JP5182494B2 - Manufacturing method of sputtering target for chalcopyrite type semiconductor film formation - Google Patents
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Description
この発明は、太陽電池の光吸収層を形成するためのカルコパイライト型半導体膜を成膜する時に使用するスパッタリングターゲットの製造方法に関するものである。 The present invention relates to a method for manufacturing a sputtering target used when forming a chalcopyrite type semiconductor film for forming a light absorption layer of a solar cell.
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合金膜、Ｃｕ−Ｇａ−Ｓｅ合金膜、Ｃｕ−Ｉｎ−Ｓｅ合金膜などのカルコパイライト型半導体膜からなる光吸収層が形成され、このカルコパイライト型半導体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。
前記カルコパイライト型半導体膜からなる光吸収層はＣｕａＩｎｂＧａｃＳｅｄ（但し、単位は原子％、２５≦ａ≦６５、０≦ｂ≦５０、０≦ｃ≦３０、３０≦ｄ≦５０、ａ＋ｂ＋ｃ＋ｄ＝１００）からなる成分組成を有することが一般に知られており、このカルコパイライト型半導体膜の成膜方法として、蒸着法により成膜する方法が知られている。この蒸着法により得られたカルコパイライト型半導体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カルコパイライト型半導体膜からなる光吸収層を形成する方法が提案されている。
このカルコパイライト型半導体膜をスパッタリング法により成膜する方法の一例として、スパッタ装置にＣｕ−ＧａターゲットおよびＩｎターゲットを同時に設置してスパッタすることによりＣｕ−Ｇａ−Ｉｎ膜を成膜し、このＣｕ−Ｇａ−Ｉｎ膜をＳｅ雰囲気中で熱処理してカルコパイライト型半導体膜であるＣｕ−Ｉｎ−Ｇａ−Ｓｅ合金膜を成膜する方法が提案されている（特許文献１参照）。そして、これらＣｕ−ＧａターゲットおよびＩｎターゲットはいずれも鋳造で作製されている。
The light-absorbing layer comprising a chalcopyrite semiconductor film Cu a In b Ga c Se d ( where unit is atomic%, 25 ≦ a ≦ 65,0 ≦ b ≦ 50,0 ≦ c ≦ 30,30 ≦ d ≦ 50, a + b + c + d = 100), and it is generally known that the chalcopyrite type semiconductor film is formed by vapor deposition. Although a light absorption layer made of a chalcopyrite semiconductor film obtained by this vapor deposition method can obtain high energy conversion efficiency, film formation by the vapor deposition method is slow because of its low speed. Therefore, a method for forming a light absorption layer made of a chalcopyrite semiconductor film by a sputtering method has been proposed.
As an example of a method for forming this chalcopyrite semiconductor film by sputtering, a Cu—Ga—In film is formed by simultaneously placing and sputtering a Cu—Ga target and an In target in a sputtering apparatus. A method of forming a Cu—In—Ga—Se alloy film, which is a chalcopyrite semiconductor film, by heat-treating a —Ga—In film in an Se atmosphere has been proposed (see Patent Document 1). And these Cu-Ga target and In target are both produced by casting.
近年、太陽電池の変換効率を高めるためるとともにコストの削減が求められており、このコスト削減の一環としてカルコパイライト型半導体膜の成膜工程の効率化が検討され始め、Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ合金ターゲット、Ｃｕ−Ｇａ−Ｓｅ合金ターゲット、Ｃｕ−Ｉｎ−Ｓｅ合金ターゲットなどを用いてスパッタすることによりカルコパイライト型半導体膜（Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ合金膜、Ｃｕ−Ｇａ−Ｓｅ合金膜、Ｃｕ−Ｉｎ−Ｓｅ合金膜など）を成膜することができるならば、前記複数のターゲットを用いる必要が無く、さらに成膜後、Ｓｅ雰囲気中で熱処理する工程を省略することができるなど製造工程を簡略化でき、それによってコストを削減できることなどから、前記Ｃｕ−Ｉｎ−Ｇａ−Ｓｅ合金ターゲット、Ｃｕ−Ｇａ−Ｓｅ合金ターゲット、Ｃｕ−Ｉｎ−Ｓｅ合金ターゲットを作製すべく研究が進められている。 In recent years, there has been a demand for reducing the cost while increasing the conversion efficiency of solar cells, and as part of this cost reduction, the study of increasing the efficiency of the chalcopyrite-type semiconductor film formation process has started, and Cu-In-Ga-Se A chalcopyrite type semiconductor film (Cu-In-Ga-Se alloy film, Cu-Ga-Se alloy film, by sputtering using an alloy target, a Cu-Ga-Se alloy target, a Cu-In-Se alloy target, etc. If it is possible to form a Cu-In-Se alloy film, etc., it is not necessary to use the plurality of targets. Further, after the film formation, a heat treatment process in a Se atmosphere can be omitted. The Cu—In—Ga—Se alloy target, Cu—Ga—S, and the like can be simplified. Alloy target, studies to produce a Cu-In-Se alloy target has been promoted.
しかし、ＳｅとＩｎおよびＳｅとＧａとは激しく反応する性質を有しており、これらターゲットを鋳造により作製すべく、Ｃｕ溶湯にＳｅ、Ｉｎおよび／またはＧａを添加すると、Ｃｕ溶湯中でＳｅとＩｎおよび／またはＧａとが激しく反応して爆発を起こし、そのために溶解鋳造してカルコパイライト型半導体ターゲットは製造できなかった。
そこで、ＣｕとＳｅは合金化し、ＣｕとＳｅは反応しない性質を利用して、まず、Ｃｕ−Ｓｅ合金溶湯を作製し、このＣｕ−Ｓｅ合金溶湯にＩｎおよび／またはＧａを添加して溶解し鋳造することによりＣｕ−Ｉｎ−Ｇａ−Ｓｅ合金ターゲット、Ｃｕ−Ｇａ−Ｓｅ合金ターゲット、Ｃｕ−Ｉｎ−Ｓｅ合金ターゲットを作製しようとしたが、Ｃｕ−Ｓｅ合金溶湯に単体として残留しているＳｅがＩｎおよび／またはＧａとが激しく反応して爆発を起こすことがあった。
However, Se and In and Se and Ga have a property of reacting violently. In order to produce these targets by casting, when Se, In and / or Ga is added to the molten Cu, Se and In are contained in the molten Cu. In and / or Ga reacts violently to cause an explosion, so that a chalcopyrite type semiconductor target could not be manufactured by melting and casting.
Therefore, using the property that Cu and Se are alloyed and Cu and Se do not react, first, a Cu—Se alloy melt is prepared, and In and / or Ga is added to this Cu—Se alloy melt and dissolved. An attempt was made to produce a Cu—In—Ga—Se alloy target, a Cu—Ga—Se alloy target, and a Cu—In—Se alloy target by casting, but Se remained as a simple substance in the molten Cu—Se alloy. In and / or Ga may react violently and cause an explosion.
そこで、本発明者らは、安全にカルコパイライト型半導体膜と同じ成分組成を有するターゲットを製造するべく研究を行なった。その結果、
（イ）単体のＣｕ粉末、Ｓｅ粉末、Ｉｎ粉末および／またはＧａ粉末を所定の成分組成となるように配合し混合して混合粉末を作製し、この混合粉末をホットプレスすることによりカルコパイライト型半導体ターゲットを製造しようとしたが、ホットプレス中にＳｅ粉末が溶け出し、ＳｅとＩｎ粉末および／またはＧａ粉末が激しく反応してホットプレス装置を破壊することがあるので好ましくない、
（ロ）ＣｕとＳｅとは合金化し、このＣｕとＳｅからなるＣｕ−Ｓｅ二元系銅合金粉末はＩｎ粉末および／またはＧａ粉末と激しく反応することは無いが、Ｓｅを高濃度で含有するＣｕ−Ｓｅ二元系銅合金粉末にはＳｅが単体で残留することがあり、Ｃｕ−Ｓｅ二元系銅合金粉末中に残留した単体のＳｅがあると、このＳｅがＩｎ粉末および／またはＧａ粉末と激しく反応することがあることから、Ｉｎおよび／またはＧａをＣｕと合金化させたＣｕ−Ｉｎ二元系銅合金粉末、Ｃｕ−Ｇａ二元系銅合金粉末およびＣｕ−Ｉｎ−Ｇａ三元系銅合金粉末をＣｕ−Ｓｅ二元系銅合金粉末を作製し、これらＣｕ−Ｉｎ二元系銅合金粉末、Ｃｕ−Ｇａ二元系銅合金粉末およびＣｕ−Ｉｎ−Ｇａ三元系銅合金粉末をＣｕ−Ｓｅ二元系銅合金粉末と混合して混合粉末を作製し、この混合粉末をホットプレスすることによりカルコパイライト型半導体膜成膜用スパッタリングターゲットを安全に量産することができる、などの研究結果が得られたのである。
Therefore, the present inventors conducted research to manufacture a target having the same component composition as that of the chalcopyrite semiconductor film. as a result,
(A) A single powdered Cu, Se powder, In powder and / or Ga powder are mixed and mixed so as to have a predetermined component composition to produce a mixed powder, and this mixed powder is hot pressed to obtain a chalcopyrite type An attempt was made to produce a semiconductor target, but Se powder melts out during hot pressing, and Se and In powder and / or Ga powder may react violently to destroy the hot pressing device, which is not preferable.
(B) Cu and Se are alloyed, and this Cu-Se binary copper alloy powder composed of Cu and Se does not react vigorously with In powder and / or Ga powder, but contains Se at a high concentration. In the Cu-Se binary copper alloy powder, Se may remain as a simple substance, and when there is a single Se remaining in the Cu-Se binary copper alloy powder, this Se is converted into In powder and / or Ga. Cu-In binary copper alloy powder, Cu-Ga binary copper alloy powder, and Cu-In-Ga ternary in which In and / or Ga are alloyed with Cu may react violently with the powder Cu-Se binary copper alloy powder, Cu-In binary copper alloy powder, Cu-Ga binary copper alloy powder and Cu-In-Ga ternary copper alloy powder Is mixed with Cu-Se binary copper alloy powder. A slip powder was prepared, the mixed powder can be safely mass-produced chalcopyrite semiconductor film deposition Sputtering target by hot pressing, is the study results, such as are 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）ＣｕとＳｅからなるＣｕ−Ｓｅ二元系銅合金粉末と、ＣｕとＩｎからなるＣｕ−Ｉｎ二元系銅合金粉末、ＣｕとＧａからなるＣｕ−Ｇａ二元系銅合金粉末およびＣｕとＩｎとＧａからなるＣｕ−Ｉｎ−Ｇａ三元系銅合金粉末のうちの１種とを、ＣｕａＩｎｂＧａｃＳｅｄ（但し、単位は原子％、２５≦ａ≦６５、０≦ｂ≦５０、０≦ｃ≦３０、３０≦ｄ≦５０、ａ＋ｂ＋ｃ＋ｄ＝１００）からなる成分組成を有するように配合し混合して混合粉末を作製し、この混合粉末をホットプレスしてホットプレス体を作製し、このホットプレス体の表面を切削するカルコパイライト型半導体膜成膜用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) C u and the Cu-Se binary copper alloy Powder consisting of Se, Cu-an In binary copper alloy powder consisting of Cu and an In, Cu-Ga binary copper alloy powder consisting of Cu and Ga and the one of Cu-in-Ga ternary copper alloy powder consisting of Cu and in and Ga, C u a in b Ga c Se d ( where unit is atomic%, 25 ≦ a ≦ 65, 0 ≦ b ≦ 50, 0 ≦ c ≦ 30, 30 ≦ d ≦ 50, a + b + c + d = 100) are mixed and mixed to prepare a mixed powder, and the mixed powder is hot pressed to be hot It has a feature in a manufacturing method of a chalcopyrite type semiconductor film-forming sputtering target for producing a press body and cutting the surface of the hot press body.
前記Ｃｕ−Ｉｎ二元系銅合金粉末はＩｎ：２０〜６０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｇａ二元系銅合金粉末はＧａ：２０〜７０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｓｅ二元系銅合金粉末はＳｅ：４０〜８０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｉｎ−Ｇａ三元系銅合金粉末はＩｎ：２０〜７０原子％、Ｇａ：１０〜５０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有することが好ましい。したがって、この発明は、
（２）前記Ｃｕ−Ｓｅ二元系銅合金粉末はＳｅ：４０〜８０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｉｎ二元系銅合金粉末はＩｎ：２０〜６０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｇａ二元系銅合金粉末はＧａ：２０〜７０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｉｎ−Ｇａ三元系銅合金粉末はＩｎ：２０〜７０原子％、Ｇａ：１０〜５０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有する前記（１）記載のカルコパイライト型半導体膜成膜用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 Cu—In binary copper alloy powder contains In: 20 to 60 atomic%, and the balance has a component composition consisting of Cu and inevitable impurities,
The Cu—Ga binary copper alloy powder contains Ga: 20 to 70 atomic%, and the remainder has a component composition consisting of Cu and inevitable impurities,
The Cu-Se binary copper alloy powder contains Se: 40 to 80 atomic%, and the remainder has a component composition consisting of Cu and inevitable impurities,
The Cu—In—Ga ternary copper alloy powder preferably contains In: 20 to 70 atom%, Ga: 10 to 50 atom%, and the balance is composed of Cu and inevitable impurities. Therefore, the present invention
(2) The Cu—Se binary copper alloy powder contains Se: 40 to 80 atomic%, and the remainder has a component composition consisting of Cu and inevitable impurities,
The Cu—In binary copper alloy powder contains In: 20 to 60 atomic%, and the balance has a component composition consisting of Cu and inevitable impurities,
The Cu—Ga binary copper alloy powder contains Ga: 20 to 70 atomic%, and the remainder has a component composition consisting of Cu and inevitable impurities,
The said Cu-In-Ga ternary system copper alloy powder contains In: 20-70 atomic%, Ga: 10-50 atomic%, The remainder has the component composition which consists of Cu and an unavoidable impurity. It is characterized by a method for producing a chalcopyrite type semiconductor film sputtering target.
この発明のカルコパイライト型半導体膜成膜用スパッタリングターゲットの製造方法で使用する原料粉末であるＣｕ−Ｓｅ二元系銅合金粉末、Ｃｕ−Ｉｎ二元系銅合金粉末、Ｃｕ−Ｇａ二元系銅合金粉末およびＣｕ−Ｉｎ−Ｇａ三元系銅合金粉末の成分組成を前述のごとく限定した理由を以下に説明する。
Ｃｕ−Ｓｅ二元系銅合金粉末：
Ｃｕ−Ｓｅ二元系銅合金粉末に含まれるＳｅを４０〜８０原子％に限定した理由は、Ｓｅが８０原子％を越えて含有すると、単体のＳｅが残ることがあり、この単体で残ったＳｅがＣｕ−Ｉｎ二元系銅合金粉末、Ｃｕ−Ｇａ二元系銅合金粉末およびＣｕ−Ｉｎ−Ｇａ三元系銅合金粉末などに含まれる単体のＩｎおよび／またはＧａと反応してホットプレス中に爆発的に反応し、ホットプレス装置を破壊する恐れがあるので好ましくなく、一方、Ｓｅが４０原子％未満含まれるＣｕ−Ｓｅ二元系銅合金粉末を用いて作製したターゲットはＳｅ含有量が３０原子％未満となってカルコパイライト型半導体膜が得られなくなるので好ましくないからである。
Ｃｕ−Ｉｎ二元系銅合金粉末：
Ｃｕ−Ｉｎ二元系銅合金粉末に含まれるＩｎを２０〜６０原子％に限定した理由は、Ｉｎが６０原子％を越えて含有すると粉末化できなくなるので好ましくなく、一方、Ｉｎが２０原子％未満含まれるＣｕ−Ｉｎ二元系銅合金粉末を用いて作製したターゲットはＩｎ含有量が５原子％未満となってカルコパイライト型半導体膜が得られなくなるので好ましくないからである。
Ｃｕ−Ｇａ二元系銅合金粉末：
Ｃｕ−Ｇａ二元系銅合金粉末に含まれるＧａを２０〜７０原子％に限定した理由は、Ｇａが７０原子％を越えて含有するとＣｕ−Ｇａ二元系銅合金粉末を焼結することができなくなるので好ましくなく、一方、Ｇａが２０原子％未満含まれるＣｕ−Ｇａ二元系銅合金粉末を用いて作製したターゲットはＧａ含有量が５原子％未満となってカルコパイライト型半導体膜が得られなくなるので好ましくないからである。
Ｃｕ−Ｉｎ−Ｇａ三元系銅合金粉末：
Ｃｕ−Ｉｎ−Ｇａ三元系銅合金粉末に含まれるＩｎを２０〜７０原子％に限定し、さらにＧａを１０〜５０原子％に限定した理由は、Ｉｎが７０原子％を越えて含有すると粉末化できなくなるので好ましくなく、さらにＧａが５０原子％を越えて含有すると粉末化できるがホットプレスで焼結することができなくなるので好ましくなく、一方、Ｉｎが２０原子％未満、Ｇａが１０原子％未満ではカルコパイライト型半導体が得られなくなるので好ましくないからである。
Cu-Se binary copper alloy powder, Cu-In binary copper alloy powder, Cu-Ga binary copper, which are raw material powders used in the manufacturing method of the sputtering target for film formation of chalcopyrite type semiconductor film of this invention The reason for limiting the component composition of the alloy powder and Cu—In—Ga ternary copper alloy powder as described above will be described below.
Cu-Se binary copper alloy powder:
The reason why Se contained in the Cu-Se binary copper alloy powder is limited to 40 to 80 atomic% is that when Se exceeds 80 atomic%, single Se may remain, and this single element remains. Se is hot pressed by reacting with single In and / or Ga contained in Cu—In binary copper alloy powder, Cu—Ga binary copper alloy powder, Cu—In—Ga ternary copper alloy powder, etc. The target produced using Cu-Se binary copper alloy powder containing less than 40 atomic% of Se is undesirable because it may explosively react inside and destroy the hot press apparatus. This is because it becomes less than 30 atomic% and a chalcopyrite semiconductor film cannot be obtained.
Cu-In binary copper alloy powder:
The reason why In contained in the Cu—In binary copper alloy powder is limited to 20 to 60 atom% is that it is not preferable if In exceeds 60 atom%, since it cannot be pulverized, while In is 20 atom%. This is because a target prepared using a Cu—In binary copper alloy powder contained less than 5% is not preferable because the In content becomes less than 5 atomic% and a chalcopyrite type semiconductor film cannot be obtained.
Cu-Ga binary copper alloy powder:
The reason why Ga contained in the Cu—Ga binary copper alloy powder is limited to 20 to 70 atomic% is that when the Ga content exceeds 70 atomic%, the Cu—Ga binary copper alloy powder is sintered. On the other hand, a target prepared using a Cu—Ga binary copper alloy powder containing less than 20 atomic% of Ga has a Ga content of less than 5 atomic% to obtain a chalcopyrite semiconductor film. This is because it is not preferable.
Cu-In-Ga ternary copper alloy powder:
The reason why In contained in Cu-In-Ga ternary copper alloy powder is limited to 20 to 70 atomic% and Ga is further limited to 10 to 50 atomic% is that powder containing In in excess of 70 atomic% When the Ga content exceeds 50 atomic%, it can be pulverized but cannot be sintered by hot pressing. On the other hand, In is less than 20 atomic% and Ga is 10 atomic%. This is because a chalcopyrite type semiconductor cannot be obtained if it is less than 1, it is not preferable.
また、この発明のカルコパイライト型半導体膜成膜用スパッタリングターゲットの製造方法で使用する原料粉末は、その平均粒径が１〜１５０μｍの範囲内にあることが好ましい。
この発明のカルコパイライト型半導体膜成膜用スパッタリングターゲットの製造方法で使用する原料粉末は、作製したＣｕ−Ｓｅ二元系銅合金溶湯、Ｃｕ−Ｉｎ二元系銅合金溶湯、Ｃｕ−Ｇａ二元系銅合金溶湯およびＣｕ−Ｉｎ−Ｇａ三元系銅合金溶湯をそれぞれアトマイズするかまたは鋳造してインゴットを作製し、このインゴットを粉砕して作製することができる。
Moreover, it is preferable that the raw material powder used with the manufacturing method of the chalcopyrite type | mold sputtering target for film-forming of this invention has the average particle diameter in the range of 1-150 micrometers.
The raw material powder used in the method for producing a chalcopyrite-type semiconductor film sputtering target of the present invention is prepared Cu—Se binary copper alloy melt, Cu—In binary copper alloy melt, Cu—Ga binary. An ingot can be produced by atomizing or casting a molten copper alloy and a Cu-In-Ga ternary copper alloy molten metal, respectively, and pulverizing the ingot.
この発明によると、ＣｕａＩｎｂＧａｃＳｅｄ（但し、単位は原子％、２５≦ａ≦６５、０≦ｂ≦５０、０≦ｃ≦３０、３０≦ｄ≦５０、ａ＋ｂ＋ｃ＋ｄ＝１００）からなる成分組成を有するターゲットを安全に量産することができ、カルコパイライト型半導体膜を一枚のターゲットを用いて１回のスパッタにより成膜することができるので、効率よく成膜することができ、したがって、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, Cu a In b Ga c Se d ( where unit is atomic%, 25 ≦ a ≦ 65,0 ≦ b ≦ 50,0 ≦ c ≦ 30,30 ≦ d ≦ 50, a + b + c + d = 100) from The target having the component composition can be safely mass-produced, and the chalcopyrite type semiconductor film can be formed by one sputtering using a single target, so that it can be efficiently formed, Therefore, it can greatly contribute to the cost reduction of the solar cell.
この発明のカルコパイライト型半導体膜成膜用スパッタリングターゲットの製造方法を具体的に説明する。
無酸素銅をＡｒガスを流しながら溶解し、得られたＣｕ溶湯にＳｅを添加し、Ｓｅ：８０質量％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有するインゴットを作製し、このインゴットを振動ミルにより粉砕し、１５０メッシュの篩を使用して分級し、
Ｓｅ：８０質量％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し平均粒径：３５μｍを有するＣｕ−Ｓｅ二元系銅合金粉末Ａ、並びに、
Ｓｅ：８５質量％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し平均粒径：３５μｍを有するＣｕ−Ｓｅ二元系銅合金粉末Ｂ、
を作製した。
The manufacturing method of the sputtering target for chalcopyrite type semiconductor film formation of this invention is demonstrated concretely.
Oxygen-free copper was melted while flowing Ar gas, Se was added to the obtained Cu molten metal, Se: 80 mass% was contained, and an ingot having a component composition consisting of Cu and inevitable impurities was produced. The ingot is pulverized by a vibration mill, classified using a 150 mesh sieve,
Se: Cu-Se binary copper alloy powder A containing 80% by mass, the remainder having a component composition consisting of Cu and inevitable impurities and having an average particle size of 35 μm, and
Se: Cu-Se binary copper alloy powder B containing 85% by mass, with the balance being a component composition consisting of Cu and inevitable impurities and having an average particle size of 35 μm,
Was made.
さらに、無酸素銅をＡｒガスを流しながら溶解し、得られたＣｕ溶湯にＩｎを添加して溶湯を作製し、この溶湯を鋳造してインゴットを作製し、このインゴットを先端にノズルを有するアルミナ製の坩堝に投入し、高周波により十分に溶解したのちノズルから溶湯を流し、アルゴンガスを吹き付けてアトマイズしたのち１５０メッシュの篩を使用して分級し、
Ｉｎ：７０質量％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し平均粒径：３５μｍを有するＣｕ−Ｉｎ二元系銅合金粉末Ｃ、並びに、
Ｉｎ：７５質量％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し平均粒径：３５μｍを有するＣｕ−Ｉｎ二元系銅合金粉末Ｄ、
を作製した。
Furthermore, oxygen-free copper is melted while flowing Ar gas, In is added to the obtained Cu molten metal to produce a molten metal, the molten metal is cast to produce an ingot, and the ingot is provided with an alumina having a nozzle at the tip. Put into a crucible made of metal, melt sufficiently by high frequency, then flow the molten metal from the nozzle, atomize by blowing argon gas and classify using a 150 mesh sieve,
In: Cu-In binary copper alloy powder C containing 70% by mass, the remainder having a component composition consisting of Cu and inevitable impurities and having an average particle size of 35 μm, and
In: Cu-In binary copper alloy powder D containing 75% by mass, the remainder having a component composition consisting of Cu and inevitable impurities and having an average particle size of 35 μm,
Was made.
さらに、Ｇａ：無酸素銅をＡｒガスを流しながら溶解し、得られたＣｕ溶湯にＧａを添加して溶湯を作製し、この溶湯を鋳造してインゴットを作製し、このインゴットを先端にノズルを有するアルミナ製の坩堝に投入し、高周波により十分に溶解したのちノズルから溶湯を流し、アルゴンガスを吹き付けてアトマイズしたのち１５０メッシュの篩を使用して分級し、
Ｇａ：７０質量％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し平均粒径：３５μｍを有するＣｕ−Ｇａ二元系銅合金粉末Ｅ、並びに、
Ｇａ：７５質量％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し平均粒径：３５μｍを有するＣｕ−Ｇａ二元系銅合金粉末Ｆ、
を作製した。
Furthermore, Ga: Oxygen-free copper is melted while flowing Ar gas, Ga is added to the obtained Cu molten metal to produce a molten metal, and this molten metal is cast to produce an ingot. It is put into a crucible made of alumina and melted sufficiently by high frequency, then the molten metal is poured from the nozzle, atomized by blowing argon gas, and classified using a 150 mesh sieve,
Ga: Cu-Ga binary copper alloy powder E containing 70% by mass, the remainder having a component composition consisting of Cu and inevitable impurities and having an average particle size of 35 μm, and
Ga: Cu-Ga binary copper alloy powder F containing 75% by mass, the remainder having a component composition consisting of Cu and inevitable impurities and having an average particle size of 35 μm,
Was made.
さらに、無酸素銅をＡｒガスを流しながら溶解し、得られたＣｕ溶湯にＩｎおよびＧａを添加して溶湯を作製し、この溶湯を鋳造してインゴットを作製し、このインゴットを先端にノズルを有するアルミナ製の坩堝に投入し、高周波により十分に溶解したのちノズルから溶湯を流し、アルゴンガスを吹き付けてアトマイズしたのち１５０メッシュの篩を使用して分級し、表１に示される成分組成および平均粒径を有するＣｕ−Ｉｎ−Ｇａ三元系銅合金粉末Ｇ〜Ｎを作製した。 Furthermore, oxygen-free copper is melted while flowing Ar gas, In and Ga are added to the obtained Cu molten metal to produce a molten metal, and the molten metal is cast to produce an ingot. The mixture is poured into a crucible made of alumina and sufficiently melted by high frequency, and then the molten metal is poured from a nozzle, atomized by blowing argon gas, classified using a 150 mesh sieve, and the component composition and average shown in Table 1 Cu-In-Ga ternary copper alloy powders G to N having a particle size were prepared.
これらＣｕ−Ｓｅ二元系銅合金粉末Ａ〜Ｂ、Ｃｕ−Ｉｎ二元系銅合金粉末Ｃ〜Ｄ、Ｃｕ−Ｇａ二元系銅合金粉末Ｅ〜Ｆ並びに表１に示される成分組成および平均粒径を有するＣｕ−Ｉｎ−Ｇａ三元系銅合金粉末Ｇ〜Ｎを表２〜３に示されるように秤量し、ロッキングミキサーで３０分以上混合し、混合して得られた混合粉末を温度：１４０℃、圧力：５．８８×１０−７Ｐａ、２時間保持の条件で焼結し、得られた焼結体を機械加工することにより表２〜３に示される成分組成を有するターゲットを作製し、本発明法１〜９および比較法１〜３を実施した。 These Cu—Se binary copper alloy powders A to B, Cu—In binary copper alloy powders C to D, Cu—Ga binary copper alloy powders E to F, and the component compositions and average grains shown in Table 1 Cu—In—Ga ternary copper alloy powders G to N having a diameter are weighed as shown in Tables 2 to 3, mixed with a rocking mixer for 30 minutes or more, and the mixed powder obtained by mixing is temperature: 140 degreeC, pressure: 5.88 * 10 <-7> Pa It sinters on the conditions hold | maintained for 2 hours, The target which has the component composition shown by Tables 2-3 is produced by machining the obtained sintered compact. And this invention method 1-9 and comparative methods 1-3 were implemented.
その結果、本発明法１〜９によると爆発することなくカルコパイライト型半導体膜成膜用スパッタリングターゲットを安全に製造することができたが、比較法１〜３ではホットプレス中に爆発が起きたり、焼結できなかったり、カルコパイライト型半導体膜成膜用ターゲットができなかったりして好ましくない現象が現れることがわかる。 As a result, according to the present invention methods 1 to 9, a sputtering target for film formation of chalcopyrite type semiconductor film could be safely produced without explosion. However, in comparison methods 1 to 3, an explosion occurred during hot pressing. It can be seen that an undesired phenomenon appears because sintering cannot be performed or a chalcopyrite type semiconductor film deposition target cannot be formed.
Claims (2)
前記Ｃｕ−Ｇａ二元系銅合金粉末はＧａ：２０〜７０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｓｅ二元系銅合金粉末はＳｅ：４０〜８０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有し、
前記Ｃｕ−Ｉｎ−Ｇａ三元系銅合金粉末はＩｎ：２０〜７０原子％、Ｇａ：１０〜５０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有することを特徴とする請求項１記載のカルコパイライト型半導体膜成膜用スパッタリングターゲットの製造方法。 The Cu—In binary copper alloy powder contains In: 20 to 60 atomic%, and the balance has a component composition consisting of Cu and inevitable impurities,
The Cu—Ga binary copper alloy powder contains Ga: 20 to 70 atomic%, and the remainder has a component composition consisting of Cu and inevitable impurities,
The Cu-Se binary copper alloy powder contains Se: 40 to 80 atomic%, and the remainder has a component composition consisting of Cu and inevitable impurities,
The Cu-In-Ga ternary copper alloy powder contains In: 20 to 70 atomic%, Ga: 10 to 50 atomic%, and the remainder has a composition composed of Cu and inevitable impurities. Item 14. A method for producing a chalcopyrite type semiconductor film sputtering target according to Item 1.
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