JPH11264070A - Manganese-iridium alloy sputtering target for forming magnetic thin film, magnetic thin film and production of manganese-iridium alloy sputtering target for forming magnetic thin film - Google Patents
Manganese-iridium alloy sputtering target for forming magnetic thin film, magnetic thin film and production of manganese-iridium alloy sputtering target for forming magnetic thin filmInfo
- Publication number
- JPH11264070A JPH11264070A JP10088240A JP8824098A JPH11264070A JP H11264070 A JPH11264070 A JP H11264070A JP 10088240 A JP10088240 A JP 10088240A JP 8824098 A JP8824098 A JP 8824098A JP H11264070 A JPH11264070 A JP H11264070A
- Authority
- JP
- Japan
- Prior art keywords
- ppm
- thin film
- less
- magnetic thin
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000575 Ir alloy Inorganic materials 0.000 title claims abstract description 35
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 33
- 239000010409 thin film Substances 0.000 title claims abstract description 30
- 238000005477 sputtering target Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- SHMWNGFNWYELHA-UHFFFAOYSA-N iridium manganese Chemical compound [Mn].[Ir] SHMWNGFNWYELHA-UHFFFAOYSA-N 0.000 title 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 11
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000004544 sputter deposition Methods 0.000 claims abstract description 9
- 238000007872 degassing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000010894 electron beam technology Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 12
- 239000010408 film Substances 0.000 abstract description 7
- 230000005292 diamagnetic effect Effects 0.000 abstract description 5
- 238000005266 casting Methods 0.000 abstract description 2
- 238000010943 off-gassing Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000005290 antiferromagnetic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
- Thin Magnetic Films (AREA)
- Hall/Mr Elements (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、磁性薄膜形成用Ｍ
ｎ−Ｉｒ合金スパッタリングターゲットに関する。特に
は、反強磁性薄膜用Ｍｎ−Ｉｒ合金スパッタリングター
ゲットに関する。The present invention relates to a magnetic thin film forming method for forming a magnetic thin film.
The present invention relates to an n-Ir alloy sputtering target. In particular, it relates to a Mn-Ir alloy sputtering target for an antiferromagnetic thin film.
【０００２】[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。 2. Description of the Related Art In recent years, magnetic recording devices such as hard disks for computers have rapidly become smaller and larger in capacity, and the recording density is expected to reach 20 Gb / in 2 in a few years. For this reason, the conventional inductive head approaches the limit as a reproducing head, and a magnetoresistive (AMR) head has begun to be used. Magnetoresistive heads are expected to grow rapidly on a worldwide scale with the expansion of the personal computer market and the like. In a few years, it has become realistic to commercialize a giant magnetoresistive (GMR) head, which is expected to have higher density. A Mn alloy has been studied as a diamagnetic film of a spin valve film used for a GMR head.
【０００３】[0003]
【発明が解決しようとする課題】スピンバルブ膜用の反
磁性膜としてはＭｎ合金、特にＭｎ−貴金属合金、例え
ばＭｎ−Ｉｒ合金が検討されている。これらは通常、焼
結あるいは溶解によって製造される。しかし、従来のＭ
ｎ−Ｉｒ合金はスパッタリングの際のガスの放出やパー
ティクルの発生が多く、耐食性にも問題があった。ま
た、磁気特性も満足すべきものではなかった。本発明
は、スパッタリングの際のガス放出やパーティクルの発
生が少なく、耐食性に優れ、しかも磁気特性も良好な反
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。As a diamagnetic film for a spin valve film, a Mn alloy, particularly a Mn-noble metal alloy, for example, a Mn-Ir alloy has been studied. These are usually produced by sintering or melting. However, the conventional M
The n-Ir alloy emits a lot of gas and generates particles during sputtering, and has a problem in corrosion resistance. Also, the magnetic properties were not satisfactory. SUMMARY OF THE INVENTION An object of the present invention is to provide a means for forming a diamagnetic film which is less likely to emit gas and particles during sputtering, has excellent corrosion resistance, and has good magnetic properties.
【０００４】[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−Ｉｒ合
金中の不純物元素、特に酸素、炭素、硫黄、水素がガス
放出やパーティクルの発生、耐食性低下の原因であるこ
とを見いだした。さらに磁気特性は主に薄膜の結晶組織
に依存し、結晶が粗大な柱状晶であるほど磁気特性が向
上することを見いだした。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, and as a result, the impurity elements in the Mn-Ir alloy, particularly, oxygen, carbon, sulfur, and hydrogen have been released. It was found that this was the cause of the generation of particles and the decrease in corrosion resistance. Furthermore, it was found that the magnetic properties mainly depend on the crystal structure of the thin film, and that the coarser the columnar crystals, the better the magnetic properties.
【０００５】本発明は、この知見に基づき、 １．酸素含有量が１０００ｐｐｍ以下、Ｓ含有量が３０
０ｐｐｍ以下、炭素含有量が１００ｐｐｍ以下、水素含
有量が１ｐｐｍ以下であることを特徴とする磁性薄膜形
成用Ｍｎ−Ｉｒ合金スパッタリングターゲット。The present invention has been made based on this finding. Oxygen content is less than 1000 ppm, S content is 30
A Mn-Ir alloy sputtering target for forming a magnetic thin film, wherein the sputtering target has a carbon content of 0 ppm or less, a carbon content of 100 ppm or less, and a hydrogen content of 1 ppm or less.
【０００６】２．酸素含有量が１００ｐｐｍ以下、Ｓ含
有量が１０ｐｐｍ以下、炭素含有量が５０ｐｐｍ以下、
水素含有量が０．５ｐｐｍ以下であることを特徴とする
磁性薄膜形成用Ｍｎ−Ｉｒ合金スパッタリングターゲッ
ト。[0006] 2. Oxygen content is 100 ppm or less, S content is 10 ppm or less, carbon content is 50 ppm or less,
A Mn-Ir alloy sputtering target for forming a magnetic thin film, wherein the hydrogen content is 0.5 ppm or less.
【０００７】３．請求項１または２に記載の磁性薄膜形
成用Ｍｎ−Ｉｒ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り形成されたことを特徴とする磁
性薄膜。[0007] 3. A magnetic thin film formed by sputtering the Mn-Ir alloy sputtering target for forming a magnetic thin film according to claim 1 or 2.
【０００８】４．酸素含有量が１０００ｐｐｍ以下、Ｓ
含有量が３００ｐｐｍ以下、炭素含有量が１００ｐｐｍ
以下、水素含有量が１ｐｐｍ以下であり、結晶組織が柱
状晶であることを特徴とするＭｎ−Ｉｒ合金磁性薄膜。[0008] 4. Oxygen content is less than 1000ppm, S
Content is 300ppm or less, carbon content is 100ppm
Hereinafter, a Mn-Ir alloy magnetic thin film having a hydrogen content of 1 ppm or less and a crystal structure of a columnar crystal.
【０００９】５．原料Ｍｎを１２５０〜１５００℃で予
備溶解した後、１１００〜１５００℃で真空蒸留するこ
とによって得た高純度Ｍｎ材料と、原料Ｉｒ粉末を１０
００〜１５００℃で脱ガス処理した後、電子ビーム溶解
することによって得た高純度Ｉｒ材料とを溶解し合金化
した後、鋳造することを特徴とする磁性薄膜形成用Ｍｎ
−Ｉｒ合金スパッタリングターゲットの製造方法、を提
供するものである。[0009] 5. After preliminarily dissolving the raw material Mn at 1250 to 1500 ° C., the high purity Mn material obtained by vacuum distillation at 1100 to 1500 ° C. and the raw material Ir powder
Mn for forming a magnetic thin film, comprising: degassing at 00 to 1500 ° C .; melting and alloying with a high-purity Ir material obtained by electron beam melting; and casting.
A method for producing an Ir alloy sputtering target.
【００１０】[0010]
【発明の実施の形態】本発明の磁性薄膜形成用Ｍｎ−Ｉ
ｒ合金スパッタリングターゲットは、Ｍｎを３０ｗｔ％
以上含有するＭｎ−Ｉｒ合金からなるものである。代表
的にはＭｎ−Ｉｒの２成分合金が上げられるが、さらに
Ｆｅ，Ｐｔ，Ｐｄ，Ｒｈ，Ｒｕ，Ｎｉ，Ｃｒ，Ｃｏ な
どを合金成分として添加した合金も含まれる。DETAILED DESCRIPTION OF THE INVENTION Mn-I for forming a magnetic thin film of the present invention
The r alloy sputtering target contains 30 wt% Mn.
It is composed of the Mn-Ir alloy contained above. Typically, a two-component alloy of Mn-Ir can be used, but an alloy further containing Fe, Pt, Pd, Rh, Ru, Ni, Cr, Co, or the like as an alloy component is also included.
【００１１】本発明のＭｎ−Ｉｒ合金スパッタリングタ
ーゲットは、不純物すなわちＭｎ，Ｉｒ及び合金成分以
外の元素が低減されたものである。特に酸素、硫黄、炭
素、水素が極力低減されたものである。酸素、硫黄、炭
素、水素は耐食性を悪化させ、パーティクル発生の原因
となり、また、磁気的特性を悪化させる原因となるた
め、酸素含有量１０００ｐｐｍ以下、好ましくは１００
ｐｐｍ以下、Ｓ含有量３００ｐｐｍ以下、好ましくは１
０ｐｐｍ以下、炭素含有量１００ｐｐｍ以下、好ましく
は５０ｐｐｍ以下、水素含有量１ｐｐｍ以下、好ましく
は０．５ｐｐｍ以下にまで低減すべきである。上記の含
有量を超えるとパーティクル発生量の増大、耐食性の著
しい低下、磁気特性不良が顕著になるため好ましくな
い。The Mn-Ir alloy sputtering target of the present invention has reduced impurities, that is, elements other than Mn, Ir and alloy components. In particular, oxygen, sulfur, carbon and hydrogen are reduced as much as possible. Oxygen, sulfur, carbon, and hydrogen deteriorate the corrosion resistance, cause particles to be generated, and cause the magnetic characteristics to deteriorate. Therefore, the oxygen content is 1000 ppm or less, preferably 100 ppm.
ppm or less, S content 300 ppm or less, preferably 1
It should be reduced to 0 ppm or less, carbon content 100 ppm or less, preferably 50 ppm or less, and hydrogen content 1 ppm or less, preferably 0.5 ppm or less. Exceeding the above contents is not preferred because the amount of generated particles is increased, the corrosion resistance is remarkably reduced, and the magnetic properties are remarkably poor.
【００１２】本発明者らはＭｎ−Ｉｒ合金中の不純物が
原料の電解Ｍｎ及びＩｒに起因するものであることか
ら、原料となるＭｎ及びＩｒのそれぞれについて高純度
化を行った。Ｍｎ原料の高純度化は、例えば下記のよう
な方法を用いることによって行うことができる。すなわ
ち、市販の粗Ｍｎを１２５０〜１５００℃で予備溶解し
た後、１１００〜１５００℃で真空蒸留を行うことによ
り不純物を除去する。Since the impurities in the Mn-Ir alloy are caused by the electrolytic Mn and Ir of the raw materials, the present inventors have made each of the raw materials Mn and Ir highly purified. Purification of the Mn raw material can be performed, for example, by using the following method. That is, impurities are removed by preliminarily dissolving commercially available crude Mn at 1250 to 1500 ° C. and performing vacuum distillation at 1100 to 1500 ° C.
【００１３】原料である粗Ｍｎとしては、市販の電解Ｍ
ｎを用いれば良い。そして、粗Ｍｎは１２５０〜１５０
０℃で予備溶解を行う。予備溶解は、ＭｇＯ，Ａｌ2Ｏ3
等のルツボを用いて不活性ガス雰囲気で保持時間１時間
以上で行う。１２５０℃未満ではＭｎが溶解せず、１５
００℃を超えるとルツボからの汚染及びＭｎの蒸発が激
しくなるため好ましくない。また、保持時間１時間未満
では未溶解Ｍｎが残るため好ましくない。ここで、予備
溶解を行うのは、揮発性の成分を除去するためである。The raw material crude Mn is commercially available electrolytic M
n may be used. And the crude Mn is 1250 to 150
Predissolve at 0 ° C. Pre-dissolution is performed using MgO, Al 2 O 3
The holding is performed in an inert gas atmosphere using a crucible such as above for a holding time of 1 hour or more. If the temperature is lower than 1250 ° C., Mn does not dissolve,
If the temperature exceeds 00 ° C., contamination from the crucible and evaporation of Mn become intense, which is not preferable. If the holding time is less than 1 hour, undissolved Mn remains, which is not preferable. Here, the preliminary dissolution is performed to remove volatile components.
【００１４】予備溶解の後、１１００〜１５００℃で真
空蒸留を行う。１１００℃未満では、蒸留時間が長くな
り過ぎ、１５００℃を超えると蒸発速度が大きく不純物
を巻き込みやすくなるため好ましくない。After the pre-dissolution, vacuum distillation is performed at 1100 to 1500 ° C. If the temperature is lower than 1100 ° C., the distillation time is too long. If the temperature is higher than 1500 ° C., the evaporation rate is high and impurities are easily involved.
【００１５】真空蒸留の際の真空度は５×１０-5〜１０
Ｔｏｒｒとする。５×１０-5Ｔｏｒｒ未満では凝縮物
が得られなくなり、１０ Ｔｏｒｒを超えるとＭｎの蒸
留にかかる時間が長くなるため好ましくない。また、真
空蒸留の際のルツボは、Ａｌ2Ｏ3 等の二重ルツボとす
るのが好ましい。なお、真空蒸留は、残留物が約５０％
以下となるまで行うのが好ましい。The degree of vacuum at the time of vacuum distillation is 5 × 10 -5 to 10
Torr. If it is less than 5 × 10 −5 Torr, no condensate can be obtained, and if it exceeds 10 Torr, the time required for distillation of Mn becomes long, which is not preferable. Further, the crucible for vacuum distillation is preferably a double crucible such as Al 2 O 3 . In addition, vacuum distillation shows that the residue is about 50%
It is preferred to carry out until the following.
【００１６】一方、Ｉｒ原料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以上のガス成分不純物の少ない高純度品
を用いるべきである。このようなＩｒ原料に対して１０
００〜１５００℃で脱ガス処理した後、電子ビーム溶解
を行いガス成分や揮発成分を除去する。なお、脱ガス処
理に先だってＩｒと低融点合金をつくり酸に溶解する金
属を添加し低融点Ｉｒ合金を製造した後、該Ｉｒ合金を
酸により浸出することによってＩｒ以外の不純物成分を
溶解除去することによってさらに高純度なＩｒ原料を得
ることができる。On the other hand, it is desirable to use the Ir raw material having a purity as high as possible. When a commercial product is used, a high purity product having a purity of 3N or more and containing few gaseous impurities should be used. For such Ir raw material, 10
After degassing at 00 to 1500 ° C, electron beam melting is performed to remove gas components and volatile components. Prior to the degassing process, a low melting point alloy is formed with Ir and a metal that dissolves in an acid is added to produce a low melting point Ir alloy. Then, the Ir alloy is leached with an acid to dissolve and remove impurity components other than Ir. By doing so, a higher purity Ir raw material can be obtained.
【００１７】上記のような方法で得られた高純度Ｍｎと
高純度Ｉｒとを溶解し合金化した後鋳造する。得られた
Ｍｎ−Ｉｒ合金インゴットを加工し、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。そしてここで得られたスパッタ
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。The high-purity Mn and high-purity Ir obtained by the above method are melted, alloyed, and then cast. The obtained Mn-Ir alloy ingot is processed and used as a sputtering target material. Basically, the purity of the target is equivalent to that of the ingot. Then, a magnetic thin film can be formed by sputtering the sputtering target obtained here.
【００１８】[0018]
【実施例】以下、実施例に基づいて説明するが、本発明
はこれによって制限されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００１９】（実施例１）原料となる電解ＭｎをＭｇＯ
坩堝を用いて１３００℃で予備溶解した後、真空蒸留
した。真空度は１０-2 Ｔｏｒｒ 、蒸留温度１４００
℃、保持時間３０分とした。蒸留したＭｎは、酸素：１
００ｐｐｍ、Ｓ：５０ｐｐｍ、Ｃ：１００ｐｐｍ、Ｈ：
０．７ｐｐｍであった。一方、市販の３ＮのＩｒ粉末
（酸素：１３００ｐｐｍ、Ｓ：＜１０ｐｐｍ、Ｃ：７６
０ｐｐｍ、Ｈ：５０ｐｐｍ）をＡｒ雰囲気下で１０００
℃、２ｈｒの脱ガス処理を行った後、電子ビーム溶解し
て、Ｉｒ粉末（酸素：１５０ｐｐｍ、Ｓ：＜１０ｐｐ
ｍ、Ｃ：１０ｐｐｍ、Ｈ：１ｐｐｍ）を得た。得られた
高純度Ｍｎと高純度Ｉｒとを１：１でＣａＯ坩堝で溶解
し合金化した。その結果、酸素：１５０ｐｐｍ、Ｓ：２
０ｐｐｍ、Ｃ：２０ｐｐｍ、Ｈ：０．７ｐｐｍのＭｎ−
Ｉｒ 合金が得られた。各原料及びＭｎ−Ｉｒ合金の組
成を表１に示す。(Example 1) Electrolytic Mn as a raw material was changed to MgO
After preliminarily melting at 1300 ° C. using a crucible, vacuum distillation was performed. Vacuum degree is 10 -2 Torr, distillation temperature is 1400
° C and a holding time of 30 minutes. Distilled Mn is oxygen: 1
00 ppm, S: 50 ppm, C: 100 ppm, H:
0.7 ppm. On the other hand, commercially available 3N Ir powder (oxygen: 1300 ppm, S: <10 ppm, C: 76
0 ppm, H: 50 ppm) in an Ar atmosphere at 1000 ppm.
After degassing at 2 ° C. for 2 hours, the mixture was melted with an electron beam to obtain Ir powder (oxygen: 150 ppm, S: <10 pp.
m, C: 10 ppm, H: 1 ppm). The obtained high-purity Mn and high-purity Ir were melted and alloyed at a ratio of 1: 1 in a CaO crucible. As a result, oxygen: 150 ppm, S: 2
0 ppm, C: 20 ppm, H: 0.7 ppm Mn-
An Ir alloy was obtained. Table 1 shows the composition of each raw material and Mn-Ir alloy.
【００２０】[0020]
【表１】 [Table 1]
【００２１】得られたＭｎ−Ｉｒ合金の一部を約１０ｍ
ｍ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℃、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−Ｉｒ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−Ｓ
ｎ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インチスライドガラス上にＭｎ−Ｉｒ合金薄膜
を１５ｎｍ形成した。この際のスライドガラス上に存在
する直径０．３μｍ以上のパーティクル数を測定した。
また、薄膜の断面の組織観察を行った。A part of the obtained Mn-Ir alloy is about 10 m
It was cut out in m-square and used as a block specimen for corrosion resistance test.
The block specimen for the corrosion resistance test was placed in a wet tester at a temperature of 35 ° C. and a humidity of 98% after the observation surface was mirror-polished.
After 72 hours, the sample was taken out and the occurrence of rust was visually observed. The remaining Mn-Ir alloy was machined to obtain a disk-shaped sputtering target having a diameter of 50 mm and a thickness of 5 mm. This sputtering target is In-S
It joined to the copper backing plate using n alloy solder, performed the sputter test using the magnetron sputtering apparatus, and formed the 15-nm-thick Mn-Ir alloy thin film on the 3-inch slide glass. At this time, the number of particles having a diameter of 0.3 μm or more existing on the slide glass was measured.
The structure of the cross section of the thin film was observed.
【００２２】（実施例２）原料となる電解ＭｎをＡｌ2
Ｏ3 坩堝を用いて１４００℃で予備溶解した後、真空蒸
留した。真空度は１０-2 Ｔｏｒｒ 、蒸留温度１３００
℃、保持時間３０分とした。蒸留したＭｎは、酸素：３
０ｐｐｍ、Ｓ：＜１０ｐｐｍ、Ｃ：１０ｐｐｍ、Ｈ：
０．８ｐｐｍであった。一方、市販の３ＮのＩｒ粉末
（酸素：１３００ｐｐｍ、Ｓ：＜１０ｐｐｍ、Ｃ：７６
０ｐｐｍ、Ｈ：５０ｐｐｍ）をＡｒ雰囲気下で１４００
℃、２ｈｒの脱ガス処理を行った後、電子ビーム溶解し
て、Ｉｒ粉末（酸素：４０ｐｐｍ、Ｓ：＜１０ｐｐｍ、
Ｃ：１０ｐｐｍ、Ｈ：１ｐｐｍ）を得た。得られた高純
度Ｍｎと高純度Ｉｒとを１：１でＣａＯ坩堝で溶解し合
金化した。その結果、酸素：７０ｐｐｍ、Ｓ：１０ｐｐ
ｍ、Ｃ：１０ｐｐｍ、Ｈ：０．２ｐｐｍ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。(Example 2) Electrolytic Mn as a raw material was changed to Al 2
After pre-melting at 1400 ° C. using an O 3 crucible, vacuum distillation was performed. Vacuum degree is 10 -2 Torr, distillation temperature is 1300
° C and a holding time of 30 minutes. Distilled Mn is oxygen: 3
0 ppm, S: <10 ppm, C: 10 ppm, H:
0.8 ppm. On the other hand, commercially available 3N Ir powder (oxygen: 1300 ppm, S: <10 ppm, C: 76
0 ppm, H: 50 ppm) in an Ar atmosphere at 1400
After degassing at 2 ° C. for 2 hours, the mixture was melted with an electron beam to obtain Ir powder (oxygen: 40 ppm, S: <10 ppm,
C: 10 ppm, H: 1 ppm). The obtained high-purity Mn and high-purity Ir were melted and alloyed at a ratio of 1: 1 in a CaO crucible. As a result, oxygen: 70 ppm, S: 10 pp
m, C: 10 ppm, H: 0.2 ppm Mn-Ir
An alloy was obtained. Table 2 shows the composition of each raw material and the Mn-Ir alloy.
【００２３】[0023]
【表２】 [Table 2]
【００２４】実施例１と同様に耐食性試験を行い、さら
にスパッタリングターゲットを作製してパーティクルの
評価試験及び薄膜の組織観察を行った。A corrosion resistance test was carried out in the same manner as in Example 1, and a sputtering target was prepared, and a particle evaluation test and a structure observation of the thin film were carried out.
【００２５】（比較例１）純度３Ｎの原料Ｍｎ粉末（酸
素：１５００ｐｐｍ、Ｓ：６００ｐｐｍ、Ｃ：１５０ｐ
ｐｍ、Ｈ：１２０ｐｐｍ）と、市販の純度３ＮのＩｒ粉
末（酸素：１３００ｐｐｍ、Ｓ：＜１０ｐｐｍ、Ｃ：７
６０ｐｐｍ、Ｈ：５０ｐｐｍ）とを１：１で溶解し合金
化した。その結果、酸素：８００ｐｐｍ、Ｓ：３１０ｐ
ｐｍ、Ｃ：２３０ｐｐｍ、Ｈ：２ｐｐｍのＭｎ−Ｉｒ合
金が得られた。各原料及びＭｎ−Ｉｒ合金の組成を表３
に示す。Comparative Example 1 Raw material Mn powder having a purity of 3N (oxygen: 1500 ppm, S: 600 ppm, C: 150 p)
pm, H: 120 ppm) and commercially available Ir powder having a purity of 3N (oxygen: 1300 ppm, S: <10 ppm, C: 7)
(60 ppm, H: 50 ppm) at a ratio of 1: 1 to form an alloy. As a result, oxygen: 800 ppm, S: 310 p
A Mn-Ir alloy having pm, C: 230 ppm and H: 2 ppm was obtained. Table 3 shows the composition of each raw material and Mn-Ir alloy.
Shown in
【００２６】[0026]
【表３】 [Table 3]
【００２７】実施例と同様に耐食性試験を行い、さらに
スパッタリングターゲットを作製してパーティクルの評
価試験及び薄膜の組織観察を行った。A corrosion resistance test was carried out in the same manner as in the examples, and a sputtering target was produced, and a particle evaluation test and a structure observation of the thin film were carried out.
【００２８】（結果）実施例１〜２、及び比較例１の耐
食性試験結果、スパッタ試験におけるパーティクル数測
定結果、および薄膜の組織観察結果を表４に示す。(Results) Table 4 shows the results of the corrosion resistance test, the measurement results of the number of particles in the sputter test, and the observation results of the structure of the thin films of Examples 1 and 2 and Comparative Example 1.
【００２９】[0029]
【表４】 [Table 4]
【００３０】その結果、酸素含有量が１０００ｐｐｍ以
下、Ｓ含有量が３００ｐｐｍ以下，Ｃ含有量が１００ｐ
ｐｍ以下、水素含有量が１ｐｐｍ以下であることを特徴
とする本発明のＭｎ−Ｉｒ合金は比較例に比べて耐食性
に優れていた。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
に比べて格段に少ないものであった。さらに、本発明の
Ｍｎ−Ｉｒ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得られたＭｎ−Ｉｒ合金薄膜も、
酸素含有量が１０００ｐｍ以下、Ｓ含有量が３００ｐｐ
ｍ以下，Ｃ含有量が１００ｐｐｍ以下、水素含有量が１
ｐｐｍ以下とターゲット組成と同様の高純度なものであ
り、その結晶組織は柱状晶であり、結晶組織の大きさも
粗大なものを得ることができ、その磁気特性は良好なも
のであったた。これに対して、比較例のターゲットを用
いて得られた薄膜は不純物含有量が多く、結晶組織は微
細な等軸晶であり、その磁気特性は不満足なものであっ
た。As a result, the oxygen content was 1000 ppm or less, the S content was 300 ppm or less, and the C content was 100 ppm.
The Mn-Ir alloy of the present invention, which is characterized by having a hydrogen content of 1 ppm or less and a hydrogen content of 1 ppm or less, was excellent in corrosion resistance as compared with the comparative example. Further, when the target of the present invention was used, the number of particles generated at the time of sputtering was much smaller than that of the comparative example. Furthermore, a Mn-Ir alloy thin film obtained by sputtering the Mn-Ir alloy sputtering target of the present invention,
Oxygen content is less than 1000 pm, S content is 300 pp
m, C content is 100 ppm or less, and hydrogen content is 1
ppm or less, which was as high as the target composition, the crystal structure was columnar, the crystal structure could be coarse, and the magnetic properties were good. On the other hand, the thin film obtained by using the target of the comparative example had a high impurity content, had a fine crystal structure of equiaxed crystals, and had unsatisfactory magnetic properties.
【００３１】[0031]
【発明の効果】本発明の酸素含有量が１０００ｐｐｍ以
下、Ｓ含有量が３００ｐｐｍ以下，Ｃ含有量が１００ｐ
ｐｍ以下、水素含有量が１ｐｐｍ以下であることを特徴
とする磁性薄膜形成用Ｍｎ−Ｉｒ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、磁気特性も良好なた反磁性膜を形
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。According to the present invention, the oxygen content of the present invention is 1000 ppm or less, the S content is 300 ppm or less, and the C content is 100 p.
pm or less, by using a Mn-Ir alloy sputtering target for forming a magnetic thin film characterized by having a hydrogen content of 1 ppm or less, a diamagnetic film having less particle generation, excellent corrosion resistance, and excellent magnetic properties can be obtained. It can be formed and is useful as a material for forming a magnetic thin film.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｆ 41/18 Ｈ０１Ｆ 41/18 Ｈ０１Ｌ 43/10 Ｈ０１Ｌ 43/10 43/12 43/12 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI H01F 41/18 H01F 41/18 H01L 43/10 H01L 43/10 43/12 43/12
Claims (5)
有量が３００ｐｐｍ以下、炭素含有量が１００ｐｐｍ以
下、水素含有量が１ｐｐｍ以下であることを特徴とする
磁性薄膜形成用Ｍｎ−Ｉｒ合金スパッタリングターゲッ
ト。An Mn-Ir alloy sputtering target for forming a magnetic thin film, wherein the oxygen content is 1000 ppm or less, the S content is 300 ppm or less, the carbon content is 100 ppm or less, and the hydrogen content is 1 ppm or less.
量が１０ｐｐｍ以下、炭素含有量が５０ｐｐｍ以下、水
素含有量が０．５ｐｐｍ以下であることを特徴とする磁
性薄膜形成用Ｍｎ−Ｉｒ合金スパッタリングターゲッ
ト。2. A Mn-Ir alloy sputtering for forming a magnetic thin film, wherein the oxygen content is 100 ppm or less, the S content is 10 ppm or less, the carbon content is 50 ppm or less, and the hydrogen content is 0.5 ppm or less. target.
用Ｍｎ−Ｉｒ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り形成されたことを特徴とする磁性
薄膜。3. A magnetic thin film formed by sputtering the Mn-Ir alloy sputtering target for forming a magnetic thin film according to claim 1 or 2.
有量が３００ｐｐｍ以下、炭素含有量が１００ｐｐｍ以
下、水素含有量が１ｐｐｍ以下であり、結晶組織が柱状
晶であることを特徴とするＭｎ−Ｉｒ合金磁性薄膜。4. An Mn-Ir having an oxygen content of 1000 ppm or less, an S content of 300 ppm or less, a carbon content of 100 ppm or less, a hydrogen content of 1 ppm or less, and a columnar crystal structure. Alloy magnetic thin film.
溶解した後、１１００〜１５００℃で真空蒸留すること
によって得た高純度Ｍｎ材料と、原料Ｉｒ粉末を１００
０〜１５００℃で脱ガス処理した後、電子ビーム溶解す
ることによって得た高純度Ｉｒ材料とを溶解し合金化し
た後、鋳造することを特徴とする磁性薄膜形成用Ｍｎ−
Ｉｒ合金スパッタリングターゲットの製造方法。5. A high-purity Mn material obtained by preliminarily dissolving a raw material Mn at 1250 to 1500 ° C. and performing vacuum distillation at 1100 to 1500 ° C. and a raw material Ir powder of 100%.
After degassing at 0 to 1500 ° C., a high-purity Ir material obtained by electron beam melting is melted and alloyed, and then cast to form a magnetic thin film-forming Mn—.
A method for producing an Ir alloy sputtering target.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08824098A JP3396420B2 (en) | 1998-03-18 | 1998-03-18 | Mn-Ir alloy sputtering target for forming magnetic thin film and Mn-Ir alloy magnetic thin film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08824098A JP3396420B2 (en) | 1998-03-18 | 1998-03-18 | Mn-Ir alloy sputtering target for forming magnetic thin film and Mn-Ir alloy magnetic thin film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002202464A Division JP3822145B2 (en) | 2002-07-11 | 2002-07-11 | Method for producing Mn-Ir alloy sputtering target for magnetic thin film formation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11264070A true JPH11264070A (en) | 1999-09-28 |
| JP3396420B2 JP3396420B2 (en) | 2003-04-14 |
Family
ID=13937345
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|---|---|---|---|
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| Country | Link |
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| JP (1) | JP3396420B2 (en) |
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|---|---|---|---|---|
| WO2002086184A1 (en) * | 2001-04-16 | 2002-10-31 | Nikko Materials Company, Limited | Manganese alloy sputtering target and method for producing the same |
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| JP2005220444A (en) * | 2005-03-31 | 2005-08-18 | Nikko Materials Co Ltd | High purity metal, sputtering target composed of high purity metal, thin film deposited by sputtering, and method for producing high purity metal |
| JP2007291522A (en) * | 2001-04-16 | 2007-11-08 | Nikko Kinzoku Kk | Manganese alloy sputtering target |
| JP2009001913A (en) * | 2008-09-16 | 2009-01-08 | Nikko Kinzoku Kk | Sputtering target composed of high purity manganese, and thin film composed of high purity manganese formed by sputtering |
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1998
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002086184A1 (en) * | 2001-04-16 | 2002-10-31 | Nikko Materials Company, Limited | Manganese alloy sputtering target and method for producing the same |
| EP1568796A1 (en) * | 2001-04-16 | 2005-08-31 | Nikko Materials Co., Ltd. | Manganese alloy sputtering target |
| CN1311096C (en) * | 2001-04-16 | 2007-04-18 | 日矿金属株式会社 | Manganese alloy sputtering target and mehtod for producing the same |
| US7229510B2 (en) | 2001-04-16 | 2007-06-12 | Nippon Mining & Metals, Co., Ltd. | Manganese alloy sputtering target and method for producing the same |
| JP2007291522A (en) * | 2001-04-16 | 2007-11-08 | Nikko Kinzoku Kk | Manganese alloy sputtering target |
| US7713364B2 (en) | 2001-04-16 | 2010-05-11 | Nippon Mining & Metals Co., Ltd. | Manganese alloy sputtering target and method for producing the same |
| JP4685059B2 (en) * | 2001-04-16 | 2011-05-18 | Ｊｘ日鉱日石金属株式会社 | Manganese alloy sputtering target |
| JP2003064473A (en) * | 2001-08-24 | 2003-03-05 | Toshiba Corp | Sputtering target, antiferromagnetic film, magnetoresistance effect element provided with the film, magnetic head, and magnetoresistance effect type random access memory |
| JP2005220444A (en) * | 2005-03-31 | 2005-08-18 | Nikko Materials Co Ltd | High purity metal, sputtering target composed of high purity metal, thin film deposited by sputtering, and method for producing high purity metal |
| JP2009001913A (en) * | 2008-09-16 | 2009-01-08 | Nikko Kinzoku Kk | Sputtering target composed of high purity manganese, and thin film composed of high purity manganese formed by sputtering |
| JP2011068992A (en) * | 2010-09-29 | 2011-04-07 | Toshiba Corp | Method for producing sputtering target |
| JP2012072498A (en) * | 2011-11-16 | 2012-04-12 | Jx Nippon Mining & Metals Corp | Sputtering target consisting of high purity manganese and thin film consisting of high purity manganese which is formed by sputtering |
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