form a chalcogen compound thin film. In this embodiment, the sheet resistance of a chalcogen compound film obtained by applying and baking a chalcogen compound paste using isopropanol as a dispersion medium was measured.

太陽電池などに用いられるカルコゲン化合物薄膜では、膜のシート抵抗が低いことが望まれている。具体的には、シート抵抗が、５００Ω／□以下であることが好ましい。   In a chalcogen compound thin film used for solar cells and the like, it is desired that the sheet resistance of the film is low. Specifically, the sheet resistance is preferably 500Ω / □ or less.

従来の方法（先願に開示の方法）により得られるカルコゲン化合物粉を用いたカルコゲン化合物薄膜では、カルコゲン化合物粉を含む乾燥粉末中に含まれる有機物（例えば炭素（Ｃ））が多く、シート抵抗が高い（例えば１０ＭΩ／□以上）問題があった。   In the chalcogen compound thin film using the chalcogen compound powder obtained by the conventional method (the method disclosed in the prior application), the organic powder (for example, carbon (C)) contained in the dry powder containing the chalcogen compound powder is large, and the sheet resistance is low. There was a problem of high (for example, 10 MΩ / □ or more).

本実施形態により作成したカルコゲン化合物粉を含む乾燥粉末はそれに含まれる有機物が少ないため、カルコゲン化合物薄膜を形成した場合に、シート抵抗を５００Ω／□未満に低減できる。   Since the dry powder containing the chalcogen compound powder prepared according to the present embodiment contains a small amount of organic matter, the sheet resistance can be reduced to less than 500 Ω / □ when the chalcogen compound thin film is formed.

以下に図２から図１２を参照して実施例を詳細に示す。尚、以下の実施例において、得られたカルコゲン化合物の各元素の元素組成比と、生成しようと意図した元素組成比とに差異がある場合でも、その差異が５％以下であれば、生成しようと意図した元素組成比の分子式で表現する場合がある。   Hereinafter, the embodiment will be described in detail with reference to FIGS. In the following examples, even if there is a difference between the elemental composition ratio of each element of the obtained chalcogen compound and the elemental composition ratio intended to be generated, if the difference is 5% or less, it will be generated. And may be expressed by the molecular formula of the intended elemental composition ratio.

ＣｕＩｎＳｅ２粒子を合成するために、硝酸銅０．１ｍｏｌと硝酸インジウム０．１ｍｏｌを純水５００ｍＬに溶かした溶液を１０００ｍＬのビーカーに入れた。続いてビーカー内を３００ｒｐｍで直径５ｃｍの羽を攪拌した状態で、水酸化ナトリウムの１Ｎ溶液を、液のｐＨ７．８になるまで滴下して、水酸化物として沈殿させ、銅・インジウムの複合水酸化物を得た。この状態で３０分放置してから、ヌッチェにより固液分離を行った。この際、採取した銅・インジウムの水酸化物のケーキを再度純水に分散させて、同様にヌッチェでろ過した。ろ液の伝導度が１０−３Ｓｍ−１以下になるまで繰り返した。取り出したケーキの一部を加熱乾燥（８０℃、１２時間、空気雰囲気）して、複合水酸化物粉末を得た。この複合水酸化物粉末のＴＥＭ（透過型電子顕微鏡）写真から、１次粒子１００個の粒径を測定し、その平均値を平均１次粒径として求めた結果、平均１次粒径は５０ｎｍ以下であることが確認された。また、加熱乾燥前後の質量から、ケーキ中に含まれる水分を測定した。得られたケーキ中の水分量は７３質量％であった。 In order to synthesize CuInSe 2 particles, a solution prepared by dissolving 0.1 mol of copper nitrate and 0.1 mol of indium nitrate in 500 mL of pure water was placed in a 1000 mL beaker. Subsequently, with a 5 cm diameter wing stirred at 300 rpm in the beaker, a 1N solution of sodium hydroxide was added dropwise until the pH of the solution reached 7.8 to precipitate as a hydroxide, and copper / indium composite water was added. An oxide was obtained. After leaving in this state for 30 minutes, solid-liquid separation was performed with Nutsche. At this time, the collected copper / indium hydroxide cake was again dispersed in pure water, and similarly filtered with Nutsche. The process was repeated until the conductivity of the filtrate was 10 −3 Sm −1 or less. A part of the taken-out cake was heat-dried (80 ° C., 12 hours, air atmosphere) to obtain a composite hydroxide powder. As a result of measuring the particle size of 100 primary particles from the TEM (transmission electron microscope) photograph of this composite hydroxide powder and determining the average value as the average primary particle size, the average primary particle size was 50 nm. It was confirmed that: Moreover, the water | moisture content contained in a cake was measured from the mass before and behind heat drying. The water content in the obtained cake was 73% by mass.

次にこの乾燥後の複合水酸化物を５ｇ取り出した。この複合水酸化物中に含まれるＣｕに対して、Ｓｅの原子比が２．４になる量のＳｅ粉末(平均粒径１μｍ)を秤量し、準備した。次に、５ｇの複合水酸化物と秤量したＳｅ粉末をヘンシェルミキサーで３０分間、混合した。この後、得られた混合粉を雰囲気制御可能な反応炉内に設置した。前記反応炉内を減圧した後、水素ガスに炉内雰囲気を置換する操作を２回繰り返した後、反応炉内に、水素ガスを、室温での流量として、０．１Ｌ／ｍｉｎ（０℃換算）を炉内に流した。この状態で、２００℃、２１０℃、２２０℃、２３０℃、２４０℃、２５０℃、２６０℃、２７０℃の８種類の温度（以下、反応温度と称することがある）まで昇温し、その温度を維持した状態で３時間保持して、反応処理をおこない反応処理済み粉末を得た。   Next, 5 g of this dried composite hydroxide was taken out. An amount of Se powder (average particle size: 1 μm) with an atomic ratio of Se of 2.4 with respect to Cu contained in the composite hydroxide was weighed and prepared. Next, 5 g of the composite hydroxide and the weighed Se powder were mixed with a Henschel mixer for 30 minutes. Thereafter, the obtained mixed powder was placed in a reaction furnace capable of controlling the atmosphere. After depressurizing the inside of the reaction furnace, the operation of substituting the atmosphere in the furnace with hydrogen gas was repeated twice, and then the hydrogen gas was flowed into the reaction furnace at a flow rate of 0.1 L / min (converted to 0 ° C.). ) Was poured into the furnace. In this state, the temperature is raised to eight types of temperatures of 200 ° C., 210 ° C., 220 ° C., 230 ° C., 240 ° C., 250 ° C., 260 ° C., and 270 ° C. (hereinafter sometimes referred to as reaction temperatures). Was maintained for 3 hours, and a reaction treatment was performed to obtain a reaction-treated powder.

図２は、得られた反応済み粉末（反応温度２５０℃）のＴＥＭ（透過型電子顕微鏡）写真を示す。   FIG. 2 shows a TEM (transmission electron microscope) photograph of the obtained reacted powder (reaction temperature 250 ° C.).

このそれぞれの温度で反応処理をおこなった８種類の反応処理済粉末に対して、１種類ずつ、粉砕処理をおこなった。前記粉砕処理は、反応処理済み粉末（１反応バッチ分）と１０ｍｍΦのジルコニアボール１ｋｇとを遊星ボールミル(ＦＲＩＴＳＣＨ社製、ｐｕｌｕｅｒｉｓｅｔｔｅ５)に 投入し、３０分間処理をおこない粉砕し、実施例１の試料１〜８を得た。   One type of pulverization treatment was performed on each of the eight types of the reaction-treated powders that had been subjected to the reaction treatment at the respective temperatures. In the pulverization treatment, the reaction-treated powder (for one reaction batch) and 1 kg of 10 mmφ zirconia balls are put into a planetary ball mill (FRITSCH, puluersette 5), treated for 30 minutes and pulverized. Sample 1 of Example 1 ~ 8 was obtained.

この試料１〜８に対し、Ｘ線回折装置（X-Ray Diffractometer、以下ＸＲＤ、株式会社リガク製 ＲＡＤ−ｒＸ）による結晶解析を行い、試料１〜試料８についてカルコゲン化合物（ＣｕＩｎＳｅ２）の生成状態を調べ、ＣｕＩｎＳｅ２粒子の生成に必要なカルコゲン化反応の反応温度を調べた。 The samples 1 to 8 are subjected to crystal analysis using an X-ray diffractometer (X-Ray Diffractometer, hereinafter referred to as XRD, RAD-rX, manufactured by Rigaku Corporation), and a chalcogen compound (CuInSe 2 ) is produced from Samples 1 to 8. The reaction temperature of the chalcogenation reaction necessary for the production of CuInSe 2 particles was examined.

図３は、この結果を示す図である。この際、Ｘ線回折は５０ｋＶ １００ｍＡの条件で測定を行ない、目的とするカルコゲン化合物（ＣｕＩｎＳｅ２）のピーク強度のうち最も高いピーク高さを、それ以外の物質によるピーク強度のうち最も高いピーク高さで割った値（以下、ピーク強度比）を求めた。ピーク強度比が、１５以上あれば、目的とするカルコゲン化合物が高純度で得られた（目的物の単相が得られた）と判定し、表１において○で示した。ピーク強度比が５以上であれば、目的とするカルコゲン化合物の含有量が高い物質が得られたと判定し、表１において、△で示した。ピーク強度比が５未満の場合は、目的とするカルコゲン化合物の含有量が低いと判定し、×で示した。この評価基準は、他の実施例でも同様である。 FIG. 3 is a diagram showing this result. At this time, the X-ray diffraction is measured under the condition of 50 kV and 100 mA, and the highest peak height among the peak intensities of the target chalcogen compound (CuInSe 2 ) is the highest among the peak intensities due to other substances. A value divided by (hereinafter, peak intensity ratio) was obtained. If the peak intensity ratio was 15 or more, it was determined that the target chalcogen compound was obtained with high purity (a single phase of the target product was obtained), and the results are shown in Table 1 with ◯. If the peak intensity ratio was 5 or more, it was judged that a substance having a high content of the target chalcogen compound was obtained, and the result is shown by Δ in Table 1. When the peak intensity ratio was less than 5, the content of the target chalcogen compound was determined to be low, and indicated by x. This evaluation criterion is the same in the other examples.

図３の結果から、カルコパイライト結晶構造を持つＣｕＩｎＳｅ２粒子を合成するためには少なくとも２２０℃以上の反応温度が必要なことが分かった。また、高純度のＣｕＩｎＳｅ２粒子を合成するためには少なくとも２３０℃以上の反応温度が必要なことが分かった。 From the results shown in FIG. 3, it was found that a reaction temperature of at least 220 ° C. or higher is required to synthesize CuInSe 2 particles having a chalcopyrite crystal structure. It was also found that a reaction temperature of at least 230 ° C. is necessary to synthesize high-purity CuInSe 2 particles.

図４は、反応温度を２５０℃として作製した試料６の粒径をレーザー光を用いた動的光散乱法による粒度分布測定装置（Ｓｙｍｐａｔｅｃｈ社製、ＮＡＮＯＰＨＯＸ）で調べた粒度分布の結果である。測定は、試料をイソプロパノールに１０μｇ／ｍＬの割合で分散させておこなった。本願での平均粒径（Ｄ５０）は、この方法で測定した値を示す。ここで、平均粒径（Ｄ５０）は、体積基準の粒度分布における５０％径であり、前記の粒度分布測定装置により描かれる体積基準の粒度分布のグラフ、すなわち、横軸に粒径Ｄ（ｎｍ）、縦軸に粒径Ｄ（ｎｍ）以下の粒子が存在する容積Ｑ（％）をとった累積粒度曲線において、Ｑ％が５０％のときの粒径Ｄ（ｎｍ）をいう。
試料６の平均粒径（Ｄ５０）は６４ｎｍ（０．０６４μｍ）であった。同様に測定をおこなった結果、試料３〜５、７、８の平均粒径（Ｄ５０）はいずれも、６０ｎｍ〜７０ｎｍの範囲内であった。 FIG. 4 shows the results of the particle size distribution obtained by examining the particle size of Sample 6 produced at a reaction temperature of 250 ° C. using a particle size distribution measuring apparatus (manufactured by Sympatech, NANOPHOX) using a dynamic light scattering method using laser light. The measurement was performed by dispersing the sample in isopropanol at a rate of 10 μg / mL. The average particle diameter (D50) in this application shows the value measured by this method. Here, the average particle diameter (D50) is a 50% diameter in the volume-based particle size distribution, and is a volume-based particle size distribution graph drawn by the particle size distribution measuring apparatus, that is, the particle diameter D (nm on the horizontal axis). ), The cumulative particle size curve in which the vertical axis represents the volume Q (%) in which particles having a particle size of D (nm) or less exist, and the particle size D (nm) when Q% is 50%.
The average particle size (D50) of Sample 6 was 64 nm (0.064 μm). As a result of the same measurement, all of the average particle diameters (D50) of Samples 3 to 5, 7, and 8 were in the range of 60 nm to 70 nm.

得られた乾燥粉末（試料６、７、８）について、蛍光Ｘ線による組成分析をおこなった。蛍光Ｘ線分析は、日本電子株式会社製ＪＳＸ−３２０１を使用して測定をおこなった。   The obtained dry powder (samples 6, 7, and 8) was subjected to composition analysis by fluorescent X-rays. X-ray fluorescence analysis was performed using JSX-3201 manufactured by JEOL Ltd.

図５は、その分析結果を示すものであり、Ｃｕを１として規格化し、構成元素の原子比で示した。各構成元素の原子比の値が、目標の値とのずれが５％以内の場合、○と判定した。これによると、目的とする組成比（Ｃｕ：Ｉｎ：Ｓｅ＝１：１：２）に近いカルコゲン化合物が得られていることが、確認された。   FIG. 5 shows the result of the analysis, which is normalized by setting Cu to 1 and indicated by the atomic ratio of the constituent elements. When the value of the atomic ratio of each constituent element was within 5% of the target value, it was judged as ◯. According to this, it was confirmed that the chalcogen compound close | similar to the target composition ratio (Cu: In: Se = 1: 1: 2) was obtained.

図６は、得られたカルコゲン化合物（試料６）のＸ線回折結果を示すグラフであり、縦軸がピーク強度[ｃｐｓ]であり、横軸が回折角（２θ）[°]である。
（比較例１）
ＣｕＩｎＳｅ２粒子を合成するために、硝酸銅０．１ｍｏｌと硝酸インジウム０．１ｍｏｌを純水５００ｍＬに溶かした溶液を１０００ｍＬのビーカーに入れた。続いてビーカー内を３００ｒｐｍで直径５ｃｍの羽を攪拌した状態で、水酸化ナトリウムの１Ｎ溶液を、液のｐＨ７．８になるまで滴下して、水酸化物として沈殿させ、銅・インジウムの複合水酸化物を得た。この状態で３０分放置してから、ヌッチェにより固液分離を行った。この際、採取した銅・インジウムの水酸化物のケーキを再度純水に分散させて、同様にヌッチェでろ過した。ろ液の伝導度が１０−３Ｓｍ−１以下になるまで繰り返した。取り出したケーキの一部を加熱乾燥（８０℃、１２時間、空気雰囲気）して、加熱乾燥前後の質量から、ケーキ中に含まれる水分を測定した。得られたケーキ中の水分量は７３質量％であった。 FIG. 6 is a graph showing the X-ray diffraction result of the obtained chalcogen compound (sample 6), in which the vertical axis represents peak intensity [cps] and the horizontal axis represents diffraction angle (2θ) [°].
(Comparative Example 1)
In order to synthesize CuInSe 2 particles, a solution prepared by dissolving 0.1 mol of copper nitrate and 0.1 mol of indium nitrate in 500 mL of pure water was placed in a 1000 mL beaker. Subsequently, with a 5 cm diameter wing stirred at 300 rpm in the beaker, a 1N solution of sodium hydroxide was added dropwise until the pH of the solution reached 7.8 to precipitate as a hydroxide, and copper / indium composite water was added. An oxide was obtained. After leaving in this state for 30 minutes, solid-liquid separation was performed with Nutsche. At this time, the collected copper / indium hydroxide cake was again dispersed in pure water, and similarly filtered with Nutsche. The process was repeated until the conductivity of the filtrate was 10 −3 Sm −1 or less. A part of the taken-out cake was heat-dried (80 ° C., 12 hours, air atmosphere), and the moisture contained in the cake was measured from the mass before and after heat-drying. The water content in the obtained cake was 73% by mass.

次にこの乾燥後の複合水酸化物を５ｇ取り出した。この複合水酸化物中に含まれるＣｕに対して、Ｓｅの原子比が２．４になる量のＳｅ粉末(平均粒径１μｍ)を秤量し、準備した。   Next, 5 g of this dried composite hydroxide was taken out. An amount of Se powder (average particle size: 1 μm) with an atomic ratio of Se of 2.4 with respect to Cu contained in the composite hydroxide was weighed and prepared.

次に、前記５ｇの水酸化物と秤量したＳｅ粉末を３００ｍＬのセパラブルフラスコに入れて、テトラエチレングリコール１００ｍＬを加えた。この状態で攪拌して、図７に記載の２００℃〜２７０℃の８種類の温度でそれぞれ５時間反応（カルコゲン化反応）させ、粉末状の生成物を得た。各温度で作製した粉末をろ紙を用いてろ過して得た粉末に対し、以下の洗浄２回繰り返しておこなった。
(洗浄)
５０ｍＬのエタノール中に得られた粉末を添加し攪拌した後、３０００ｒｐｍ、５分間の条件で遠心分離を実施し、上澄みの液体を除去した。 Next, the 5 g hydroxide and the weighed Se powder were placed in a 300 mL separable flask, and 100 mL of tetraethylene glycol was added. The mixture was stirred in this state and reacted (chalcogenation reaction) for 5 hours at each of eight temperatures of 200 ° C. to 270 ° C. shown in FIG. 7 to obtain a powdery product. The following washing was repeated twice for the powder obtained by filtering the powder prepared at each temperature using a filter paper.
(Washing)
The powder obtained in 50 mL of ethanol was added and stirred, and then centrifuged at 3000 rpm for 5 minutes to remove the supernatant liquid.

前記洗浄済みの粉末を、空気雰囲気下で８０℃、１２時間、乾燥し、乾燥粉末（比較例１の試料１〜８）を得た。   The washed powder was dried at 80 ° C. for 12 hours in an air atmosphere to obtain a dry powder (Samples 1 to 8 of Comparative Example 1).

図７及び図８は、得られた試料１〜８に対して、実施例１と同様のＸ線回折装置による評価をおこなった評価結果を示す。図７は、比較例１による試料の状態を評価した結果であり、図８は、比較例１によるカルコゲン化合物粉のＸ線回折結果を示すグラフである。図８で、２θ＝２２°付近に認められるピークは、測定ステージの材質に起因するものである。また、実施例１と同様の方法で試料４、６の平均粒径（Ｄ５０）を測定した結果、いずれも２０ｎｍ以下であった。   7 and 8 show the evaluation results obtained by evaluating the obtained samples 1 to 8 with the same X-ray diffractometer as in Example 1. FIG. FIG. 7 shows the result of evaluating the state of the sample according to Comparative Example 1, and FIG. 8 is a graph showing the X-ray diffraction result of the chalcogen compound powder according to Comparative Example 1. In FIG. 8, the peak observed near 2θ = 22 ° is attributed to the material of the measurement stage. Moreover, as a result of measuring the average particle diameter (D50) of the samples 4 and 6 by the method similar to Example 1, all were 20 nm or less.

実施例１の試料４、６、８と比較例１の試料４、６について、波長分散型蛍光Ｘ線分析で、試料中の炭素量を評価した。評価は、装置として、波長分散型蛍光Ｘ線分析装置（ブルカー・エイエックスエス株式会社製、Ｓ８ ＴＩＧＥＲ）用いて試料中のカーボン含有量を測定し、カーボン含有量を質量％で算出した。   With respect to Samples 4, 6, and 8 in Example 1 and Samples 4 and 6 in Comparative Example 1, the amount of carbon in the samples was evaluated by wavelength dispersion type fluorescent X-ray analysis. Evaluation was made by measuring the carbon content in the sample using a wavelength dispersion type fluorescent X-ray analyzer (S8 TIGER, manufactured by Bruker AXS Co., Ltd.) as an apparatus, and calculating the carbon content in mass%.

図９は、この測定結果を示す。比較例１と比較して実施例１の試料は、炭素量が劇的に低減されていた。これにより、後述するように、本実施形態のカルコゲン化合物粉を用いることにより、シート抵抗の低いカルコゲン化合物薄膜を形成できる。   FIG. 9 shows the measurement results. Compared to Comparative Example 1, the sample of Example 1 had a dramatically reduced carbon content. Thereby, the chalcogen compound thin film with low sheet resistance can be formed by using the chalcogen compound powder of this embodiment as described later.

次に、実施例１の試料４、６と比較例１の試料４、６の粉末を用いて、ペーストを作成し、そのペーストを塗布・焼成することにより、カルコゲン化合物薄膜を形成し、その膜の導電性を下記の方法で評価した。   Next, a paste is prepared using the powders of Samples 4 and 6 of Example 1 and Samples 4 and 6 of Comparative Example 1, and the paste is applied and fired to form a chalcogen compound thin film. The electrical conductivity of was evaluated by the following method.

試料４、６の粉末の含有量が５０質量％となるようにして、前記粉末とイソプロパノールを攪拌装置（遊星ボールミル、ＦＲＩＴＳＣＨ社製、ｐｕｌｕｅｒｉｓｅｔｔｅ５）で１０分間混合してペーストを作成した。このペーストをバーコーターを用いて、厚さ１０μｍで青板ガラス上にＭｏ膜を厚さ１μｍで形成した基板上に塗布し、この膜を大気中１１０℃で１時間乾燥した。この膜を２５０℃で大気中にて２時間加熱した。この後、窒素と水素の混合ガス（水素ガス５容量％）の雰囲気中で５７５℃、１時間の焼成を行い、カルコゲン化合物薄膜（ＣｕＩｎＳｅ２膜）を形成した。 The powders of Samples 4 and 6 were mixed at 50% by mass, and the powder and isopropanol were mixed for 10 minutes with a stirrer (Planet Ball Mill, manufactured by FRITSCH, puluersette 5) to prepare a paste. Using a bar coater, this paste was applied onto a substrate having a thickness of 10 μm and a Mo film formed on a soda-lime glass at a thickness of 1 μm, and this film was dried in the atmosphere at 110 ° C. for 1 hour. This film was heated at 250 ° C. in the atmosphere for 2 hours. Then, baking was performed at 575 ° C. for 1 hour in an atmosphere of a mixed gas of nitrogen and hydrogen (hydrogen gas 5% by volume) to form a chalcogen compound thin film (CuInSe 2 film).

図１０は、カルコゲン化合物薄膜のシート抵抗を三菱化学株式会社製、ＭＣＰ-Ｔ４１０を用いて測定した結果を示す。比較例１の試料を使用した場合は、膜のシート抵抗が１０ＭΩ／□以上あるため、値を測定できなかったが、実施例１の試料（試料４、６）を使用した場合には、膜のシート抵抗が４００Ω／□未満であった。ペーストを作成する際の粉末の含有量を、前記の５０質量％から、２０質量％、４０質量％、７０質量％に変更し、その他の条件は上記と同様で、カルコゲン化合物薄膜を作成し、そのシート抵抗を測定した結果は、上記と同様であり、比較例１の試料（試料４、６）の粉末を使用した場合は、膜のシート抵抗が１０ＭΩ／□以上のあるため値を測定できず、実施例１の粉末（試料４、６）を使用した場合には、膜のシート抵抗が４００Ω／□未満であることを確認した。   FIG. 10 shows the result of measuring the sheet resistance of the chalcogen compound thin film using MCP-T410 manufactured by Mitsubishi Chemical Corporation. When the sample of Comparative Example 1 was used, the value could not be measured because the sheet resistance of the film was 10 MΩ / □ or more, but when the sample of Example 1 (Samples 4 and 6) was used, the film The sheet resistance was less than 400Ω / □. The content of the powder when creating the paste was changed from 50% by mass to 20% by mass, 40% by mass, and 70% by mass, and other conditions were the same as above, and a chalcogen compound thin film was created. The result of measuring the sheet resistance is the same as described above. When the powder of the sample of Comparative Example 1 (Samples 4 and 6) is used, the value can be measured because the sheet resistance of the film is 10 MΩ / □ or more. First, when the powder of Example 1 (Samples 4 and 6) was used, it was confirmed that the sheet resistance of the film was less than 400Ω / □.

既述の如く、カルコゲン化合物薄膜を太陽電池などに用いる場合には、シート抵抗が低いことが望まれている。具体的にはシート抵抗は、５００Ω／□以下が好ましい。実施例１の試料４，６を使用した場合には前記シート抵抗を満足することができた。   As described above, when the chalcogen compound thin film is used for a solar cell or the like, it is desired that the sheet resistance is low. Specifically, the sheet resistance is preferably 500Ω / □ or less. When the samples 4 and 6 of Example 1 were used, the sheet resistance could be satisfied.

図１１は実施例１の試料４、６および比較例１の試料４、６の４試料それぞれを用いて形成した膜について、炭素量をＳＥＭ−ＥＤＳで評価した結果を示す。比較例１の試料を用いて形成した膜では、測定された炭素量は、３質量％であったが、実施例１の試料を用いて形成した膜について測定された炭素量は、０．１質量％未満と少ないことが分かった。また、つまり本実施形態では、乾燥粉末（カルコゲン化合物粉）中の炭素量が少ないため、これを用いたカルコゲン化合物薄膜のシート抵抗値が大幅に低減しているといえる。   FIG. 11 shows the results of evaluating the carbon content by SEM-EDS for films formed using Samples 4 and 6 of Example 1 and Samples 4 and 6 of Comparative Example 1, respectively. In the film formed using the sample of Comparative Example 1, the carbon amount measured was 3% by mass, but the carbon amount measured for the film formed using the sample of Example 1 was 0.1%. It was found to be less than less than mass%. In other words, in this embodiment, since the amount of carbon in the dry powder (chalcogen compound powder) is small, it can be said that the sheet resistance value of the chalcogen compound thin film using the dry powder is greatly reduced.

図１２は、実施例１の試料６（図１２（Ａ））と比較例１の試料６（図１２（Ｂ））を用いて、前記の方法で形成した膜の断面をＳＥＭで観察した結果を示す。この結果から、本実施例では焼結が進行しているが、比較例のものは焼結が進行していないことが確認された。   FIG. 12 shows a result of observing a cross section of the film formed by the above method with an SEM using the sample 6 of Example 1 (FIG. 12A) and the sample 6 of Comparative Example 1 (FIG. 12B). Indicates. From this result, it was confirmed that although the sintering progressed in this example, the comparative example did not progress.

Claims (13)

一般式ＣｕａＩｎｂＧａ1-ｂＳｅｃＳｄ（0.65≦ａ≦1.2、0≦b≦1、1.9≦C＋d≦2.4）で表され、平均粒径（Ｄ５０）が５ｎｍ以上、０．５μｍ未満で、炭素量が０．２質量％以下であることを特徴とするカルコゲン化合物粉。 It is represented by the general formula Cu a In b Ga 1-b Se c S d (0.65 ≦ a ≦ 1.2,0 ≦ b ≦ 1,1.9 ≦ C + d ≦ 2.4), an average particle diameter (D50) 5nm or more, 0.5 [mu] m The chalcogen compound powder is characterized by having a carbon content of 0.2% by mass or less. 前記炭素量が０．１質量％未満であることを特徴とする請求項１に記載のカルコゲン化合物粉。   The chalcogen compound powder according to claim 1, wherein the carbon content is less than 0.1 mass%. 請求項１に記載のカルコゲン化合物粉と分散媒を含有することを特徴とするカルコゲン化合物ペースト。   A chalcogen compound paste comprising the chalcogen compound powder according to claim 1 and a dispersion medium. 前記分散媒がアルコールであることを特徴とする請求項３に記載のカルコゲン化合物ペースト。   The chalcogen compound paste according to claim 3, wherein the dispersion medium is alcohol. 前記ペースト中の前記カルコゲン化合物粉の含有量が２０質量％〜８０質量％であることを特徴とする請求項４に記載のカルコゲン化合物ペースト。   The chalcogen compound paste according to claim 4, wherein the content of the chalcogen compound powder in the paste is 20% by mass to 80% by mass. 平均１次粒径が０．３μｍ以下の銅およびインジウムを含む金属源と、セレン、セレン化合物、硫黄、硫黄化合物の群より選択された１種以上とを、還元性ガス中で、２００℃以上、４００℃以下に加熱し、カルコゲン化合物を生成する工程と、
前記カルコゲン化合物を粉砕する工程と、
を具備することを特徴とする請求項１に記載のカルコゲン化合物粉の製造方法。 A metal source containing copper and indium having an average primary particle size of 0.3 μm or less and at least one selected from the group of selenium, selenium compounds, sulfur and sulfur compounds in a reducing gas at 200 ° C. or higher Heating to 400 ° C. or lower to produce a chalcogen compound;
Crushing the chalcogen compound;
The method for producing a chalcogen compound powder according to claim 1, comprising: 前記金属源は、金属水酸化物粉末であることを特徴とする請求項６に記載のカルコゲン化合物粉の製造方法。   The method of producing a chalcogen compound powder according to claim 6, wherein the metal source is a metal hydroxide powder. 前記金属源は、金属酸化物粉末または金属水酸化物と酸化物の混合物であることを特徴とする請求項６に記載のカルコゲン化合物粉の製造方法。   The method for producing a chalcogen compound powder according to claim 6, wherein the metal source is a metal oxide powder or a mixture of a metal hydroxide and an oxide. 前記金属源は、ガリウムを含むことを特徴とする請求項７または請求項８に記載のカルコゲン化合物粉の製造方法。   The said metal source contains gallium, The manufacturing method of the chalcogen compound powder of Claim 7 or Claim 8 characterized by the above-mentioned. 前記還元性ガスは水素ガス、または水素と不活性ガスの混合ガスのいずれかであることを特徴とする請求項７から請求項９のいずれかに記載のカルコゲン化合物粉の製造方法。   The method for producing a chalcogen compound powder according to any one of claims 7 to 9, wherein the reducing gas is either hydrogen gas or a mixed gas of hydrogen and an inert gas. 前記還元性ガス中で２２０℃以上に加熱することを特徴とする請求項６に記載のカルコゲン化合物粉の製造方法。   The method for producing a chalcogen compound powder according to claim 6, wherein heating is performed to 220 ° C. or higher in the reducing gas. 前記還元性ガスは水素化セレンまたは水素化硫黄を含むことを特徴とする請求項７から請求項９のいずれかに記載のカルコゲン化合物粉の製造方法。   The method for producing a chalcogen compound powder according to any one of claims 7 to 9, wherein the reducing gas contains selenium hydride or sulfur hydride. 前記金属源を水素化セレンまたは水素化硫黄を含む前記還元性ガス中で２２０℃以上に加熱することを特徴とする請求項７から請求項９のいずれかに記載のカルコゲン化合物粉の製造方法。   The method for producing a chalcogen compound powder according to any one of claims 7 to 9, wherein the metal source is heated to 220 ° C or higher in the reducing gas containing selenium hydride or sulfur hydride.
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