JP4957968B2 - Cu-In-Ga ternary sintered alloy sputtering target and method for producing the same - Google Patents
Cu-In-Ga ternary sintered alloy sputtering target and method for producing the same Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims description 19
- 239000000956 alloy Substances 0.000 title claims description 19
- 238000005477 sputtering target Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002245 particle Substances 0.000 claims description 33
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 238000009689 gas atomisation Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 38
- 238000004544 sputter deposition Methods 0.000 description 22
- 229910002056 binary alloy Inorganic materials 0.000 description 15
- 229910002059 quaternary alloy Inorganic materials 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 230000031700 light absorption Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
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- 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
Description
この発明は、太陽電池の光吸収層を形成するためのＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜を形成するときに使用するＣｕ−Ｉｎ−Ｇａ三元系焼結合金スパッタリングターゲットおよびその製造方法に関するものである。 The present invention relates to a Cu—In—Ga ternary sintered alloy sputtering target used for forming a Cu—In—Ga—Se quaternary alloy film for forming a light absorption layer of a solar cell, and its production. It is about the method.
近年、化合物半導体による薄膜太陽電池が実用に供せられるようになり、この化合物半導体による薄膜太陽電池は、ソーダライムガラス基板の上にプラス電極となるＭｏ電極層を形成し、このＭｏ電極層の上にＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなる光吸収層が形成され、このＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなるこの光吸収層の上にＺｎＳ、ＣｄＳなどからなるバッファ層が形成され、このバッファ層の上にマイナス電極となる透明電極層が形成された基本構造を有している。
前記Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなる光吸収層の形成方法として、蒸着法により成膜する方法が知られており、この方法により得られたＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなる光吸収層は高いエネルギー変換効率が得られるものの、蒸着法による成膜は速度が遅いためにコストがかかる。そのために、スパッタリング法によってＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなる光吸収層を形成する方法が提案されている（特許文献１参照）。
このＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜をスパッタリングにより成膜する方法として、まず、Ｉｎターゲットを使用してスパッタリングによりＩｎ膜を成膜し、このＩｎ膜の上にＣｕ−Ｇａ二元系合金ターゲットを使用してスパッタリングすることによりＣｕ−Ｇａ二元系合金膜を成膜し、得られたＩｎ膜およびＣｕ−Ｇａ二元系合金膜からなる積層膜をＳｅ雰囲気中で熱処理してＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜を形成する方法が提案されている。そして、前記Ｃｕ−Ｇａ二元系合金ターゲットとしてＧａ：１〜４０重量％を含有し、残部がＣｕからなる組成を有するＣｕ−Ｇａ二元系合金ターゲットが知られており（特許文献２参照）、このＣｕ−Ｇａ二元系合金ターゲットは一般に鋳造で作製されている。
As a method of forming a light absorption layer made of the Cu—In—Ga—Se quaternary alloy film, a method of forming a film by vapor deposition is known, and Cu—In—Ga—Se four obtained by this method is known. Although a light absorption layer made of a ternary alloy film can provide high energy conversion efficiency, film formation by vapor deposition is slow because of its slow speed. Therefore, a method of forming a light absorption layer made of a Cu—In—Ga—Se quaternary alloy film by a sputtering method has been proposed (see Patent Document 1).
As a method of forming this Cu—In—Ga—Se quaternary alloy film by sputtering, first, an In film is formed by sputtering using an In target, and a Cu—Ga binary is formed on this In film. A Cu—Ga binary alloy film is formed by sputtering using a system alloy target, and the obtained laminated film composed of the In film and the Cu—Ga binary alloy film is heat-treated in an Se atmosphere. A method of forming a Cu—In—Ga—Se quaternary alloy film has been proposed. And the Cu-Ga binary system alloy target which contains Ga: 1-40weight% as said Cu-Ga binary system alloy target and the remainder consists of Cu is known (refer patent document 2). The Cu—Ga binary alloy target is generally produced by casting.
近年、太陽電池の変換効率を一層高めるとともに、太陽電池の一層のコストダウンが求められており、そのために前記Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜を一層効率良く成膜することが求められている。
そこで、本発明者らは、従来法では、Ｉｎターゲットを使用してスパッタリングによりＩｎ膜を成膜し、このＩｎ膜の上にＣｕ−Ｇａ二元系合金ターゲットを使用してスパッタリングすることによりＣｕ−Ｇａ二元系合金膜を成膜してＩｎ膜およびＣｕ−Ｇａ二元系合金膜からなる積層膜を形成していたのを、Ｃｕ−Ｉｎ−Ｇａ三元系合金ターゲットを使用して一回のスパッタリングによりＣｕ−Ｉｎ−Ｇａ三元系合金膜を成膜すれば、成膜工程を一工程省略することができ、この成膜工程を一工程省略ことにより一層のコストダウンを図ることができるとの考えに基づいて、Ｃｕ−Ｉｎ−Ｇａ三元系合金溶湯を作製し、このＣｕ−Ｉｎ−Ｇａ三元系合金溶湯を鋳造することによりＣｕ−Ｉｎ−Ｇａ三元系合金からなる鋳造ターゲットを作製し、このＣｕ−Ｉｎ−Ｇａ三元系合金からなる鋳造ターゲットを用いてスパッタリングすることによりＣｕ−Ｉｎ−Ｇａ三元系合金膜を成膜した。
ところが、このＣｕ−Ｉｎ−Ｇａ三元系合金からなる鋳造ターゲットを用いてスパッタリングすると極端に多くのパーティクルが発生し、太陽電池のＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなる光吸収層を形成するためのＣｕ−Ｉｎ−Ｇａ三元系合金膜として供することができなかった。
In recent years, there has been a demand for further increasing the conversion efficiency of the solar cell and further reducing the cost of the solar cell. For that purpose, it is required to form the Cu—In—Ga—Se quaternary alloy film more efficiently. It has been.
Therefore, in the conventional method, the inventors have formed an In film by sputtering using an In target, and sputtering the Cu film using a Cu—Ga binary alloy target on the In film. A Cu-In-Ga ternary alloy target was used to form a laminated film composed of an In film and a Cu-Ga binary alloy film by forming a -Ga binary alloy film. If a Cu—In—Ga ternary alloy film is formed by one-time sputtering, the film forming process can be omitted, and the cost can be further reduced by omitting this film forming process. Based on the idea that it can be made, a Cu-In-Ga ternary alloy molten metal is produced, and this Cu-In-Ga ternary alloy molten metal is cast to form a Cu-In-Ga ternary alloy casting. Create target It was deposited Cu-In-Ga ternary alloy film by sputtering using a cast target of the Cu-In-Ga ternary alloy.
However, when a sputtering target made of this Cu—In—Ga ternary alloy is used for sputtering, an extremely large number of particles are generated, and a light absorption layer made of a Cu—In—Ga—Se quaternary alloy film of a solar cell. It was not possible to use as a Cu—In—Ga ternary alloy film for forming.
本発明者らは、Ｃｕ−Ｉｎ−Ｇａ三元系合金からなるターゲットを用いてパーティクルを発生させることなくスパッタリングすることによりＣｕ−Ｉｎ−Ｇａ三元系合金膜を成膜し、このＣｕ−Ｉｎ−Ｇａ三元系合金膜をＳｅ雰囲気中で熱処理してＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜を形成するべくさらに研究を行った。その結果、
（イ）Ｃｕ−Ｉｎ−Ｇａ三元系合金からなるターゲットを用いてスパッタリングする際に発生するパーティクルはターゲット素地中に分散しているＩｎ相およびＩｎが拡散している相（以下、Ｉｎ含有相という）の大きさが影響を及ぼし、ターゲット素地中に生成しているＩｎ含有相の粒径が大きなターゲットを用いてスパッタリングすると、スパッタリング中にパーティクルが発生する、
（ロ）鋳造により作製したＣｕ−Ｉｎ−Ｇａ三元系合金からなるターゲットの素地中に分散しているＩｎ含有相は粒径が２０μｍ以上の大きなＩｎ含有相が生成しており、この素地中に粒径が２０μｍ以上の大きなＩｎ含有相を有するターゲットを用いてスパッタリングするとパーティクルが発生する、
（ハ）しかし、ターゲット素地に分散するＩｎ含有相の粒径が微細になるほどスパッタリング中に発生するパーティクルの数が少なくなり、ターゲット素地中に分散しているＩｎ含有相の最大粒径が１０μｍ以下になると、パーティクルの発生が無くなる、
（ニ）素地中に分散するＩｎ含有相の最大粒径が１０μｍ以下のターゲットを得るには、原料として、Ｇａ：２０〜５０質量％を含有し、残部がＣｕからなる高Ｇａ含有Ｃｕ−Ｇａ二元系母合金、ＩｎおよびＣｕを用意し、これら原料をＩｎ：４０〜６０質量％、Ｇａ：１〜４５質量％を含有し、残部がＣｕからなる成分組成となるように秤量し溶解して得られた溶湯をガスアトマイズすることによりＣｕ−Ｉｎ−Ｇａ三元系合金粉末を作製し、得られたＣｕ−Ｉｎ−Ｇａ三元系合金粉末を高圧焼結することにより作製することができる、などの研究結果が得られたのである。
The present inventors formed a Cu-In-Ga ternary alloy film by sputtering without generating particles using a target made of a Cu-In-Ga ternary alloy, and this Cu-In Further research was carried out to form a Cu—In—Ga—Se quaternary alloy film by heat-treating the —Ga ternary alloy film in an Se atmosphere. as a result,
(A) Particles generated when sputtering using a target made of a Cu—In—Ga ternary alloy are an In phase dispersed in the target substrate and a phase in which In is diffused (hereinafter referred to as an In-containing phase). When the sputtering is performed using a target having a large particle size of the In-containing phase generated in the target substrate, particles are generated during the sputtering.
(B) The In-containing phase dispersed in the target substrate made of the Cu—In—Ga ternary alloy produced by casting produces a large In-containing phase having a particle size of 20 μm or more. When particles are sputtered using a target having a large In-containing phase with a particle size of 20 μm or more, particles are generated.
(C) However, the finer the particle size of the In-containing phase dispersed in the target substrate, the smaller the number of particles generated during sputtering, and the maximum particle size of the In-containing phase dispersed in the target substrate is 10 μm or less. Then, the generation of particles disappears.
(D) In order to obtain a target having a maximum particle size of 10 μm or less of the In-containing phase dispersed in the substrate, the raw material contains Ga: 20 to 50% by mass, and the balance is high Ga-containing Cu—Ga composed of Cu. A binary master alloy, In and Cu are prepared, and these raw materials contain In: 40 to 60 mass%, Ga: 1 to 45 mass%, and are weighed and dissolved so as to have a component composition consisting of Cu. It is possible to produce a Cu-In-Ga ternary alloy powder by gas atomizing the molten metal obtained, and to produce the Cu-In-Ga ternary alloy powder obtained by high-pressure sintering. The research results were obtained.
この発明は、かかる研究結果に基づいてなされたものであって、
（１）Ｉｎ：４０〜６０質量％、Ｇａ：１〜４５質量％を含有し、残部がＣｕからなる成分組成を有するＣｕ−Ｉｎ−Ｇａ三元系焼結合金スパッタリングターゲットであって、このスパッタリングターゲットの素地中に分散しているＩｎ含有合金相の最大粒径が１０μｍ以下であるＣｕ−Ｉｎ−Ｇａ三元系焼結合金スパッタリングターゲット、
（２）原料として、Ｇａ：２０〜５０質量％を含有し、残部がＣｕからなる高Ｇａ含有Ｃｕ−Ｇａ二元系母合金、ＩｎおよびＣｕを用意し、これら原料をＩｎ：４０〜６０質量％、Ｇａ：１〜４５質量％を含有し、残部がＣｕからなる成分組成となるように秤量し、溶解して得られた溶湯をガスアトマイズすることによりＣｕ−Ｉｎ−Ｇａ三元系合金粉末を作製し、得られたＣｕ−Ｉｎ−Ｇａ三元系合金粉末を高圧焼結するＣｕ−Ｉｎ−Ｇａ三元系焼結合金スパッタリングターゲットの製造方法、に特徴を有するものである。
The present invention has been made based on the results of such research,
(1) A Cu—In—Ga ternary sintered alloy sputtering target containing In: 40 to 60% by mass, Ga: 1 to 45% by mass, and the balance being composed of Cu. A Cu—In—Ga ternary sintered alloy sputtering target in which the maximum particle size of the In-containing alloy phase dispersed in the target substrate is 10 μm or less,
(2) As a raw material, Ga: 20-50 mass% is contained, the high Ga content Cu-Ga binary system master alloy which consists of Cu and remainder, In and Cu are prepared, In: 40-60 mass %, Ga: 1 to 45% by mass, with the balance being a component composition comprising Cu, and by gas atomizing the melt obtained by melting, Cu-In-Ga ternary alloy powder is obtained. The Cu—In—Ga ternary alloy powder produced and obtained is characterized by a method for producing a Cu—In—Ga ternary sintered alloy sputtering target in which high pressure sintering is performed.
この発明のＣｕ−Ｉｎ−Ｇａ三元系焼結合金スパッタリングターゲットに含まれるＩｎの含有量を４０〜６０質量％に限定した理由は、Ｉｎが４０質量％未満では焼結性が悪くなると共にターゲット素地中のＩｎ含有相の最大粒径が大きくなり、このターゲットを用いてスパッタリングするとパーティクルが発生するので好ましくなく、一方、Ｉｎを６０質量％を越えて含有すると、Ｉｎ含有相の最大粒径が大きくなってスパッタリングに際してパーティクルが発生するようになるので好ましくないからである。
また、Ｇａの含有量を１〜４５質量％に限定した理由は、Ｇａが１質量％未満では焼結性が悪くなると共にターゲット素地中のＩｎ含有相の最大粒径が大きくなってパーティクルが発生するので好ましくなく、一方、Ｇａが４５質量％を越えて含有すると、加工性が悪くなると共にターゲット素地中のＩｎ含有相の最大粒径が大きくなってパーティクルが発生するので好ましくないからである。
The reason why the content of In contained in the Cu—In—Ga ternary sintered alloy sputtering target of the present invention is limited to 40 to 60% by mass is that if the In content is less than 40% by mass, the sinterability becomes worse and the target The maximum particle size of the In-containing phase in the substrate becomes large, and particles are generated when sputtering using this target, which is not preferable. On the other hand, when the In content exceeds 60% by mass, the maximum particle size of the In-containing phase is increased. This is because it becomes large and particles are generated during sputtering, which is not preferable.
Moreover, the reason for limiting the Ga content to 1 to 45 mass% is that if Ga is less than 1 mass%, the sinterability deteriorates and the maximum particle size of the In-containing phase in the target substrate increases and particles are generated. On the other hand, if the Ga content exceeds 45% by mass, the processability is deteriorated and the maximum particle size of the In-containing phase in the target substrate is increased to generate particles, which is not preferable.
この発明のＩｎ：４０〜６０質量％、Ｇａ：１〜４５質量％を含有し、残部がＣｕからなる成分組成を有するＣｕ−Ｉｎ−Ｇａ三元系焼結合金スパッタリングターゲットを製造する際に使用するＣｕ−Ｉｎ−Ｇａ三元系合金粉末は、Ｇａ：２０〜５０質量％含有するＣｕ−Ｇａ二元系合金原料、Ｃｕ原料、Ｉｎ原料を溶解し、得られた溶湯を直径：１〜３ｍｍのノズルから流し出し、この流れ出た溶湯に向かってアルゴンガス、窒素ガスなどの不活性ガスを高圧で吹き付けて３〜１２５μｍの範囲内の粒径を有するＣｕ−Ｉｎ−Ｇａ二元系合金アトマイズ粉末を作製する。この流れ出た溶湯に向かって吹き付ける不活性ガスの圧力を調整することによりアトマイズ粉末の粒径を調節することができる。
Ｇａは融点（２９．７８０℃）が低いのでＧａ単独では常温でも液体となって溶解原料としては取り扱いにくい。そのため、Ｇａを添加するには常温で固体状態を保ち粉砕が可能なＧａ：２０〜５０質量％を含有するＣｕ−Ｇａ二元系合金とし、これを原料として添加する。そして溶解して得られたＣｕ−Ｉｎ−Ｇａ三元系合金溶湯に含まれるＧａはアトマイズ時に溶湯の流動性を向上させ、ノズル部の詰まりを防止する作用がある。
Used when producing a Cu—In—Ga ternary sintered alloy sputtering target containing In: 40 to 60% by mass and Ga: 1 to 45% by mass of the present invention, with the balance being composed of Cu. The Cu—In—Ga ternary alloy powder to be dissolved is a Cu—Ga binary alloy raw material, Cu raw material, and In raw material containing Ga: 20 to 50% by mass, and the resulting molten metal has a diameter of 1 to 3 mm. Cu—In—Ga binary alloy atomized powder having a particle size in the range of 3 to 125 μm by spraying an inert gas such as argon gas or nitrogen gas at a high pressure toward the molten metal flowing out from the nozzle Is made. The particle size of the atomized powder can be adjusted by adjusting the pressure of the inert gas sprayed toward the molten metal that has flowed out.
Since Ga has a low melting point (29.780 ° C.), Ga alone becomes a liquid at room temperature and is difficult to handle as a melting raw material. Therefore, in order to add Ga, a Cu—Ga binary alloy containing Ga: 20 to 50% by mass that maintains a solid state at room temperature and can be crushed is added as a raw material. Ga contained in the molten Cu—In—Ga ternary alloy obtained by melting has the effect of improving the fluidity of the molten metal during atomization and preventing clogging of the nozzle portion.
この発明によると、Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなる光吸収層をスパッタリングにより形成する際にパーティクルを発生させることなくＣｕ−Ｉｎ−Ｇａ三元系合金膜を成膜することができ、したがって従来のようなＩｎ膜の成膜工程を省略することができるので従来の成膜工程よりも少ない工程でＣｕ−Ｉｎ−Ｇａ−Ｓｅ四元系合金膜からなる光吸収層を形成することができ、太陽電池のコスト削減に大いに貢献し得るものである。 According to the present invention, the Cu—In—Ga ternary alloy film is formed without generating particles when the light absorption layer made of the Cu—In—Ga—Se quaternary alloy film is formed by sputtering. Therefore, the conventional In film forming step can be omitted, and therefore, a light absorption layer made of a Cu—In—Ga—Se quaternary alloy film is formed with fewer steps than the conventional film forming step. Can greatly contribute to the cost reduction of solar cells.
実施例
表１に示される成分組成を有するＣｕ−Ｇａ二元系合金原料Ａ〜Ｇを用意し、さら純Ｃｕ原料、純Ｉｎ原料を用意した。
Example Cu-Ga binary alloy raw materials A to G having the component composition shown in Table 1 were prepared, and pure Cu raw material and pure In raw material were prepared.
表１に示されるＣｕ−Ｇａ二元系合金原料Ａ〜Ｇに、純Ｃｕ原料およびＩｎ原料を表２に示される成分組成となるようにカーボン坩堝に装入し高周波溶解し、得られた溶湯を坩堝に装着したノズルから流れ出し、アルゴンの高圧ガスを吹き付けて平均粒径：３５μｍのＣｕ−Ｉｎ−Ｇａ三元系合金粉末を作製した。このＣｕ−Ｉｎ−Ｇａ三元系合金粉末をＡｒ雰囲気中、圧力：１９６ＭＰａ、温度：１４０℃、３０分間保持の条件でホットプレスすることにより表２に示される成分組成を有するＣｕ−Ｉｎ−Ｇａ三元系合金ホットプレス体を作製し、得られたホットプレス体の表面を切削してターゲットに仕上げることにより、本発明Ｃｕ−Ｉｎ−Ｇａ三元系焼結合金ターゲット（以下、本発明ターゲットという）１〜７および比較Ｃｕ−Ｉｎ−Ｇａ三元系焼結合金ターゲット（以下、比較ターゲットという）１〜５を作製した。
得られた本発明ターゲット１〜７および比較ターゲット１〜５の断面組織を電子プローブマイクロアナライザ（ＪＸＡ−８５００Ｆ）（日本電子株式会社製）で観察し、Ｉｎ含有合金相の最大粒径を測定し、その結果を表２に示した。
The Cu—Ga binary alloy raw materials A to G shown in Table 1 were charged with a pure Cu raw material and an In raw material in a carbon crucible so as to have the component composition shown in Table 2 and melted at high frequency, and the resulting molten metal From a nozzle mounted on the crucible and sprayed with a high pressure gas of argon to produce a Cu—In—Ga ternary alloy powder having an average particle size of 35 μm. This Cu—In—Ga ternary alloy powder is hot-pressed in an Ar atmosphere under the conditions of pressure: 196 MPa, temperature: 140 ° C., and holding for 30 minutes, so that Cu—In—Ga having the component composition shown in Table 2 is obtained. A ternary alloy hot-pressed body is prepared, and the surface of the obtained hot-pressed body is cut into a target to obtain a Cu-In-Ga ternary sintered alloy target (hereinafter referred to as the present invention target). ) 1-7 and comparative Cu-In-Ga ternary sintered alloy targets (hereinafter referred to as comparative targets) 1-5.
The cross-sectional structures of the obtained inventive targets 1 to 7 and comparative targets 1 to 5 were observed with an electron probe microanalyzer (JXA-8500F) (manufactured by JEOL Ltd.), and the maximum particle size of the In-containing alloy phase was measured. The results are shown in Table 2.
従来例
表１に示される成分組成を有するＣｕ−Ｇａ二元系合金原料Ａに、純Ｃｕ原料およびＩｎ原料を表２に示される成分組成となるようにカーボン坩堝に装入し高周波溶解し、得られた溶湯を鋳型に鋳造してインゴットを作製し、このインゴットの表面を切削してターゲットに仕上げることにより従来Ｃｕ−Ｉｎ−Ｇａ三元系鋳造合金ターゲット（以下、従来ターゲットという）１を作製した。この従来ターゲット１の断面組織を電子プローブマイクロアナライザ（ＪＸＡ−８５００Ｆ）（日本電子株式会社製）で観察し、Ｉｎ含有合金相の最大粒径を測定し、その結果を表２に示した。
Prior art Cu-Ga binary alloy raw material A having the component composition shown in Table 1 was charged with pure Cu raw material and In raw material into a carbon crucible so as to have the component composition shown in Table 2, and then melted at high frequency. The obtained molten metal is cast into a mold to produce an ingot, and the surface of this ingot is cut to finish it as a target, thereby producing a conventional Cu-In-Ga ternary cast alloy target (hereinafter referred to as conventional target) 1. did. The cross-sectional structure of this conventional target 1 was observed with an electron probe microanalyzer (JXA-8500F) (manufactured by JEOL Ltd.), the maximum particle size of the In-containing alloy phase was measured, and the results are shown in Table 2.
更に、本発明ターゲット１〜７、比較ターゲット１〜５および従来ターゲット１を市販のスパッタリング装置にセットし、
真空到達度：５×１０−５Ｐａ、
電力：８００Ｗ、
雰囲気：Ａｒガス、
ターゲットと基板との距離：７０ｍｍ、
の条件で１時間スパッタを行い、異常放電回数をアーキングカウンターにて測定し、その結果を表２に示した。
Furthermore, this invention target 1-7, comparative target 1-5, and the conventional target 1 are set to a commercially available sputtering apparatus,
Degree of vacuum: 5 × 10 −5 Pa,
Power: 800W
Atmosphere: Ar gas,
The distance between the target and the substrate: 70 mm,
Sputtering was performed for 1 hour under these conditions, and the number of abnormal discharges was measured with an arcing counter. The results are shown in Table 2.
表１〜２に示される結果から、最大粒径：１００μｍの大きなＩｎ含有相を有する鋳造組織からなる従来ターゲット１は、スパッタリングに際して異常放電回数が格段に多く発生するが、これに対してターゲット素地中に分散しているＩｎ含有相の最大粒径が１０μｍ以下の微細なＩｎ含有相を有する本発明ターゲット１〜７はスパッタリングに際した異常放電は全く発生しないことから、本発明ターゲット１〜７は従来ターゲット１に比べて格段に優れていることがわかる。しかし、成分組成がこの発明から外れた値を有する比較ターゲット１〜４および最大粒径が１０μｍを越え２０μｍ未満の大きさのＩｎ含有相を有する比較ターゲット５はスパッタリングに際した異常放電が発生するので好ましくないことが分かる。 From the results shown in Tables 1 and 2, the conventional target 1 composed of a cast structure having a large In-containing phase having a maximum particle size of 100 μm generates a significantly large number of abnormal discharges during sputtering. Since the present invention targets 1-7 having a fine In-containing phase having a maximum particle size of the In-containing phase dispersed therein of 10 μm or less do not generate any abnormal discharge during sputtering, the present invention targets 1-7 are It can be seen that it is much better than the conventional target 1. However, the comparative targets 1 to 4 having a component composition deviating from the present invention and the comparative target 5 having an In-containing phase with a maximum particle size of more than 10 μm and less than 20 μm cause abnormal discharge during sputtering. It turns out that it is not preferable.
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| US20110089030A1 (en) * | 2009-10-20 | 2011-04-21 | Miasole | CIG sputtering target and methods of making and using thereof |
| US8709335B1 (en) | 2009-10-20 | 2014-04-29 | Hanergy Holding Group Ltd. | Method of making a CIG target by cold spraying |
| US8709548B1 (en) | 2009-10-20 | 2014-04-29 | Hanergy Holding Group Ltd. | Method of making a CIG target by spray forming |
| CN102199751B (en) * | 2010-03-25 | 2014-06-04 | 慧濠光电科技股份有限公司 | Manufacturing method of CIGS target material |
| WO2011148600A1 (en) * | 2010-05-24 | 2011-12-01 | 株式会社アルバック | Process for producing cu-in-ga alloy powder, process for producing cu-in-ga-se alloy powder, process for producing sintered cu-in-ga-se alloy, cu-in-ga alloy powder, and cu-in-ga-se alloy powder |
| DE102011012034A1 (en) * | 2011-02-22 | 2012-08-23 | Heraeus Materials Technology Gmbh & Co. Kg | Tubular sputtering target |
| JP2015017297A (en) * | 2013-07-10 | 2015-01-29 | 三菱マテリアル株式会社 | In-BASED CYLINDRICAL SPUTTERING TARGET, AND MANUFACTURING METHOD OF THE SAME |
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