JP5024659B2 - Method for producing Co-based sintered alloy sputtering target for forming magnetic recording film with less generation of particles - Google Patents
Method for producing Co-based sintered alloy sputtering target for forming magnetic recording film with less generation of particles Download PDFInfo
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Description
この発明は、ハードディスクの高密度磁気記録媒体に適用される磁気記録膜、特に垂直磁気記録媒体に適用される磁気記録膜を形成するためのスパッタリングターゲットの製造方法に関するものである。 The present invention relates to a method of manufacturing a sputtering target for forming a magnetic recording film applied to a high-density magnetic recording medium of a hard disk, particularly a magnetic recording film applied to a perpendicular magnetic recording medium.
ハードディスク装置は一般にコンピューターやデジタル家電等の外部記録装置として用いられており、記録密度の一層の向上が求められている。そのため、近年、超高密度の記録を実現できる垂直磁気記録方式が注目されてきた。この垂直磁気記録方式は、従来の面内記録方式と異なり、原理的に高密度化するほど記録磁化が安定すると言われており、すでに実用化されている。この垂直磁気記録方式のハードディスク媒体の磁気記録層に適用する材料の有力な候補としてＣｏＣｒＰｔ−ＳｉＯ２グラニュラ磁気記録膜が提案されており、この磁気記録膜は高性能な磁気記録膜であることが必要である。これに適用可能な磁気記録膜の一つとしてＣｏＣｒＰｔ−ＳｉＯ２グラニュラ磁気記録膜が提案されており、このＣｏＣｒＰｔ−ＳｉＯ２グラニュラ磁気記録膜はＣｒおよびＰｔを含むＣｏ基焼結合金相と二酸化珪素相の混合相を有するＣｏ基焼結合金スパッタリングターゲットを用いてマグネトロンスパッタ法により作製することが知られている。
このＣｏ基焼結合金スパッタリングターゲットは、通常、二酸化珪素粉末、Ｃｒ粉末、Ｐｔ粉末およびＣｏ粉末を、二酸化珪素：２〜１５モル％、Ｃｒ：３〜２０モル％、Ｐｔ：５〜３０モル％を含有し、残部：Ｃｏからなる組成となるように配合し混合したのち、ホットプレスまたは熱間静水圧プレスなどの方法で加圧焼結することにより作製されることが知られており、前記二酸化珪素粉末として高温火炎加水分解法で製造された二酸化珪素粉末を使用し、ターゲットの素地中に分散する二酸化珪素相を１０μｍ以下の極めて細かい組織とすることによってパーティクルの発生を少なくしている（特許文献１、特許文献２などを参照）。
さらに、前記ＳｉＯ２のほかにＴｉＯ、Ｃｒ２Ｏ３、ＴｉＯ２、Ｔａ２Ｏ５、Ａｌ２Ｏ３、ＢｅＯ２、ＭｇＯ、ＴｈＯ２、ＺｒＯ２、ＣｅＯ２、Ｙ２Ｏ３などの非磁性酸化物が使用できることが知られている（特許文献３、４参照）。
This Co-based sintered alloy sputtering target usually comprises silicon dioxide powder, Cr powder, Pt powder and Co powder, silicon dioxide: 2 to 15 mol%, Cr: 3 to 20 mol%, Pt: 5 to 30 mol%. It is known that the remainder is prepared by mixing and mixing so as to be a composition consisting of Co, and then pressure sintering by a method such as hot pressing or hot isostatic pressing, Generation of particles is reduced by using silicon dioxide powder produced by a high-temperature flame hydrolysis method as silicon dioxide powder, and making the silicon dioxide phase dispersed in the target substrate a very fine structure of 10 μm or less ( (See Patent Document 1, Patent Document 2, etc.).
Further, in addition to the SiO 2 , nonmagnetic materials such as TiO, Cr 2 O 3 , TiO 2 , Ta 2 O 5 , Al 2 O 3 , BeO 2 , MgO, ThO 2 , ZrO 2 , CeO 2 , and Y 2 O 3. It is known that oxides can be used (see Patent Documents 3 and 4).
しかし、前記従来の方法で作製したＣｏ基焼結合金スパッタリングターゲットは、パーティクルの発生が避けられず、一層パーティクル発生の少ないＣｏ基焼結合金からなるスパッタリングターゲットが求められていた。 However, the Co-based sintered alloy sputtering target produced by the conventional method inevitably generates particles, and a sputtering target made of a Co-based sintered alloy with less generation of particles has been demanded.
そこで、本発明者は、一層パーティクル発生の少ないＣｏ基焼結合金スパッタリングターゲットを得るべく研究を行なったところ、
（イ）ターゲットの素地中に絶対最大長（粒子の輪郭線上の任意の２点間距離の最大値）が１０μｍを越える粗大なＣｒとＯを主成分とする凝集体または析出物（以下、クロム酸化物凝集体という）が分散していることがパーティクル発生の一因となっていること、
（ロ）この粗大なクロム酸化物凝集体が素地中に存在しないようにするには、原料粉末として、Ｃｒ粉末の代わりに、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなる成分組成を有するＰｔとＣｒの二元合金粉末（以下、Ｃｒ−Ｐｔ二元系合金粉末という）を使用することが好ましいこと、
（ハ）この粗大なクロム酸化物凝集体が素地中に存在しないようにするには、原料粉末として、Ｃｒ粉末の代わりに、Ｃｒ−Ｐｔ二元系合金粉末およびＣｒ：５０〜７０原子％を含有し、残部がＣｏからなるＣｒとＣｏの二元系合金粉末（以下、Ｃｏ−Ｃｒ二元系合金粉末という）を使用することが好ましいこと、などの知見を得たのである。
Therefore, the present inventor conducted research to obtain a Co-based sintered alloy sputtering target with less particle generation,
(A) Aggregates or precipitates (hereinafter referred to as chromium) whose main components are coarse Cr and O whose absolute maximum length (maximum value of the distance between any two points on the particle outline) exceeds 10 μm in the target substrate. That the dispersion of oxide aggregates) contributes to particle generation,
(B) In order to prevent the coarse chromium oxide aggregates from being present in the substrate, the raw material powder contains Pt: 10 to 90 atomic% instead of Cr powder, with the balance being Cr. It is preferable to use a binary alloy powder of Pt and Cr having a composition (hereinafter referred to as a Cr-Pt binary alloy powder),
(C) In order to prevent the coarse chromium oxide aggregates from being present in the substrate, instead of Cr powder, Cr—Pt binary alloy powder and Cr: 50 to 70 atomic% are used as raw material powder. It has been found that it is preferable to use Cr and Co binary alloy powder (hereinafter referred to as Co—Cr binary alloy powder) containing Co and the balance being Co.
この発明は、かかる知見に基づいてなされたものであって、
（１）原料粉末として、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなる成分組成のＣｒ−Ｐｔ二元系合金粉末、Ｐｔ粉末、非磁性酸化物粉末およびＣｏ粉末を用意し、これら原料粉末を非磁性酸化物：２〜１５モル％、Ｃｒ：３〜２０モル％、Ｐｔ：５〜３０モル％を含有し、残部：Ｃｏからなる成分組成となるように配合し混合したのち、加圧焼結するパーティクル発生の少ない磁気記録膜形成用Ｃｏ基焼結合金スパッタリングターゲットの製造方法、
（２）原料粉末としてＰｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末、Ｃｒ：５０〜７０原子％を含有し、残部がＣｏからなるＣｏ−Ｃｒ二元系合金粉末、Ｐｔ粉末、非磁性酸化物粉末およびＣｏ粉末を用意し、これら原料粉末を非磁性酸化物：２〜１５モル％、Ｃｒ：３〜２０モル％、Ｐｔ：５〜３０モル％を含有し、残部：Ｃｏからなる成分組成となるように配合し混合したのち、加圧焼結するパーティクル発生の少ない磁気記録膜形成用Ｃｏ基焼結合金スパッタリングターゲットの製造方法、
（３）原料粉末としてＰｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末、Ｃｒ：５０〜７０原子％を含有し、残部がＣｏからなるＣｏ−Ｃｒ二元系合金粉末、非磁性酸化物粉末およびＣｏ粉末を用意し、これら原料粉末を非磁性酸化物：２〜１５モル％、Ｃｒ：３〜２０モル％、Ｐｔ：５〜３０モル％を含有し、残部：Ｃｏからなる成分組成となるように配合し混合したのち、加圧焼結するパーティクル発生の少ない磁気記録膜形成用Ｃｏ基焼結合金スパッタリングターゲットの製造方法、に特徴を有するものである。
This invention has been made based on such knowledge,
(1) As a raw material powder, a Cr—Pt binary alloy powder, a Pt powder, a nonmagnetic oxide powder, and a Co powder having a component composition containing Pt: 10 to 90 atomic% and the balance being Cr are prepared. After mixing and mixing these raw material powders so as to contain a non-magnetic oxide: 2 to 15 mol%, Cr: 3 to 20 mol%, Pt: 5 to 30 mol%, and the balance: a component composition consisting of Co , A method for producing a Co-based sintered alloy sputtering target for forming a magnetic recording film with less particle generation under pressure sintering,
(2) Cr—Pt binary alloy powder containing Pt: 10 to 90 atomic% as a raw material powder and the balance being made of Cr, Co—Cr containing 50% to 70 atomic% of Cr and the balance being made of Co Binary alloy powder, Pt powder, nonmagnetic oxide powder and Co powder are prepared. These raw material powders are nonmagnetic oxide: 2 to 15 mol%, Cr: 3 to 20 mol%, Pt: 5 to 30 mol. %, And the balance: a method for producing a Co-based sintered alloy sputtering target for forming a magnetic recording film for forming a magnetic recording film with less generation of particles after being mixed and mixed so as to have a component composition consisting of Co,
(3) Cr—Pt binary alloy powder containing Pt: 10 to 90 atomic% as a raw material powder and the balance being made of Cr, Co—Cr containing 50 to 70 atomic% of Cr and the balance being made of Co Binary alloy powder, nonmagnetic oxide powder and Co powder are prepared, and these raw material powders contain nonmagnetic oxide: 2 to 15 mol%, Cr: 3 to 20 mol%, Pt: 5 to 30 mol% The remainder is characterized by a method for producing a Co-based sintered alloy sputtering target for forming a magnetic recording film with less particle generation that is pressure-sintered after being mixed and mixed so as to have a component composition consisting of Co. is there.
前記（１）、（２）および（３）記載の加圧焼結は、ホットプレスまたは熱間静水圧プレスである。したがって、この発明は、
（４）前記加圧焼結は、ホットプレスまたは熱間静水圧プレスである前記（１）、（２）または（３）記載のパーティクル発生の少ない磁気記録膜形成用Ｃｏ基焼結合金スパッタリングターゲットの製造方法、に特徴を有するものである。
The pressure sintering described in the above (1), (2) and (3) is a hot press or a hot isostatic press. Therefore, the present invention
(4) The Co-based sintered alloy sputtering target for forming a magnetic recording film with less generation of particles according to (1), (2) or (3), wherein the pressure sintering is hot pressing or hot isostatic pressing. The manufacturing method is characterized.
この発明のパーティクル発生の少ない磁気記録膜形成用Ｃｏ基焼結合金スパッタリングターゲットの製造方法において使用するＣｒ−Ｐｔ二元系合金粉末の成分組成を前記のごとく限定した理由は、Ｐｔが１０原子％未満あるいはＰｔが９０原子％を越えて含有すると粉末中に金属間化合物の他にＰｔとＣｒとの結合が弱い固溶体Ｃｒが存在する割合が多くなり、混合時や焼結時にＣｒが酸素や非磁性酸化物と反応しやすく、Ｃｒ酸化凝集体を形成しやすくなるため好ましくないからである。Ｃｒ−Ｐｔ二元系合金粉末におけるＰｔ含有量の一層好ましい範囲はＰｔ：１５〜２５原子％である。この原料粉末として使用するＣｒ−Ｐｔ二元系合金粉末の粒径は、１５０μmより大きいと粉砕が十分進みにくいため、１５０μm以下が好ましく、分級などにより７５μm以下、さらには４５μm以下とするのが好ましい。 The reason why the component composition of the Cr—Pt binary alloy powder used in the manufacturing method of the Co-based sintered alloy sputtering target for forming a magnetic recording film with less particle generation of the present invention is limited as described above is that Pt is 10 atomic%. If the content of Pt is less than 90% by atom or less than 90 atomic%, the proportion of solid solution Cr having a weak bond between Pt and Cr in addition to the intermetallic compound increases in the powder. This is because it is not preferable because it easily reacts with the magnetic oxide and easily forms Cr oxide aggregates. A more preferable range of the Pt content in the Cr—Pt binary alloy powder is Pt: 15 to 25 atomic%. The particle diameter of the Cr—Pt binary alloy powder used as the raw material powder is preferably 150 μm or less, and is preferably 75 μm or less, more preferably 45 μm or less by classification etc. .
また、この発明のパーティクル発生の少ない磁気記録膜形成用Ｃｏ基焼結合金スパッタリングターゲットの製造方法において使用するＣｏ−Ｃｒ二元系合金粉末の成分組成を前記のごとく限定した理由は、Ｃｒが５０原子％未満または７０原子％を越えて含有すると、粉末中に金属間化合物の他にＣｏとＣｒの結合が弱い固溶体Ｃｏまたは固溶体Ｃｒが存在する割合が多くなり、混合時や焼結時にＣｒが酸素や非磁性酸化物と反応して粗大なクロム酸化物凝集体を形成しやすくなるので好ましくないからである。Ｃｏ−Ｃｒ二元系合金粉末に含まれるＣｒの一層好ましい範囲は５４〜６７原子％である。この原料粉末として使用するＣｏ−Ｃｒ二元系合金粉末の粒径は、１５０μmより大きいと粉砕が十分進みにくいため、１５０μm以下が好ましく、分級などにより７５μm以下、さらには４５μm以下とするのが好ましい。 Moreover, the reason why the component composition of the Co—Cr binary alloy powder used in the method for producing a Co-based sintered alloy sputtering target for forming a magnetic recording film with less particle generation of the present invention is limited as described above is that Cr is 50 If the content is less than 70% or more than 70% by atom, the ratio of the solid solution Co or the solid solution Cr, in which the bond between Co and Cr is weak in addition to the intermetallic compound, increases in the powder. This is because it tends to react with oxygen and nonmagnetic oxides to form coarse chromium oxide aggregates, which is not preferable. A more preferable range of Cr contained in the Co—Cr binary alloy powder is 54 to 67 atomic%. The particle diameter of the Co—Cr binary alloy powder used as the raw material powder is preferably 150 μm or less, preferably 75 μm or less, and more preferably 45 μm or less by classification or the like, since pulverization is difficult to proceed sufficiently if it is larger than 150 μm. .
クロム酸化物凝集体がパーティクル発生の原因となる理由は、クロム酸化物凝集体は非常にもろく、スパッタ中に脱落したり異常放電を生じたりし、またクロム酸化物凝集体のサイズが大きい場合にはターゲットの加工中にターゲット表面から脱落し、脱落した部分に欠陥が形成されるからである。Ｃｒを合金化したＣｒ−Ｐｔ二元系合金粉末またはＣｒ−Ｐｔ二元系合金粉末とＣｏ−Ｃｒ二元系合金粉末とを原料粉末として使用することにより、酸素や非磁性酸化物との反応による酸化が生じがたくなるためクロム酸化物凝集体の生成が抑制されパーティクルの発生は少なくなると考えられる。 The reason why chromium oxide aggregates cause particle generation is that chromium oxide aggregates are very fragile, fall off during spattering, cause abnormal discharge, and when the size of chromium oxide aggregates is large. This is because it falls off from the target surface during processing of the target, and a defect is formed in the dropped part. Reaction with oxygen and nonmagnetic oxide by using Cr-Pt binary alloy powder alloyed with Cr or Cr-Pt binary alloy powder and Co-Cr binary alloy powder as raw material powder It is considered that the generation of chromium oxide aggregates is suppressed and the generation of particles is reduced because the oxidation due to is difficult to occur.
つぎに、この発明のパーティクル発生の少ない磁気記録膜形成用Ｃｏ基焼結合金スパッタリングターゲットの製造方法において使用するＣｏ粉末、Ｐｔ粉末はいずれも５０％粒径が５０μｍ以下（一層好ましくは５０％粒径が４０μｍ以下）、さらに非磁性酸化物粉末は５０％粒径が２０μｍ以下（一層好ましくは５０％粒径が１０μｍ以下）とすることが好ましい。その理由はＣｏ粉末、Ｐｔ粉末がこれ以上大きいと混合後に均一な組織が得られにくいためである。また、非磁性酸化物粉末の粒径がこれ以上大きくなると混合粉砕工程を経てもターゲット中に１０μｍ以上の大きな非磁性酸化物が存在しやすくなり、これがスパッタ中の異常放電やパーティクル発生の原因となるからである。前記原料粉末の混合は不活性ガス雰囲気中で行なうことが好ましい。これは混合中にＣｒが酸素と結合してクロム酸化物凝集体が形成されるのをより一層防止するからである。 Next, the Co powder and the Pt powder used in the method for producing a Co-based sintered alloy sputtering target for forming a magnetic recording film with less particle generation according to the present invention have a 50% particle size of 50 μm or less (more preferably 50% particle size). Further, the nonmagnetic oxide powder preferably has a 50% particle size of 20 μm or less (more preferably a 50% particle size of 10 μm or less). The reason is that if the Co powder and the Pt powder are larger than this, it is difficult to obtain a uniform structure after mixing. Further, when the particle size of the nonmagnetic oxide powder is larger than this, a large nonmagnetic oxide of 10 μm or more is likely to be present in the target even after the mixing and pulverization process, which causes abnormal discharge and particle generation during sputtering. Because it becomes. The raw material powder is preferably mixed in an inert gas atmosphere. This is because it further prevents Cr from being combined with oxygen to form chromium oxide aggregates during mixing.
この発明は、一層パーティクル発生の少ない優れた磁気記録膜を形成することができるスパッタリングターゲットを提供することができ、コンピューター並びにデジタル家電等の産業の発展に大いに貢献し得るものである。 The present invention can provide a sputtering target capable of forming an excellent magnetic recording film with less generation of particles, and can greatly contribute to the development of industries such as computers and digital home appliances.
原料粉末として、表１に示される成分組成を有するＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｓをガスアトマイズ法により作製した。これらガスアトマイズ法により得られたＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｓは５０％粒径が９５μｍであったので、これらＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｓを４５μｍの目開きを持つ篩により分級し、レーザー回折法により測定される５０％粒径がいずれも３５μｍとなるように分級した。
さらに原料粉末として、表２に示される成分組成を有するＣｏ−Ｃｒ二元系合金粉末ａ〜ｊをガスアトマイズ法により作製した。これらガスアトマイズ法により得られたＣｏ−Ｃｒ二元系合金粉末ａ〜ｊは５０％粒径が９５μｍであったので、これらＣｏ−Ｃｒ二元系合金粉末ａ〜ｊを４５μｍの目開きを持つ篩により分級し、レーザー回折法により測定される５０％粒径がいずれも３５μｍとなるように分級した。さらに市販の５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１５μｍのＰｔ粉末、５０％粒径：３μｍのＳｉＯ２粉末、５０％粒径：３μｍのＴｉＯ２粉末、５０％粒径：３μｍのＴａ２Ｏ５粉末、および５０％粒径：１０μｍのＣｒ粉末を用意した。
As raw material powders, Cr—Pt binary alloy powders A to S having the component compositions shown in Table 1 were prepared by a gas atomization method. Since the Cr—Pt binary alloy powders A to S obtained by the gas atomization method had a 50% particle size of 95 μm, the Cr—Pt binary alloy powders A to S were sieved with a 45 μm mesh. And 50% particle size measured by the laser diffraction method was 35 μm.
Furthermore, as raw material powders, Co—Cr binary alloy powders a to j having the component compositions shown in Table 2 were produced by a gas atomization method. Since the Co-Cr binary alloy powders a to j obtained by the gas atomizing method had a 50% particle size of 95 μm, the Co—Cr binary alloy powders a to j were sieved with a 45 μm opening. And 50% particle size measured by the laser diffraction method was 35 μm. Further, commercially available 50% particle size: 10 μm Co powder, 50% particle size: 15 μm Pt powder, 50% particle size: 3 μm SiO 2 powder, 50% particle size: 3 μm TiO 2 powder, 50% particle size: 3 μm Ta 2 O 5 powder and 50% particle size: 10 μm Cr powder were prepared.
実施例１
これら原料粉末を表３に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。
得られた混合粉末を真空ホットプレス装置に充填し、真空雰囲気中、温度：１２００℃、圧力：１５ＭＰａ、３時間保持の条件で真空ホットプレスすることによりホットプレス体を作製し、このホットプレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有し、かつＣｒ：１０．１モル％、Ｐｔ：１５．６モル％、ＳｉＯ２：８．０モル％を含有し、残部Ｃｏからなる成分組成を有するターゲットを作製することにより本発明法１〜１１、比較法１および従来法１を実施した。
Example 1
These raw material powders were blended so as to have the blending composition shown in Table 3, and the obtained blended powder was put into a 10-liter container together with zirconia balls as a grinding medium, and the atmosphere in the container was placed in an Ar gas atmosphere. After replacement, the container was sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder.
The obtained mixed powder is filled in a vacuum hot press apparatus, and a hot press body is produced by vacuum hot pressing in a vacuum atmosphere under conditions of temperature: 1200 ° C., pressure: 15 MPa, and 3 hours. And has a size of diameter: 152.4 mm, thickness: 3 mm, and contains Cr: 10.1 mol%, Pt: 15.6 mol%, SiO 2 : 8.0 mol%, The present invention methods 1 to 11, the comparative method 1, and the conventional method 1 were carried out by producing a target having a component composition composed of the balance Co.
前記本発明法１〜１１、比較法１および従来法１で作製したターゲットの素地中に分散するクロム酸化物凝集体の絶対最大長（粒子の輪郭線上の任意の２点間距離の最大値）をＥＰＭＡにより測定し、絶対最大長が１０μｍを越える粗大なクロム酸化物凝集体の存在の有無を表３に示した。
ＥＰＭＡによるクロム酸化物凝集体の絶対最大長の測定は、次のようにして行なった。前記本発明法１〜１１、比較法１および従来法１で作製したホットプレス体から試料を切り出して断面を樹脂に埋め、鏡面研磨した。この断面組織についてフィールドエミッションＥＰＭＡ（日本電子社製ＪＸＡ−８５００Ｆ）により、加速電圧：１５ｋＶ、照射電流：５×１０−８Ａの条件で１０００倍の倍率にて面分析を実施し、Ｃｒの元素マッピング像を得た。このＣｒの元素マッピング像は出来るだけＣｒが富化した領域（すなわちクロム酸化物凝集体）を明確に判別できるよう、コントラストおよび色調をつけた画像とした。得られたＣｒの元素マッピング像を画質を落とさずにビットマップ形式の画像ファイルとして保存し、この画像を別途パソコンの画像処理ソフト（三谷商事社製、Ｗｉｎ Ｒｏｏｆ）に読み込ませて二値化し、マトリックスよりＣｒが富化している領域の絶対最大長を画像処理により計測した。二値化の際にはＣｒ富化領域の大きさが元の画像と変化しないようにしきい値を選んだ。計測時の長さのキャリブレーションについては元のＥＰＭＡによるＣｒの元素マッピング像に表示されたスケールバーを用いた。
The absolute maximum length of the chromium oxide aggregates dispersed in the substrate of the target prepared by the above-mentioned inventive methods 1 to 11, comparative method 1 and conventional method 1 (maximum value of the distance between any two points on the particle outline) Table 3 shows the presence or absence of coarse chromium oxide aggregates having an absolute maximum length exceeding 10 μm.
The absolute maximum length of the chromium oxide aggregates by EPMA was measured as follows. A sample was cut out from the hot press body produced by the above-mentioned inventive methods 1 to 11, comparative method 1 and conventional method 1, the cross section was filled in resin, and mirror-polished. This cross-sectional structure was subjected to surface analysis at 1000 times magnification under the conditions of acceleration voltage: 15 kV, irradiation current: 5 × 10 −8 A by field emission EPMA (JXA-8500F manufactured by JEOL Ltd.), and Cr element A mapping image was obtained. The element mapping image of Cr was an image with contrast and color tone so that the Cr-enriched region (that is, the chromium oxide aggregate) could be clearly discriminated. The obtained Cr element mapping image is saved as an image file in bitmap format without degrading the image quality, and this image is separately read into a personal computer image processing software (Mitani Corp., Win Roof) and binarized, The absolute maximum length of the region enriched with Cr from the matrix was measured by image processing. In binarization, a threshold value was selected so that the size of the Cr-enriched area did not change from the original image. For the calibration of the length at the time of measurement, a scale bar displayed on the element mapping image of Cr by the original EPMA was used.
さらに、前記本発明法１〜１１、比較法１および従来法１で得られたターゲットを有機溶剤により脱脂し、ついで真空中、１５０℃、８時間保持真空乾燥を行なったのち銅製のバッキングプレートに接合して市販のスパッタ装置に装着し、
到達真空度：５×１０−５Ｐａ、
電力：直流８００Ｗ、
Ａｒガス圧：６．０Ｐａ、
ターゲット基板間距離：６０ｍｍ、
基板加熱：なし、
の条件でプレスパッタを行い、ターゲット表面加工層を除去したのち、一旦チャンバーを大気開放して、防着板などのチャンバー部材の清掃を行った。その後、再び上記真空度に達するまで真空引きを行い、真空引き後、３０分のプレスパッタを行ってターゲット表面の大気吸着成分や金属酸化層の除去を行ったのち、４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜した。同じ条件で合計２５枚の４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜し、成膜後のウエハについて市販の異物検査装置によりウエハ表面に付着した１．０μｍ以上のパーティクル数を計測し、２５枚の平均値を算出し、その結果を表３に示した。
Furthermore, after degreasing the targets obtained in the above-mentioned inventive methods 1 to 11, comparative method 1 and conventional method 1 with an organic solvent, and then vacuum-drying at 150 ° C. for 8 hours in a vacuum, a copper backing plate was used. Join and attach to a commercially available sputtering device,
Ultimate vacuum: 5 × 10 −5 Pa,
Power: DC 800W,
Ar gas pressure: 6.0 Pa,
Target substrate distance: 60mm,
Substrate heating: None,
Pre-sputtering was performed under the conditions described above, and after the target surface processed layer was removed, the chamber was once opened to the atmosphere, and chamber members such as a deposition prevention plate were cleaned. Thereafter, vacuuming is performed again until the degree of vacuum is reached, and after vacuuming, pre-sputtering is performed for 30 minutes to remove the air adsorbing components and the metal oxide layer on the target surface. S: A magnetic recording film of 100 nm was formed. Under the same conditions, a magnetic recording film having a thickness of 100 nm is formed on a total of 25 4-inch Si wafers, and the number of particles of 1.0 μm or more adhering to the wafer surface by a commercially available foreign substance inspection apparatus for the formed wafers. The average value of 25 sheets was calculated, and the results are shown in Table 3.
表３に示される結果から、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｋを原料粉末として配合して作製する本発明法１〜１１で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＳｉＯ２粉末を配合し混合して作製する従来法１により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有するＣｒ−Ｐｔ二元系合金粉末Ｒを使用する比較法１で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。 From the results shown in Table 3, the present invention methods 1 to 11 are prepared by blending Cr—Pt binary alloy powders A to K containing Pt: 10 to 90 atomic% and the balance being Cr as raw material powders. The targets prepared in the above are 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% without adding Cr—Pt binary alloy powder. % Particle size: It can be seen that the generation of particles is less than that of the target prepared by the conventional method 1 prepared by mixing and mixing SiO 2 powder of 3 μm. However, the target produced by Comparative Method 1 using the Cr—Pt binary alloy powder R having a component composition deviating from the scope of the present invention is preferable because the generation of particles increases. I understand that there is no.
実施例２
表１に示されるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｇ、Ｃｏ粉末、Ｐｔ粉末およびＳｉＯ２粉末を表４に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。このようにして得られた混合粉末をＳＵＳ製の容器に充填し、５５０℃、１２時間保持の真空脱ガス処理を行なったのち、ＳＵＳ容器を密封して混合粉末を真空封入した。この混合粉末を充填したＳＵＳ容器について、温度：１２００℃、圧力：１００ＭＰａ、３時間保持の条件で熱間静水圧プレスを施し、その後、ＳＵＳ容器を開封してＣｒ：１７．１モル％、Ｐｔ：１５．３モル％、ＳｉＯ２：１０．０モル％を含有し、残部がＣｏからなる成分組成を有する熱間静水圧プレス体を作製し、この熱間静水圧プレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製することにより本発明法１２〜１８、比較法２および従来法２を実施した。前記本発明法１２〜１８、比較法２および従来法２で作製したターゲットについて実施例１と同じ測定を行い、その結果を表４に示した。
Example 2
The Cr—Pt binary alloy powders A to G, Co powder, Pt powder and SiO 2 powder shown in Table 1 are blended so as to have the blending composition shown in Table 4, and the resulting blended powder is used as a grinding medium. The zirconia balls were put into a 10-liter container, the atmosphere in the container was replaced with an Ar gas atmosphere, and then the container was sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder. The mixed powder thus obtained was filled in a SUS container and subjected to vacuum degassing treatment at 550 ° C. for 12 hours, and then the SUS container was sealed and the mixed powder was vacuum sealed. The SUS container filled with this mixed powder was subjected to hot isostatic pressing under the conditions of temperature: 1200 ° C., pressure: 100 MPa, 3 hours, and then the SUS container was opened, Cr: 17.1 mol%, Pt : A hot isostatic press body containing 15.3 mol%, SiO 2 : 10.0 mol%, and the balance being composed of Co was prepared, and the hot isostatic press body was cut The present invention methods 12-18, comparative method 2 and conventional method 2 were carried out by producing targets having dimensions of diameter: 152.4 mm and thickness: 3 mm. The same measurements as in Example 1 were performed on the targets prepared by the above-described inventive methods 12 to 18, comparative method 2 and conventional method 2, and the results are shown in Table 4.
表４に示される結果から、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｇを原料粉末として配合して作製する本発明法１２〜１８で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＳｉＯ２粉末を配合し混合して作製する従来法２により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有するＣｒ−Ｐｔ合金粉末Ｒを使用する比較法２で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。 From the results shown in Table 4, the present invention methods 12 to 18 are prepared by blending Cr—Pt binary alloy powders A to G containing Pt: 10 to 90 atomic% and the balance being Cr, as raw material powders. The targets prepared in the above are 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% without adding Cr—Pt binary alloy powder. % Particle size: It can be seen that the generation of particles is less than that of the target prepared by the conventional method 2 prepared by mixing and mixing SiO 2 powder of 3 μm. However, a target produced by Comparative Method 2 using a Cr—Pt alloy powder R having a component composition that deviates from the scope of the present invention is not preferable because the generation of particles increases. I understand.
実施例３
表１に示されるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｊ、表２に示されるＣｏ−Ｃｒ二元系合金粉末ａ〜ｈ、Ｃｏ粉末、Ｐｔ粉末およびＳｉＯ２粉末を表５に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。
得られた混合粉末を得られた混合粉末を真空ホットプレス装置に充填し、真空雰囲気中、温度：１２００℃、圧力：１５ＭＰａ、３時間保持の条件で真空ホットプレスすることによりＣｒ：１１．３モル％、Ｐｔ：１２．２モル％、ＳｉＯ２：６．０モル％を含有し、残部がＣｏからなる成分組成を有するホットプレス体を作製し、このホットプレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製することにより本発明法１９〜２８、比較法３および従来法３を実施した。
Example 3
The composition shown in Table 5 includes the Cr—Pt binary alloy powders A to J shown in Table 1, the Co—Cr binary alloy powders a to h shown in Table 2, Co powder, Pt powder, and SiO 2 powder. The resulting blended powder was put into a 10-liter container together with zirconia balls serving as a grinding medium, the atmosphere in the container was replaced with an Ar gas atmosphere, and the container was then sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder.
The obtained mixed powder was filled in a vacuum hot press apparatus, and was subjected to vacuum hot pressing in a vacuum atmosphere under the conditions of temperature: 1200 ° C., pressure: 15 MPa, 3 hours, Cr: 11.3. A hot press body having a component composition containing mol%, Pt: 12.2 mol%, SiO 2 : 6.0 mol%, and the balance consisting of Co is prepared, and the hot press body is cut to obtain a diameter: The present invention methods 19 to 28, comparative method 3 and conventional method 3 were carried out by producing a target having dimensions of 152.4 mm and thickness: 3 mm.
前記本発明法１９〜２８および比較法３および従来法３で作製したターゲットの素地中に分散するクロム酸化物凝集体の絶対最大長（粒子の輪郭線上の任意の２点間距離の最大値）をＥＰＭＡにより測定し、絶対最大長が１０μｍを越える粗大なクロム酸化物凝集体の存在の有無を表５に示した。
ＥＰＭＡによるクロム酸化物凝集体の絶対最大長の測定は、前記本発明法１９〜２８および比較法３および従来法３で作製したターゲットから試料を切り出して断面を樹脂に埋め、鏡面研磨し、以下、実施例１と同じ方法で行なった。
Absolute maximum length of chromium oxide aggregates dispersed in the substrate of the target produced by the above-described methods 19 to 28 of the present invention, comparative method 3 and conventional method 3 (maximum value of the distance between any two points on the particle contour) Table 5 shows the presence or absence of coarse chromium oxide aggregates having an absolute maximum length exceeding 10 μm.
The absolute maximum length of chromium oxide aggregates by EPMA is measured by cutting out a sample from the targets prepared in the above-mentioned methods 19 to 28 of the present invention, comparative method 3 and conventional method 3, filling the cross section with resin, mirror polishing, The same method as in Example 1 was performed.
さらに、前記本発明法１９〜２８および比較法３および従来法３で得られたターゲットを有機溶剤により脱脂し、ついで真空中、１５０℃、８時間保持真空乾燥を行なったのち銅製のバッキングプレートに接合して市販のスパッタ装置に装着し、実施例１と同じ条件でプレスパッタを行い、ターゲット表面加工層を除去したのち、一旦チャンバーを大気開放して、防着板などのチャンバー部材の清掃を行った。その後、再び上記真空度に達するまで真空引きを行い、真空引き後、３０分のプレスパッタを行ってターゲット表面の大気吸着成分や金属酸化層の除去を行ったのち、４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜した。同じ条件で合計２５枚の４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜し、成膜後のウエハについて市販の異物検査装置によりウエハ表面に付着した１．０μｍ以上のパーティクル数を計測し、２５枚の平均値を算出し、その結果を表５に示した。 Further, the targets obtained in the above-mentioned methods 19 to 28, comparative method 3 and conventional method 3 were degreased with an organic solvent, and then vacuum-dried at 150 ° C. for 8 hours in a vacuum, and then applied to a copper backing plate. After joining and mounting on a commercially available sputtering apparatus, pre-sputtering is performed under the same conditions as in Example 1 and the target surface processed layer is removed, the chamber is once opened to the atmosphere, and chamber members such as a deposition plate are cleaned. went. Thereafter, vacuuming is performed again until the degree of vacuum is reached, and after vacuuming, pre-sputtering is performed for 30 minutes to remove the air adsorbing components and the metal oxide layer on the target surface. S: A magnetic recording film of 100 nm was formed. Under the same conditions, a magnetic recording film having a thickness of 100 nm is formed on a total of 25 4-inch Si wafers, and the number of particles of 1.0 μm or more adhering to the wafer surface by a commercially available foreign substance inspection apparatus for the formed wafers. The average value of 25 sheets was calculated, and the results are shown in Table 5.
表５に示される結果から、表１のＣｒ−Ｐｔ二元系合金粉末および表２のＣｏ−Ｃｒ二元系合金粉末を原料粉末として配合して作製した本発明法１９〜２８で作製したターゲットは、表５のＣｒ−Ｐｔ二元系合金粉末およびＣｏ−Ｃｒ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＳｉＯ２粉末を配合し混合する従来法３により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｏ−Ｃｒ合金粉末がこの発明の範囲から外れた成分組成を有する表２のＣｏ−Ｃｒ合金粉末ｉを使用する比較法３で作製したターゲットは１．０μｍ以上のパーティクルの発生が多くなるので好ましくないことが分かる。 From the results shown in Table 5, the targets prepared by the present invention methods 19 to 28 were prepared by blending the Cr—Pt binary alloy powder of Table 1 and the Co—Cr binary alloy powder of Table 2 as raw material powders. Without adding the Cr—Pt binary alloy powder and the Co—Cr binary alloy powder of Table 5, 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle It can be seen that the generation of particles is less than that of the target produced by the conventional method 3 in which a Pt powder having a diameter of 15 μm and a SiO 2 powder having a 50% particle diameter of 3 μm are mixed and mixed. However, the target produced by the comparative method 3 using the Co—Cr alloy powder i in Table 2 having a component composition outside the scope of the present invention of the Co—Cr alloy powder generates more particles of 1.0 μm or more. It turns out that it is not preferable.
実施例４
Ｐｔ粉末を使用せず、必要なＰｔ成分はすべて表１のＣｒ−Ｐｔ二元系合金粉末Ｋ〜Ｑの添加により含有させること、および加圧焼結を実施例２と同様の熱間静水圧プレスにより実施する以外は実施例３と全く同じ条件で本発明法２９〜３５、比較法４および従来法４を実施し、Ｃｒ：１１．８モル％、Ｐｔ：１５．５モル％、ＳｉＯ２：９．０モル％を含有し、残部がＣｏからなる成分組成を有する熱間静水圧プレス体を作製し、この熱間静水圧プレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製した。前記本発明法２９〜３５、比較法４および従来法４で作製したターゲットについて実施例１と同じ測定を行い、その結果を表６に示した。
Example 4
No Pt powder is used, and all necessary Pt components are contained by adding the Cr—Pt binary alloy powders K to Q shown in Table 1, and hot isostatic pressure is the same as in Example 2 under pressure sintering. the present invention method in exactly the same conditions as in example 3 except that performed by pressing 29 to 35, and comparison made method 4 and the conventional method 4, Cr: 11.8 mol%, Pt: 15.5 mol%, SiO 2 : A hot isostatic pressing body containing 9.0 mol% and the balance comprising Co was prepared, and the hot isostatic pressing body was cut to obtain a diameter: 152.4 mm, thickness: A target having a dimension of 3 mm was produced. The same measurements as in Example 1 were performed on the targets prepared by the above-described inventive methods 29 to 35, comparative method 4, and conventional method 4, and the results are shown in Table 6.
表６に示される結果から、本発明法２９〜３５で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末およびＣｏ−Ｃｒ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＳｉＯ２粉末を配合し混合して作製する従来法４により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有する表１のＣｒ−Ｐｔ合金粉末ＳおよびＣｏ−Ｃｒ二元系合金粉末がこの発明の範囲から外れた成分組成を有する表２のＣｏ−Ｃｒ二元系ｊを使用する比較法４で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。
From the results shown in Table 6, the targets prepared by the inventive methods 29-35 were found to have a 50% particle size: 10 μm Co without adding Cr—Pt binary alloy powder and Co—Cr binary alloy powder. Compared with the target produced by the conventional method 4 prepared by mixing and mixing powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% particle size: 3 μm SiO 2 powder It can be seen that the generation of particles is small. However, the Cr—Pt alloy powder S and the Co—Cr binary alloy powder of Table 1 in which the Cr—Pt binary alloy powder has a component composition deviating from the scope of the present invention are included in the composition of the present invention. It can be seen that the target produced by the comparative method 4 using the Co—Cr binary system j in Table 2 having Table 2 is not preferable because the generation of particles increases.
実施例５
原料粉末を表７に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。得られた混合粉末を真空ホットプレス装置に充填し、真空雰囲気中、温度：１２００℃、圧力：１５ＭＰａ、３時間保持の条件で真空ホットプレスすることによりホットプレス体を作製し、このホットプレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有し、かつＣｒ：１４．７モル％、Ｐｔ：１６．６モル％、ＴｉＯ２：８．０モル％を含有し、残部Ｃｏからなる成分組成を有するターゲットを作製することにより本発明法３６〜４４、比較法５および従来法５を実施した。
前記本発明法３６〜４４、比較法５および従来法５で作製したターゲットの素地中に分散するクロム酸化物凝集体の絶対最大長（粒子の輪郭線上の任意の２点間距離の最大値）を実施例１と同様にしてＥＰＭＡにより測定し、絶対最大長が１０μｍを越える粗大なクロム酸化物凝集体の存在の有無を表７に示した。
さらに、前記本発明法３６〜４４、比較法５および従来法５で得られたターゲットを有機溶剤により脱脂し、ついで真空中、１５０℃、８時間保持真空乾燥を行なったのち銅製のバッキングプレートに接合して市販のスパッタ装置に装着し、実施例１と同じの条件でプレスパッタを行い、ついで実施例１と同様にしてウエハ表面に付着した１．０μｍ以上のパーティクル数を計測し、２５枚の平均値を算出し、その結果を表７に示した。
Example 5
The raw material powder is blended so as to have the blending composition shown in Table 7, and the obtained blended powder is put into a 10 liter container together with zirconia balls as a grinding medium, and the atmosphere in the container is replaced with an Ar gas atmosphere. Then, the container was sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder. The obtained mixed powder is filled in a vacuum hot press apparatus, and a hot press body is produced by vacuum hot pressing in a vacuum atmosphere under conditions of temperature: 1200 ° C., pressure: 15 MPa, and 3 hours. And has a size of diameter: 152.4 mm, thickness: 3 mm, and contains Cr: 14.7 mol%, Pt: 16.6 mol%, TiO 2 : 8.0 mol%, The present invention methods 36 to 44, the comparative method 5 and the conventional method 5 were carried out by producing a target having a component composition consisting of the balance Co.
Absolute maximum length of chromium oxide aggregates dispersed in the target substrate prepared by the above-described inventive methods 36 to 44, comparative method 5 and conventional method 5 (maximum value of the distance between any two points on the particle contour) Was measured by EPMA in the same manner as in Example 1, and the presence or absence of coarse chromium oxide aggregates having an absolute maximum length exceeding 10 μm was shown in Table 7.
Further, the targets obtained in the above-mentioned inventive methods 36 to 44, comparative method 5 and conventional method 5 were degreased with an organic solvent, and then vacuum-dried at 150 ° C. for 8 hours in a vacuum, and then applied to a copper backing plate. Bonded and mounted on a commercially available sputtering apparatus, pre-sputtering was performed under the same conditions as in Example 1, and then the number of particles of 1.0 μm or more adhering to the wafer surface was measured in the same manner as in Example 1 to obtain 25 sheets. The average value was calculated and the results are shown in Table 7.
表７に示される結果から、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｋを原料粉末として配合して作製する本発明法３６〜４４で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴｉＯ２粉末を配合し混合して作製する従来法５により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有するＣｒ−Ｐｔ二元系合金粉末Ｒを使用する比較法５で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。
From the results shown in Table 7, the present invention methods 36 to 44 are prepared by blending Cr—Pt binary alloy powders A to K containing Pt: 10 to 90 atomic% and the balance being Cr as raw material powders. The targets prepared in the above are 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% without adding Cr—Pt binary alloy powder. % Particle size: It can be seen that the generation of particles is less than that of the target prepared by the conventional method 5 prepared by mixing and mixing TiO 2 powder of 3 μm. However, a target produced by Comparative Method 5 using a Cr—Pt binary alloy powder R having a component composition that deviates from the scope of the present invention is preferable because the generation of particles increases. I understand that there is no.
実施例６
表１に示されるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｇ、Ｃｏ粉末、Ｐｔ粉末およびＴｉＯ２粉末を表８に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。このようにして得られた混合粉末をＳＵＳ製の容器に充填し、５５０℃、１２時間保持の真空脱ガス処理を行なったのち、ＳＵＳ容器を密封して混合粉末を真空封入した。この混合粉末を充填したＳＵＳ容器について、温度：１２００℃、圧力：１００ＭＰａ、３時間保持の条件で熱間静水圧プレスを施し、その後、ＳＵＳ容器を開封してＣｒ：１３．５モル％、Ｐｔ：１４．４モル％、ＴｉＯ２：１０．０モル％を含有し、残部がＣｏからなる成分組成を有する熱間静水圧プレス体を作製し、この熱間静水圧プレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製することにより本発明法４５〜５３、比較法６および従来法６を実施した。前記本発明法４５〜５３、比較法６および従来法６で作製したターゲットについて実施例１と同じ測定を行い、その結果を表８に示した。
Example 6
The Cr—Pt binary alloy powders A to G, Co powder, Pt powder and TiO 2 powder shown in Table 1 are blended so as to have the blending composition shown in Table 8, and the obtained blended powder is used as a grinding medium. The zirconia balls were put into a 10-liter container, the atmosphere in the container was replaced with an Ar gas atmosphere, and then the container was sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder. The mixed powder thus obtained was filled in a SUS container and subjected to vacuum degassing treatment at 550 ° C. for 12 hours, and then the SUS container was sealed and the mixed powder was vacuum sealed. The SUS container filled with this mixed powder was subjected to hot isostatic pressing under the conditions of temperature: 1200 ° C., pressure: 100 MPa, 3 hours, and then the SUS container was opened, Cr: 13.5 mol%, Pt : 14.4 mol%, TiO 2 : 10.0 mol%, the hot isostatic press body which has the component composition which the remainder consists of Co is produced, and this hot isostatic press body is cut and processed. Inventive methods 45-53, comparative method 6 and conventional method 6 were carried out by producing a target having dimensions of diameter: 152.4 mm and thickness: 3 mm. The same measurements as in Example 1 were performed on the targets prepared in the above-described inventive methods 45 to 53, comparative method 6 and conventional method 6, and the results are shown in Table 8.
表８に示される結果から、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｇを原料粉末として配合して作製する本発明法４５〜５３で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴｉＯ２粉末を配合し混合して作製する従来法６により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有するＣｒ−Ｐｔ合金粉末Ｒを使用する比較法６で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。
From the results shown in Table 8, the present invention method 45 to 53 is prepared by blending Cr—Pt binary alloy powders A to G containing Pt: 10 to 90 atomic% and the balance being Cr as raw material powders. The targets prepared in the above are 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% without adding Cr—Pt binary alloy powder. % Particle size: It can be seen that the generation of particles is less than that of the target produced by the conventional method 6 produced by mixing and mixing TiO 2 powder of 3 μm. However, a target produced by Comparative Method 6 using a Cr—Pt alloy powder R having a component composition that deviates from the scope of the present invention is not preferable because the generation of particles increases. I understand.
実施例７
表１に示されるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｊ、表２に示されるＣｏ−Ｃｒ二元系合金粉末ａ〜ｈ、Ｃｏ粉末、Ｐｔ粉末およびＴｉＯ２粉末を表９に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。
得られた混合粉末を得られた混合粉末を真空ホットプレス装置に充填し、真空雰囲気中、温度：１２００℃、圧力：１５ＭＰａ、３時間保持の条件で真空ホットプレスすることによりＣｒ：１３．２モル％、Ｐｔ：１２．２モル％、ＴｉＯ２：６．０モル％を含有し、残部がＣｏからなる成分組成を有するホットプレス体を作製し、このホットプレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製することにより本発明法５４〜６３、比較法７および従来法７を実施した。
Example 7
Table 9 shows Cr-Pt binary alloy powders A to J shown in Table 1, Co-Cr binary alloy powders a to h shown in Table 2, Co powder, Pt powder, and TiO 2 powder. The resulting blended powder was put into a 10-liter container together with zirconia balls serving as a grinding medium, the atmosphere in the container was replaced with an Ar gas atmosphere, and the container was then sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder.
The obtained mixed powder was filled in a vacuum hot press apparatus, and was subjected to vacuum hot pressing in a vacuum atmosphere at a temperature of 1200 ° C., a pressure of 15 MPa, and a holding time of 3 hours, Cr: 13.2. A hot press body having a component composition containing mol%, Pt: 12.2 mol%, TiO 2 : 6.0 mol%, and the balance consisting of Co is prepared, and the hot press body is cut to obtain a diameter: The present invention methods 54 to 63, comparative method 7 and conventional method 7 were carried out by producing a target having dimensions of 152.4 mm and thickness: 3 mm.
前記本発明法５４〜６３および比較法７および従来法７で作製したターゲットの素地中に分散するクロム酸化物凝集体の絶対最大長（粒子の輪郭線上の任意の２点間距離の最大値）をＥＰＭＡにより測定し、絶対最大長が１０μｍを越える粗大なクロム酸化物凝集体の存在の有無を表９に示した。
ＥＰＭＡによるクロム酸化物凝集体の絶対最大長の測定は、前記本発明法５４〜６３および比較法７および従来法７で作製したターゲットから試料を切り出して断面を樹脂に埋め、鏡面研磨し、以下、実施例１と同じ方法で行なった。
Absolute maximum length of chromium oxide aggregates dispersed in the substrate of the target produced by the above-mentioned methods 54 to 63 of the present invention, comparative method 7 and conventional method 7 (maximum value of the distance between any two points on the particle contour) Table 9 shows the presence or absence of coarse chromium oxide aggregates having an absolute maximum length exceeding 10 μm.
The absolute maximum length of chromium oxide aggregates by EPMA is measured by cutting out a sample from the targets prepared in the above-mentioned method 54 to 63 of the present invention and comparative method 7 and conventional method 7, filling the cross section with resin, mirror polishing, The same method as in Example 1 was performed.
さらに、前記本発明法５４〜６３および比較法７および従来法７で得られたターゲットを有機溶剤により脱脂し、ついで真空中、１５０℃、８時間保持真空乾燥を行なったのち銅製のバッキングプレートに接合して市販のスパッタ装置に装着し、実施例１と同じ条件でプレスパッタを行い、ターゲット表面加工層を除去したのち、一旦チャンバーを大気開放して、防着板などのチャンバー部材の清掃を行った。その後、再び上記真空度に達するまで真空引きを行い、真空引き後、３０分のプレスパッタを行ってターゲット表面の大気吸着成分や金属酸化層の除去を行ったのち、４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜した。同じ条件で合計２５枚の４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜し、成膜後のウエハについて市販の異物検査装置によりウエハ表面に付着した１．０μｍ以上のパーティクル数を計測し、２５枚の平均値を算出し、その結果を表９に示した。 Further, the targets obtained in the above-mentioned methods 54 to 63 of the present invention, the comparative method 7 and the conventional method 7 were degreased with an organic solvent, then vacuum-dried at 150 ° C. for 8 hours in a vacuum, and then applied to a copper backing plate. After joining and mounting on a commercially available sputtering apparatus, pre-sputtering is performed under the same conditions as in Example 1 and the target surface processed layer is removed, the chamber is once opened to the atmosphere, and chamber members such as a deposition plate are cleaned. went. Thereafter, vacuuming is performed again until the degree of vacuum is reached, and after vacuuming, pre-sputtering is performed for 30 minutes to remove the air adsorbing components and the metal oxide layer on the target surface. S: A magnetic recording film of 100 nm was formed. Under the same conditions, a magnetic recording film having a thickness of 100 nm is formed on a total of 25 4-inch Si wafers, and the number of particles of 1.0 μm or more adhering to the wafer surface by a commercially available foreign substance inspection apparatus for the formed wafers. The average value of 25 sheets was calculated, and the result is shown in Table 9.
表９に示される結果から、表１のＣｒ−Ｐｔ二元系合金粉末および表２のＣｏ−Ｃｒ二元系合金粉末を原料粉末として配合して作製した本発明法５４〜６３で作製したターゲットは、表９のＣｒ−Ｐｔ二元系合金粉末およびＣｏ−Ｃｒ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴｉＯ２粉末を配合し混合する従来法７により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｏ−Ｃｒ合金粉末がこの発明の範囲から外れた成分組成を有する表２のＣｏ−Ｃｒ合金粉末ｉを使用する比較法７で作製したターゲットは１．０μｍ以上のパーティクルの発生が多くなるので好ましくないことが分かる。
From the results shown in Table 9, targets prepared by the present invention methods 54 to 63 prepared by blending the Cr—Pt binary alloy powder of Table 1 and the Co—Cr binary alloy powder of Table 2 as raw material powders Without adding the Cr—Pt binary alloy powder and the Co—Cr binary alloy powder of Table 9 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle It can be seen that the generation of particles is less than that of the target prepared by the conventional method 7 in which a Pt powder having a diameter of 15 μm and a TiO 2 powder having a 50% particle diameter: 3 μm are mixed and mixed. However, the target produced by the comparative method 7 using the Co—Cr alloy powder i of Table 2 having a component composition outside the scope of the present invention of the Co—Cr alloy powder generates more particles of 1.0 μm or more. It turns out that it is not preferable.
実施例８
Ｐｔ粉末を使用せず、必要なＰｔ成分はすべて表１のＣｒ−Ｐｔ二元系合金粉末Ｋ〜Ｑの添加により含有させること、非磁性酸化物粉末としてＴｉＯ２粉末を使用すること、および加圧焼結を実施例２と同様の熱間静水圧プレスにより実施する以外は実施例３と全く同じ条件で本発明法６４〜７０、比較法８および従来法８を実施し、Ｃｒ：９．１モル％、Ｐｔ：１０．９モル％、ＴｉＯ２：９．０モル％を含有し、残部がＣｏからなる成分組成を有する熱間静水圧プレス体を作製し、この熱間静水圧プレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製した。前記本発明法６４〜７０、比較法８および従来法８で作製したターゲットについて実施例１と同じ測定を行い、その結果を表１０に示した。
Example 8
Pt powder is not used, and all necessary Pt components are contained by adding the Cr—Pt binary alloy powders K to Q in Table 1, using TiO 2 powder as the nonmagnetic oxide powder, and adding Except that the pressure sintering is performed by the same hot isostatic pressing as in Example 2, the present invention methods 64 to 70, the comparative method 8 and the conventional method 8 are performed under exactly the same conditions as in Example 3, and Cr: 9. A hot isostatic press body containing 1 mol%, Pt: 10.9 mol%, TiO 2 : 9.0 mol%, and having a component composition consisting of Co as the balance was produced. Was cut to produce a target having a diameter of 152.4 mm and a thickness of 3 mm. The same measurements as in Example 1 were performed on the targets prepared by the above-described inventive methods 64-70, comparative method 8, and conventional method 8, and the results are shown in Table 10.
表１０に示される結果から、本発明法６４〜７０で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末およびＣｏ−Ｃｒ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴｉＯ２粉末を配合し混合して作製する従来法８により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有する表１のＣｒ−Ｐｔ合金粉末ＳおよびＣｏ−Ｃｒ二元系合金粉末がこの発明の範囲から外れた成分組成を有する表２のＣｏ−Ｃｒ二元系ｊを使用する比較法８で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。
From the results shown in Table 10, the target prepared by the present invention method 64-70 is 50% particle size: 10 μm Co without adding Cr—Pt binary alloy powder and Co—Cr binary alloy powder. Compared to the target prepared by the conventional method 8 prepared by mixing and mixing powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% particle size: 3 μm TiO 2 powder It can be seen that the generation of particles is small. However, the Cr—Pt alloy powder S and the Co—Cr binary alloy powder of Table 1 in which the Cr—Pt binary alloy powder has a component composition deviating from the scope of the present invention are included in the composition of the present invention. It can be seen that the target produced by the comparative method 8 using the Co—Cr binary system j in Table 2 having Table 2 is not preferable because the generation of particles increases.
実施例９
原料粉末を表１１に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。得られた混合粉末を真空ホットプレス装置に充填し、真空雰囲気中、温度：１２００℃、圧力：１５ＭＰａ、３時間保持の条件で真空ホットプレスすることによりホットプレス体を作製し、このホットプレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有し、かつＣｒ：１０．１モル％、Ｐｔ：１５．６モル％、Ｔａ２Ｏ５：８．０モル％を含有し、残部Ｃｏからなる成分組成を有するターゲットを作製することにより本発明法７１〜７９、比較法９および従来法９を実施した。
前記本発明法７１〜７９、比較法９および従来法９で作製したターゲットの素地中に分散するクロム酸化物凝集体の絶対最大長（粒子の輪郭線上の任意の２点間距離の最大値）を実施例１と同様にしてＥＰＭＡにより測定し、絶対最大長が１０μｍを越える粗大なクロム酸化物凝集体の存在の有無を表１１に示した。
さらに、前記本発明法７１〜７９、比較法９および従来法９で得られたターゲットを有機溶剤により脱脂し、ついで真空中、１５０℃、８時間保持真空乾燥を行なったのち銅製のバッキングプレートに接合して市販のスパッタ装置に装着し、実施例１と同じの条件でプレスパッタを行い、ついで実施例１と同様にしてウエハ表面に付着した１．０μｍ以上のパーティクル数を計測し、２５枚の平均値を算出し、その結果を表１１に示した。
Example 9
The raw material powder is blended so as to have the blending composition shown in Table 11, and the obtained blended powder is put into a 10 liter container together with zirconia balls as a grinding medium, and the atmosphere in the container is replaced with an Ar gas atmosphere. Then, the container was sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder. The obtained mixed powder is filled in a vacuum hot press apparatus, and a hot press body is produced by vacuum hot pressing in a vacuum atmosphere under conditions of temperature: 1200 ° C., pressure: 15 MPa, and 3 hours. Has a diameter of 152.4 mm, a thickness of 3 mm, and contains Cr: 10.1 mol%, Pt: 15.6 mol%, Ta 2 O 5 : 8.0 mol% Then, the present invention methods 71 to 79, the comparative method 9 and the conventional method 9 were carried out by producing a target having a component composition consisting of the remainder Co.
Absolute maximum length of chromium oxide aggregates dispersed in the substrate of the target prepared by the above-mentioned methods 71 to 79 of the present invention, comparative method 9 and conventional method 9 (maximum value of the distance between any two points on the particle contour) Was measured by EPMA in the same manner as in Example 1, and the presence or absence of coarse chromium oxide aggregates having an absolute maximum length exceeding 10 μm was shown in Table 11.
Further, after degreasing the targets obtained in the present invention methods 71 to 79, comparative method 9 and conventional method 9 with an organic solvent, followed by vacuum drying at 150 ° C. for 8 hours in a vacuum, a copper backing plate was used. Bonded and mounted on a commercially available sputtering apparatus, pre-sputtering was performed under the same conditions as in Example 1, and then the number of particles of 1.0 μm or more adhering to the wafer surface was measured in the same manner as in Example 1 to obtain 25 sheets. The average value was calculated, and the results are shown in Table 11.
表１１に示される結果から、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｋを原料粉末として配合して作製する本発明法７１〜７９で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴａ２Ｏ５粉末を配合し混合して作製する従来法９により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有するＣｒ−Ｐｔ二元系合金粉末Ｒを使用する比較法９で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。 From the results shown in Table 11, the present invention methods 71 to 79 are prepared by blending Cr—Pt binary alloy powders A to K containing Pt: 10 to 90 atomic% and the balance being Cr as raw material powders. The targets prepared in the above are 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% without adding Cr—Pt binary alloy powder. % Particle size: It can be seen that the generation of particles is less than that of the target prepared by the conventional method 9 prepared by mixing and mixing Ta 2 O 5 powder of 3 μm. However, a target produced by Comparative Method 9 using a Cr—Pt binary alloy powder R having a component composition outside the scope of the present invention is preferable because the generation of particles increases. I understand that there is no.
実施例１０
表１に示されるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｇ、Ｃｏ粉末、Ｐｔ粉末およびＴａ２Ｏ５粉末を表１２に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。このようにして得られた混合粉末をＳＵＳ製の容器に充填し、５５０℃、１２時間保持の真空脱ガス処理を行なったのち、ＳＵＳ容器を密封して混合粉末を真空封入した。この混合粉末を充填したＳＵＳ容器について、温度：１２００℃、圧力：１００ＭＰａ、３時間保持の条件で熱間静水圧プレスを施し、その後、ＳＵＳ容器を開封してＣｒ：１３．６モル％、Ｐｔ：１４．６モル％、Ｔａ２Ｏ５：３．０モル％を含有し、残部がＣｏからなる成分組成を有する熱間静水圧プレス体を作製し、この熱間静水圧プレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製することにより本発明法８０〜８８、比較法１０および従来法１０を実施した。前記本発明法８０〜８８、比較法１０および従来法１０で作製したターゲットについて実施例１と同じ測定を行い、その結果を表１２に示した。
Example 10
The Cr—Pt binary alloy powders A to G, Co powder, Pt powder and Ta 2 O 5 powder shown in Table 1 were blended so as to have the blend composition shown in Table 12, and the resulting blended powder was pulverized. A 10-liter container was put together with zirconia balls as a medium, the atmosphere in the container was replaced with an Ar gas atmosphere, and then the container was sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder. The mixed powder thus obtained was filled in a SUS container and subjected to vacuum degassing treatment at 550 ° C. for 12 hours, and then the SUS container was sealed and the mixed powder was vacuum sealed. The SUS container filled with this mixed powder was subjected to hot isostatic pressing under conditions of temperature: 1200 ° C., pressure: 100 MPa, and 3 hours, and then the SUS container was opened and Cr: 13.6 mol%, Pt : 14.6 mol%, Ta 2 O 5 : 3.0 mol%, a hot isostatic press body having a component composition consisting of Co is produced, and the hot isostatic press body is cut. Then, the present invention methods 80 to 88, comparative method 10 and conventional method 10 were carried out by producing targets having dimensions of diameter: 152.4 mm and thickness: 3 mm. The same measurements as in Example 1 were performed on the targets prepared by the above-described inventive methods 80 to 88, comparative method 10, and conventional method 10, and the results are shown in Table 12.
表１２に示される結果から、Ｐｔ：１０〜９０原子％を含有し、残部がＣｒからなるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｇを原料粉末として配合して作製する本発明法８０〜８８で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴａ２Ｏ５粉末を配合し混合して作製する従来法１０により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有するＣｒ−Ｐｔ合金粉末Ｒを使用する比較法１０で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。 From the results shown in Table 12, the present invention method 80 to 88 prepared by blending Cr—Pt binary alloy powders A to G containing Pt: 10 to 90 atomic% and the balance of Cr as raw material powders. The targets prepared in the above are 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder and 50% without adding Cr—Pt binary alloy powder. % Particle size: It can be seen that the generation of particles is less than that of the target prepared by the conventional method 10 prepared by mixing and mixing Ta 2 O 5 powder of 3 μm. However, the target produced by the comparative method 10 using the Cr—Pt alloy powder R having a component composition in which the Cr—Pt binary alloy powder deviates from the scope of the present invention is not preferable because the generation of particles increases. I understand.
実施例１１
表１に示されるＣｒ−Ｐｔ二元系合金粉末Ａ〜Ｊ、表２に示されるＣｏ−Ｃｒ二元系合金粉末ａ〜ｈ、Ｃｏ粉末、Ｐｔ粉末およびＴｉＯ２粉末を表１３に示される配合組成となるように配合し、得られた配合粉末を粉砕媒体となるジルコニアボールと共に１０リットルの容器に投入し、この容器内の雰囲気をＡｒガス雰囲気中で置換し、その後、容器を密閉した。この容器をボールミルで１６時間回転させ、混合粉末を作製した。
得られた混合粉末を得られた混合粉末を真空ホットプレス装置に充填し、真空雰囲気中、温度：１２００℃、圧力：１５ＭＰａ、３時間保持の条件で真空ホットプレスすることによりＣｒ：１４．７モル％、Ｐｔ：１６．７モル％、Ｔａ２Ｏ５：２．０モル％を含有し、残部がＣｏからなる成分組成を有するホットプレス体を作製し、このホットプレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製することにより本発明法８９〜９８、比較法１１および従来法１１を実施した。
Example 11
Table 13 shows Cr-Pt binary alloy powders A to J shown in Table 1, Co-Cr binary alloy powders a to h shown in Table 2, Co powder, Pt powder and TiO 2 powder. The resulting blended powder was put into a 10-liter container together with zirconia balls serving as a grinding medium, the atmosphere in the container was replaced with an Ar gas atmosphere, and the container was then sealed. This container was rotated with a ball mill for 16 hours to produce a mixed powder.
The obtained mixed powder was filled in a vacuum hot press apparatus and subjected to vacuum hot pressing in a vacuum atmosphere at a temperature of 1200 ° C., a pressure of 15 MPa, and a holding time of 3 hours, Cr: 14.7. A hot press body having a component composition containing mol%, Pt: 16.7 mol%, Ta 2 O 5 : 2.0 mol%, and the balance consisting of Co is prepared, and the hot press body is cut. The present method 89-98, the comparative method 11, and the conventional method 11 were implemented by producing the target which has a diameter: 152.4mm and thickness: 3mm.
前記本発明法８９〜９８および比較法１１および従来法１１で作製したターゲットの素地中に分散するクロム酸化物凝集体の絶対最大長（粒子の輪郭線上の任意の２点間距離の最大値）をＥＰＭＡにより測定し、絶対最大長が１０μｍを越える粗大なクロム酸化物凝集体の存在の有無を表１３に示した。
ＥＰＭＡによるクロム酸化物凝集体の絶対最大長の測定は、前記本発明法８９〜９８および比較法１１および従来法１１で作製したターゲットから試料を切り出して断面を樹脂に埋め、鏡面研磨し、以下、実施例１と同じ方法で行なった。
Absolute maximum length of chromium oxide aggregates dispersed in the substrate of the target prepared by the present invention method 89-98 and comparative method 11 and conventional method 11 (maximum value of the distance between any two points on the particle contour) Table 13 shows the presence or absence of coarse chromium oxide aggregates having an absolute maximum length exceeding 10 μm.
The absolute maximum length of the chromium oxide aggregates by EPMA is measured by cutting out a sample from the targets prepared in the above-mentioned method 89 to 98 of the present invention, the comparative method 11 and the conventional method 11, filling the cross section with resin, mirror polishing, The same method as in Example 1 was performed.
さらに、前記本発明法８９〜９８および比較法１１および従来法１１で得られたターゲットを有機溶剤により脱脂し、ついで真空中、１５０℃、８時間保持真空乾燥を行なったのち銅製のバッキングプレートに接合して市販のスパッタ装置に装着し、実施例１と同じ条件でプレスパッタを行い、ターゲット表面加工層を除去したのち、一旦チャンバーを大気開放して、防着板などのチャンバー部材の清掃を行った。その後、再び上記真空度に達するまで真空引きを行い、真空引き後、３０分のプレスパッタを行ってターゲット表面の大気吸着成分や金属酸化層の除去を行ったのち、４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜した。同じ条件で合計２５枚の４インチＳｉウエハ上に厚さ：１００ｎｍの磁気記録膜を成膜し、成膜後のウエハについて市販の異物検査装置によりウエハ表面に付着した１．０μｍ以上のパーティクル数を計測し、２５枚の平均値を算出し、その結果を表１３に示した。 Further, the targets obtained in the present invention methods 89 to 98, the comparative method 11 and the conventional method 11 were degreased with an organic solvent, then vacuum-dried at 150 ° C. for 8 hours in a vacuum, and then applied to a copper backing plate. After joining and mounting on a commercially available sputtering apparatus, pre-sputtering is performed under the same conditions as in Example 1 and the target surface processed layer is removed, the chamber is once opened to the atmosphere, and chamber members such as a deposition plate are cleaned. went. Thereafter, vacuuming is performed again until the degree of vacuum is reached, and after vacuuming, pre-sputtering is performed for 30 minutes to remove the air adsorbing components and the metal oxide layer on the target surface. S: A magnetic recording film of 100 nm was formed. Under the same conditions, a magnetic recording film having a thickness of 100 nm is formed on a total of 25 4-inch Si wafers, and the number of particles of 1.0 μm or more adhering to the wafer surface by a commercially available foreign substance inspection apparatus for the formed wafers. The average value of 25 sheets was calculated, and the result is shown in Table 13.
表１３に示される結果から、表１のＣｒ−Ｐｔ二元系合金粉末および表２のＣｏ−Ｃｒ二元系合金粉末を原料粉末として配合して作製した本発明法８９〜９８で作製したターゲットは、表１３のＣｒ−Ｐｔ二元系合金粉末およびＣｏ−Ｃｒ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴｉＯ２粉末を配合し混合する従来法１１により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｏ−Ｃｒ合金粉末がこの発明の範囲から外れた成分組成を有する表２のＣｏ−Ｃｒ合金粉末ｉを使用する比較法１１で作製したターゲットは１．０μｍ以上のパーティクルの発生が多くなるので好ましくないことが分かる。 From the results shown in Table 13, targets prepared by the present invention methods 89 to 98 prepared by blending the Cr—Pt binary alloy powder of Table 1 and the Co—Cr binary alloy powder of Table 2 as raw material powders Are 50% particle size: 10 μm Co powder, 50% particle size: 10 μm Cr powder, 50% particle without adding the Cr—Pt binary alloy powder and Co—Cr binary alloy powder of Table 13 It can be seen that the generation of particles is less than that of the target produced by the conventional method 11 in which a Pt powder having a diameter of 15 μm and a TiO 2 powder having a 50% particle diameter of 3 μm are mixed and mixed. However, the target produced by the comparative method 11 using the Co—Cr alloy powder i in Table 2 having a component composition outside the scope of the present invention of the Co—Cr alloy powder generates more particles of 1.0 μm or more. It turns out that it is not preferable.
実施例１２
Ｐｔ粉末を使用せず、必要なＰｔ成分はすべて表１のＣｒ−Ｐｔ二元系合金粉末Ｋ〜Ｑの添加により含有させること、非磁性酸化物粉末としてＴａ２Ｏ５粉末を使用すること、および加圧焼結を実施例２と同様の熱間静水圧プレスにより実施する以外は実施例３と全く同じ条件で本発明法６４〜７０、比較法８および従来法８を実施し、Ｃｒ：１７．５モル％、Ｐｔ：１９．４モル％、Ｔａ２Ｏ５：３．０モル％を含有し、残部がＣｏからなる成分組成を有する熱間静水圧プレス体を作製し、この熱間静水圧プレス体を切削加工して直径：１５２．４ｍｍ、厚さ：３ｍｍの寸法を有するターゲットを作製した。前記本発明法９９〜１０５、比較法１２および従来法１２で作製したターゲットについて実施例１と同じ測定を行い、その結果を表１４に示した。
Example 12
Pt powder is not used, all necessary Pt components are contained by adding Cr-Pt binary alloy powders K to Q in Table 1, and Ta 2 O 5 powder is used as a nonmagnetic oxide powder. In addition, the present invention methods 64 to 70, comparative method 8 and conventional method 8 were carried out under exactly the same conditions as in Example 3 except that the hot sintering was performed by the same hot isostatic pressing as in Example 2. Cr: 17.5 mol%, Pt: 19.4 mol%, Ta 2 O 5: 3.0 contained mol%, to prepare a hot isostatic pressing having a component composition and the balance being Co, between the heat A hydrostatic press was cut to produce a target having dimensions of 152.4 mm in diameter and 3 mm in thickness. The same measurements as in Example 1 were performed on the targets prepared by the present invention methods 99 to 105, comparative method 12 and conventional method 12, and the results are shown in Table 14.
表１４に示される結果から、本発明法９９〜１０５で作製したターゲットは、Ｃｒ−Ｐｔ二元系合金粉末およびＣｏ−Ｃｒ二元系合金粉末を添加することなく５０％粒径：１０μｍのＣｏ粉末、５０％粒径：１０μｍのＣｒ粉末、５０％粒径：１５μｍのＰｔ粉末および５０％粒径：３μｍのＴａ２Ｏ５粉末を配合し混合して作製する従来法１２により作製したターゲットに比べて、パーティクルの発生が少ないことが分かる。しかし、Ｃｒ−Ｐｔ二元系合金粉末がこの発明の範囲から外れた成分組成を有する表１のＣｒ−Ｐｔ合金粉末ＳおよびＣｏ−Ｃｒ二元系合金粉末がこの発明の範囲から外れた成分組成を有する表２のＣｏ−Ｃｒ二元系ｊを使用する比較法１２で作製したターゲットはパーティクルの発生が多くなるので好ましくないことが分かる。 From the results shown in Table 14, the targets prepared by the present invention methods 99 to 105 are 50% particle size: 10 μm Co without adding Cr—Pt binary alloy powder and Co—Cr binary alloy powder. A target prepared by the conventional method 12 prepared by mixing and mixing powder, 50% particle size: 10 μm Cr powder, 50% particle size: 15 μm Pt powder, and 50% particle size: 3 μm Ta 2 O 5 powder In comparison, it can be seen that the generation of particles is small. However, the Cr—Pt alloy powder S and the Co—Cr binary alloy powder of Table 1 in which the Cr—Pt binary alloy powder has a component composition deviating from the scope of the present invention are included in the composition of the present invention. It can be seen that the target produced by the comparative method 12 using the Co—Cr binary system j in Table 2 having Table 2 is not preferable because the generation of particles increases.
Claims (7)
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| JP2007078223A JP5024659B2 (en) | 2006-09-08 | 2007-03-26 | Method for producing Co-based sintered alloy sputtering target for forming magnetic recording film with less generation of particles |
| US12/294,691 US20100270146A1 (en) | 2006-03-31 | 2007-03-30 | Method for manufacturing co-base sintered alloy sputtering target for formation of magnetic recording film which is less likely to generate partricles, and co-base sintered alloy sputtering target for formation of magnetic recording film |
| TW096111554A TW200808980A (en) | 2006-03-31 | 2007-03-30 | Method for producing Co-based sintered alloy sputtering target used for forming magnetic recording film with reduced generation of particles, and Co-based sintered alloy sputtering target used for forming magnetic recording film |
| PCT/JP2007/057223 WO2007116834A1 (en) | 2006-03-31 | 2007-03-30 | METHOD FOR MANUFACTURING Co-BASE SINTERED ALLOY SPUTTERING TARGET FOR FORMATION OF MAGNETIC RECORDING FILM WHICH IS LESS LIKELY TO GENERATE PARTICLES, AND Co-BASE SINTERED ALLOY SPUTTERING TARGET FOR FORMATION OF MAGNETIC RECORDING FILM |
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| JP2007078223A Expired - Fee Related JP5024659B2 (en) | 2006-03-31 | 2007-03-26 | Method for producing Co-based sintered alloy sputtering target for forming magnetic recording film with less generation of particles |
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| JP5748639B2 (en) * | 2011-11-17 | 2015-07-15 | 田中貴金属工業株式会社 | Magnetron sputtering target and method for manufacturing the same |
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| JP3494302B2 (en) * | 1991-03-26 | 2004-02-09 | 日立金属株式会社 | Co-Cr-Pt magnetic recording medium target |
| JPH0598433A (en) * | 1991-08-30 | 1993-04-20 | Mitsubishi Materials Corp | Manufacture of target for sputtering |
| JP2001236643A (en) * | 2000-02-23 | 2001-08-31 | Fuji Electric Co Ltd | Sputtering target for manufacturing magnetic recording medium, method of manufacturing magnetic recording medium by using the same, and magnetic recording medium |
| JP2004339586A (en) * | 2003-05-19 | 2004-12-02 | Mitsubishi Materials Corp | Sputtering target for forming magnetic recording film, and its production method |
| JP2005097657A (en) * | 2003-09-24 | 2005-04-14 | Mitsubishi Materials Corp | Sputtering target for forming magnetic layer having reduced production of particle |
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