JP3891549B2 - Mn alloy material for magnetic material, Mn alloy sputtering target and magnetic thin film - Google Patents
Mn alloy material for magnetic material, Mn alloy sputtering target and magnetic thin film Download PDFInfo
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/18—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by cathode sputtering
- H01F41/183—Sputtering targets therefor
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Description
【０００１】
【発明の属する技術分野】
本発明は、磁性材用Ｍｎ合金材料、Ｍｎ合金スパッタリングターゲット及び磁性薄膜に関する。特には、反強磁性薄膜用Ｍｎ合金、Ｍｎ合金スパッタリングターゲット及び反強磁性薄膜に関する。
【０００２】
【従来の技術】
コンピュータ用のハードディスクなどの磁気記録装置は、近年急速に小型大容量化が進み、数年後にはその記録密度は２０Ｇｂ／ｉｎ２ に達すると予想される。このため、再生ヘッドとしては従来の誘導型ヘッドが限界に近づき、磁気抵抗効果型（ＡＭＲ）ヘッドが用いられ始めている。
磁気抵抗効果型ヘッドは、パソコン市場等の拡大に伴い世界的規模で今後急成長が見込まれている。そして、数年のうちには、さらに高密度が期待されている巨大磁気抵抗効果型（ＧＭＲ）ヘッドが実用化されることが現実的となってきた。
ＧＭＲヘッドに使用されるスピンバルブ膜の反磁性膜としてＭｎ合金が検討されている。
【０００３】
【発明が解決しようとする課題】
スピンブルブ膜用の反磁性膜としてはＭｎ合金、特にＭｎ−Ｆｅ合金等が検討されている。しかし、Ｍｎ−Ｆｅ合金は耐食性に問題があるため実用化の可能性は小さかった。耐食性を改善するためにＭｎ中に貴金属を使用する試みも行われているが、貴金属が高価であることと、貴金属を添加した場合でもなお十分な耐食性を得ることができないという問題があった。
本発明は、耐食性に優れた反磁性膜を形成するための手段を提供することを目的とした。
【０００４】
【課題を解決するための手段】
上記の課題を解決するために本発明者らは鋭意研究を行った結果、Ｍｎ合金中の不純物元素が、特に酸素及び硫黄が耐腐食性を劣化させていることを見いだした。
【０００５】
本発明は、この知見に基づき、
１．Ｍｎと合金を形成する合金成分が、Ｆｅ，Ｉｒから選択された１種または２種以上であり、不純物（Ｍｎおよび合金成分以外の元素）含有量が合計で５００ｐｐｍ以下、酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下であることを特徴とする磁性材用Ｍｎ合金材料
【０００６】
２．Ｍｎと合金を形成する合金成分が、Ｆｅ，Ｉｒ，Ｒｈ，Ｒｕから選択された１種または２種以上であり、不純物（Ｍｎおよび合金成分以外の元素）含有量が合計で５００ｐｐｍ以下、酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下であることを特徴とする磁性材用Ｍｎ合金材料
【０００７】
３．Ｍｎ−Ｆｅ合金，Ｍｎ−Ｉｒ合金又はＭｎ−Ｒｈ−Ｒｕ合金からなり、不純物（Ｍｎおよび合金成分以外の元素）含有量が合計で５００ｐｐｍ以下、酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下であることを特徴とする磁性材用Ｍｎ合金材料
【０００８】
４．Ｍｎと合金を形成する合金成分が、Ｆｅ，Ｉｒから選択された１種または２種以上であり、不純物（Ｍｎおよび合金成分以外の元素）含有量が合計で５００ｐｐｍ以下、酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下であることを特徴とする磁性薄膜形成用Ｍｎ合金スパッタリングターゲット
【０００９】
５．Ｍｎと合金を形成する合金成分が、Ｆｅ，Ｉｒ，Ｒｈ，Ｒｕから選択された１種または２種以上であり、不純物（Ｍｎおよび合金成分以外の元素）含有量が合計で５００ｐｐｍ以下、酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下であることを特徴とする磁性薄膜形成用Ｍｎ合金スパッタリングターゲット
【００１０】
６．Ｍｎ−Ｆｅ合金，Ｍｎ−Ｉｒ合金又はＭｎ−Ｒｈ−Ｒｕ合金からなり、不純物（Ｍｎおよび合金成分以外の元素）含有量が合計で５００ｐｐｍ以下、酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下であることを特徴とする磁性薄膜形成用Ｍｎ合金スパッタリングターゲット
【００１１】
７．上記４〜６のそれぞれに記載の磁性薄膜形成用Ｍｎ合金スパッタリングターゲットをスパッタリングすることによって形成されたことを特徴とする磁性薄膜。
を提供するものである。
【００１２】
【発明の実施の形態】
本発明の磁性材用Ｍｎ合金材料は、Ｍｎを主成分として含有する合金からなるものである。Ｍｎ以外の合金成分としては、Ｆｅ，Ｉｒ，Ｒｈ，Ｒｕを挙げることができる。特にＭｎ−Ｆｅ系、ＭｎＩｒ系、Ｍｎ−Ｒｈ−Ｒｕ系などの合金などが反磁性膜形成用として有用である。
【００１３】
そして酸素及び硫黄含有量が低減されたものである。酸素及び硫黄は耐食性を低下させる大きな原因となるため、酸素含有量１００ｐｐｍ以下、Ｓ含有量２０ｐｐｍ以下にまで低減すべきである。
【００１４】
さらに、不純物すなわち、Ｍｎ及び合金成分以外の元素の含有量が合計で５００ｐｐｍ以下にまで低減されたものであることが好ましい。Ｍｎ及び合金成分以外の不純物は、磁気的特性を悪化させ、また耐食性低下の原因ともなるため、極力低減することが望まれており合計で５００ｐｐｍ以下に低減するべきである。不純物含有量が合計で５００ｐｐｍを越えると、磁気的特性不良が顕著となりまた耐食性も著しく低下するため好ましくない。
【００１５】
上記のような、不純物を低減したＭｎ合金材料は以下のような方法で作成することができる。
本発明者らはＭｎ合金中の不純物、特に酸素と硫黄が原料の電解Ｍｎに起因するものであることから、原料となるＭｎの高純度化を行った。
市販されている電解Ｍｎに脱酸剤としてＣａ，Ｍｇ，Ｌａ等を加え、高周波溶解を行うことによって酸素、硫黄を除去した。特に不活性ガス雰囲気、減圧下での溶解を行った場合には、酸素、硫黄のみならず他の不純物元素も十分に低減できるため好ましい。
また、Ｍｎを高純度化するための別の方法として、電解Ｍｎを予備溶解した後、さらに真空蒸留を行うことによっても不純物を低減することが可能である。
【００１６】
一方、Ｍｎ以外の合金成分元素についてもできるだけ高純度のものを使用するのが望ましく、市販品を使用する場合には純度３Ｎ以上の高純度品を用いるべきである。必要に応じて、真空脱ガス処理等を行い、ガス成分不純物等を除去する。
【００１７】
上記のような方法で得られたＭｎとＭｎ以外の合金成分元素とを溶解し合金化した後鋳造する。得られた合金インゴットを機械加工し、スパッタリングターゲット材とする。基本的には、ターゲットの純度はインゴットと同等である。
そして、ここで得ることができたスパッタリングターゲットをスパッタリングすることによって磁性薄膜を形成することが可能である。
【００１８】
【実施例】
以下、実施例を比較例と対比して説明するが、本発明はこれによって制限されるものではない。
【００１９】
（実施例１）
原料となる電解Ｍｎを、ＭｇＯ坩堝を用いて高周波溶解した。雰囲気はＡｒ雰囲気とした。温度が１４００°Ｃに到達後、脱酸剤としてＬａを１ｗｔ％添加した。５分間保持した後、タンディシュを介してスラグを除去し、その後金型に鋳造した。冷却後、インゴットを取り出した。その結果、酸素：５０ｐｐｍ、Ｓ：１０ｐｐｍ、不純物量が合計で２２１ｐｐｍのＭｎを得た。
得られたＭｎと市販の純度４ＮのＦｅ（酸素：５０ｐｐｍ、Ｓ：１ｐｐｍ）とを１：１で溶解し合金化した。その結果、酸素：５０ｐｐｍ、Ｓ：６ｐｐｍ、不純物（ＭｎおよびＦｅ以外の元素）含有量が合計で１３２ｐｐｍのＭｎ-Ｆｅ合金が得られた。
各原料及びＭｎ-Ｆｅ合金の組成を表１に示す。
【００２０】
【表１】
得られたＭｎ-Ｆｅ合金の一部を約１０ｍｍ角で切り出し、耐食性試験用のブロック試片とした。
耐食性試験用のブロック試片は、観察面を鏡面研磨した後、温度３５°Ｃ、湿度９８％の湿潤試験器内に入れた。７２時間後、試料を取り出し錆の発生状況を目視で観察した。
残りのＭｎ-Ｆｅ合金は、機械加工を行い、直径５０ｍｍ、厚さ５ｍｍの円板状のスパッタリングターゲットとした。このスパッタリングターゲットを、Ｉｎ-Ｓｎ合金はんだを用いて銅製のバッキングプレートと接合し、マグネトロンスパッタ装置を用いてスパッタ試験を行い、３インチＳｉウエハー上にＭｎ-Ｆｅ合金薄膜を形成した。
この際のウエハー１枚当たりに存在する直径０．３μｍ以上のパーティクル数を測定した。
【００２２】
（実施例２）
原料となる電解Ｍｎを、ＭｇＯ坩堝を用いて高周波溶解した。雰囲気はＡｒ雰囲気とした。温度が１４００°Ｃに到達後、脱酸剤としてＬａを１ｗｔ％添加した。５分間保持した後、タンディシュを介してスラグを除去し、その後金型に鋳造した。冷却後、インゴットを取り出した。その結果、酸素：５０ｐｐｍ、Ｓ：１０ｐｐｍ、不純物量が合計で２２３ｐｐｍのＭｎを得た。
得られたＭｎと、市販の純度２〜３ＮのＩｒ粉末（酸素：１３００ｐｐｍ、Ｓ：１ｐｐｍ）を真空脱ガスして得たＩｒ（酸素：１００ｐｐｍ、Ｓ：１ｐｐｍ）とを１：１で溶解し合金化した。
その結果、酸素：７０ｐｐｍ、Ｓ：６ｐｐｍ、不純物（ＭｎおよびＩｒ以外の元素）含有量が合計で２２０ｐｐｍのＭｎ−Ｉｒ合金が得られた。
各原料及びＭｎ−Ｉｒ合金の組成を表２に示す。そして上記実施例１と同様に耐食性試験及びスパッタ試験を行った。
【００２３】
【表２】
（実施例３）
原料となる電解Ｍｎを、Ａｌ２Ｏ３坩堝を用いて１３００°Ｃで予備溶解した後、１４００°Ｃで真空蒸留した。真空度は１０−２Ｔｏｒｒ 、蒸留温度１４００°Ｃ、保持時間３０分とした。蒸留したＭｎは、酸素：３０ｐｐｍ、Ｓ：１０ｐｐｍ、不純物量が合計で１２２ｐｐｍであった。
得られたＭｎと市販の４ＮのＦｅ（酸素：４０ｐｐｍ、Ｓ：１０ｐｐｍ）とを１：１で、Ａｌ２Ｏ３坩堝で溶解し合金化した。その結果、酸素：５０ｐｐｍ、Ｓ：<１０ｐｐｍ、不純物（Ｍｎ及びＦｅ以外の元素）含有量が合計で１０６ｐｐｍのＭｎ-Ｆｅ 合金が得られた。
各原料及びＭｎ-Ｆｅ合金の組成を表３に示す。そして、上記実施例１と同様に耐食性試験及びスパッタ試験を行った。
【００２５】
【表３】
（実施例４）
原料となる電解Ｍｎを、Ａｌ２Ｏ３坩堝を用いて１３００°Ｃで予備溶解した後、１４００°Ｃで真空蒸留した。真空度は１０−２ Ｔｏｒｒ 、蒸留温度１４００°Ｃ、保持時間３０分とした。蒸留したＭｎは、酸素：３０ｐｐｍ、Ｓ：<１０ｐｐｍ、不純物量が合計で１４１ｐｐｍであった。
得られたＭｎと市販の３ＮのＩｒ粉末（酸素：１３００ｐｐｍ、Ｓ：<１０ｐｐｍ）を真空脱ガスして得たＩｒ粉末（酸素：１００ｐｐｍ、Ｓ：<１０ｐｐｍ）とを５５：４５で、Ａｌ２Ｏ３坩堝で溶解し合金化した。その結果、酸素：７０ｐｐｍ、Ｓ：<１０ｐｐｍ、不純物（Ｍｎ及びＩｒ以外の元素）含有量が合計で１７５ｐｐｍのＭｎ−Ｉｒ 合金が得られた。
各原料及びＭｎ−Ｉｒ合金の組成を表４に示す。そして、上記実施例１と同様に耐食性試験及びスパッタ試験を行った。
【００２７】
【表４】
（比較例１）
純度２〜３Ｎの原料Ｍｎ粉末（酸素：１０００ｐｐｍ、Ｓ：４００ｐｐｍ）と、市販の純度３ＮのＦｅ（酸素：１２０ｐｐｍ、Ｓ：４０ｐｐｍ）とを１：１で溶解し合金化した。その結果、酸素：６００ｐｐｍ、Ｓ：２２０ｐｐｍ、不純物（ＭｎおよびＦｅ以外の元素）含有量が合計で１２２０ｐｐｍのＭｎ-Ｆｅ合金が得られた。
各原料及びＭｎ-Ｆｅ合金の組成を表５に示す。上記と同様に耐食性試験及びスパッタ試験を行った。
【００２９】
【表５】
（比較例２）
純度２〜３Ｎの原料Ｍｎ粉末（酸素：１０００ｐｐｍ、Ｓ：４００ｐｐｍ）と、市販の純度２〜３ＮのＩｒ粉末（酸素：１３００ｐｐｍ、Ｓ：１ｐｐｍ）とを５５：４５で溶解し合金化した。その結果、酸素：１１００ｐｐｍ、Ｓ：２００ｐｐｍ、不純物（ＭｎおよびＩｒ以外の元素）含有量が合計で２１００ｐｐｍのＭｎ-Ｆｅ合金が得られた。
各原料及びＭｎ-Ｆｅ合金の組成を表６に示す。上記と同様に耐食性試験及びスパッタ試験を行った。
【００３１】
【表６】
（比較例３）
純度３Ｎの原料Ｍｎ粉末（酸素：１０００ｐｐｍ、Ｓ：４００ｐｐｍ）と、市販の純度３ＮのＦｅ（酸素：１２０ｐｐｍ、Ｓ：４０ｐｐｍ）とを１：１で溶解し合金化した。その結果、酸素：５６０ｐｐｍ、Ｓ：２２０ｐｐｍ、不純物（ＭｎおよびＦｅ以外の元素）含有量が合計で１６３１ ｐｐｍのＭｎ-Ｆｅ合金が得られた。
各原料及びＭｎ-Ｆｅ合金の組成を表７に示す。上記と同様に耐食性試験及びスパッタ試験を行った。
【００３３】
【表７】
（比較例４）
純度２〜３Ｎの原料Ｍｎ粉末（酸素：１０００ｐｐｍ、Ｓ：４００ｐｐｍ）と、市販の純度２〜３ＮのＩｒ粉末（酸素：１３００ｐｐｍ、Ｓ：１ｐｐｍ）とを５５：４５で溶解し合金化した。その結果、酸素：１１００ｐｐｍ、Ｓ：２００ｐｐｍ、不純物（ＭｎおよびＩｒ以外の元素）含有量が合計で２４４３ｐｐｍのＭｎ-Ｆｅ合金が得られた。
各原料及びＭｎ-Ｆｅ合金の組成を表８に示す。上記と同様に耐食性試験及びスパッタ試験を行った。
【００３５】
【表８】
（結果）
実施例１〜４及び比較例１〜４の耐食性試験結果及びスパッタ試験におけるパーティクル数測定結果を表９に示す。
【００３７】
【表９】
その結果、表９に示すように、本発明の酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下、さらに不純物（Ｍｎおよび合金成分以外の元素）合計量が５００ｐｐｍ以下であるＭｎ合金は、比較例に比べて格段に優れた耐食性を示した。
また、本発明のターゲットを用いた場合には、スパッタの際に発生するパーティクル数も比較例に比べてはるかに少ないことがわかる。
以上から、本発明の磁性材用Ｍｎ合金材料、Ｍｎ合金スパッタリングターゲット及び磁性薄膜は、比較例に示す従来技術には存在しない、優れた特性を有するものである。
【００３９】
【発明の効果】
本発明の酸素含有量が１００ｐｐｍ以下、Ｓ含有量が２０ｐｐｍ以下、さらに不純物（Ｍｎおよび合金成分以外の元素）合計量が５００ｐｐｍ以下であることを特徴とする磁性材用Ｍｎ合金材料から形成した磁性薄膜形成用Ｍｎ合金スパッタリングターゲットを用いることによって、パーティクル発生が少なく、耐食性に優れた反磁性膜を形成することが可能であり、磁性薄膜形成用材料として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a Mn alloy material for a magnetic material, a Mn alloy sputtering target, and a magnetic thin film. In particular, it relates to a Mn alloy for antiferromagnetic thin films, a Mn alloy sputtering target, and an antiferromagnetic thin film.
[0002]
[Prior art]
In recent years, magnetic recording apparatuses such as hard disks for computers have been rapidly reduced in size and capacity, and the recording density is expected to reach 20 Gb / in 2 in a few years. For this reason, conventional inductive heads are approaching the limit as reproducing heads, and magnetoresistive (AMR) heads are beginning to be used.
The magnetoresistive head is expected to grow rapidly on a global scale with the expansion of the personal computer market. In a few years, it has become practical that a giant magnetoresistive (GMR) head that is expected to have a higher density will be put into practical use.
Mn alloys have been studied as diamagnetic films for spin valve films used in GMR heads.
[0003]
[Problems to be solved by the invention]
As a diamagnetic film for a spin blob film, a Mn alloy, particularly a Mn—Fe alloy or the like has been studied. However, since the Mn—Fe alloy has a problem in corrosion resistance, the possibility of practical use was small. Attempts have been made to use noble metals in Mn to improve corrosion resistance, but there are problems that the noble metals are expensive and that even when noble metals are added, sufficient corrosion resistance cannot be obtained.
An object of the present invention is to provide a means for forming a diamagnetic film excellent in corrosion resistance.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors conducted extensive research and found that impurity elements in the Mn alloy, particularly oxygen and sulfur, deteriorate the corrosion resistance.
[0005]
The present invention is based on this finding,
1. The alloy component that forms an alloy with Mn is one or more selected from Fe and Ir, the total content of impurities (elements other than Mn and alloy components) is 500 ppm or less, and the oxygen content is 100 ppm or less Mn alloy material for magnetic material, characterized in that S content is 20 ppm or less
2. The alloy component that forms an alloy with Mn is one or more selected from Fe, Ir, Rh, and Ru, and the content of impurities (elements other than Mn and alloy components) is 500 ppm or less in total, containing oxygen Mn alloy material for magnetic material, characterized in that the amount is 100 ppm or less and the S content is 20 ppm or less.
3. Made of Mn-Fe alloy, Mn-Ir alloy or Mn-Rh-Ru alloy, the total content of impurities (elements other than Mn and alloy components) is 500 ppm or less, the oxygen content is 100 ppm or less, and the S content is 20 ppm or less. Mn alloy material for magnetic material, characterized in that
4). The alloy component that forms an alloy with Mn is one or more selected from Fe and Ir, the total content of impurities (elements other than Mn and alloy components) is 500 ppm or less, and the oxygen content is 100 ppm or less A Mn alloy sputtering target for forming a magnetic thin film characterized in that the S content is 20 ppm or less.
5). The alloy component that forms an alloy with Mn is one or more selected from Fe, Ir, Rh, and Ru, and the content of impurities (elements other than Mn and alloy components) is 500 ppm or less in total, containing oxygen Mn alloy sputtering target for forming a magnetic thin film, characterized in that the amount is 100 ppm or less and the S content is 20 ppm or less.
6). Made of Mn-Fe alloy, Mn-Ir alloy or Mn-Rh-Ru alloy, the total content of impurities (elements other than Mn and alloy components) is 500 ppm or less, the oxygen content is 100 ppm or less, and the S content is 20 ppm or less. Mn alloy sputtering target for forming a magnetic thin film characterized in that
7). 7. A magnetic thin film formed by sputtering the Mn alloy sputtering target for forming a magnetic thin film according to each of 4 to 6 above.
Is to provide.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The Mn alloy material for magnetic material of the present invention is made of an alloy containing Mn as a main component. Examples of alloy components other than Mn include Fe, Ir, Rh, and Ru. In particular, alloys such as Mn—Fe, MnIr, and Mn—Rh—Ru are useful for forming a diamagnetic film.
[0013]
And oxygen and sulfur content are reduced. Oxygen and sulfur cause a significant decrease in corrosion resistance and should be reduced to an oxygen content of 100 ppm or less and an S content of 20 ppm or less.
[0014]
Furthermore, it is preferable that the content of impurities other than Mn and alloy components is reduced to 500 ppm or less in total. Impurities other than Mn and alloy components deteriorate the magnetic properties and cause a decrease in corrosion resistance. Therefore, it is desired to reduce them as much as possible and should be reduced to 500 ppm or less in total. If the impurity content exceeds 500 ppm in total, the magnetic property defect becomes remarkable, and the corrosion resistance is remarkably lowered.
[0015]
The Mn alloy material with reduced impurities as described above can be produced by the following method.
Since the impurities in the Mn alloy, in particular oxygen and sulfur, are attributed to the raw material electrolytic Mn, the present inventors have refined the raw material Mn.
Oxygen and sulfur were removed by adding Ca, Mg, La or the like as a deoxidizer to commercially available electrolytic Mn and performing high-frequency dissolution. In particular, when dissolution is performed in an inert gas atmosphere and under reduced pressure, not only oxygen and sulfur but also other impurity elements can be sufficiently reduced, which is preferable.
Further, as another method for increasing the purity of Mn, impurities can be reduced by preliminarily dissolving electrolytic Mn and further performing vacuum distillation.
[0016]
On the other hand, it is desirable to use an alloy component element other than Mn as high as possible, and when using a commercial product, a high-purity product having a purity of 3N or more should be used. If necessary, vacuum degassing is performed to remove gas component impurities and the like.
[0017]
The Mn obtained by the above method and alloy component elements other than Mn are melted and alloyed, and then cast. The obtained alloy ingot is machined to obtain a sputtering target material. Basically, the purity of the target is equivalent to that of the ingot.
And it is possible to form a magnetic thin film by sputtering the sputtering target obtained here.
[0018]
【Example】
Hereinafter, examples will be described in comparison with comparative examples, but the present invention is not limited thereto.
[0019]
Example 1
Electrolytic Mn as a raw material was melted at high frequency using a MgO crucible. The atmosphere was an Ar atmosphere. After the temperature reached 1400 ° C., 1 wt% La was added as a deoxidizer. After holding for 5 minutes, the slag was removed through a tundish and then cast into a mold. After cooling, the ingot was taken out. As a result, Mn having oxygen: 50 ppm, S: 10 ppm, and a total amount of impurities of 221 ppm was obtained.
The obtained Mn and commercially available 4N purity Fe (oxygen: 50 ppm, S: 1 ppm) were melted and alloyed at 1: 1. As a result, an Mn—Fe alloy with oxygen: 50 ppm, S: 6 ppm, and impurities (elements other than Mn and Fe) totaling 132 ppm was obtained.
Table 1 shows the composition of each raw material and the Mn—Fe alloy.
[0020]
[Table 1]
A part of the obtained Mn—Fe alloy was cut out at about 10 mm square to obtain a block specimen for a corrosion resistance test.
The block specimen for the corrosion resistance test was mirror-polished on the observation surface, and then placed in a humidity tester having a temperature of 35 ° C. and a humidity of 98%. After 72 hours, the sample was taken out and the occurrence of rust was visually observed.
The remaining Mn—Fe alloy was machined to obtain a disk-like sputtering target having a diameter of 50 mm and a thickness of 5 mm. This sputtering target was joined to a copper backing plate using In—Sn alloy solder, and a sputtering test was performed using a magnetron sputtering apparatus to form a Mn—Fe alloy thin film on a 3-inch Si wafer.
At this time, the number of particles having a diameter of 0.3 μm or more present per wafer was measured.
[0022]
(Example 2)
Electrolytic Mn as a raw material was melted at high frequency using a MgO crucible. The atmosphere was an Ar atmosphere. After the temperature reached 1400 ° C., 1 wt% La was added as a deoxidizer. After holding for 5 minutes, the slag was removed through a tundish and then cast into a mold. After cooling, the ingot was taken out. As a result, Mn with oxygen: 50 ppm, S: 10 ppm, and the total amount of impurities was 223 ppm.
The obtained Mn and Ir (oxygen: 100 ppm, S: 1 ppm) obtained by vacuum degassing of commercially available Ir powder (oxygen: 1300 ppm, S: 1 ppm) having a purity of 2 to 3 N were dissolved at a ratio of 1: 1. Alloyed.
As a result, an Mn—Ir alloy having a total content of oxygen of 70 ppm, S: 6 ppm, and impurities (elements other than Mn and Ir) of 220 ppm was obtained.
Table 2 shows the composition of each raw material and the Mn—Ir alloy. Then, the corrosion resistance test and the sputtering test were performed in the same manner as in Example 1.
[0023]
[Table 2]
(Example 3)
Electrolytic Mn as a raw material was pre-dissolved at 1300 ° C. using an Al 2 O 3 crucible and then vacuum distilled at 1400 ° C. The degree of vacuum was 10 −2 Torr, the distillation temperature was 1400 ° C., and the retention time was 30 minutes. Distilled Mn was oxygen: 30 ppm, S: 10 ppm, and the total amount of impurities was 122 ppm.
The obtained Mn and commercially available 4N Fe (oxygen: 40 ppm, S: 10 ppm) were melted and alloyed at a ratio of 1: 1 in an Al 2 O 3 crucible. As a result, an Mn—Fe 2 alloy having a total of 106 ppm of oxygen (50 ppm), S: <10 ppm, and impurities (elements other than Mn and Fe) was obtained.
Table 3 shows the composition of each raw material and the Mn—Fe alloy. Then, the corrosion resistance test and the sputtering test were performed in the same manner as in Example 1.
[0025]
[Table 3]
Example 4
Electrolytic Mn as a raw material was pre-dissolved at 1300 ° C. using an Al 2 O 3 crucible and then vacuum distilled at 1400 ° C. The degree of vacuum was 10 −2 Torr, the distillation temperature was 1400 ° C., and the retention time was 30 minutes. Distilled Mn was oxygen: 30 ppm, S: <10 ppm, and the total amount of impurities was 141 ppm.
The obtained Mn and Ir powder (oxygen: 100 ppm, S: <10 ppm) obtained by vacuum degassing of commercially available 3N Ir powder (oxygen: 1300 ppm, S: <10 ppm) at 55:45, Al 2 It melted and alloyed in an O 3 crucible. As a result, an Mn—Ir alloy having a total of 175 ppm of oxygen: 70 ppm, S: <10 ppm, and impurities (elements other than Mn and Ir) was obtained.
Table 4 shows the composition of each raw material and the Mn—Ir alloy. Then, the corrosion resistance test and the sputtering test were performed in the same manner as in Example 1.
[0027]
[Table 4]
(Comparative Example 1)
Raw material Mn powder having a purity of 2 to 3N (oxygen: 1000 ppm, S: 400 ppm) and commercially available Fe of 3N purity (oxygen: 120 ppm, S: 40 ppm) were melted at 1: 1 to be alloyed. As a result, an Mn—Fe alloy having oxygen: 600 ppm, S: 220 ppm, and a total content of impurities (elements other than Mn and Fe) of 1220 ppm was obtained.
Table 5 shows the composition of each raw material and the Mn—Fe alloy. Corrosion resistance test and sputter test were conducted in the same manner as above.
[0029]
[Table 5]
(Comparative Example 2)
Raw material Mn powder having a purity of 2 to 3N (oxygen: 1000 ppm, S: 400 ppm) and commercially available Ir powder having a purity of 2 to 3N (oxygen: 1300 ppm, S: 1 ppm) were melted and alloyed at 55:45. As a result, an Mn—Fe alloy having oxygen of 1100 ppm, S of 200 ppm, and impurities (elements other than Mn and Ir) in total of 2100 ppm was obtained.
Table 6 shows the composition of each raw material and the Mn—Fe alloy. Corrosion resistance test and sputter test were conducted in the same manner as above.
[0031]
[Table 6]
(Comparative Example 3)
A raw material Mn powder of 3N purity (oxygen: 1000 ppm, S: 400 ppm) and commercially available Fe of 3N purity (oxygen: 120 ppm, S: 40 ppm) were melted and alloyed at 1: 1. As a result, an Mn—Fe alloy having oxygen: 560 ppm, S: 220 ppm, and a total content of impurities (elements other than Mn and Fe) of 1631 ppm was obtained.
Table 7 shows the composition of each raw material and the Mn—Fe alloy. Corrosion resistance test and sputter test were conducted in the same manner as above.
[0033]
[Table 7]
(Comparative Example 4)
Raw material Mn powder having a purity of 2 to 3N (oxygen: 1000 ppm, S: 400 ppm) and commercially available Ir powder having a purity of 2 to 3N (oxygen: 1300 ppm, S: 1 ppm) were melted and alloyed at 55:45. As a result, an Mn—Fe alloy having oxygen: 1100 ppm, S: 200 ppm, and impurities (elements other than Mn and Ir) totaling 2443 ppm was obtained.
Table 8 shows the composition of each raw material and the Mn—Fe alloy. Corrosion resistance test and sputter test were conducted in the same manner as above.
[0035]
[Table 8]
(result)
Table 9 shows the corrosion resistance test results of Examples 1 to 4 and Comparative Examples 1 to 4 and the particle number measurement results in the sputtering test.
[0037]
[Table 9]
As a result, as shown in Table 9, Mn alloys having an oxygen content of 100 ppm or less, an S content of 20 ppm or less, and a total amount of impurities (elements other than Mn and alloy components) of 500 ppm or less are compared. Compared to the examples, the corrosion resistance was much better.
It can also be seen that when the target of the present invention is used, the number of particles generated during sputtering is much smaller than that of the comparative example.
From the above, the Mn alloy material for magnetic materials, the Mn alloy sputtering target, and the magnetic thin film of the present invention have excellent characteristics that do not exist in the prior art shown in the comparative examples.
[0039]
【The invention's effect】
Magnetic material formed from a Mn alloy material for magnetic materials, wherein the oxygen content of the present invention is 100 ppm or less, the S content is 20 ppm or less, and the total amount of impurities (elements other than Mn and alloy components) is 500 ppm or less. By using a Mn alloy sputtering target for forming a thin film, it is possible to form a diamagnetic film with less generation of particles and excellent corrosion resistance, which is useful as a material for forming a magnetic thin film.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001329175A JP3891549B2 (en) | 1997-07-31 | 2001-10-26 | Mn alloy material for magnetic material, Mn alloy sputtering target and magnetic thin film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-219012 | 1997-07-31 | ||
| JP21901297 | 1997-07-31 | ||
| JP2001329175A JP3891549B2 (en) | 1997-07-31 | 2001-10-26 | Mn alloy material for magnetic material, Mn alloy sputtering target and magnetic thin film |
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| JP33228697A Division JP3544293B2 (en) | 1997-07-31 | 1997-11-18 | Mn alloy material for magnetic material, Mn alloy sputtering target and magnetic thin film |
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| JP3891549B2 true JP3891549B2 (en) | 2007-03-14 |
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