JP2011252227A - Cr-Ti ALLOY TARGET MATERIAL - Google Patents
Cr-Ti ALLOY TARGET MATERIAL Download PDFInfo
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- JP2011252227A JP2011252227A JP2011102721A JP2011102721A JP2011252227A JP 2011252227 A JP2011252227 A JP 2011252227A JP 2011102721 A JP2011102721 A JP 2011102721A JP 2011102721 A JP2011102721 A JP 2011102721A JP 2011252227 A JP2011252227 A JP 2011252227A
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- 239000013077 target material Substances 0.000 title claims abstract description 50
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 26
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910010169 TiCr Inorganic materials 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 21
- 238000005245 sintering Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 238000000879 optical micrograph Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004356 Ti Raw Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- Physical Vapour Deposition (AREA)
- Magnetic Record Carriers (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
本発明は、磁気記録媒体の下地層およびシード層として使用されるＣｒ−Ｔｉ層を形成するためのＣｒ−Ｔｉ合金ターゲット材に関するものである。 The present invention relates to a Cr—Ti alloy target material for forming a Cr—Ti layer used as an underlayer and a seed layer of a magnetic recording medium.
近年、磁気記録技術の進歩は著しく、ドライブの小型化と大容量化のため、磁気記録媒体の高密度化の検討が盛んに行われている。しかしながら、現在、世の中に広く普及している面内磁気記録方式の磁気記録媒体でドライブの小型化と高記録密度化を同時に実現しようとすると、１ビットの記録に用いる領域が小さくなり、周囲の磁区と打ち消しあって磁力を失ってしまう。そこで、更なる高記録密度化を実現できる方式として、垂直磁気記録方式が実用化され、現在、主流となっている。また、さらなる高記録密度を目指し、パターンドメディア、熱アシスト記録方式などの新しい記録方式の開発が進められている。 2. Description of the Related Art In recent years, magnetic recording technology has been remarkably advanced, and studies on increasing the density of magnetic recording media have been actively conducted in order to reduce the size and increase the capacity of drives. However, if an attempt is made to simultaneously realize downsizing and high recording density of a magnetic recording medium of the in-plane magnetic recording system that is widely used in the world, the area used for 1-bit recording becomes small, It cancels out the magnetic domain and loses its magnetic force. Therefore, a perpendicular magnetic recording method has been put into practical use as a method capable of realizing further higher recording density, and is now mainstream. In addition, with the aim of higher recording density, new recording methods such as patterned media and heat-assisted recording are being developed.
垂直磁気記録方式とは、垂直磁気記録媒体の磁性膜を媒体面に対して磁化容易軸が垂直に配向するように形成したものであり、記録密度を上げてもビット内の反磁界が小さく、記録再生特性の低下が少ない高記録密度化に適した方式である。垂直磁気記録媒体は、基板／下地層／軟磁性裏打ち層／シード層／Ｒｕ中間層／ＣｏＰｔＣｒ−ＳｉＯ２磁性層／保護層からなる多層構造が一般的である。前記の下地層およびシード層の一部にはＣｒ−Ｔｉ層が形成されている。 The perpendicular magnetic recording system is a magnetic film of a perpendicular magnetic recording medium formed so that the easy axis of magnetization is oriented perpendicular to the medium surface, and even if the recording density is increased, the demagnetizing field in the bit is small, This method is suitable for increasing the recording density with little deterioration in recording / reproducing characteristics. A perpendicular magnetic recording medium generally has a multilayer structure including a substrate / underlayer / soft magnetic backing layer / seed layer / Ru intermediate layer / CoPtCr—SiO 2 magnetic layer / protective layer. A Cr—Ti layer is formed on part of the underlayer and seed layer.
磁気記録媒体の成膜はマグネトロンスパッタリング法により行われる。マグネトロンスパッタリング法とは、ターゲット材と呼ばれる母材の背面に永久磁石を配置し、ターゲット材の表面に磁束を漏洩させて、漏洩磁束領域にグロー放電プラズマを収束し、高速成膜を可能とする方法である。磁気記録媒体は各層ごとに独立した成膜室を備えたスパッタ装置を用いて製造される。 The magnetic recording medium is formed by magnetron sputtering. With magnetron sputtering, a permanent magnet is placed on the back of a base material called a target material, magnetic flux is leaked to the surface of the target material, glow discharge plasma is focused on the leakage magnetic flux region, and high-speed film formation is possible. Is the method. The magnetic recording medium is manufactured using a sputtering apparatus provided with an independent film forming chamber for each layer.
ターゲット材は、所望の薄膜組成に調整された板材で、一般的に、溶解法や粉末焼結法によって製造されている。前記のＣｒ−Ｔｉ層の形成に用いられるＣｒ−Ｔｉ合金ターゲット材は粉末焼結法によって製造されている。
しかし、Ｃｒ−Ｔｉ合金ターゲット材は機械的性質において脆く、割れが発生しやすいため、組織の改良が試みられている。例えば、Ｔｉを５〜３６原子％含有するＣｒ−Ｔｉ合金ターゲット材において、抗折力を２５０Ｎ／ｍｍ２以上とすることで、スパッタリングの際の熱応力による破断やターゲット加工中のチッピングを防止可能であることが提案されている（特許文献１参照）。
The target material is a plate material adjusted to a desired thin film composition, and is generally manufactured by a melting method or a powder sintering method. The Cr—Ti alloy target material used for forming the Cr—Ti layer is manufactured by a powder sintering method.
However, since the Cr—Ti alloy target material is brittle in mechanical properties and easily cracks, attempts have been made to improve the structure. For example, in a Cr-Ti alloy target material containing 5 to 36 atomic percent of Ti, fracture strength due to thermal stress during sputtering and chipping during target processing can be prevented by setting the bending strength to 250 N / mm 2 or more. Has been proposed (see Patent Document 1).
上述した特許文献１に開示されたＣｒ−Ｔｉ合金ターゲット材は、ターゲット組織中に抗折力の高い金属Ｔｉ相を存在させることで、ターゲット材の抗折力の低下を防止するもので、加工中やスパッタリングの際に破断を抑制する上で有効である。
しかしながら、本発明者が、粉末焼結法によるＣｒ−Ｔｉ合金ターゲット材をスパッタリングしたところ、ターゲット材から多量のパーティクルと呼ばれる異物が発生する問題があることを確認した。そして、その主原因として、ターゲット材のスパッタ面にノジュールと呼ばれる突起物が多量に発生する現象を確認した。
本発明の目的は、上記課題を解決し、スパッタリング時にパーティクル発生を抑制可能なＣｒ−Ｔｉ合金ターゲット材を提供することである。
The Cr—Ti alloy target material disclosed in Patent Document 1 described above prevents a decrease in the bending strength of the target material by causing a metal Ti phase having a high bending strength to exist in the target structure. This is effective in suppressing breakage during and during sputtering.
However, when the present inventors sputtered a Cr—Ti alloy target material by a powder sintering method, it was confirmed that there was a problem that a large amount of foreign matters called particles were generated from the target material. As a main cause, a phenomenon that a large amount of protrusions called nodules are generated on the sputtering surface of the target material was confirmed.
An object of the present invention is to provide a Cr—Ti alloy target material that can solve the above-described problems and can suppress generation of particles during sputtering.
本発明者は、スパッタリング時のパーティクル発生原因を調査した結果、ターゲット組織中のＣｒ−Ｔｉ金属間化合物相がノジュール発生の主原因であることを確認した。そして、ターゲット組織中に存在するＣｒ−Ｔｉ金属間化合物相（ＴｉＣｒ２相）を極限まで低減することが有効であることを見いだし本発明に到達した。
すなわち本発明は、Ｔｉを４０〜６０原子％含有し、残部Ｃｒおよび不可避的不純物からなるＣｒ−Ｔｉ合金ターゲット材であって、スパッタ面のＸ線回折におけるＣｒ相の（１１０）面の回折ピーク強度をＡ、ＴｉＣｒ２化合物相の（３１１）面の回折ピーク強度をＢとするとき、相対強度比Ｂ／Ａが１０％以下であるＣｒ−Ｔｉ合金ターゲット材である。
As a result of investigating the cause of particle generation during sputtering, the present inventor has confirmed that the Cr—Ti intermetallic compound phase in the target structure is the main cause of nodule generation. The inventors have found that it is effective to reduce the Cr—Ti intermetallic compound phase (TiCr 2 phase) present in the target structure to the limit, and have reached the present invention.
That is, the present invention is a Cr—Ti alloy target material containing 40 to 60 atomic% of Ti, the balance being Cr and inevitable impurities, and a diffraction peak of the (110) plane of the Cr phase in the X-ray diffraction of the sputter surface. When the intensity is A and the diffraction peak intensity of the (311) plane of the TiCr 2 compound phase is B, the relative intensity ratio B / A is a Cr—Ti alloy target material of 10% or less.
本発明により、スパッタリングの際のノジュールを抑制したＣｒ−Ｔｉ合金ターゲット材が実現でき、磁気記録媒体用のＣｒ−Ｔｉ膜を安定的に成膜することが可能となる。 According to the present invention, a Cr—Ti alloy target material in which nodules during sputtering are suppressed can be realized, and a Cr—Ti film for a magnetic recording medium can be stably formed.
上述したように、本発明の重要な特徴は、スパッタリングの際のパーティクルを抑制すべく、ターゲット組織中に存在するＣｒ−Ｔｉ金属間化合物相（ＴｉＣｒ２相）を極微量に制御する点にある。 As described above, an important feature of the present invention is that the Cr—Ti intermetallic compound phase (TiCr 2 phase) present in the target structure is controlled in an extremely small amount so as to suppress particles during sputtering. .
本発明のＣｒ−Ｔｉ合金ターゲット材は、Ｔｉを４０〜６０原子％含有し、残部Ｃｒおよび不可避的不純物からなるものである。
Ｔｉ含有量を上記の範囲に規定した理由は、薄膜の密着性が高く、下地層やシード層の一部とした際に、結晶性に優れた薄膜を形成でき、高い記録再生特性を備えた磁気記録媒体を製造できるためである。なお、この組成範囲においては、ＴｉＣｒ２相に起因したパーティクルの問題が顕在化しやすいため、本発明のＴｉＣｒ２相を極微量に制御したターゲット材が極めて有効な解決手段となる。
The Cr—Ti alloy target material of the present invention contains 40 to 60 atomic% of Ti, and consists of the balance Cr and inevitable impurities.
The reason why the Ti content is defined in the above range is that the adhesion of the thin film is high, and when it is used as a part of the underlayer or seed layer, a thin film with excellent crystallinity can be formed, and high recording / reproducing characteristics are provided. This is because a magnetic recording medium can be manufactured. In this composition range, the problem of particles caused by the TiCr 2 phase is likely to be manifested, so that the target material in which the TiCr 2 phase of the present invention is controlled in an extremely small amount is an extremely effective solution.
本発明のＣｒ−Ｔｉ合金ターゲット材は、Ｃｒ−Ｔｉ金属間化合物相（ＴｉＣｒ２相）を極微量に制御する観点から、スパッタ面のＸ線回折におけるＣｒ相の（１１０）面の回折ピーク強度をＡ、ＴｉＣｒ２相の（３１１）面の回折ピーク強度をＢとするとき、相対強度比Ｂ／Ａが１０％以下とする。
焼結組織であるＣｒ−Ｔｉ合金ターゲット材の組織中には、Ｃｒ相、Ｔｉ相、ＣｒとＴｉとの拡散相としてＴｉＣｒ２相が形成される。ターゲット材組織中に拡散相として形成されるＴｉＣｒ２相を低減することは、ターゲット材の組織中に存在するＣｒ相の最密充填面である（１１０）面とＴｉＣｒ２相の（３１１）面とのＸ線回折ピーク強度の相対強度比をより小さくすることで評価可能である。
スパッタ面のＸ線回折におけるＣｒ相の（１１０）面の回折ピーク強度をＡ、ＴｉＣｒ２相の（３１１）面の回折ピーク強度をＢとするときの相対強度比を１０％以下に定めた理由は、ノジュール化しやすいＴｉＣｒ２相の存在比率をスパッタリング時に問題にならない範囲まで低減するためである。なお、ＴｉＣｒ２相がノジュール化する原因は、金属間化合物であるため純Ｃｒ相や純Ｔｉ相よりも原子間の結合力が強く、スパッタ率が低いためと考えられる。相対強度比Ｂ／Ａは好ましくは５％以下であり、さらに好ましくは３％以下である。
From the viewpoint of controlling the Cr—Ti intermetallic compound phase (TiCr 2 phase) in a very small amount, the Cr—Ti alloy target material of the present invention has a diffraction peak intensity of the (110) plane of the Cr phase in the X-ray diffraction of the sputtering surface. Where A and the diffraction peak intensity of the (311) plane of the TiCr 2- phase are B, the relative intensity ratio B / A is 10% or less.
In the structure of the Cr—Ti alloy target material that is a sintered structure, a Cr phase, a Ti phase, and a TiCr 2 phase are formed as a diffusion phase of Cr and Ti. Reducing the TiCr 2 phase formed as a diffusion phase in the target material structure is the (110) plane which is the closest packed surface of the Cr phase existing in the target material structure and the (311) plane of the TiCr 2 phase. It can be evaluated by making the relative intensity ratio of the X-ray diffraction peak intensities smaller.
Reason for setting the relative intensity ratio to 10% or less when the diffraction peak intensity of the (110) plane of the Cr phase in the X-ray diffraction of the sputter surface is A and the diffraction peak intensity of the (311) plane of the TiCr 2 phase is B This is because the abundance ratio of the TiCr 2 phase that is likely to be nodulated is reduced to a range that does not cause a problem during sputtering. The reason why the TiCr 2 phase is converted into a nodule is considered to be because the intermetallic compound has a stronger bonding force between atoms than the pure Cr phase or the pure Ti phase, and the sputtering rate is low. The relative intensity ratio B / A is preferably 5% or less, more preferably 3% or less.
また、Ｃｒ−Ｔｉ合金ターゲット材においては、スパッタ時の異常放電を抑制する観点から、不可避的に含まれる不純物の中で、特に酸素およびＦｅの含有量をより低減することが望ましい。
不可避的不純物として含まれる酸素は、典型的にはターゲット組織中に酸化物として存在し、この酸化物は絶縁体であるため、異常放電の基点になりやすい。そのため、異常放電の発生を抑制するため酸素含有量は８００質量ｐｐｍ以下に低減することが好ましい。
また、不可避的不純物として含まれるＦｅも、異常放電の基点になりやすいため、２００質量ｐｐｍ以下まで低減することが好ましい。
In addition, in the Cr—Ti alloy target material, it is desirable to further reduce the contents of oxygen and Fe, among impurities inevitably contained, from the viewpoint of suppressing abnormal discharge during sputtering.
Oxygen contained as an unavoidable impurity typically exists as an oxide in the target structure, and since this oxide is an insulator, it is likely to become a starting point for abnormal discharge. Therefore, it is preferable to reduce the oxygen content to 800 mass ppm or less in order to suppress the occurrence of abnormal discharge.
Moreover, since Fe contained as an unavoidable impurity tends to be a base point of abnormal discharge, it is preferably reduced to 200 mass ppm or less.
本発明のＣｒ−Ｔｉ合金ターゲット材の製造方法としては、原料粉末にＣｒ粉末とＴｉ粉末を用い、加圧焼結を適用することで前述した組織を実現することができる。加圧焼結法としては、熱間静水圧プレス法、ホットプレス法、通電焼結法などを適用することができる。
特に、焼結温度を９５０℃以下とすることで、Ｃｒ相とＴｉ相の界面に生成されるＴｉＣｒ２相の厚さを極限まで低減することができる。この際、加圧圧力を２０ＭＰａ以上とすることで焼結密度の低下を伴うことなく健全な焼結体が得られる。なお、十分な焼結密度を得るためには焼結温度は７５０℃以上であることが望ましい。
As a method for producing the Cr—Ti alloy target material of the present invention, the above-described structure can be realized by using Cr powder and Ti powder as raw material powder and applying pressure sintering. As the pressure sintering method, a hot isostatic pressing method, a hot pressing method, an electric current sintering method, or the like can be applied.
In particular, by setting the sintering temperature to 950 ° C. or less, the thickness of the TiCr 2 phase generated at the interface between the Cr phase and the Ti phase can be reduced to the limit. At this time, a sound sintered body can be obtained without reducing the sintered density by setting the pressure to 20 MPa or more. In order to obtain a sufficient sintered density, the sintering temperature is desirably 750 ° C. or higher.
本発明のターゲット材の製造に用いる原料粉末としては、加圧焼結の際にＣｒとＴｉとの拡散相として形成されるＴｉＣｒ２相を抑制するため、Ｃｒ粉末を粗粒に制御することが望ましく、粒径としては、３２メッシュ以下、かつ３２５メッシュ以上とすることが好ましい。それは、３２メッシュを超えたＣｒ粉末を使用する場合にはターゲット材の組織中に粗大なＣｒ相を残存させることがあるためであり、３２５メッシュ未満の微細なＣｒ粉末を使用する場合にはＴｉ粉末との拡散が進みやすくＴｉＣｒ２相の形成を十分に抑制できないためである。
また、予め酸素を低減した粉末を用いることでターゲット材の酸素含有量を低減することができるため、例えば、高純度電解Ｃｒ粉砕粉末を、水素雰囲気中で還元熱処理を施したものを使用することが好ましい。Ｃｒ粉末の粒径を３２５メッシュ以上とすることは比表面積が大きく酸素含有量が高い微細な粉末を除去するためにも望ましい。
As the raw material powder used for the production of the target material of the present invention, it is possible to control the Cr powder to coarse particles in order to suppress the TiCr 2 phase formed as a diffusion phase of Cr and Ti during pressure sintering. Desirably, the particle size is preferably 32 mesh or less and 325 mesh or more. This is because when a Cr powder exceeding 32 mesh is used, a coarse Cr phase may remain in the structure of the target material. When a fine Cr powder less than 325 mesh is used, Ti is used. This is because diffusion with the powder easily proceeds and the formation of the TiCr 2 phase cannot be sufficiently suppressed.
Moreover, since the oxygen content of the target material can be reduced by using a powder in which oxygen is reduced in advance, for example, a high-purity electrolytic Cr pulverized powder that has been subjected to a reduction heat treatment in a hydrogen atmosphere should be used. Is preferred. Setting the particle size of the Cr powder to 325 mesh or more is also desirable for removing fine powder having a large specific surface area and a high oxygen content.
また、Ｔｉ粉末についても、例えば、Ｔｉ原料を水素雰囲気で熱処理して得られたＴｉ水素化物を粉砕した後、脱水素処理を施した水素化粉砕脱水素のＴｉ粉末を用いることでターゲット材の酸素含有量を低減することができる。さらに、ガスアトマイズ法により製造されたＴｉ粉末を使用することもターゲット材の酸素含有量を低減する上で有効である。それは、ガスアトマイズのＴｉ粉末は球状に近く比表面積が小さく粉末表面に吸着する酸素含有量が低いため、さらにターゲット材中の酸素含有量を低減することができるためである。Ｔｉ粉末の粒径は１００メッシュ以下が好ましい。 In addition, for Ti powder, for example, after pulverizing Ti hydride obtained by heat-treating Ti raw material in a hydrogen atmosphere, dehydrogenation-treated hydrogen pulverized dehydrogenated Ti powder is used to obtain the target material. The oxygen content can be reduced. Furthermore, using Ti powder produced by the gas atomization method is also effective in reducing the oxygen content of the target material. This is because the gas atomized Ti powder is spherical and has a small specific surface area and a low oxygen content adsorbed on the powder surface, so that the oxygen content in the target material can be further reduced. The particle size of the Ti powder is preferably 100 mesh or less.
まず、水素雰囲気で還元処理を施した市販の純度９９．９９％のＣｒ粉末を表１に示す篩で篩別した粉末を準備した。また、Ｔｉ粉末として、純度９９．９％の水素化粉砕脱水素Ｔｉ粉末、ガスアトマイズＴｉ粉末をそれぞれ１００メッシュの篩で篩別した粉末を準備した。
上記で準備した粉末を、Ｃｒ−５０Ｔｉ（原子％）となるように粉末を混合し、軟鋼製のカプセルに充填し脱気封止した後、温度９５０℃、圧力１２０ＭＰａ、保持時間１時間の条件で熱間静水圧プレス（ＨＩＰ）によって加圧焼結し、焼結体を作製した。得られた各焼結体を直径１８０ｍｍ×厚さ１０ｍｍに機械加工してＣｒ−Ｔｉ合金ターゲット材を作製した。
また、従来例として粉末焼結法により製造された市販のＣｒ−５０Ｔｉ（原子％）のターゲット材も準備した。
なお、得られた各ターゲット材に関して、酸素含有量を不活性ガス融解赤外線吸収法により、Ｆｅ含有量を誘導結合プラズマ発行分光分析法により分析した。また、上記の各ターゲット材をアルキメデス法により測定した密度からの相対密度を算出し、以上の分析、測定結果を表１に示す。
First, a powder obtained by screening a commercially available Cr powder with a purity of 99.99% subjected to reduction treatment in a hydrogen atmosphere with a sieve shown in Table 1 was prepared. Further, as the Ti powder, a powder obtained by sieving the hydrogenated pulverized dehydrogenated Ti powder having a purity of 99.9% and the gas atomized Ti powder with a 100 mesh sieve was prepared.
The powder prepared above is mixed with powder so as to be Cr-50Ti (atomic%), filled in a mild steel capsule and deaerated and sealed, and then the temperature is 950 ° C., the pressure is 120 MPa, and the holding time is 1 hour. And sintered under pressure by hot isostatic pressing (HIP) to produce a sintered body. Each obtained sintered body was machined into a diameter of 180 mm and a thickness of 10 mm to prepare a Cr—Ti alloy target material.
In addition, a commercially available Cr-50Ti (atomic%) target material manufactured by a powder sintering method was also prepared as a conventional example.
In addition, regarding each obtained target material, the oxygen content was analyzed by the inert gas fusion infrared absorption method, and the Fe content was analyzed by inductively coupled plasma emission spectroscopy. Moreover, the relative density from the density which measured said each target material by the Archimedes method was computed, and the above analysis and a measurement result are shown in Table 1.
上記で作製した各ターゲット材を株式会社リガク製 Ｘ線回折装置ＲＩＮＴ２０００を使用し、線源にＣｏを用いて、Ｘ線回折法により回折ピーク強度を測定した。測定結果からＣｒ相の（１１０）面の回折ピーク強度（Ａ）とＴｉＣｒ２化合物相の（３１１）面の回折ピーク強度（Ｂ）の相対強度比（Ｂ／Ａ）を算出して表１に示す。
具体的な測定例として、図１に本発明例２のＣｒ−Ｔｉ合金ターゲット材の光学顕微鏡像を示し、図２に本発明例２のＸ線回折法による各回折ピークを同定した結果を示す。図１において、白色部は金属Ｃｒ相、黒色部は金属Ｔｉ相であり、焼結による金属間拡散により金属Ｃｒ相と金属Ｔｉ相の境界部にＴｉＣｒ２化合物相がわずかに形成されたことがわかる。
The diffraction peak intensity was measured by the X-ray diffraction method for each of the target materials prepared above using an X-ray diffractometer RINT2000 manufactured by Rigaku Corporation, using Co as a radiation source. From the measurement results, the relative intensity ratio (B / A) of the diffraction peak intensity (A) of the (110) plane of the Cr phase and the diffraction peak intensity (B) of the (311) plane of the TiCr 2 compound phase is calculated and shown in Table 1. Show.
As a specific measurement example, FIG. 1 shows an optical microscope image of the Cr—Ti alloy target material of Invention Example 2, and FIG. 2 shows the result of identifying each diffraction peak by the X-ray diffraction method of Invention Example 2. . In FIG. 1, the white portion is the metallic Cr phase and the black portion is the metallic Ti phase, and a slight TiCr 2 compound phase is formed at the boundary between the metallic Cr phase and the metallic Ti phase due to intermetallic diffusion caused by sintering. Recognize.
また、上記で作製したターゲット材をＤＣマグネトロンスパッタ装置のチャンバ内に配置し、チャンバ内を１×１０−６Ｐａ以下となるまで減圧した後、Ａｒガス圧０．３Ｐａ、投入電力１５００Ｗの条件にて５時間のスパッタを行った。次いで、各ターゲット材のスパッタ面のエロージョン部について、走査型電子顕微鏡を用いて観察した９４５μｍ×１２７０μｍの視野で確認された短径５μｍ以上のノジュール数を測定した。測定結果を表１に示す。 Further, the target material prepared above is placed in the chamber of the DC magnetron sputtering apparatus, and after reducing the pressure in the chamber to 1 × 10 −6 Pa or less, the Ar gas pressure is 0.3 Pa and the input power is 1500 W. For 5 hours. Next, for the erosion portion of the sputtering surface of each target material, the number of nodules having a minor axis of 5 μm or more, which was confirmed with a field of view of 945 μm × 1270 μm observed using a scanning electron microscope, was measured. The measurement results are shown in Table 1.
表１から、相対強度比Ｂ／Ａが１０％以下である本発明例１〜本発明例３では、従来例の相対強度比Ｂ／Ａ＝１５．８％よりも、スパッタリングの際に発生する短径５μｍ以上のノジュール発生を大きく低減できたことが確認できた。 From Table 1, in the present invention example 1 to the present invention example 3 in which the relative intensity ratio B / A is 10% or less, the relative intensity ratio B / A of the conventional example is 15.8%, which occurs during sputtering. It was confirmed that the generation of nodules having a minor axis of 5 μm or more could be greatly reduced.
次に実施例２として、水素雰囲気で還元処理を施した市販の純度９９．９９％のＣｒ粉末を表２に示す篩で篩別した粉末を準備した。また、Ｔｉ粉末として、純度９９．９％の水素化粉砕脱水素Ｔｉ粉末、ガスアトマイズＴｉ粉末をそれぞれ１００メッシュの篩で篩別した粉末を準備した。 Next, as Example 2, a powder obtained by screening a commercially available Cr powder with a purity of 99.99% subjected to reduction treatment in a hydrogen atmosphere with a sieve shown in Table 2 was prepared. Further, as the Ti powder, a powder obtained by sieving the hydrogenated pulverized dehydrogenated Ti powder having a purity of 99.9% and the gas atomized Ti powder with a 100-mesh sieve was prepared.
上記で準備した粉末を、表２の組成となるように混合し、軟鋼製のカプセルに充填し脱気封止した後、表２に示すＨＩＰ温度で、圧力１２０ＭＰａ、保持時間１時間の条件で熱間静水圧プレス（ＨＩＰ）によって加圧焼結し、焼結体を作製した。得られた各焼結体を直径１８０ｍｍ×厚さ１０ｍｍに機械加工してＣｒ−Ｔｉ合金ターゲット材を作製した。
なお、得られた各ターゲット材に関して評価をした結果を表２に示す。
The powder prepared above was mixed so as to have the composition shown in Table 2, filled in a mild steel capsule and degassed and sealed, then at the HIP temperature shown in Table 2 under the conditions of a pressure of 120 MPa and a holding time of 1 hour. The sintered compact was produced by pressure sintering by hot isostatic pressing (HIP). Each obtained sintered body was machined into a diameter of 180 mm and a thickness of 10 mm to prepare a Cr—Ti alloy target material.
In addition, Table 2 shows the results of evaluation on the obtained target materials.
具体的な測定例として、図３に本発明例１１のＣｒ−Ｔｉ合金ターゲット材の光学顕微鏡像を示し、図４に本発明例１１のＸ線回折法により存在する相を同定した結果を示す。図３において、白色部は金属Ｃｒ相、黒色部は金属Ｔｉ相、金属Ｃｒ相と金属Ｔｉ相の界面部はＴｉＣｒ２化合物相である。本発明例によると、金属Ｃｒ相と金属Ｔｉ相の境界部に形成されるＴｉＣｒ２化合物相の存在比率を示す回折ピーク強度がより低減されていることがわかる。 As a specific measurement example, FIG. 3 shows an optical microscope image of the Cr—Ti alloy target material of Example 11 of the present invention, and FIG. 4 shows the result of identifying phases existing by the X-ray diffraction method of Example 11 of the present invention. . In FIG. 3, the white portion is a metallic Cr phase, the black portion is a metallic Ti phase, and the interface portion between the metallic Cr phase and the metallic Ti phase is a TiCr 2 compound phase. According to the example of the present invention, it can be seen that the diffraction peak intensity indicating the abundance ratio of the TiCr 2 compound phase formed at the boundary between the metal Cr phase and the metal Ti phase is further reduced.
表２から、本発明例５〜本発明例１２は、表１に記載する従来例のＴｉＣｒ２化合物相の相対強度比Ｂ／Ａ＝１５．８％に比べ、相対強度比Ｂ／Ａが全て１０％以下に抑制されていることがわかる。
また、本発明例５〜本発明例１２のＣｒ−Ｔｉ合金ターゲット材を用いて同様のスパッタリングを行なったところ、問題となるパーティクルの発生が確認されず、本発明の有効性が確認できた。
From Table 2, the present invention example 5 to the present invention example 12 have all the relative strength ratio B / A compared to the relative strength ratio B / A = 15.8% of the conventional TiCr 2 compound phase described in Table 1. It turns out that it is suppressed to 10% or less.
Moreover, when similar sputtering was performed using the Cr—Ti alloy target material of Invention Example 5 to Invention Example 12, generation of problematic particles was not confirmed, and the effectiveness of the present invention was confirmed.
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