JPH0548281B2 - - Google Patents
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- Publication number
- JPH0548281B2 JPH0548281B2 JP10763587A JP10763587A JPH0548281B2 JP H0548281 B2 JPH0548281 B2 JP H0548281B2 JP 10763587 A JP10763587 A JP 10763587A JP 10763587 A JP10763587 A JP 10763587A JP H0548281 B2 JPH0548281 B2 JP H0548281B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- metal
- alloy
- rare earth
- mixture
- 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.)
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- 239000000843 powder Substances 0.000 claims description 80
- 239000000956 alloy Substances 0.000 claims description 63
- 229910045601 alloy Inorganic materials 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 229910052723 transition metal Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000004663 powder metallurgy Methods 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052689 Holmium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000004678 hydrides Chemical class 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910000095 alkaline earth hydride Inorganic materials 0.000 claims description 3
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 description 19
- 239000010409 thin film Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910017061 Fe Co Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、光磁気記録媒体の磁性金属薄膜の形
成をスパツタリングで製造するのに好適である焼
結合金からなるスパツタリング用ターゲツトの製
造方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a sputtering target made of a sintered alloy, which is suitable for producing a magnetic metal thin film of a magneto-optical recording medium by sputtering. .
近年、情報を高密度で記録でき、再生、消去さ
らに再記録を容易に行なうことができる記録媒体
として光磁気記録媒体が開発され、その記録層を
形成する磁性金属薄膜として希土類元素と遷移金
属からなる非晶質合金（Tb−Fe−Co、Gd−Tb
−Feなど）は、記録に必要なエネルギーが少な
くてすむこと、粒界ノイズが現われないこと、さ
らに比較的容易に大型のものが作成できること等
の多くの利点を持つため実用上注目されている。
In recent years, magneto-optical recording media have been developed as recording media that can record information at high density and that can be easily reproduced, erased, and re-recorded.The magnetic metal thin film that forms the recording layer is made of rare earth elements and transition metals. amorphous alloys (Tb−Fe−Co, Gd−Tb
-Fe, etc.) are attracting attention for practical use because they have many advantages, such as requiring less energy for recording, no grain boundary noise, and the ability to relatively easily produce large-sized materials. .
このように、光磁気記録媒体において希土類−
遷移金属合金薄膜が注目されているが、その形成
方法としては、化学めつき法、スパツタリング
法、イオンプレーテイング法、真空蒸着法等が用
いられている。これらの方法の中でも、得られる
磁性薄膜の品質が良好であることから、スパツタ
リング法が優れている。 In this way, in magneto-optical recording media, rare earth
Transition metal alloy thin films are attracting attention, and methods for forming them include chemical plating methods, sputtering methods, ion plating methods, vacuum evaporation methods, and the like. Among these methods, the sputtering method is superior because the quality of the obtained magnetic thin film is good.
スパツタリング法ではターゲツトが必要である
が、歩留が良く、組成変化が少なくて目的組成の
合金薄膜を得やすい点で、合金型のターゲツトが
有利である。 Although a target is required in the sputtering method, an alloy type target is advantageous in that it has a good yield, little change in composition, and it is easy to obtain an alloy thin film having the desired composition.
さて、ターゲツトとして用いる希土類元素−遷
移金属合金の製造方法として、従来、希土類元素
と遷移金属をアーク放電等によつて溶解させて合
金化する方法があるが、希土類元素が高活性であ
るため歩留が悪く、また偏析が起り易く、空孔を
含むインゴツトが生じ易い上、希土類元素と遷移
金属の合金の持つ極めて脆いという金属間化合物
に特有な性質が現われてしまい、特に大型の合金
塊の作成時にヒビ、割れなどが発生し易いという
問題がある。 Now, as a method for producing a rare earth element-transition metal alloy used as a target, there is a conventional method of melting rare earth elements and transition metals by arc discharge etc., but since rare earth elements are highly active, it is difficult to process In addition, the property of intermetallic compounds such as poor retention, segregation, and pore-containing ingots, which are extremely brittle of alloys of rare earth elements and transition metals, appears, especially in large alloy lumps. There is a problem in that cracks and cracks are likely to occur during production.
これに対して、希土類元素粉末と遷移金属粉末
の混合物または希土類元素と遷移金属を所要組成
で含む合金粉末を原料とし、その原料粉末を粉末
冶金法により焼結する方法によると、ヒビ、割れ
などを回避することができる。 On the other hand, if a mixture of rare earth element powder and transition metal powder or an alloy powder containing the required composition of rare earth element and transition metal is used as a raw material and the raw material powder is sintered using a powder metallurgy method, cracks and cracks may occur. can be avoided.
しかし、上記の粉末冶金法に供される原料合金
粉末は、従来、特開昭60−230903号公報に記載の
ように、成分金属を溶解して得られた合金塊を粉
砕して製造されるものであつたが、希土類元素は
空気中で酸化され易いという性質があるので、粉
砕時に得られる合金粉末の酸素含有量が増し、そ
の結果、焼結体の酸素含有量も高いものとなるこ
とは避けられない。この焼結合金中の酸素は、ス
パツタリング法、で作成した薄膜の光磁気特性を
著しく低下させるという問題がある。焼結金属中
の酸素含有量を低減するためには、前記の粉砕工
程を有機溶媒中または不活性雰囲気中で行なう必
要があるが、工程が繁雑となる上製造コストが非
常に高くなるという欠点がある。
However, the raw material alloy powder used in the above-mentioned powder metallurgy method is conventionally manufactured by crushing an alloy ingot obtained by melting component metals, as described in Japanese Patent Application Laid-open No. 60-230903. However, since rare earth elements have the property of being easily oxidized in the air, the oxygen content of the alloy powder obtained during crushing increases, and as a result, the oxygen content of the sintered body also increases. is unavoidable. There is a problem in that oxygen in this sintered alloy significantly deteriorates the magneto-optical properties of a thin film produced by sputtering. In order to reduce the oxygen content in the sintered metal, it is necessary to perform the above-mentioned pulverization process in an organic solvent or in an inert atmosphere, but this has the drawbacks that the process is complicated and the manufacturing cost is extremely high. There is.
そこで、本発明の目的は、上記問題点を解決
し、スパツタリング法により、光磁気記録媒体の
記録層として良好な特性を有する金属薄膜を形成
するのに有用である低酸素含有量の焼結合金製タ
ーゲツトの製造方法を提供することにある。 SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems and to provide a sintered alloy with a low oxygen content that is useful for forming a metal thin film having good properties as a recording layer of a magneto-optical recording medium by a sputtering method. An object of the present invention is to provide a method for manufacturing a manufactured target.
本発明は、プラセオジム（Pr）、ネオジム
（Nd）、サマリウム（Sm）、ガドリウム（Gd）、
テルビウム（Tb）、ジスプロシウム（Dy）、ホル
ミウム（Ho）およびエルビウム（Er）の少なく
とも１種を含む希土類元素の酸化物粉末と；鉄
（Fe）、ニツケル（Ni）およびコバルト（Co）の
少なくとも１種を含む遷移金属の金属粉末、その
酸化物粉末およびその塩化物粉末から選ばれる少
なくとも１種と；アルカリ金属、アルカリ土類金
属およびこれらの水素化物から選ばれる少なくと
も１種との混合物を、不活性ガス雰囲気中または
真空下で加熱した後、反応生成混合物を湿式処理
して、希土類−遷移金属合金粉末を得、該粉末を
含む金属粉末を粉末冶金法により焼結させること
からなる、光磁気記録媒体の製造に用いるスパツ
タリング用焼結合金製ターゲツトの製造方法を提
供するものである。
The present invention includes praseodymium (Pr), neodymium (Nd), samarium (Sm), gadolinium (Gd),
Rare earth element oxide powder containing at least one of terbium (Tb), dysprosium (Dy), holmium (Ho) and erbium (Er); and at least one of iron (Fe), nickel (Ni) and cobalt (Co). A mixture of at least one selected from a metal powder of a transition metal containing a species, an oxide powder thereof, and a chloride powder thereof; and at least one selected from an alkali metal, an alkaline earth metal, and a hydride thereof; magneto-optical method, which consists of wet-processing the reaction product mixture after heating in an active gas atmosphere or under vacuum to obtain a rare earth-transition metal alloy powder, and sintering the metal powder containing the powder by powder metallurgy. The present invention provides a method for manufacturing a sintered alloy target for sputtering used in the manufacture of recording media.
また、本発明は上記製造方法において加熱に供
する前記混合物に、さらにアルカリ金属塩化物お
よびアルカリ土類金属塩化物から選ばれる少なく
とも１種を含有させる焼結合金製ターゲツトの製
造方法をも提供するものである。 The present invention also provides a method for producing a sintered alloy target, in which the mixture subjected to heating in the production method further contains at least one selected from alkali metal chlorides and alkaline earth metal chlorides. It is.
本発明で用いられる希土類元素は、Pr、Nd、
Sm、Gd、Tb、Dy、HoおよびErの少なくとも
１種を含有しなければならないが、特に、Gd、
Tb、Dy、HoおよびErの少なくとも１種を含有
することが好ましい。希土類元素としては、これ
ら以外の希土類元素を含有してもよく、この場合
得られる金属薄膜の光磁気特性の点で、Pr、
Nd、Sm、Gd、Tb、Dy、HoおよびErのうちの
用いられるものの合計が、用いられる希土類元素
と遷移金属元素の全体に対し20〜80重量％、特に
30〜60重量％であることが好ましい。Pr、Nd、
Sm、Gd、Tb、Dy，HoおよびEr以外の希土類
元素としては、ランタン（La）、セリウム（Ce）、
ユウロピウム（Eu）、ツリウム（Tm）、イツテル
ビウム（Yb）、ルテチウム（Lu）、プロメチウム
（Pm）、イツトリウム(Y)およびスカンジウム
（Sc）があげられている。これら希土類元素の酸
化物粉末は１種単独でも２種以上の混合物として
も用いることができる。これらの粉末の粒度は特
に限定されないが、平均粒径が１〜50μｍ（フイ
ツシヤー・サブシーブ・サイザー法、以下同じ）
が好ましい。 The rare earth elements used in the present invention include Pr, Nd,
It must contain at least one of Sm, Gd, Tb, Dy, Ho and Er, especially Gd,
It is preferable to contain at least one of Tb, Dy, Ho and Er. As the rare earth element, rare earth elements other than these may be contained, and in terms of the magneto-optical properties of the resulting metal thin film, Pr,
The total amount of Nd, Sm, Gd, Tb, Dy, Ho and Er used is 20 to 80% by weight based on the total of rare earth elements and transition metal elements used, especially
It is preferably 30 to 60% by weight. Pr, Nd,
Rare earth elements other than Sm, Gd, Tb, Dy, Ho and Er include lanthanum (La), cerium (Ce),
These include europium (Eu), thulium (Tm), ytterbium (Yb), lutetium (Lu), promethium (Pm), yttrium (Y), and scandium (Sc). These rare earth element oxide powders can be used alone or as a mixture of two or more. The particle size of these powders is not particularly limited, but the average particle size is 1 to 50 μm (Fitscher subsieve sizer method, the same applies hereinafter).
is preferred.
また、本発明で用いられる遷移金属元素として
は、Fe、CoおよびNiの少なくとも１種を含有し
なければならない。遷移金属としては、Fe、Co
およびNi以外の遷移金属を含有してもよい。Fe、
Co、Ni以外の遷移金属の種類は特に制限されな
い（ただし、前記希土類元素を除く）が、代表的
な例としては、マンガン（Mn）、クロム（Cr）、
バナジウム(V)、チタン（Ti）等が挙げられる。 Furthermore, the transition metal element used in the present invention must contain at least one of Fe, Co, and Ni. Transition metals include Fe, Co
and may contain transition metals other than Ni. Fe,
The types of transition metals other than Co and Ni are not particularly limited (excluding the rare earth elements mentioned above), but typical examples include manganese (Mn), chromium (Cr),
Examples include vanadium (V) and titanium (Ti).
これらの遷移金属は１種単独でも２種以上の混
合物もしくは合金として用いることもできる。遷
移金属の形態は、金属粉末（合金粉末を含む）、
酸化物粉末および塩化物粉末のいずれでもよく、
これらの混合物でもよい（以下単に「遷移金属粉
末等」という）。通常は金属粉末として用いるこ
とが好ましい。酸化物や塩化物を使用する場合は
金属粉末の一部として用いるのが好ましいが、そ
の金属の使用量が少量である場合にはその金属の
全量を酸化物および／または塩化物として用いる
ことができる。遷移金属粉末等の粒度は特に限定
されないが、得られる合金粉末の粒度および合金
組成の均一性から粒度100メツシユ（Tyler、以
下同じ）以下が望ましい。また、原料金属粉末の
粒度は、一般に目標粒度の1/2以下が望ましい。
したがつて、例えば粉末冶金原料として好ましい
粒度100メツシユ以下の微細な合金粉末を製造す
るためには、粒度200メツシユ以下の金属粉末の
使用が好ましい。 These transition metals can be used alone or as a mixture or alloy of two or more. The forms of transition metals are metal powders (including alloy powders),
Either oxide powder or chloride powder may be used,
A mixture of these may also be used (hereinafter simply referred to as "transition metal powder etc."). It is usually preferable to use it as a metal powder. When using an oxide or chloride, it is preferable to use it as part of the metal powder, but if the amount of the metal used is small, it is preferable to use the entire amount of the metal as the oxide and/or chloride. can. The particle size of the transition metal powder, etc. is not particularly limited, but it is desirable to have a particle size of 100 mesh (Tyler, hereinafter the same) or less in view of the particle size of the obtained alloy powder and the uniformity of the alloy composition. Furthermore, it is generally desirable that the particle size of the raw metal powder is 1/2 or less of the target particle size.
Therefore, for example, in order to produce a fine alloy powder with a particle size of 100 mesh or less, which is preferable as a raw material for powder metallurgy, it is preferable to use metal powder with a particle size of 200 mesh or less.
本発明に用いられるアルカリ金属、アルカリ土
類金属およびこれらの水素化物（以下、単に「ア
ルカリ金属等」という）は、還元剤としても働く
ものである。具体例としてはリチウム、ナトリウ
ム、カリウム、マグネシウムおよびその水素化物
が挙げられるが、取扱い上の安全性およびコスト
の点からカルシウムが好ましい。またこれらの金
属または金属水素化物は粒状または粉末状のもの
が使用されるが、コストの点からは粒度４メツシ
ユ以下の粒状金属カルシウムが好ましい。これら
の還元剤の使用量は、反応当量（希土類酸化物お
よびその他の金属成分の原料として酸化物や塩化
物が用いられた場合にはそれらを還元するのに必
要な化学量論的量）の1.1〜3.0倍量が好ましく、
1.5〜2.0倍量が特に好ましい。 The alkali metals, alkaline earth metals, and hydrides thereof (hereinafter simply referred to as "alkali metals, etc.") used in the present invention also function as reducing agents. Specific examples include lithium, sodium, potassium, magnesium, and their hydrides, but calcium is preferred from the viewpoint of handling safety and cost. These metals or metal hydrides may be used in granular or powdered form, but from the viewpoint of cost, granular metallic calcium having a particle size of 4 mesh or less is preferred. The amount of these reducing agents used is based on the reaction equivalent (the stoichiometric amount required to reduce rare earth oxides and other metal components when oxides and chlorides are used as raw materials). 1.1 to 3.0 times the amount is preferable,
Particularly preferred is 1.5 to 2.0 times the amount.
本発明の製造方法において、加熱に供する混合
物に場合によつて含まれるアルカリ金属塩化物お
よびアルカリ土類金属塩化物（以下「アルカリ金
属塩化物」等という）は、原料として用いられる
金属粉末や生成合金粉末の粒子が互いに溶着、結
合したり、副生するアルカリ金属等の酸化物の粒
子と結合するのを抑制し、また塊状混合物として
得られる反応生成物の湿式処理における崩壊を促
す働きをするものである。またアルカリ金属等、
酸素、炭素などの不純物含有量をいつそう低減す
ることができる。このアルカリ金属塩化物等とし
ては、例えば、リチウム、ナトリウム、カリウ
ム、マグネシウムの塩化物が挙げられ、水和物を
含んでいない無水のものが好ましい。中でも、加
熱した際に揮発性をほとんど示さず、コストの点
でも有利である無水塩化カルシウムが特に好まし
い。これらのアルカリ金属塩化物等の使用量は、
希土類酸化物の量に対して１〜30重量％が好まし
く、特に生成分である希土類−遷移金属合金粉末
中のカルシウム等のアルカリ金属等の含有量およ
び酸素含有量を極力低くし、かつ、より微細な合
金粉末の製造を望む場合には、３〜20重量％が特
に好ましい。 In the production method of the present invention, alkali metal chlorides and alkaline earth metal chlorides (hereinafter referred to as "alkali metal chlorides" etc.) that may be contained in the mixture to be heated are metal powders used as raw materials and It prevents particles of alloy powder from welding and bonding with each other and particles of by-product oxides such as alkali metals, and also works to promote disintegration of the reaction product obtained as a lumpy mixture during wet processing. It is something. Also, alkali metals, etc.
The content of impurities such as oxygen and carbon can be reduced at any time. Examples of the alkali metal chlorides include chlorides of lithium, sodium, potassium, and magnesium, and anhydrous ones that do not contain hydrates are preferred. Among these, anhydrous calcium chloride is particularly preferred because it exhibits almost no volatility when heated and is advantageous in terms of cost. The amount of these alkali metal chlorides, etc. used is
The amount is preferably 1 to 30% by weight based on the amount of rare earth oxide, and in particular, the content of alkali metals such as calcium and oxygen content in the rare earth-transition metal alloy powder, which is a product component, should be as low as possible, and 3 to 20% by weight is particularly preferred if it is desired to produce a fine alloy powder.
本発明によれば、まず、上述した稀土類酸化物
粉末等原料の混合物が不活性ガス雰囲気中または
真空下、例えば10-5Torr以下において加熱に供
される。 According to the present invention, first, a mixture of raw materials such as the rare earth oxide powder described above is heated in an inert gas atmosphere or under vacuum, for example, at 10 -5 Torr or less.
各原料は十分に混合されるが、この取扱いは乾
燥した不活性ガス雰囲気など吸湿が起らない条件
下で実施される。得られた混合物は、前記のとお
り不活性ガス雰囲気または真空下で加熱される。
ここで、用いられる不活性ガス雰囲気としては、
アルゴン、チツ素等を挙げることができる。ま
た、このときの加熱温度は900〜1300℃、特に950
〜1100℃の範囲が好ましく、加熱時間は特に制約
されないが、組成が均一な合金粉末が得られるた
めには１〜10時間が好ましい。この加熱処理によ
り得られる反応生成物は、目的とする希土類−遷
移金属合金のほか副生するアルカリ金属等の酸化
物、未反応のアルカリ金属等を含む塊状の混合物
である。 Each raw material is thoroughly mixed, but this handling is carried out under conditions where moisture absorption does not occur, such as in a dry inert gas atmosphere. The resulting mixture is heated under an inert gas atmosphere or under vacuum as described above.
Here, the inert gas atmosphere used is:
Examples include argon and nitrogen. Also, the heating temperature at this time is 900 to 1300℃, especially 950℃.
The heating time is preferably in the range of 1100°C to 1100°C, and although the heating time is not particularly limited, the heating time is preferably 1 to 10 hours in order to obtain an alloy powder with a uniform composition. The reaction product obtained by this heat treatment is a lumpy mixture containing the target rare earth-transition metal alloy, by-product oxides such as alkali metals, unreacted alkali metals, and the like.
次に、得られたこの塊状混合物に湿式処理を施
す。ここで、湿式処理は反応生成物混合物を必要
により水蒸気中に放置後、水中に投入し撹拌する
などの方法で水と接触させればよく、必要に応じ
て酸処理を施す。反応生成混合物を水と接触させ
ると、これに含まれている残留アルカリ金属等お
よび副生酸化物は水と反応し、例えばCa（OH）2
等のアルカリ金属等の水酸化物を生成して溶解す
るので塊状混合物は崩壊する。崩壊によつて生じ
たスラリーを撹拌後、デカンテーシヨンによつて
上部のアルカリ金属等の水酸化物の懸濁物を除去
し、注水−撹拌−デカンテーシヨンの操作を繰り
返すことによつて該水酸化物を得られた合金粉末
から除去することができる。また、一部残留した
水酸化物は、酢酸あるいは塩酸を用いてPH３〜
６、好ましくはPH４〜５において洗浄することに
よつて完全に除去することができる。このような
湿式処理を経て得られた合金粉末は、例えば、水
洗後、アルコールあるいはアセトン等の有機溶剤
で洗浄、脱水し、真空乾燥すればよい。反応生成
物である塊状の混合物の湿式処理における崩壊
は、アルカリ金属塩化物等の有無によつて次のよ
うな差がみられる。アルカリ金属塩化物等の混合
がない場合には、ほぼ完全に崩壊するのに20〜30
時間を要するが、アルカリ金属塩化物等を混合し
た場合には崩壊は５〜30分で完結する。 Next, the obtained lump mixture is subjected to wet processing. Here, in the wet treatment, the reaction product mixture may be left in steam if necessary, and then brought into contact with water by a method such as pouring into water and stirring, and acid treatment is performed if necessary. When the reaction product mixture is brought into contact with water, residual alkali metals, etc. and by-product oxides contained therein react with water, such as Ca(OH) 2
Since hydroxides of alkali metals and the like are generated and dissolved, the lumpy mixture disintegrates. After stirring the slurry produced by the disintegration, the suspension of hydroxides such as alkali metals at the top is removed by decantation, and the slurry is removed by repeating the operations of water injection, stirring, and decantation. Hydroxide can be removed from the resulting alloy powder. In addition, some remaining hydroxide can be removed using acetic acid or hydrochloric acid to
6, preferably by washing at pH 4 to 5. The alloy powder obtained through such a wet treatment may be washed with water, washed with an organic solvent such as alcohol or acetone, dehydrated, and dried in vacuum, for example. The disintegration of a lumpy mixture, which is a reaction product, during wet processing differs as follows depending on the presence or absence of an alkali metal chloride. If there is no mixture of alkali metal chlorides, etc., it takes 20 to 30 minutes for almost complete disintegration.
Although it takes time, when an alkali metal chloride or the like is mixed, the disintegration is completed in 5 to 30 minutes.
また、得られる合金粉末中の不純物含有量（重
量％）の点では、例えば、還元剤としてカルシウ
ムを使用した場合を例に述べると、アルカリ金属
塩化物等を混合しない場合は、Ca：0.1〜0.2％、
Ｃ：0.05〜0.15％、O2：0.2〜0.4％と不純物含有
量が低く、光磁気記録媒体の金属薄膜作成に用い
るスパツタリング用ターゲツトの原料粉末として
良好な純度を有している。一方、アルカリ金属塩
化物等を混合した場合は、Ca：0.1％以下、Ｃ：
0.02％以下、O2：0.2％以下と不純物含有量が極
めて低く、不純物に対するアルカリ金属塩化物等
の優れた効果が現われ、前記スパツタリング用タ
ーゲツトの原料粉末として特に優れたものが得ら
れる。 In addition, in terms of the impurity content (wt%) in the obtained alloy powder, for example, taking the case where calcium is used as a reducing agent, if an alkali metal chloride etc. is not mixed, Ca: 0.1 ~ 0.2%,
It has a low impurity content of 0.05 to 0.15% for C and 0.2 to 0.4% for O 2 , and has a good purity as a raw material powder for sputtering targets used to create metal thin films for magneto-optical recording media. On the other hand, when alkali metal chlorides etc. are mixed, Ca: 0.1% or less, C:
The impurity content is extremely low, 0.02% or less, O 2 : 0.2% or less, and the alkali metal chloride has an excellent effect on impurities, making it possible to obtain a particularly excellent raw material powder for the sputtering target.
こうして得られた合金粉末または該合金粉末を
含む金属粉末を、次に、粉末冶金法による焼結に
供し、焼結合金を製造する。 The alloy powder thus obtained or the metal powder containing the alloy powder is then subjected to sintering by a powder metallurgy method to produce a sintered alloy.
このとき、焼結に供する金属粉末は、上記で得
られた合金粉末単独でもよいし、必要に応じて
Fe、Ni、Co等の遷移金属粉末を適当量混合して
組成調整を行なつた金属粉末でもよい。 At this time, the metal powder to be subjected to sintering may be the alloy powder obtained above alone, or may be used as necessary.
A metal powder whose composition is adjusted by mixing an appropriate amount of transition metal powder such as Fe, Ni, or Co may also be used.
粉末冶金法による金属粉末の焼結は、例えば、
合金粉末又は合金粉末を含む金属粉末を、常温で
0.5〜5t／cm2の圧力で単純圧縮するか、0.5〜2t／
cm2の圧力で静水圧プレスにて成形した後、真空あ
るいはAr雰囲気中、900〜1300℃の温度で１〜５
時間焼結する常圧焼結法、真空中、0.1〜0.5t／cm2
の圧力で800〜1200℃の温度で１〜５時間焼結す
る熱間加圧法、更には弾性体中に封入後、800〜
1200℃の温度、0.1〜2t／cm2の圧力で１〜５時間
焼結する熱間静水圧加圧法等により焼結を行なう
ことができる。 Sintering of metal powder by powder metallurgy is, for example,
Alloy powder or metal powder containing alloy powder at room temperature.
Simple compression with a pressure of 0.5-5t/ cm2 or 0.5-2t/cm2
After molding with a hydrostatic press at a pressure of cm2 , it is molded at a temperature of 900 to 1300℃ in a vacuum or Ar atmosphere for 1 to 5
Pressureless sintering method for time sintering, in vacuum, 0.1-0.5t/cm 2
Hot pressing method involves sintering at a pressure of 800 to 1200℃ for 1 to 5 hours, and furthermore, after sintering in an elastic body,
Sintering can be carried out by a hot isostatic pressing method in which sintering is performed at a temperature of 1200° C. and a pressure of 0.1 to 2 t/cm 2 for 1 to 5 hours.
アルカリ金属塩化物等を用いる場合には、これ
は、熱還元反応で生じる熱の吸収剤として働き、
これにより原料の金属粉末および生成合金粉末の
粒子同士が焼結するのを防止し、また副生する
CaO等アルカリ金属等の酸化物に固溶して生成合
金粉末とCaO等アルカリ金属等の酸化物との分離
性を高めるものと考えられる。 When using alkali metal chlorides, etc., this acts as an absorber for the heat generated in the thermal reduction reaction,
This prevents particles of raw metal powder and produced alloy powder from sintering with each other, and also prevents by-products from sintering.
It is thought that it dissolves in an oxide of an alkali metal such as CaO and improves the separation between the produced alloy powder and the oxide of an alkali metal such as CaO.
本発明の方法により製造される光磁気記録媒体
の金属薄膜作成用希土類−遷移金属合金製ターゲ
ツトとしては、Tb−Fe系合金、Dy−Fe系合金、
Gd−Tb−Fe系合金、Gd−Tb−Co系合金、Tb
−Fe−Co系合金、Tb−Co系合金、Tb−Dy−Fe
−Co系合金、Nd−Dy−Fe−Co系合金等が挙げ
られるが、これらに限定されるものではない。 Examples of rare earth-transition metal alloy targets for forming metal thin films of magneto-optical recording media produced by the method of the present invention include Tb-Fe alloys, Dy-Fe alloys,
Gd-Tb-Fe alloy, Gd-Tb-Co alloy, Tb
-Fe-Co alloy, Tb-Co alloy, Tb-Dy-Fe
-Co alloy, Nd-Dy-Fe-Co alloy, etc., but are not limited to these.
次に、本発明の方法を実施例により具体的に説
明する。
Next, the method of the present invention will be specifically explained using examples.
実施例 １
Tb−Fe−Co合金粉末（目標組成（重量％）
Tb：55％、Fe：42％、Co：３％）の製造を目的
として、それぞれ純度が99.9％以上の、Tb4O7
（平均粒径3μｍ以下）407.4ｇ、鉄粉（粒度200メ
ツシユ以下）250.6ｇ、コバルト扮（粒度200メツ
シユ以下）20.4ｇ、金属カルシウム（粒度４メツ
シユ以下）305.1ｇ、および無水塩化カルシウム
（粒度100メツシユ以下）40.7ｇを配合し、十分に
混合した。混合物をステンレススチール製の反応
容器に入れ、高純度アルゴンガスの気流中で1000
℃まで約１時間で昇温し、その温度で５時間保持
した後室温まで冷却した。生成した塊状の混合物
1012.3ｇを５の水に投入した。塊状の混合物が
崩壊後、生じたスラリーから上層のCa（OH）2懸
濁物をデカンテーシヨンによつて分離し注水した
後、スラリーを５分間撹拌し、再びデカンテーシ
ヨンを行つた。この注水−撹拌−デカンテーシヨ
ンの操作を繰り返して合金粉末から酸化カルシウ
ムを十分に分離した。合金粉末に水を加えたスラ
リーに、PH4.5になるように撹拌しながら希酢酸
を滴下し、これを20分間保持した。これを濾過し
て、得られた合金粉末を水洗後エタノールで数回
洗浄し、50℃、１×10-2Torrで12時間真空乾燥
した。このようにして得られた金属粉末の組成
（重量％）は、Tb：55.4％、Co：3.4％、Fe：
41.0％であり、不純物であるO2は0.10重量％と極
めて微量であつた。得られた合金粉末の540ｇを
内径130mmの黒鉛製の成形品に装入して熱間加圧
した。熱間加圧の条件として、真空度を５×
10-5Torrとし、粉末を加圧するために、0.15t／
cm2の圧力を1000℃に昇温するまで加え、昇温後は
圧力を0.25t／cm2としその温度を１時間保持した。
得られた焼結体を室温まで冷却した後、成形器か
ら取り出す際、成形器への付着は殆んどなく容易
に取り出せた。目視にて、焼結合金のヒビ、割れ
を観察したが全く見あたらず、透過Ｘ線を照射し
て内部を検査したがヒビ、割れは観測されなかつ
た。Example 1 Tb-Fe-Co alloy powder (target composition (weight%)
Tb 4 O 7 with a purity of 99.9% or more for the purpose of producing Tb: 55%, Fe: 42%, Co: 3%).
(average particle size 3μm or less) 407.4g, iron powder (particle size 200 mesh or less) 250.6g, cobalt powder (particle size 200 mesh or less) 20.4g, metallic calcium (particle size 4 mesh or less) 305.1g, and anhydrous calcium chloride (particle size 100 mesh or less). 40.7g of the following ingredients were added and mixed thoroughly. The mixture was placed in a stainless steel reaction vessel and heated for 1000 min in a stream of high-purity argon gas.
The temperature was raised to °C in about 1 hour, maintained at that temperature for 5 hours, and then cooled to room temperature. The resulting lumpy mixture
1012.3g was added to the water in Step 5. After the lumpy mixture was broken down, the upper Ca(OH) 2 suspension was separated from the resulting slurry by decantation, water was added, the slurry was stirred for 5 minutes, and decantation was performed again. This operation of pouring water, stirring, and decanting was repeated to sufficiently separate calcium oxide from the alloy powder. Dilute acetic acid was added dropwise to a slurry of alloy powder and water with stirring until the pH reached 4.5, and this was maintained for 20 minutes. This was filtered, and the obtained alloy powder was washed with water and ethanol several times, and vacuum-dried at 50° C. and 1×10 −2 Torr for 12 hours. The composition (wt%) of the metal powder thus obtained was: Tb: 55.4%, Co: 3.4%, Fe:
The amount of O 2 as an impurity was 0.10% by weight, which was extremely small. 540 g of the obtained alloy powder was charged into a graphite molded product with an inner diameter of 130 mm and hot pressed. As a condition for hot pressurization, the degree of vacuum is 5×
10 -5 Torr, and to pressurize the powder, 0.15t/
A pressure of cm 2 was applied until the temperature rose to 1000° C. After the temperature was raised, the pressure was increased to 0.25 t/cm 2 and that temperature was maintained for 1 hour.
After the obtained sintered body was cooled to room temperature, when it was taken out from the molding machine, there was almost no adhesion to the molding machine and it could be easily taken out. The sintered alloy was visually observed for cracks and cracks, but no cracks were found.The interior was inspected by irradiating transmitted X-rays, but no cracks or cracks were observed.
この焼結合金の数ケ所からサンプリングを高純
度アルゴン雰囲気下で行ないO2を分析した結果、
O2含有量は0.11±0.02重量％であつた。 As a result of sampling the sintered alloy from several locations under a high-purity argon atmosphere and analyzing O 2 ,
The O2 content was 0.11±0.02% by weight.
上記と同様にして得られた焼結合金（内径130
mm、厚さ4.5mm）をターゲツトとして使用し、ス
パツタリング法（アルゴンガス圧：６×
10-5Torr、スパツタリング電力：4W／cm2、基
板：ソーダガラス）により薄膜（膜厚：3000Å）
を作製し、光磁気特性を測定したところ、次のよ
うな良好な光磁気特性を有した膜が得られた。 Sintered alloy obtained in the same manner as above (inner diameter 130
mm, thickness 4.5 mm) as a target, and sputtering method (argon gas pressure: 6×
10 -5 Torr, sputtering power: 4W/cm 2 , substrate: soda glass) to form a thin film (film thickness: 3000Å)
When a film was prepared and its magneto-optical properties were measured, a film with the following good magneto-optical properties was obtained.
極磁気力−回転角（θK）：0.30°
保磁力（Hc）：400kAｍ-1
比較例 １
Tb−Fe−Co合金粉末（目標組成（重量％）
Tb：55％、Fe：42％、Co：３％）の製造を目的
として、Tb−Fe母合金（Tb：75重量％、Fe：
25重量％）680ｇ、電解鉄225ｇ、電解コバルト27
ｇをアルミナルツボ中に装入し高周波誘導加熱炉
により真空中で溶解鋳造した。鋳塊は、アルゴン
雰囲気中で粗粉砕後、エタノールを入れたボール
ミル中で微粉砕して、平均粒径が25μｍの粉末と
した。このようにして得られた合金粉末の組成
（重量％）は、Tb：54.6％、Co：2.98％、Fe：
41.8％であり、不純物であるO2は0.55％であつ
た。得られた合金粉末を、実施例１と同様にして
熱間加圧した。得られた焼結体を成形器から取り
出す際、成形器への付着が若干観察され、焼結体
の表面観察によると一部ザラザラした凹部が存在
していた。焼結合金のヒビ、割れは、目視でも透
過Ｘ線照射でも観測されなかつた。Polar magnetic force - rotation angle (θ K ): 0.30° Coercive force (Hc): 400 kAm -1 Comparative example 1 Tb-Fe-Co alloy powder (target composition (weight %)
For the purpose of producing Tb-Fe master alloy (Tb: 75% by weight, Fe: 3%),
25% by weight) 680g, electrolytic iron 225g, electrolytic cobalt 27
g was charged into an aluminum crucible and melted and cast in a vacuum using a high frequency induction heating furnace. The ingot was coarsely pulverized in an argon atmosphere and then finely pulverized in a ball mill containing ethanol to obtain powder with an average particle size of 25 μm. The composition (wt%) of the alloy powder thus obtained was: Tb: 54.6%, Co: 2.98%, Fe:
41.8%, and O 2 , an impurity, was 0.55%. The obtained alloy powder was hot pressed in the same manner as in Example 1. When the obtained sintered body was removed from the molding machine, some adhesion to the molding machine was observed, and when the surface of the sintered body was observed, some rough recesses were present. No cracks or cracks in the sintered alloy were observed either visually or by transmitted X-ray irradiation.
この焼結体の数ヶ所からサンプリングを高純度
アルゴン雰囲気下で行ないO2を分析した結果、
O2含有量は0.58±0.03重量％であつた。 As a result of sampling from several locations of this sintered body in a high-purity argon atmosphere and analyzing O 2 ,
The O2 content was 0.58±0.03% by weight.
上記と同様にして別に得られた焼結合金をター
ゲツトとして使用し、実施例１と同様にして薄膜
を作製した所、実施例１より長時間要した。得ら
れた薄膜の光磁気特性は次のようであつた。 When a thin film was prepared in the same manner as in Example 1 using a sintered alloy separately obtained in the same manner as above as a target, it took a longer time than in Example 1. The magneto-optical properties of the obtained thin film were as follows.
極磁気力−回転角（θk）：0.27°
保磁力（Hc）：250kAｍ-1
〔発明の効果〕
本発明の製法によると、O2含有量が極めて低
い希土類−遷移金属焼結合金製のスパツタリング
用ターゲツトを製造することができ、得られる合
金ターゲツトは希土類元素の偏析、空孔などがな
く均質である。しかがつて、光磁気記録媒体の磁
性金属薄膜を製造する際に、スパツタリング法の
ターゲツトとして好適であり、得られる金属薄膜
は光磁気特性に優れている。Polar magnetic force - rotation angle (θ k ): 0.27° Coercive force (Hc): 250 kAm -1 [Effects of the invention] According to the production method of the present invention, a rare earth-transition metal sintered alloy with an extremely low O 2 content is produced. A target for sputtering can be manufactured, and the resulting alloy target is homogeneous without segregation of rare earth elements, pores, etc. Therefore, it is suitable as a target for sputtering when producing a magnetic metal thin film for a magneto-optical recording medium, and the resulting metal thin film has excellent magneto-optical properties.
本発明の製法は、このようなスパツタリング用
焼結合金製ターゲツトを任意の目的組成を有する
ものとして、歩留り良く、容易に製造することが
できる。また、この方法には粉砕工程が不要であ
り、焼結合金を少ない工程で目的の形状を有する
ものとして容易に製造することができる。 According to the manufacturing method of the present invention, such a sintered alloy target for sputtering having any desired composition can be easily manufactured with good yield. Further, this method does not require a pulverization step, and a sintered alloy having a desired shape can be easily produced with a small number of steps.
Claims (1)
リニウム、テルビウム、ジスプロシウム、ホルミ
ウムおよびエリビウムの少なくとも１種を含む希
土類元素の酸化物粉末と；鉄、ニツケルおよびコ
バルトの少なくとも１種を含む遷移金属の金属粉
末、その酸化物粉末およびその塩化物粉末から選
ばれる少なくとも１種と；アルカリ金属、アルカ
リ土類金属およびこれらの水素化物から選ばれる
少なくとも１種との混合物を、不活性ガス雰囲気
中または真空下で加熱した後、反応生成混合物を
湿式処理して、希土類−遷移金属合金粉末を得、
該粉末もしくは該粉末を含む金属粉末を粉末冶金
法により焼結させることからなる、光磁気記録媒
体の製造に用いるスパツタリング用焼結合金製タ
ーゲツトの製造方法。 ２ プラセオジム、ネオジム、サマリウム、ガド
リニウム、テルビウム、ジスプロシウム、ホルミ
ウムおよびエルビウムの少なくとも１種を含む希
土類元素の酸化物粉末と；鉄、ニツケルおよびコ
バルトの少なくとも１種を含む遷移金属の金属粉
末、その酸化物粉末およびその塩化物粉末から選
ばれる少なくとも１種と；アルカリ金属、アルカ
リ土類金属およびこれらの水素化物から選ばれる
少なくとも１種と；アルカリ金属塩化物およびア
ルカリ土類金属塩化物から選ばれる少なくとも１
種との混合物を、不活性ガス雰囲気中または真空
下で加熱した後、反応生成混合物を湿式処理して
希土類−遷移金属合金粉末を得、該粉末もしくは
該粉末を含む金属粉末を粉末冶金法により焼結さ
せることからなる、光磁気記録媒体製造に用いる
スパツタリング用焼結合金製ターゲツトの製造方
法。[Scope of Claims] 1. A rare earth element oxide powder containing at least one of praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, and eribium; and a transition metal oxide powder containing at least one of iron, nickel, and cobalt. A mixture of at least one selected from metal powder, oxide powder thereof, and chloride powder thereof; and at least one selected from alkali metals, alkaline earth metals, and hydrides thereof is heated in an inert gas atmosphere or in vacuum. wet processing the reaction product mixture to obtain a rare earth-transition metal alloy powder;
A method for producing a sintered alloy target for sputtering used in producing a magneto-optical recording medium, the method comprising sintering the powder or a metal powder containing the powder by a powder metallurgy method. 2 Rare earth element oxide powder containing at least one of praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium and erbium; transition metal metal powder containing at least one of iron, nickel and cobalt, and its oxide At least one selected from powders and their chloride powders; At least one selected from alkali metals, alkaline earth metals, and hydrides thereof; At least one selected from alkali metal chlorides and alkaline earth metal chlorides.
After heating the mixture with seeds in an inert gas atmosphere or under vacuum, the reaction product mixture is wet-processed to obtain a rare earth-transition metal alloy powder, and the powder or a metal powder containing the powder is processed by powder metallurgy. A method of manufacturing a sintered alloy target for sputtering used in manufacturing a magneto-optical recording medium, the method comprising sintering the target.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-99808 | 1986-04-30 | ||
| JP9980886 | 1986-04-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63105909A JPS63105909A (en) | 1988-05-11 |
| JPH0548281B2 true JPH0548281B2 (en) | 1993-07-21 |
Family
ID=14257158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10763587A Granted JPS63105909A (en) | 1986-04-30 | 1987-04-30 | Production of sintered alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63105909A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11241104A (en) | 1997-12-25 | 1999-09-07 | Nichia Chem Ind Ltd | Samarium-iron-nitrogen series alloy powder and its production |
| JP4491844B2 (en) * | 1998-07-24 | 2010-06-30 | 東ソー株式会社 | Sputtering target |
| JP6601432B2 (en) * | 2017-02-03 | 2019-11-06 | 株式会社豊田中央研究所 | Manufacturing method of magnetic powder |
| JP7137830B2 (en) * | 2018-07-18 | 2022-09-15 | 国立研究開発法人産業技術総合研究所 | Method for producing alloy particles and alloy particles |
| CN112134374B (en) * | 2020-09-21 | 2023-07-28 | 赣州嘉通新材料有限公司 | High-temperature-resistant and oxidation-resistant neodymium iron boron magnetic steel structure for new energy automobile |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS497296A (en) * | 1972-05-27 | 1974-01-22 | ||
| CA1020377A (en) * | 1973-04-19 | 1977-11-08 | Robert E. Cech | Rare earth intermetallic compounds produced by a reduction-diffusion process |
| CH624193A5 (en) * | 1978-05-02 | 1981-07-15 | Tulcea Sa | Safety shut-off device for a pressurised fluid circuit or pipeline |
| JPS5527602A (en) * | 1978-08-18 | 1980-02-27 | Fujitsu Ltd | Electron beam exposure device |
| JPS6160809A (en) * | 1984-09-03 | 1986-03-28 | Sumitomo Special Metals Co Ltd | Production of rare earth alloy powder |
-
1987
- 1987-04-30 JP JP10763587A patent/JPS63105909A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63105909A (en) | 1988-05-11 |
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