JPH0430450B2 - - Google Patents
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- Publication number
- JPH0430450B2 JPH0430450B2 JP61246217A JP24621786A JPH0430450B2 JP H0430450 B2 JPH0430450 B2 JP H0430450B2 JP 61246217 A JP61246217 A JP 61246217A JP 24621786 A JP24621786 A JP 24621786A JP H0430450 B2 JPH0430450 B2 JP H0430450B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- less
- present
- cao
- vapor deposition
- 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.)
- Expired - Lifetime
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- 239000000956 alloy Substances 0.000 claims description 52
- 229910045601 alloy Inorganic materials 0.000 claims description 50
- 238000007740 vapor deposition Methods 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 230000005291 magnetic effect Effects 0.000 description 35
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 24
- 239000010409 thin film Substances 0.000 description 24
- 239000000292 calcium oxide Substances 0.000 description 23
- 235000012255 calcium oxide Nutrition 0.000 description 23
- 229910003271 Ni-Fe Inorganic materials 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 239000002184 metal Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 230000035699 permeability Effects 0.000 description 18
- 229910052719 titanium Inorganic materials 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 238000004544 sputter deposition Methods 0.000 description 13
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910000889 permalloy Inorganic materials 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011819 refractory material Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 229910001004 magnetic alloy Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910000815 supermalloy Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Thin Magnetic Films (AREA)
Description
［産業上の利用分野］
本発明は蒸着用Ni−Fe基合金に係り、特にそ
の高透磁率を利用したヘツド材や磁気記録材料の
下地材料として用いられる薄膜の製造に好適な蒸
着用Ni−Fe基合金に関する。
［従来の技術］
非磁性基板上に磁性合金薄膜を形成した磁気記
録材料は周知である。
この磁気記録材料の薄膜を製造する方法として
は、スパツタリングや真空蒸着、イオンプレーテ
イング等の蒸着法が広く用いられている。
特にスパツタリング法は、均一な内部組成で一
定の合金元素を含んだターゲツト材が得られさえ
すれば、スパツタリング装置内の圧力をコントロ
ールしながら組成的に均一な薄膜を得ることがで
きる点で有利である。
磁性合金薄膜を形成する強磁性合金としては、
ニツケル合金、コバルト合金、鉄合金などが従来
より用いられているが、これらのうち、Ni−Fe
基合金は、透磁率が大きいことから種々のものが
実用されている。例えばNi−Fe系の35〜90％Ni
合金は高い透磁率を有する合金という意味でパー
マロイ（Pemalloy）と称され、特に70〜80％Ni
合金はパーマロイ（PA）と称し、弱磁場で初透
磁率μo、最大透磁率μｍが大きい。特に近年は
薄膜ヘツドと共に、垂直磁気記録材料の下地材と
して注目されている。
ところで、パーマロイの大きな透磁率は高温度
（約600℃以上）から急冷して得られるので、製品
の特性が不均一になりやすい。この欠点を改善す
るために、Mo、Cr、Cu、Nbなどの元素を加え
て規則格子の生成を抑制し、徐冷状態で極めて大
きな透磁率が再現性よく得られている。
［発明が解決しようとする問題点］
従来より用いられている磁性合金について種々
検討を重ねたところ、酸素、窒素、硫黄、炭素、
その他金属酸化物等の介在物が比較的多量に含ま
れており、得られる薄膜の磁気特性に多大な悪影
響をもたらすことが認められた。
［問題点を解決するための手段］
本発明は上記従来の実情に鑑み、不純物含有量
の少ない高特性磁性薄膜を安定かつ効率的に得る
ことができる蒸着用Ni−Fe基合金を提供するべ
くなされたものであつて、
Ni35〜85重量％、Mo、Cr、Cu及びNbよりな
る群から選ばれる１種又は２種以上３〜15重量
％、Al0.005〜１重量％、Ti1重量％以下、Ca及
び／又はMg300ppm以下、並びに、不純物とし
てO30ppm以下及びN30ppm以下を含有し、残部
が実質的にFeであることを特徴とする蒸着用Ni
−Fe基合金、
を要旨とするものである。
即ち、本発明者は、蒸着用合金の不純物に起因
する問題を解決し、高特性磁性薄膜を得るべく、
鋭意検討を重ねた結果、蒸着用Ni−Fe基合金中
に、特定量のCa及び／又はMgとAl及びTiとを
含有させることにより、不純物含有量の少ない合
金が得られ、しかもCa及び／又はMgとAl及び／
又はTiとによるゲツタ作用により、蒸着雰囲気
中のガス成分をも低減し、極めて高純度で高特性
の磁性薄膜を得ることができることを見出し、本
発明を完成させた。
以下、本発明につき詳細に説明する。
なお、本明細書において、「％」は「重量％」
を表すものである。
本発明の蒸着用Ni−Fe基合金は、真空蒸着あ
るいはスパツタリング、イオンプレーテイング等
の蒸着用材料として用いられ、磁性薄膜の製造等
に利用されるものであつて、その組成は、下記の
通りである。
Ni：35〜82％
Mo、Cr、Cu及びNbの１種以上：
３〜15％
Fe：残部
Al：0.005〜１％
Ti：１％以下
Ca及び／又はMg：300ppm以下
Ｏ：30ppm以下
Ｎ：30ppm以下
以下に本発明の合金組成の限定理由について説
明する。
本発明の蒸着用Ni−Fe基合金において、Niは
35〜85％とする。これは、この範囲のNi含有率
にて、極めて高い透磁率が得られるためであつ
て、好ましいNi含有率は70〜85％、特に78.5％と
することにより、著しく高い透磁率が得られる。
Mo、Cr、Cu、Nbは、前述の如く、透磁率の
改善、磁気特性の改善に有効に作用する。しかし
ながら、その含有量があまりに多過ぎるとNi−
Fe基合金の高透磁率特性に悪影響を及ぼすこと
から、その含有量は３〜15％、好ましくはMo3
〜８％、Cr3〜15％、Cu5〜15％、Nb3〜15％と
する。
本発明の蒸着用Ni−Fe基合金のNiと上記Mo、
Cr、Cu、Nbとの成分比（％）の具体例として
は、下記のようなパーマロイＣ級合金系のものが
挙げられる。
1040合金：72Ni−14Cu−3Mo−Fe
ミユーメタル：77Ni−5Cu−4Mo−Fe
Cr−パーマロイ：78.5Ni−3.8Cu−Fe
Mo−パーマロイ：79Ni−4Mo−Fe
スーパーマロイ：79Ni−5Mo−Fe
ハードパーム：79Ni−9Nb−Fe
Al及びTiは、合金の溶製を行なう際に、Ca、
Mgと共に合金の清浄化に作用し、また蒸着雰囲
気中にてガス成分を捕促するゲツタ作用を有す
る。ただし、Al、Tiはその量があまりに多過ぎ、
合金特性に影響を及ぼす量であつて好ましくな
く、このため本発明においては、各々１％以下と
する。当然のことながら、Al、Tiは、その量が
あまりに少な過ぎると上記清浄化作用及びゲツタ
作用による十分な効果が得られないことから、特
にAlは0.005％以上とする。本発明においては、
Al0.005〜0.5％及びTi0.5％以下、より好ましく
は、Al0.05〜0.2％及びTi0.2％以下とするのが望
ましい。なお、Al又はTiは、固溶Al又は固溶Ti
の形態で合金中に存在することにより、本発明の
効果を奏するものであるので、Al又はTiの存在
形態は固溶状態であることが重要である。
Ca及びMgは前述の如くAl及び／又はTiと共
に合金の清浄化に作用し、またゲツタ作用を奏す
る。Ca及びMgは、その含有量があまりに多過ぎ
ると合金特性に影響を及ぼし、また、金属間化合
物の析出により合金を脆くすることがある。この
ため、本発明においてはCa及び／又はMgの含有
量は300ppm以下とする。一方、Ca及び／又は
Mgの含有量は少な過ぎても、Ca、Mgによる十
分な清浄化作用及びゲツタ作用が現れない。この
ようなことから、Ca、Mg含有量は、各々、５〜
100ppmの範囲、好ましくは各々10〜50ppmの範
囲とするのが好ましい。なお、CaはCaOないし
CaO−Al2O3の形態では本発明の効果は奏し得
ず、同様に、MgはMgOの形態では本発明の効果
を奏し得ないことから、合金中のCa、Mgの存在
形態は金属Ca、金属Mgであることが重要であ
る。
合金中の不純物であるＯ、Ｎの量が多いと、蒸
着に使用した際に、蒸着雰囲気の真空度を悪化さ
せたり、また良好な蒸着が行なえず、高特性の磁
性薄膜が得られない。このため、合金中のＯ含有
量は30ppm以下、好ましくは20ppm以下、Ｎ含有
量は30ppm以下、好ましくは20ppm以下とする。
なお、本発明において、Si、Mn、Ｐ、Ｓ等の
不純物が合金中に不可避的に含有されるのは、特
に問題とはならないが、上述したことと同様の理
由から、本発明において、合金中の他の不純物は
できるだけ少なくするのが良く、例えば、Si含有
量は0.1％以下、Mn含有量は0.05％以下、Ｐ含有
量は50ppm以下、Ｓ含有量は10ppm以下とするの
が好ましい。
このような本発明の蒸着用Ni−Fe基合金は、
例えば、以下に説明する方法に従つて製造するこ
とができる。
即ち、まず、合金化のためのNi、Fe、Mo、
Cr、Cu及びNbの１種以上、Al、Tiの金属又は
合金材料を、内面がCaO質耐火材で構成された容
器中で、真空又はアルゴン等の不活性ガス雰囲気
等の非酸化性雰囲気にて、常法例えば高周波ある
いは低周波誘導加熱法等で加熱して溶解すること
により、所望の組成の合金溶湯を得る。
本発明において、用いられる容器の内面を構成
するCaO質耐火材としては、カルシア（CaO）、
ラルナイト（安定化2CaO・SiO2）、メルウイナ
イト（3CaO・MgO・2SiO2）、アノルサイト
（CaO・Al2O3・2SiO2）ならびにCaOを富化した
ドロマイト等が挙げられるが、特に、電融カルシ
アが好適である。
このようなカルシア質炉材は、そのCaO含有率
が40％以上、特に60％以上のものが好ましい。
CaOは高融点であると共に、高温で極めて安定
であり、溶製にあたり、金属酸化物を生成して溶
湯を不純物により汚染することがなく、高清浄な
溶湯を得ることが可能とされる。
特に、CaO含有量の高いCaO質耐火材で内面が
構成された容器を用いた場合には、脱Ｏ、脱Ｓ、
脱介在物等の精錬作用も奏され、極めて有利であ
る。
しかも、溶湯中にAl及びTiが存在するため、
溶湯中の脱Ｏ、脱Ｓが行なわれ、これに伴つて脱
Ｎも起こる。また、炉壁材のCaOとAlとの反応
により溶湯中へのCaの溶出もおこる。即ち、Al
は溶湯中のＯ及び炉壁のCaOと溶湯中のＳと反応
して
CaO＋Ｓ→CaS＋Ｏ
となつて生じたＯと反応して、
2Al＋3O→Al2O3
となり、Al2O3を生じる。また溶湯中のAlは炉壁
のCaOと反応して
2Al＋3CaO→Al2O3＋3Ca（ｇ）
となり、これによつてもAl2O3が生じる。（この
場合、生じたCaは、ガスとなつて系外に抜ける
が、一部が合金中に残留して、本発明の合金の
Ca含有量を満足させる。）
Al2O3は次式の如く炉壁のCaOと反応して。
3CaO・Al2O3又は12CaO・7Al2O3の活性な層が
炉壁表面に形成される。
Al2O3＋3CaO→3CaO・Al2O3
7Al2O3＋12CaO→
12CaO・7Al2O3
この12CaO・7Al2O3及び3CaO・Al2O3、特に
3CaO・Al2O3は溶湯の脱Ｓ能が高く、脱Ｓが良
好に進行する。
このように、Alにより脱Ｏが、またAlの還元
作用により生じた活性な3CaO・Al2O3、12CaO、
7Al2O3やCaOにより脱Ｓが行なわれる。
また、耐火材がCaO−MgO系の容器を用いて
溶製を行なつた場合、Caと共にMgの溶出も見ら
れ、溶湯中に金属態Mgが残留し、Caと同様に蒸
着時にゲツタ作用を奏し、その効果を補完し、更
に強力なものとする。即ち、炉壁のMgOは
3MgO＋CaO＋2Al→CaO・Al2O3＋3Mg（ｇ）
となり、生じたMgの一部が合金中に残留する。
また溶湯中のＮは前述のAlとCaOとの反応に
より生じたCa等の蒸発（沸騰）等に伴つて溶湯
中から離脱し、溶湯中のＮ量も低減される。
Tiは、Alの作用を補完し、更にAlと同様の作
用により脱Ｏ、脱Ｓ、脱Ｎを行なう。
従つて、内面がCaO質耐火材で構成された容器
中で溶製を行なうことにより、本発明の低Ｏ、低
Ｎ含有量のNi−Fe基合金を容易に得ることがで
きる。
ところで、本発明においては、内面がCaO質耐
火材で構成された容器中にて溶製する際に、Al
及びTiを冷却固化後のAl及びTi残留量が本発明
の範囲、即ち、Al0.005〜１％及びTi1％以下と
なるように添加するのであるが、溶製に用いる容
器の内面を、特にCaO及びMgO（MgO含有率60
〜15％）のカルシア系耐火物よりなるものとする
ことにより、Al及びTiの添加により、溶湯中へ
CaだけでなくMgの溶出も認められ、得られる合
金中のCa、Mg含有量を容易に本発明の範囲即ち
300ppm以下とすることができる。
このようにして得られた合金溶湯を、常法に従
つて非酸化性雰囲気下で鋳造する。
このような方法によれば、Ni35〜85重量％、
Mo、Cr、Cu及びNbよりなる群から選ばれる１
種又は２種以上３〜15％、Al0.005〜１％、Ti1
％以下、Ca及び／又はMg300ppm以下、不純物
としてO30ppm以下及びN30ppm以下を含有し、
残部が実質的にFeである本発明の蒸着用Ni−Fe
基合金を極めて容易に製造することができる。
［作用］
本発明の蒸着用Ni−Fe基合金は、Ｏ、Ｎ含有
量が少ないため、高特性の磁性薄膜を得ることが
できる。
また、本発明の蒸着用Ni−Fe基合金に含有さ
れるAl及びTi、Ca、Mgは、真空蒸着又はスパ
ツタリング等の蒸着雰囲気中にて、
4Al＋3O2→2Al2O3
2Al＋N2→2AlN
2Ca＋O2→2CaO
3Ca＋N2→Ca3N2
のように反応して、雰囲気中のガス成分を低下さ
せる、いわゆるゲツタ作用を奏する。
Ti、Mgについても同様にそれぞれAl、Caの
作用を下式のように補完して良好なゲツタ作用を
奏する。
Ti＋O2→TiO2
Ti＋N2→TiN2
2Mg＋O2→2MgO
3Mg＋N2→Mg3N2
このため、蒸着時の薄膜形成安定性及び形成速
度を向上させると共に、得られる薄膜は高純度で
磁気特性が大幅に改善され、高特性薄膜を高生産
効率で製造することを可能とする。
［実施例］
以下、実施例について説明する。
実施例 １
第１表に示す組成のNi−Fe基合金を蒸着用材
料として用い、下記仕様のスパツタリング装置に
て、直径10cmのガラス基盤上に各３回ずつ薄膜を
形成した。なお、基盤加熱温度は150℃とした。
スパツタリング装置仕様
マグネトロンタイプ高周波スパツタリング装置
最大出力：1KW
到達真空度：10-7torr
ターゲツト寸法：100mm（φ）×３mmmm（ｔ）
[Industrial Application Field] The present invention relates to a Ni-Fe based alloy for deposition, and in particular to a Ni-Fe base alloy for deposition, which is suitable for manufacturing thin films that are used as base materials for head materials and magnetic recording materials, taking advantage of its high magnetic permeability. Regarding Fe-based alloys. [Prior Art] A magnetic recording material in which a magnetic alloy thin film is formed on a nonmagnetic substrate is well known. Vapor deposition methods such as sputtering, vacuum evaporation, and ion plating are widely used as methods for producing thin films of magnetic recording materials. In particular, the sputtering method is advantageous in that it is possible to obtain a compositionally uniform thin film while controlling the pressure inside the sputtering device, as long as a target material containing a certain alloying element with a uniform internal composition is obtained. be. As a ferromagnetic alloy that forms a magnetic alloy thin film,
Nickel alloys, cobalt alloys, iron alloys, etc. have been used conventionally, but among these, Ni-Fe
Various base alloys are in practical use because they have high magnetic permeability. For example, 35 to 90% Ni in Ni-Fe system
The alloy is called permalloy because it has high magnetic permeability, and it is especially made of 70-80% Ni.
The alloy is called permalloy (PA) and has a large initial magnetic permeability μo and maximum magnetic permeability μm in a weak magnetic field. Particularly in recent years, it has attracted attention as a base material for perpendicular magnetic recording materials, along with thin film heads. By the way, permalloy's high magnetic permeability is obtained by rapidly cooling it from a high temperature (approximately 600 degrees Celsius or higher), which tends to result in non-uniform product properties. In order to improve this drawback, elements such as Mo, Cr, Cu, and Nb are added to suppress the formation of ordered lattices, and extremely high magnetic permeability can be obtained with good reproducibility under slow cooling conditions. [Problems to be solved by the invention] After conducting various studies on conventionally used magnetic alloys, we found that oxygen, nitrogen, sulfur, carbon,
It was found that a relatively large amount of other inclusions such as metal oxides were included, and this had a significant adverse effect on the magnetic properties of the resulting thin film. [Means for Solving the Problems] In view of the above-mentioned conventional circumstances, the present invention aims to provide a Ni-Fe-based alloy for deposition, which can stably and efficiently produce a high-performance magnetic thin film with a low impurity content. 35 to 85% by weight of Ni, 3 to 15% by weight of one or more types selected from the group consisting of Mo, Cr, Cu, and Nb, 0.005 to 1% by weight of Al, and 1% by weight or less of Ti. , Ca and/or Mg 300 ppm or less, and O 30 ppm or less and N 30 ppm or less as impurities, with the balance being substantially Fe.
-Fe-based alloy. That is, the present inventors aimed to solve the problem caused by impurities in the deposition alloy and obtain a high-characteristic magnetic thin film.
As a result of extensive studies, we have found that by incorporating specific amounts of Ca and/or Mg and Al and Ti into the Ni-Fe base alloy for vapor deposition, an alloy with low impurity content can be obtained. Or Mg and Al and/or
Alternatively, the inventors have discovered that the getter action of Ti can also reduce the gas components in the deposition atmosphere and obtain a magnetic thin film with extremely high purity and high characteristics, and have completed the present invention. Hereinafter, the present invention will be explained in detail. In addition, in this specification, "%" is "weight%"
It represents. The Ni-Fe-based alloy for deposition of the present invention is used as a material for deposition in vacuum deposition, sputtering, ion plating, etc., and is used for manufacturing magnetic thin films, etc., and its composition is as follows. It is. Ni: 35-82% One or more of Mo, Cr, Cu and Nb: 3-15% Fe: Balance Al: 0.005-1% Ti: 1% or less Ca and/or Mg: 300ppm or less O: 30ppm or less N: 30 ppm or less The reasons for limiting the alloy composition of the present invention will be explained below. In the Ni-Fe base alloy for vapor deposition of the present invention, Ni is
35-85%. This is because an extremely high magnetic permeability can be obtained with a Ni content in this range, and a preferable Ni content of 70 to 85%, particularly 78.5%, allows an extremely high magnetic permeability to be obtained. As mentioned above, Mo, Cr, Cu, and Nb effectively act to improve magnetic permeability and magnetic properties. However, if the content is too high, Ni−
Since it has a negative effect on the high magnetic permeability properties of Fe-based alloys, its content should be 3 to 15%, preferably Mo3
~8%, Cr3~15%, Cu5~15%, and Nb3~15%. Ni of the Ni-Fe-based alloy for vapor deposition of the present invention and the above Mo,
Specific examples of the component ratio (%) of Cr, Cu, and Nb include permalloy C-class alloys as shown below. 1040 alloy: 72Ni−14Cu−3Mo−Fe Miu metal: 77Ni−5Cu−4Mo−Fe Cr−permalloy: 78.5Ni−3.8Cu−Fe Mo−permalloy: 79Ni−4Mo−Fe Supermalloy: 79Ni−5Mo−Fe Hard palm: 79Ni-9Nb-Fe Al and Ti are processed by Ca,
Together with Mg, it acts to clean the alloy, and also has a getter effect that traps gas components in the deposition atmosphere. However, the amounts of Al and Ti are too large,
These amounts are undesirable as they affect the alloy properties, so in the present invention, each is set at 1% or less. Naturally, if the amounts of Al and Ti are too small, sufficient effects of the above-mentioned cleaning action and getter action cannot be obtained, so the content of Al in particular should be 0.005% or more. In the present invention,
It is desirable that Al be 0.005 to 0.5% and Ti be 0.5% or less, more preferably Al be 0.05 to 0.2% and Ti be 0.2% or less. Note that Al or Ti is solid solution Al or solid solution Ti.
Since the effects of the present invention are achieved by existing in the alloy in this form, it is important that Al or Ti exists in a solid solution state. As mentioned above, Ca and Mg work together with Al and/or Ti to clean the alloy and also have a getter action. If the content of Ca and Mg is too high, it may affect the properties of the alloy, and may also cause the alloy to become brittle due to the precipitation of intermetallic compounds. Therefore, in the present invention, the content of Ca and/or Mg is set to 300 ppm or less. On the other hand, Ca and/or
Even if the Mg content is too low, sufficient cleaning and scavenging effects by Ca and Mg will not occur. For this reason, the Ca and Mg contents should be 5 to 5, respectively.
A range of 100 ppm, preferably 10 to 50 ppm each is preferred. In addition, Ca is CaO or
The effect of the present invention cannot be achieved in the form of CaO-Al 2 O 3 , and similarly, the effect of the present invention cannot be achieved in the form of MgO, so the existence form of Ca and Mg in the alloy is metal Ca. , it is important that the metal is Mg. If the amount of impurities such as O and N in the alloy is large, the degree of vacuum in the deposition atmosphere may deteriorate when the alloy is used for vapor deposition, or good vapor deposition may not be performed, making it impossible to obtain a magnetic thin film with high characteristics. Therefore, the O content in the alloy is 30 ppm or less, preferably 20 ppm or less, and the N content is 30 ppm or less, preferably 20 ppm or less. In the present invention, it is not a particular problem that impurities such as Si, Mn, P, and S are unavoidably contained in the alloy. Other impurities in the material are preferably reduced as much as possible; for example, the Si content is preferably 0.1% or less, the Mn content is 0.05% or less, the P content is 50ppm or less, and the S content is 10ppm or less. Such a Ni-Fe-based alloy for vapor deposition of the present invention is
For example, it can be manufactured according to the method described below. That is, first, Ni, Fe, Mo,
One or more of Cr, Cu, and Nb, Al, and Ti metals or alloy materials are placed in a non-oxidizing atmosphere such as vacuum or an inert gas atmosphere such as argon in a container whose inner surface is made of CaO refractory material. Then, a molten alloy having a desired composition is obtained by heating and melting using a conventional method such as a high frequency or low frequency induction heating method. In the present invention, the CaO refractory material constituting the inner surface of the container used is calcia (CaO),
Larnite (stabilized 2CaO・SiO 2 ), melwinite (3CaO・MgO・2SiO 2 ), anorsite (CaO・Al 2 O 3・2SiO 2 ), and CaO-enriched dolomite are included, but in particular, fused calcia is suitable. Such calcia furnace material preferably has a CaO content of 40% or more, particularly 60% or more. CaO has a high melting point and is extremely stable at high temperatures. During melting, CaO does not generate metal oxides and contaminate the molten metal with impurities, making it possible to obtain a highly clean molten metal. In particular, when using a container whose inner surface is made of a CaO-based refractory material with a high CaO content,
It also has a refining effect such as removal of inclusions, which is extremely advantageous. Moreover, since Al and Ti are present in the molten metal,
O and S are removed from the molten metal, and along with this, N is also removed. In addition, Ca is leached into the molten metal due to the reaction between CaO and Al in the furnace wall material. That is, Al
reacts with O in the molten metal, CaO on the furnace wall, and S in the molten metal to form CaO+S→CaS+O, and reacts with the generated O to form 2Al+3O→Al 2 O 3 to produce Al 2 O 3 . Furthermore, Al in the molten metal reacts with CaO on the furnace wall to form 2Al+3CaO→Al 2 O 3 +3Ca(g), and this also produces Al 2 O 3 . (In this case, the generated Ca becomes a gas and escapes from the system, but some of it remains in the alloy and
Satisfy Ca content. ) Al 2 O 3 reacts with CaO on the furnace wall as shown in the following equation.
An active layer of 3CaO.Al 2 O 3 or 12CaO.7Al 2 O 3 is formed on the furnace wall surface. Al 2 O 3 +3CaO→3CaO・Al 2 O 3 7Al 2 O 3 +12CaO→ 12CaO・7Al 2 O 3This 12CaO・7Al 2 O 3 and 3CaO・Al 2 O 3 , especially
3CaO.Al 2 O 3 has a high ability to remove S from molten metal, and S removal progresses well. In this way, active 3CaO・Al 2 O 3 , 12CaO,
S removal is performed using 7Al 2 O 3 and CaO. In addition, when the refractory material is melted using a CaO-MgO-based container, Mg is also eluted along with Ca, and metallic Mg remains in the molten metal, causing a gettuding effect during vapor deposition like Ca. play, complement the effect, and make it even more powerful. That is, MgO on the furnace wall becomes 3MgO+CaO+2Al→CaO.Al 2 O 3 +3Mg (g), and a part of the generated Mg remains in the alloy. Further, N in the molten metal is removed from the molten metal due to evaporation (boiling) of Ca, etc. generated by the reaction between Al and CaO as described above, and the amount of N in the molten metal is also reduced. Ti complements the action of Al, and also removes O, S, and N through the same actions as Al. Therefore, by carrying out melting in a container whose inner surface is made of a CaO refractory material, the low O and low N content Ni-Fe base alloy of the present invention can be easily obtained. By the way, in the present invention, Al
and Ti are added so that the residual amounts of Al and Ti after cooling and solidification are within the range of the present invention, that is, 0.005 to 1% Al and 1% Ti. CaO and MgO (MgO content 60
~15%) by adding Al and Ti to the molten metal.
The elution of not only Ca but also Mg was observed, making it easy to determine the Ca and Mg contents in the resulting alloy within the range of the present invention.
It can be 300ppm or less. The molten alloy thus obtained is cast in a non-oxidizing atmosphere according to a conventional method. According to this method, Ni35-85% by weight,
1 selected from the group consisting of Mo, Cr, Cu and Nb
Species or 2 or more types 3-15%, Al0.005-1%, Ti1
% or less, contains Ca and/or Mg 300ppm or less, O 30ppm or less and N 30ppm or less as impurities,
Ni-Fe for vapor deposition of the present invention, the balance being substantially Fe
The base alloy can be produced very easily. [Function] Since the Ni-Fe-based alloy for vapor deposition of the present invention has a low content of O and N, a magnetic thin film with high characteristics can be obtained. Moreover, Al, Ti, Ca, and Mg contained in the Ni-Fe-based alloy for vapor deposition of the present invention are 4Al+3O 2 →2Al 2 O 3 2Al+N 2 →2AlN 2Ca+O 2 in a vapor deposition atmosphere such as vacuum evaporation or sputtering. →2CaO 3Ca+N 2 →Ca 3 N 2 It reacts as follows, producing a so-called getter effect that lowers the gas components in the atmosphere. Similarly, Ti and Mg also complement the effects of Al and Ca, respectively, as shown in the following equations, and exhibit good getter effects. Ti＋O 2 →TiO 2 Ti＋N 2 →TiN 2 2Mg＋O 2 →2MgO 3Mg＋N 2 →Mg 3 N 2This improves the stability and formation speed of thin film formation during vapor deposition, and the resulting thin film has high purity and significantly improved magnetic properties. This makes it possible to manufacture high-performance thin films with high production efficiency. [Example] Examples will be described below. Example 1 Using a Ni-Fe based alloy having the composition shown in Table 1 as a material for vapor deposition, thin films were formed three times each on a glass substrate with a diameter of 10 cm using a sputtering apparatus having the following specifications. Note that the substrate heating temperature was 150°C. Sputtering equipment specifications Magnetron type high frequency sputtering equipment Maximum output: 1KW Ultimate vacuum: 10 -7 torr Target dimensions: 100mm (φ) x 3mmmm (t)
【表】【table】
【表】
スパツタ電力、アルゴンガス圧を変えて、各蒸
着用材料により形成された薄膜の膜厚を調べた結
果を、それぞれ第１図、第２図に示す。
第１図、第２図より、本発明の蒸着用Ni−Fe
基合金は、バツチごとのバラツキが少なく、均質
な上に膜形成効率が高いことが認められる。
実施例 ２
実施例１で用いたスパツタリング装置及び基盤
を用い、第１表のNo.１〜８の蒸着用合金にて、
Ar圧又は基板加熱温度を変えて、それぞれ3μｍ
厚さの薄膜を３回ずつ形成して高透磁率薄膜を作
成した。なお、スパツタ電圧は500Wで行なつた。
得られた高透磁率材料薄膜の保磁率Hcを調べ、
基盤加熱温度又はAr圧との関係をそれぞれ第３
図、第４図に示す。
第３図及び第４図より、本発明の蒸着用Ni−
Fe基合金によれば、極めて保磁率の低い高透磁
率な磁性材料がバラツキなく安定して得られるこ
とが認められる。また、基盤加熱等の生産上手数
がかかる工程も省略することができ、工業上極め
て有利となる。
実施例 ３
実施例２において、No.１及び２の合金材料より
基盤加熱温度200℃、Ar圧４×10-2torrにて得ら
れた高透磁率材料について、その磁気特性を調べ
た結果を第２表に示す。第２表には同時に比較合
金No.５、６の値も示した。[Table] Figures 1 and 2 show the results of examining the thickness of thin films formed with each deposition material while varying the sputtering power and argon gas pressure. From Fig. 1 and Fig. 2, Ni-Fe for vapor deposition of the present invention is shown.
It is recognized that the base alloy has little variation from batch to batch, is homogeneous, and has high film formation efficiency. Example 2 Using the sputtering equipment and substrate used in Example 1, the vapor deposition alloys No. 1 to 8 in Table 1 were prepared.
3μm by changing Ar pressure or substrate heating temperature
A high magnetic permeability thin film was created by forming a thin film of the same thickness three times. Note that the sputtering voltage was 500W. We investigated the coercivity Hc of the obtained thin film of high magnetic permeability material,
The relationship with base heating temperature or Ar pressure is
It is shown in Fig. 4. From FIG. 3 and FIG. 4, it can be seen that Ni-
It is recognized that Fe-based alloys can stably obtain magnetic materials with extremely low coercivity and high magnetic permeability without variation. In addition, it is possible to omit steps such as substrate heating that require a lot of production time, which is extremely advantageous industrially. Example 3 The results of investigating the magnetic properties of the high magnetic permeability materials obtained from the alloy materials No. 1 and 2 at a base heating temperature of 200°C and an Ar pressure of 4×10 -2 torr in Example 2 are as follows. Shown in Table 2. Table 2 also shows the values for comparative alloys No. 5 and 6.
【表】
第２表より、本発明の蒸着用Ni−Fe基合金に
より得られる高透磁率材料はヒステリシス特性に
優れ、透磁率が高く、極めて高特性のものである
ことがが認められる。
［発明の効果］
以上詳述した通り、本発明の蒸着用Ni−Fe基
合金は、Ｏ、Ｎ含有量が少ない上に、Al及びTi
とCa及び／又はMgによるゲツタ作用により、蒸
着雰囲気中のガス成分が大幅に低減される。
このため、蒸着による膜形成安定性及び膜形成
速度が向上されるとともに、得られる薄膜は高純
度で極めて磁気特性に優れたものとなる。
従つて、本発明の蒸着用Ni−Fe基合金によれ
ば、高特性薄膜を高効率で得ることができ、本発
明の蒸着用Ni−Fe基合金は、高透磁率材料の薄
膜製造用蒸着材料として極めて有用である。[Table] From Table 2, it is recognized that the high magnetic permeability material obtained from the Ni-Fe based alloy for vapor deposition of the present invention has excellent hysteresis characteristics, high magnetic permeability, and extremely high characteristics. [Effects of the Invention] As detailed above, the Ni-Fe-based alloy for vapor deposition of the present invention has low O and N contents, and also contains Al and Ti.
Due to the getter action of Ca and/or Mg, the gas components in the deposition atmosphere are significantly reduced. Therefore, the stability and speed of film formation by vapor deposition are improved, and the obtained thin film has high purity and extremely excellent magnetic properties. Therefore, according to the Ni-Fe-based alloy for vapor deposition of the present invention, a thin film with high characteristics can be obtained with high efficiency, and the Ni-Fe-based alloy for vapor deposition of the present invention can be used for vapor deposition for manufacturing thin films of high magnetic permeability materials. Extremely useful as a material.
第１図、第２図は実施例１で得られた結果を示
すグラフであつて、それぞれ、スパツタ電圧、ア
ルゴン圧、スパツタ時間と得られる膜厚との関係
を示す。第３図及び第４図は実施例２で得られた
結果を示すグラフであつて、それぞれ、基盤加熱
温度、アルゴン圧と磁気記録材料の保磁率との関
係を示す。
FIGS. 1 and 2 are graphs showing the results obtained in Example 1, and show the relationships between the sputtering voltage, argon pressure, sputtering time, and the resulting film thickness, respectively. FIGS. 3 and 4 are graphs showing the results obtained in Example 2, and show the relationships between substrate heating temperature, argon pressure, and coercivity of the magnetic recording material, respectively.
Claims (1)
なる群から選ばれる１種又は２種以上３〜15重量
％、Al0.005〜１重量％、Ti1重量％以下、Ca及
び／又はMg300ppm以下、並びに不純物として
O30ppm以下及びN30ppm以下を含有し、残部が
実質的にFeであることを特徴とする蒸着用Ni−
Fe基合金。1 35 to 85% by weight of Ni, 3 to 15% by weight of one or more selected from the group consisting of Mo, Cr, Cu, and Nb, 0.005 to 1% by weight of Al, 1% by weight or less of Ti, 300ppm of Ca and/or Mg Below, as well as impurities
Ni- for vapor deposition characterized by containing 30ppm or less of O and 30ppm or less of N, with the remainder being substantially Fe.
Fe-based alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24621786A JPS63100148A (en) | 1986-10-16 | 1986-10-16 | Ni-fe-base alloy for vapor deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24621786A JPS63100148A (en) | 1986-10-16 | 1986-10-16 | Ni-fe-base alloy for vapor deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63100148A JPS63100148A (en) | 1988-05-02 |
| JPH0430450B2 true JPH0430450B2 (en) | 1992-05-21 |
Family
ID=17145254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24621786A Granted JPS63100148A (en) | 1986-10-16 | 1986-10-16 | Ni-fe-base alloy for vapor deposition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63100148A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2777319B2 (en) * | 1993-07-30 | 1998-07-16 | 財団法人電気磁気材料研究所 | Wear-resistant high-permeability alloy, method for producing the same, and magnetic recording / reproducing head |
| JP4047114B2 (en) * | 2002-09-13 | 2008-02-13 | アルプス電気株式会社 | Thin film magnetic head |
| JP4948122B2 (en) * | 2006-11-06 | 2012-06-06 | 株式会社ジェイテクト | Whetstone with inclined grooves |
| JP5532767B2 (en) * | 2009-09-04 | 2014-06-25 | 大同特殊鋼株式会社 | NiCu alloy target material for Cu electrode protection film |
| JP6639922B2 (en) * | 2016-01-20 | 2020-02-05 | 国立大学法人広島大学 | Silicon carbide semiconductor device and method of manufacturing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62186511A (en) * | 1986-02-12 | 1987-08-14 | Hitachi Metals Ltd | Target member |
-
1986
- 1986-10-16 JP JP24621786A patent/JPS63100148A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62186511A (en) * | 1986-02-12 | 1987-08-14 | Hitachi Metals Ltd | Target member |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63100148A (en) | 1988-05-02 |
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