JP2015071830A - Cu-Ga-BASED ALLOY SPUTTERING TARGET MATERIAL WITH LOW OXYGEN CONTENT - Google Patents
Cu-Ga-BASED ALLOY SPUTTERING TARGET MATERIAL WITH LOW OXYGEN CONTENT Download PDFInfo
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本発明は、太陽電池の光吸収薄膜層を製造するための低酸素Ｃｕ−Ｇａ系合金スパッタリングターゲット材に関する。 The present invention relates to a low oxygen Cu—Ga based alloy sputtering target material for producing a light absorbing thin film layer of a solar cell.
従来より、太陽電池の光吸収層を製造するためのスパッタリングターゲット材として、Ｃｕ−Ｇａ系ターゲット材が用いられている。このＣｕ−Ｇａ系ターゲット材は、例えば特開２０００−７３１６３号公報（特許文献１）に開示されているように、Ｇａの組成を１５重量％から７０重量％として溶解法により鋳造することにより、含有酸素を２００ｐｐｍ以下の低酸素にすることで、スパッタリングにより成膜中に異常放電やパーティクル、スプラッシュの発生がなく、酸化物による汚染もなく、高品質で組成の正確な太陽電池の光吸収層用薄膜を成膜することができるというものである。このように鋳造法により製造されることが多い。 Conventionally, a Cu—Ga based target material has been used as a sputtering target material for producing a light absorption layer of a solar cell. For example, as disclosed in JP-A-2000-73163 (Patent Document 1), this Cu-Ga-based target material is cast by a melting method with a Ga composition of 15 wt% to 70 wt%, By reducing the oxygen content to 200 ppm or less, there is no abnormal discharge, particles or splash during film formation by sputtering, no contamination by oxides, high quality and accurate composition of light absorption layer of solar cell A thin film can be formed. Thus, it is often manufactured by a casting method.
しかしながら、特許文献１に示す溶解法による鋳造法の場合には、溶解鋳造して作製した高Ｇａ含有Ｃｕ−Ｇａ二元系合金ターゲットは、Ｇａの含有量が増すにつれて、硬くかつ脆くなり、Ｇａが３０質量％以上含む高Ｇａ含有Ｃｕ−Ｇａ二元系合金ターゲットは、表面を切削加工して製品に仕上げる時に割れまたは欠損が発生し、不良品が多く発生するので、歩留りが悪くなるという問題がある。 However, in the case of the casting method by the melting method shown in Patent Document 1, the high Ga content Cu—Ga binary alloy target produced by melt casting becomes hard and brittle as the Ga content increases. The high Ga content Cu—Ga binary alloy target containing 30% by mass or more causes cracking or chipping when the surface is cut into a finished product, resulting in many defective products, resulting in poor yield. There is.
そのために、特許文献１に示す溶解法による鋳造法に代わって、例えば、特開２００８−１３８２３２号公報（特許文献２）や特開２０１０−２６５５４４号公報（特許文献３）が開示されている。上記特許文献１のような、Ｇａ濃度が高くなるに伴い、硬くかつ脆くなり、機械加工時に割れや欠けを発生する鋳造法と比較して、ミクロ組織が微細で、かつ高強度が得られる粉末冶金法として、特に高濃度のＧａを含むターゲットの製造に用いられている。 Therefore, instead of the casting method based on the melting method shown in Patent Document 1, for example, Japanese Patent Application Laid-Open No. 2008-138232 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2010-265544 (Patent Document 3) are disclosed. As described in Patent Document 1, as the Ga concentration increases, the powder becomes harder and more brittle and has a finer microstructure and higher strength than a casting method that generates cracks and chips during machining. As a metallurgical method, it is particularly used for the production of a target containing a high concentration of Ga.
しかしながら、上記した粉末冶金法によるターゲット材は、一般に鋳造法によるターゲット材と比較し、酸素値が高くなるという課題がある。例えば、特許文献１における実施例１に記載されている真空溶解鋳造法で作製されたＣｕ−Ｇａ系ターゲット材の酸素含有量が２５ｐｐｍであるのに対し、特許文献３における実施例に記載されている粉末冶金法で作製されたＣｕ−Ｇａ系ターゲット材の酸素含有量は２５０〜３１０ｐｐｍと高いターゲット材が示されている。 However, the above-described target material by the powder metallurgy method has a problem that the oxygen value is generally higher than the target material by the casting method. For example, the oxygen content of the Cu-Ga based target material produced by the vacuum melting casting method described in Example 1 in Patent Document 1 is 25 ppm, whereas it is described in the Example in Patent Document 3. A target material having a high oxygen content of 250 to 310 ppm is shown for a Cu-Ga-based target material produced by powder metallurgy.
一方、特許文献２では低Ｇａと高Ｇａの粉末を混合した原料粉末を固化成形しているが、Ｃｕ−Ｇａ系合金は２元状態図からわかるとおり、Ｇａ含有量が増加するに伴い、固相線（溶融開始温度）が急激に低下するため、固化成形時の溶融を避けるために固化成形温度を極端に低く設定せざるを得なくなるという問題がある。したがって、特許文献２において、低Ｇａと高Ｇａの混合粉末を用いた原料粉末を固化成形するためには高温固化成形するには問題がある。また、特許文献２の場合は低酸素Ｃｕ−Ｇａ系合金粉末については何らの解明もされていない。
上述したように、特許文献１は、鋳造法のため、硬くかつ脆くなり、機械加工時に割れや欠けを発生する問題があり、一般に粉末冶金法によるターゲット材に移行されて来ている。しかし、また、粉末冶金法による特許文献２のような、混合粉末を用いる場合は、実施例に示すように全て２００℃と低い温度で固化成形されている。このように低い固化成形温度では十分にターゲット材の密度を上昇できない場合があり、特許文献１の段落［０００４］に記載されている通り、低密度、高酸素はスパッタ時に異常放電やパーティクルの発生の原因になるという問題がある。 As described above, Patent Document 1 has a problem that it is hard and brittle because of a casting method, and has a problem of cracking or chipping during machining, and has generally been shifted to a target material by a powder metallurgy method. However, when using the mixed powder as in Patent Document 2 by the powder metallurgy method, all are solidified and molded at a low temperature of 200 ° C. as shown in the examples. In such a low solidification molding temperature, the density of the target material may not be sufficiently increased. As described in paragraph [0004] of Patent Document 1, low density and high oxygen cause abnormal discharge and generation of particles during sputtering. There is a problem of causing.
また、２相以上の構成相からなるターゲット材も、各相のスパッタ率の違いなどが原因でスパッタの後半にターゲット材の表面に凹凸が発生し、パーティクルの増加による薄膜の不良率増加が生じる課題がある。また、特許文献３に開示する酸素含有量は２５０〜３１０ｐｐｍと高いターゲット材が提案されている。しかしながら、このような最低でも２５０ｐｐｍと高い酸素含有量では、スパッタリングによる成膜中に異常放電やパーティクル、スプラッシュの発生を抑制し、酸化物による汚染もなく、高品質で組成の正確な太陽電池の光吸収層用薄膜を成膜させるには必ずしも十分でない。 In addition, target materials consisting of two or more constituent phases also have irregularities on the surface of the target material in the latter half of sputtering due to differences in the sputtering rate of each phase, resulting in an increase in thin film defect rate due to an increase in particles. There are challenges. Further, a target material having a high oxygen content of 250 to 310 ppm disclosed in Patent Document 3 has been proposed. However, with such a high oxygen content of at least 250 ppm, the generation of abnormal discharge, particles and splash during film formation by sputtering is suppressed, and there is no contamination by oxides. It is not always sufficient to form a light absorbing layer thin film.
上述のような粉末冶金法の課題である高い酸素含有量を改善するため、発明者は原料となる合金粉末の組成とガスアトマイズ法等による酸素含有量、結晶粒径および固化成形温度を詳細に研究した結果、本発明に至った。その発明の要旨とするところは、
（１）原子％で、Ｇａを２５％以上、４０％未満含み、残部Ｃｕおよび不可避的不純物からなり、酸素含有量が２５０ｐｐｍ未満、かつ結晶粒径が１０μｍ超〜３５μｍとしたことを特徴とするＣｕ−Ｇａ系合金スパッタリングターゲット材にある。
In order to improve the high oxygen content, which is a problem of the powder metallurgy method as described above, the inventors have studied in detail the composition of the alloy powder as a raw material, the oxygen content by the gas atomization method, the crystal grain size and the solidification molding temperature. As a result, the present invention has been achieved. The gist of the invention is that
(1) Atomic%, containing Ga of 25% or more and less than 40%, remaining Cu and inevitable impurities, oxygen content of less than 250 ppm, and crystal grain size of more than 10 μm to 35 μm Cu-Ga alloy sputtering target material.
以上述べたように、本発明により、太陽電池の光吸収薄膜層を製造するための低酸素Ｃｕ−Ｇａ系スパッタリングターゲット材を提供することを可能とした。 As described above, according to the present invention, it is possible to provide a low oxygen Cu—Ga based sputtering target material for producing a light absorbing thin film layer of a solar cell.
以下、本発明について詳細に説明する。
本発明の最も重要な点は、Ｇａ含有量と結晶粒径により、酸素含有量の低いＣｕ−Ｇａ系ターゲット材を得ることにある。本発明におけるＧａ含有量の領域のＣｕ−Ｇａ合金をガスアトマイズ法等の製造法により粉末とすると、Ｇａが２５％未満、もしくは４０％以上の含有量に当たる範囲のＣｕ−Ｇａ系合金よりも酸素含有量が低くなることを見出した。
Hereinafter, the present invention will be described in detail.
The most important point of the present invention is to obtain a Cu—Ga based target material having a low oxygen content depending on the Ga content and the crystal grain size. When the Cu-Ga alloy in the region of Ga content in the present invention is powdered by a manufacturing method such as a gas atomizing method, the oxygen content is higher than that of a Cu-Ga alloy in which Ga is less than 25% or 40% or more. The amount was found to be lower.
この現象の詳細な原因は定かではないが、Ｃｕ−Ｇａ系の２元状態図において、本発明におけるＧａ含有量の領域で生成する相は、主にＣｕ9 Ｇａ4 相であり、この相と酸素の親和性が低いことが影響しているのではないかと考えられる。 Although the detailed cause of this phenomenon is not clear, in the Cu-Ga based binary phase diagram, the phase generated in the Ga content region in the present invention is mainly the Cu 9 Ga 4 phase. This may be due to the low affinity of oxygen.
一般的に金属粉末は真空中であっても高温に加熱されると周囲のわずかに残存する酸素と反応し、酸素含有量が増加する傾向がある。しかしながら、本合金においては４００℃未満の低温で固化成形した場合に、特に酸素含有量の増加が大きく、４００℃以上の高温で固化成形した場合に酸素含有量の増加が小さく抑えられることを見出した。この現象についての詳細な原因は不明であるが、本合金の主相であるＣｕ9 Ｇａ4 相の酸素との親和性が低く、真空中で４００℃以上の高温に加熱すると酸素を含有できる平衡値が、４００℃未満の低い温度よりも小さくなるのではないかと考えられる。なお、上述のように単一合金粉末を原料として固化成形に用いることで、より高い温度での固化成形が可能になる。また、本発明によるＣｕ−Ｇａ系ターゲット材は結晶粒径が１０μｍ超〜３５μｍであり、特許文献３よりも比較的粗大である。 In general, even when the metal powder is heated to a high temperature even in a vacuum, it reacts with the slightly remaining oxygen in the surrounding area and tends to increase the oxygen content. However, in this alloy, it has been found that the increase in oxygen content is particularly large when solidified at a low temperature of less than 400 ° C., and the increase in oxygen content can be suppressed to a small extent when solidified at a high temperature of 400 ° C. or higher. It was. The detailed cause of this phenomenon is unknown, but the affinity with oxygen in the Cu 9 Ga 4 phase, which is the main phase of this alloy, is low, and it can contain oxygen when heated to a high temperature of 400 ° C. or higher in a vacuum. It is thought that the value is smaller than a low temperature of less than 400 ° C. As described above, by using a single alloy powder as a raw material for solidification molding, solidification molding at a higher temperature becomes possible. Further, the Cu—Ga based target material according to the present invention has a crystal grain size of more than 10 μm to 35 μm, which is relatively coarser than Patent Document 3.
一般に本合金系では結晶粒が微細になることで高い強度が得られるとされているが、上述のように本発明によるターゲット材は比較的粗大な結晶粒度である。しかしながら、十分に実用に耐える強度を有していることがわかった。この理由として、本発明ターゲット材は酸素含有量が低いため、結晶粒度が比較的粗大であっても、粒界の酸化物などが少なく、強度に優れている可能性があると思われる。特に、酸素含有量を２５０ｐｐｍ未満とすることで高い強度が得られることを見出した。なお、アトマイズ粉末の結晶粒径は本発明範囲の結晶粒径より十分に小さいが、固化成形温度の上昇にともない固化成形体の結晶粒径は大きくなる。したがって、４００〜８５０℃で固化成形することにより、本発明範囲の粒径の固化成形体を得ることができる。 Generally, in this alloy system, it is said that high strength can be obtained by making crystal grains fine, but as described above, the target material according to the present invention has a relatively coarse crystal grain size. However, it has been found that it has sufficient strength to withstand practical use. The reason for this is that the target material of the present invention has a low oxygen content, so that even if the crystal grain size is relatively coarse, there are few oxides at the grain boundaries and the strength may be excellent. In particular, it has been found that high strength can be obtained by setting the oxygen content to less than 250 ppm. Although the crystal grain size of the atomized powder is sufficiently smaller than the crystal grain size within the range of the present invention, the crystal grain size of the solidified molded body increases as the solidification molding temperature rises. Therefore, a solidified molded product having a particle size within the range of the present invention can be obtained by solidification molding at 400 to 850 ° C.
以下、本発明に係る規制した理由を説明する。
Ｇａを２５％以上、４０％未満
Ｇａ含有量が２５％以上、４０％未満の範囲にすることで、２００ｐｐｍ以下の低い酸素含有量を有するＣｕ−Ｇａ系合金粉末が実現できる。２５％未満もしくは４０％以上では、酸素含有量が増加してしまう。その理由は、上述したように、Ｃｕ−Ｇａ系の２元状態図において、上記範囲でのＧａ含有量の領域で生成する相が、主にＣｕ9 Ｇａ4 相で、この相と酸素との親和性が低いことが影響すると考えられる。特にガスアトマイズ法等の製造法により顕著であり、その範囲を２５％以上、４０％未満とした。好ましくは２９％超え、３８％以下、より好ましくは３０％以上、３５％以下とする。
Hereinafter, the reason for the regulation according to the present invention will be described.
Cu-Ga type alloy powder which has a low oxygen content of 200 ppm or less is realizable by making Ga content 25% or more and less than 40% Ga content in the range of 25% or more and less than 40%. If it is less than 25% or 40% or more, the oxygen content increases. The reason is that, as described above, in the Cu-Ga based binary phase diagram, the phase generated in the Ga content region in the above range is mainly the Cu 9 Ga 4 phase, and this phase and oxygen Low affinity is considered to have an effect. In particular, it is remarkable by a manufacturing method such as a gas atomizing method, and the range is set to 25% or more and less than 40%. Preferably it exceeds 29% and is 38% or less, more preferably 30% or more and 35% or less.
スパッタリングターゲット材の酸素含有量が２５０ｐｐｍ未満
酸素含有量が２５０ｐｐｍ未満であると、スパッタリングによる成膜中に異常放電やパーティクル、スプラッシュの発生がなく、酸化物による汚染もなく、高品質で組成の正確な太陽電池の光吸収層用薄膜を成膜できることから、その上限を２５０ｐｐｍ未満とした。また、この範囲の酸素含有量とすることにより高い強度も同時に得られる。好ましくは２００ｐｐｍ以下とする。より好ましくは１８０ｐｐｍ以下とする。
If the oxygen content of the sputtering target material is less than 250 ppm, and the oxygen content is less than 250 ppm, there will be no abnormal discharge, particles and splash during film formation by sputtering, no contamination by oxides, high quality and accurate composition. Since the thin film for light absorption layers of a solar cell can be formed, the upper limit was made less than 250 ppm. Moreover, high intensity | strength is simultaneously obtained by setting it as the oxygen content of this range. Preferably it is 200 ppm or less. More preferably, it is 180 ppm or less.
結晶粒径が１０μｍ超〜３５μｍ
結晶粒径が１０μｍ以下となると十分な成形温度とすることができず、また、成形時の酸素量上昇の抑制効果が得られない。
Crystal grain size more than 10μm ~ 35μm
When the crystal grain size is 10 μm or less, a sufficient molding temperature cannot be obtained, and the effect of suppressing an increase in the amount of oxygen during molding cannot be obtained.
実質単一の合金粉末を用いる同じＧａ量のターゲット材を粉末冶金法で作製する場合、低Ｇａと高Ｇａ粉末の混合とするより、単一合金とするほうが、より高い温度で固化成形ができるため好ましい。その理由は、上述したように、Ｃｕ−Ｇａ系の２元状態図から分かるように、Ｇａ含有量が増加するに伴い、固相線（溶融開始温度）が急激に低下するため、固化成形時の溶融を避けるために固化成形温度を低く設定せざるを得ないことから、より高い温度で固化成形を行いたくとも固化成形温度を高く設定できないからである。なお、本発明において、実質単一の合金粉末を用いるとは、同等Ｇａ量の合金粉末でも、アトマイズのロットによりＧａ量は不可避的に前後する。このように同等Ｇａ量で異ロットの粉末を混合したものも、実質単一の合金粉末とみなして扱う。 When a target material having the same Ga amount using a substantially single alloy powder is produced by the powder metallurgy method, a single alloy can be solidified at a higher temperature than a mixture of low Ga and high Ga powder. Therefore, it is preferable. As described above, the reason is that, as can be seen from the Cu-Ga binary phase diagram, as the Ga content increases, the solidus line (melting start temperature) rapidly decreases. This is because the solidification molding temperature must be set low in order to avoid melting, and therefore the solidification molding temperature cannot be set high even if solidification molding is performed at a higher temperature. In the present invention, the fact that a substantially single alloy powder is used means that the Ga amount inevitably varies depending on the lot of atomization even if the alloy powder has an equivalent Ga amount. A mixture of powders of different lots with the same Ga amount is treated as a substantially single alloy powder.
粉末製造法
本合金粉末はガスアトマイズ法やディスクアトマイズ法に代表される水アトマイズ法以外のアトマイズ法により作製することが好ましい。すなわち、真空溶解法などで得た溶製材や急冷薄帯法により得た薄帯を原料にこれらを粉砕する粉砕法や水アトマイズ法などの方法では酸素含有量が高くなってしまう。なお、タンク内の置換や溶湯に吹き付けるガスはＡｒがある。
Powder Production Method The alloy powder is preferably produced by an atomizing method other than the water atomizing method represented by the gas atomizing method and the disk atomizing method. That is, the oxygen content becomes high in methods such as a pulverization method or a water atomization method in which a melted material obtained by a vacuum melting method or the like or a ribbon obtained by a rapid cooling ribbon method is used as a raw material. Note that Ar is used as a gas to be replaced in the tank or blown to the molten metal.
以下、本発明について、実施例によって具体的に説明する。
表１に示す組成に秤量した溶解原料を、耐火物坩堝にて２０ｋｇ溶解し、内径８ｍｍのノズルからこの溶湯を出湯し、表１に示すガスによって噴霧した。これら粉末を目開き５００μｍの網により分級し、５００μｍ以下の粉末について酸素分析を行なった。作製した合金粉末を表２の組み合わせで合計組成となるように混合した原料粉末とした。なお、表２において、１種類の合金粉末のみ記載しているものは、他の粉末と混合することなく、単一合金粉末を原料粉末として用いたものである。また、組成の後に続く括弧は噴霧ガスを示す。
Hereinafter, the present invention will be specifically described by way of examples.
20 kg of the melted raw material weighed to the composition shown in Table 1 was melted in a refractory crucible, this molten metal was discharged from a nozzle having an inner diameter of 8 mm, and sprayed with the gas shown in Table 1. These powders were classified with a mesh having an opening of 500 μm, and oxygen analysis was performed on powders having a size of 500 μm or less. The produced alloy powder was mixed as shown in Table 2 so that the total composition was obtained. In Table 2, what is described in only one type of alloy powder is a single alloy powder used as a raw material powder without being mixed with other powders. The parentheses following the composition indicate the atomizing gas.
これらの原料粉末を表２に示す条件で固化成形し、その固化成形体から試料を切り出し、酸素含有量を分析した。なお、ホットプレス法は直径１０５ｍｍの黒鉛型を用い、高さ約１０ｍｍとなるように真空中で固化成形した。ＨＩＰ法では直径１５０ｍｍで高さ１００ｍｍの炭素鋼の容器を用い、これに粉末を充填後、脱気封入し、固化成形した。また、いずれの工法においても、成形体のほぼ中央部より、ワイヤーカットおよび平面研磨により酸素分析用の試料を作製した。また、比較として、減圧したＡｒ雰囲気中の耐火物坩堝内で誘導溶解した原料を、直径が１０５ｍｍで高さが１００ｍｍの鋳型に鋳込んだものを、鋳造材として比較材とした。 These raw material powders were solidified and molded under the conditions shown in Table 2, samples were cut out from the solidified molded bodies, and the oxygen content was analyzed. In the hot press method, a graphite mold having a diameter of 105 mm was used, and solidified and molded in a vacuum so that the height was about 10 mm. In the HIP method, a carbon steel container having a diameter of 150 mm and a height of 100 mm was used, filled with powder, degassed and sealed, and solidified. In any of the construction methods, a sample for oxygen analysis was produced from approximately the center of the molded body by wire cutting and planar polishing. For comparison, a comparative material was prepared by casting a raw material inductively melted in a refractory crucible in a decompressed Ar atmosphere into a mold having a diameter of 105 mm and a height of 100 mm.
ターゲット材の結晶粒径としては、作製したターゲット材から切り出した試験片を鏡面研磨し、この研磨面を酸溶液で腐食し光学顕微鏡写真を撮影し、この写真に一定長さの試験直線を引き、この直線と結晶粒界との交点の数を測定し、試験直線長さと交点の数の比、すなわち、［試験直線長さ（μｍ）］／［交点の数（個）］により評価した。また、ターゲットの抗折強度は、作製したターゲット材から２ｍｍ角で長さが２０ｍｍの試験片を採取し、３点曲げ抗折試験機により評価した。 As for the crystal grain size of the target material, a test piece cut out from the prepared target material is mirror-polished, the polished surface is corroded with an acid solution, an optical micrograph is taken, and a test straight line of a certain length is drawn on this photograph. Then, the number of intersections between the straight line and the grain boundary was measured, and evaluated by the ratio of the test straight line length to the number of the intersections, that is, [test straight line length (μm)] / [number of intersections (pieces)]. In addition, the bending strength of the target was evaluated by taking a 2 mm square test piece having a length of 20 mm from the prepared target material and using a three-point bending bending tester.
表１に示すように、Ｎｏ．１〜６は本発明例であり、Ｎｏ．７〜８は比較例である。比較例Ｎｏ．７は、合金粉末の組成であるＧａの含有量が低いために酸素含有量が高い。比較例Ｎｏ．８は、合金粉末の組成であるＧａの含有量が高いために比較例Ｎｏ．７と同様に、酸素含有量が高い。これに対し、本発明例であるＮｏ．１〜６は、いずれも本発明条件を満足し、Ａｒガスで噴霧した粉末の酸素分析値はいずれも１００ｐｐｍ〜１８０ｐｐｍと低い値を示した。 As shown in Table 1, no. Nos. 1 to 6 are examples of the present invention. 7 to 8 are comparative examples. Comparative Example No. No. 7 has a high oxygen content because the content of Ga, which is the composition of the alloy powder, is low. Comparative Example No. No. 8 is comparative example No. 8 because the content of Ga which is the composition of the alloy powder is high. Similar to 7, the oxygen content is high. On the other hand, No. which is an example of the present invention. Nos. 1 to 6 all satisfied the conditions of the present invention, and the oxygen analysis values of the powder sprayed with Ar gas all showed low values of 100 ppm to 180 ppm.
この表２に示すように、Ｎｏ．１〜８は本発明例であり、Ｎｏ．９〜１２は比較例である。比較例Ｎｏ．９は、原料合金粉末の組成であるＧａの含有量が低いために酸素含有量が高くなる。そのためにスパッタ成膜時に異常放電やパーテクルが発生し、酸化物による汚染がされる。比較例Ｎｏ．１０は、合金粉末の組成であるＧａの含有量が高いために酸素含有量が高くなり、スパッタ成膜時に異常放電やパーテクルが発生し、酸化物による汚染がされる。 As shown in Table 2, no. 1-8 are examples of the present invention. 9 to 12 are comparative examples. Comparative Example No. No. 9 has a high oxygen content because the content of Ga, which is the composition of the raw material alloy powder, is low. For this reason, abnormal discharge and particles occur during sputtering film formation, and contamination with oxides occurs. Comparative Example No. No. 10 has a high content of Ga, which is the composition of the alloy powder, so that the oxygen content is high, and abnormal discharge and particles occur during sputtering film formation, resulting in contamination with oxides.
比較例Ｎｏ．１１は、スパッタリングターゲット材の酸素含有量が高く、かつ結晶粒径が小さいために十分な成形温度とすることができず、抗折強度が得られず、かつ、酸素が高いためにスパッタ成膜時に異常放電やパーテクルが発生し、酸化物による汚染がされる。比較例Ｎｏ．１２は、結晶粒径が大きくアトマイズ法ではなく鋳造のため、十分な抗折強度が得られず、また、加工性が悪い。 Comparative Example No. No. 11 is a sputtering target material because the oxygen content of the sputtering target material is high and the crystal grain size is small, so that a sufficient molding temperature cannot be obtained, the bending strength cannot be obtained, and the oxygen content is high. Occasionally, abnormal discharges and particles occur, causing contamination with oxides. Comparative Example No. No. 12 has a large crystal grain size and is not an atomizing method but is cast, so that a sufficient bending strength cannot be obtained, and workability is poor.
これに対し、本発明例であるＮｏ．１〜８は、いずれも本発明条件を満足したスパッタリングターゲット材は３５０ＭＰａ以上の高い抗折強度を有し、いずれもワイヤカットや平面研磨など、通常の機械加工により、寸法は外径が１０１．６ｍｍで厚さが５ｍｍのスパッタリングターゲット材への加工が可能であった。 On the other hand, No. which is an example of the present invention. Nos. 1 to 8 are sputtering target materials that satisfy the conditions of the present invention, and have a high bending strength of 350 MPa or more, and all have an outer diameter of 101. Processing to a sputtering target material having a thickness of 6 mm and a thickness of 5 mm was possible.
以上のように、本発明により、酸素が低減され、最適な成形温度が得られ、３５０ＭＰａ以上の高い抗折強度を有し、かつ加工性の優れたスパッタリングターゲット材を得ることが出来、このスパッタリングターゲット材を用いてスパッタリングを行った時に安定かつ効率良く、膜組成の均一なＣｕ−Ｇａスパッタリング膜を、例えば薄膜太陽電池の光吸収層を構成する層として形成することができる極めて優れた効果を奏するものである。
特許出願人 山陽特殊製鋼株式会社
代理人 弁理士 椎 名 彊
As described above, according to the present invention, oxygen can be reduced, an optimum molding temperature can be obtained, and a sputtering target material having a high bending strength of 350 MPa or more and excellent workability can be obtained. When a sputtering is performed using a target material, a Cu-Ga sputtering film having a uniform and uniform film composition can be formed, for example, as a layer constituting a light absorption layer of a thin film solar cell. It is what you play.
Patent Applicant Sanyo Special Steel Co., Ltd.
Attorney: Attorney Shiina
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02250964A (en) * | 1989-03-24 | 1990-10-08 | Hitachi Metals Ltd | Sendust alloy target and production thereof |
| JP2000309865A (en) * | 1999-02-25 | 2000-11-07 | Nikko Materials Co Ltd | Ni-P ALLOY SPUTTERING TARGET AND ITS MANUFACTURE |
| JP2010265544A (en) * | 2009-04-14 | 2010-11-25 | Kobelco Kaken:Kk | Cu-Ga ALLOY SPUTTERING TARGET AND PROCESS FOR MANUFACTURING THEREOF |
| WO2011010529A1 (en) * | 2009-07-23 | 2011-01-27 | Jx日鉱日石金属株式会社 | Sintered cu-ga alloy sputtering target, method for producing the target, light-absorbing layer formed from sintered cu-ga alloy sputtering target, and cigs solar cell using the light-absorbing layer |
| WO2011013471A1 (en) * | 2009-07-27 | 2011-02-03 | Jx日鉱日石金属株式会社 | Sintered cu-ga sputtering target and method for producing the target |
| JP2012031508A (en) * | 2010-06-28 | 2012-02-16 | Hitachi Metals Ltd | Cu-Ga ALLOY TARGET MATERIAL AND METHOD FOR MANUFACTURING THE SAME |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02250964A (en) * | 1989-03-24 | 1990-10-08 | Hitachi Metals Ltd | Sendust alloy target and production thereof |
| JP2000309865A (en) * | 1999-02-25 | 2000-11-07 | Nikko Materials Co Ltd | Ni-P ALLOY SPUTTERING TARGET AND ITS MANUFACTURE |
| JP2010265544A (en) * | 2009-04-14 | 2010-11-25 | Kobelco Kaken:Kk | Cu-Ga ALLOY SPUTTERING TARGET AND PROCESS FOR MANUFACTURING THEREOF |
| WO2011010529A1 (en) * | 2009-07-23 | 2011-01-27 | Jx日鉱日石金属株式会社 | Sintered cu-ga alloy sputtering target, method for producing the target, light-absorbing layer formed from sintered cu-ga alloy sputtering target, and cigs solar cell using the light-absorbing layer |
| WO2011013471A1 (en) * | 2009-07-27 | 2011-02-03 | Jx日鉱日石金属株式会社 | Sintered cu-ga sputtering target and method for producing the target |
| JP2012031508A (en) * | 2010-06-28 | 2012-02-16 | Hitachi Metals Ltd | Cu-Ga ALLOY TARGET MATERIAL AND METHOD FOR MANUFACTURING THE SAME |
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