JP2002275625A - Ru TARGET MATERIAL AND PRODUCTION METHOD THEREFOR - Google Patents
Ru TARGET MATERIAL AND PRODUCTION METHOD THEREFORInfo
- Publication number
- JP2002275625A JP2002275625A JP2001078798A JP2001078798A JP2002275625A JP 2002275625 A JP2002275625 A JP 2002275625A JP 2001078798 A JP2001078798 A JP 2001078798A JP 2001078798 A JP2001078798 A JP 2001078798A JP 2002275625 A JP2002275625 A JP 2002275625A
- Authority
- JP
- Japan
- Prior art keywords
- target material
- powder
- target
- present
- grain size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013077 target material Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 abstract description 16
- 238000003754 machining Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 12
- 239000010409 thin film Substances 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000009832 plasma treatment Methods 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910015801 BaSrTiO Inorganic materials 0.000 description 1
- 101000831940 Homo sapiens Stathmin Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 102100024237 Stathmin Human genes 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Physical Vapour Deposition (AREA)
- Semiconductor Memories (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体ＬＳＩ等に
用いられる薄膜材料を形成するためのＲｕターゲット材
およびその製造方法に関するものである。[0001] 1. Field of the Invention [0002] The present invention relates to a Ru target material for forming a thin film material used for a semiconductor LSI or the like, and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】近年、情報機器の高速化、低消費電力
化、大容量化要求にともなって、半導体ＬＳＩの微細化
と高集積化が進んでいる。また、デバイス構造進化と同
時に薄膜材料に新しい材料が検討されている。特に、パ
ソコンのメインメモリとして汎用性の高いＤＲＡＭで
は、キャパシタ誘電体に従来用いられていたＳｉＯ２よ
り誘電率の高いＢａＳｒＴｉＯ３（ＢＳＴ）が検討され
ている。これに併せ、ＤＲＡＭ製造過程における高温度
プロセスへの耐性からキャパシタ電極材料としてＲｕが
検討されている。また、Ｒｕの薄膜は、ハードディスク
等の磁気記録媒体に適用できる半強磁性カップリング層
としても適用されるようになってきている。2. Description of the Related Art In recent years, with the demand for higher speed, lower power consumption, and higher capacity of information equipment, miniaturization and higher integration of semiconductor LSIs have been advanced. In addition, new materials for thin film materials are being studied simultaneously with device structure evolution. In particular, for a DRAM having high versatility as a main memory of a personal computer, BaSrTiO 3 (BST) having a higher dielectric constant than SiO 2 conventionally used for a capacitor dielectric is being studied. At the same time, Ru is being studied as a capacitor electrode material because of its resistance to high-temperature processes in the DRAM manufacturing process. Further, the Ru thin film has been applied also as a semi-ferromagnetic coupling layer applicable to a magnetic recording medium such as a hard disk.
【０００３】上述したＲｕのキャパシタ電極膜等のＲｕ
薄膜は、実質的に薄膜組成と同様の組成を有するターゲ
ットを用いてスパッタリング法により成膜するので、タ
ーゲットの特性は重要である。たとえば、電極膜用Ｒｕ
ターゲットとしては、特開２０００−３４５６３号など
に原料粉末を高純度化し、高純度の原料粉末を焼結した
Ｒｕターゲットについて開示されている。また、上記Ｒ
ｕターゲットの製造方法については、前記の特開２００
０−３４５６３号に記載の化学沈殿還元により得た微細
粉末を焼結する方法の他に、特開平８−３０２４６２号
に電子ビームによって溶解して高純度化を行うＥＢ法が
開示されている。[0003] Ru such as the above-mentioned Ru capacitor electrode film or the like.
Since a thin film is formed by a sputtering method using a target having substantially the same composition as the thin film composition, characteristics of the target are important. For example, Ru for electrode film
JP-A-2000-34563 discloses a Ru target obtained by purifying a raw material powder and sintering the high-purity raw material powder. In addition, the above R
For the method of manufacturing the u target, see the aforementioned JP-A-200
In addition to the method of sintering fine powder obtained by chemical precipitation reduction described in JP-A-34-5633, Japanese Patent Application Laid-Open No. 8-302462 discloses an EB method of melting and purifying a fine powder by an electron beam.
【０００４】[0004]
【発明が解決しようとする課題】半導体メモリ、特にＤ
ＲＡＭの大容量化、高信頼性を実現するために、キャパ
シタ電極とするＲｕ薄膜の高純度化、薄膜の均一性が求
められている。したがって、膜の純度と薄膜の均一性は
ターゲット材の影響が大きいので、Ｒｕターゲットとし
ては、高純度で高密度のターゲット材が追求されてき
た。しかし、本発明者の検討によると、従来の手法によ
り製造したターゲットでは、ターゲット自体の靭性不
足、あるいは機械加工が難しいという新たな問題に直面
した。Ｒｕターゲットを現実の製品とするためには、成
膜効率・均一性等の薄膜特性に加えて、機械加工性とい
った製造コストに直結する技術の改良が重要に課題とな
った。SUMMARY OF THE INVENTION Semiconductor memories, especially D
In order to realize large capacity and high reliability of the RAM, it is required that the Ru thin film used as the capacitor electrode be highly purified and uniform. Therefore, since the target material has a great influence on the purity of the film and the uniformity of the thin film, a high-purity and high-density target material has been pursued as the Ru target. However, according to the study of the present inventor, the target manufactured by the conventional method faces a new problem that the target itself has insufficient toughness or that machining is difficult. In order to make a Ru target an actual product, it has become an important issue to improve thin-film characteristics such as film formation efficiency and uniformity, as well as technology that directly relates to manufacturing costs such as machinability.
【０００５】具体的には、上述の特開平８−３０２４６
２号のように、局部的にＥＢ溶解を行うと、組織が粗大
化しがちでターゲット材の深さ方向で組織が不均一とな
りやすく、極めて脆く、靭性が不足するため、スパッタ
リング時の加熱によってターゲットに割れが生ずるとい
う問題が確認される。More specifically, the above-mentioned Japanese Patent Application Laid-Open No. H8-30246 has been disclosed.
As in No. 2, when EB is locally melted, the structure tends to become coarse and the structure tends to be non-uniform in the depth direction of the target material, and the target material is extremely brittle and lacks toughness. The problem that cracks occur in the steel is confirmed.
【０００６】一方、特開２０００−３４５６３号に開示
されるＲｕターゲットは、化学沈殿還元によって得た粉
末を採用するため、組織は極めて微細、具体的には、結
晶粒径が数μｍ以下と微細となる。このターゲットの脆
性は改善されるが、極めて硬く、機械加工時に割れ（欠
け）易いという問題がある。また、熱伝導性が悪く、ス
パッタ中の冷却効率が低く、スパッタ中の割れるという
問題もある。本発明の目的は、上記問題点に鑑み、靭性
が高く、機械加工特性も良好なＲｕターゲット材を提供
することである。On the other hand, the Ru target disclosed in Japanese Patent Application Laid-Open No. 2000-34563 employs a powder obtained by chemical precipitation reduction, and therefore has a very fine structure, specifically, a crystal grain size of several μm or less. Becomes Although the brittleness of the target is improved, there is a problem that it is extremely hard and easily cracks (chips) during machining. There is also a problem that thermal conductivity is poor, cooling efficiency during sputtering is low, and cracking occurs during sputtering. In view of the above problems, an object of the present invention is to provide a Ru target material having high toughness and excellent machining characteristics.
【０００７】[0007]
【課題を解決するための手段】本発明者の鋭意的な研究
の結果、Ｒｕターゲットにおいては、靭性と硬さがミク
ロ組織における結晶粒径に対して顕著に変化することを
突き止め、特定の結晶粒系範囲にすることおよび破断面
に存在する細粒部と粗大部を排除することで良好な機械
加工特性と靭性を付与できることを見出し、本発明に至
った。As a result of earnest research by the present inventors, it has been found that in the Ru target, the toughness and hardness change remarkably with respect to the crystal grain size in the microstructure. The present inventors have found that good machining characteristics and toughness can be imparted by setting the grain size in the range and eliminating the fine and coarse portions present in the fractured surface, and have reached the present invention.
【０００８】すなわち本発明は相対密度９８％以上、ミ
クロ組織における平均結晶粒径８〜１００μｍであり、
かつ破断面に存在する１０〜１００μｍの粒が５０面積
％以上であるＲｕターゲット材である。また、本発明の
Ｒｕターゲット材は純度が５Ｎ以上であることが好まし
く、さらに、硬さが４００Ｈｖ以下、抗折力が３５０Ｍ
Ｐａ以上、熱伝導率が１２０Ｗ／ｍ・Ｋ以上であること
が好ましい。That is, in the present invention, the relative density is 98% or more, the average crystal grain size in the microstructure is 8 to 100 μm,
In addition, the target material is a Ru target material in which 10 to 100 μm grains existing in the fracture surface are 50 area% or more. Further, the Ru target material of the present invention preferably has a purity of 5 N or more, and further has a hardness of 400 Hv or less and a transverse rupture strength of 350 M
It is preferable that the thermal conductivity is Pa or more and the thermal conductivity is 120 W / m · K or more.
【０００９】また、上述した本発明のＲｕターゲット材
は、粉末原料を熱プラズマ中に通過させ、球状化させた
Ｒｕ粉末を加圧焼結し、焼結体のミクロ組織における平
均結晶粒径を８〜１００μｍ、破断面に存在する１０〜
１００μｍの粒を５０面積％以上に調整することにより
製造することができる。In the Ru target material of the present invention described above, the powder raw material is passed through a thermal plasma, the spheroidized Ru powder is sintered under pressure, and the average crystal grain size in the microstructure of the sintered body is reduced. 8 to 100 μm, 10 existing on the fracture surface
It can be manufactured by adjusting the grain size of 100 μm to 50% by area or more.
【００１０】[0010]
【発明の実施の形態】以下、本発明について詳しく説明
する。本発明の半導体用Ｒｕターゲット材の重要な特徴
の一つは、平均結晶粒径を８〜１００μｍに調整すると
ともに、破断面組織の微細な結晶粒と粗大な結晶粒を低
減したことである。上述したように、本発明者の検討に
よれば、従来のように化学沈殿還元法により得られた粉
末原料を焼結して得られたターゲット材は組織が著しく
微細となり、これによって硬さが過度に高くなり、機械
加工性を劣化ものとなる。さらに、微細な結晶粒径の組
織は熱伝導率の低下を招き、スパッタ中のターゲット割
れを引き起こす原因となる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. One of the important features of the Ru target material for a semiconductor according to the present invention is that the average crystal grain size is adjusted to 8 to 100 μm and the fine and coarse crystal grains having a fracture surface structure are reduced. As described above, according to the study of the present inventors, the target material obtained by sintering the powder raw material obtained by the conventional chemical precipitation reduction method has a remarkably fine structure, and the hardness is thereby reduced. It becomes excessively high and deteriorates machinability. Further, a structure having a fine crystal grain size causes a decrease in thermal conductivity, which causes a target crack during sputtering.
【００１１】本発明者は、ミクロ組織における結晶粒径
と機械加工性および硬さの関係を検討し、ターゲット材
の平均粒径が８μｍ未満では、機械加工における割れ発
生率が急激に上昇するため、平均結晶粒径の下限を８μ
ｍに規定した。安定的に割れ発生量を抑制するために
は、平均結晶粒径の下限は１０μｍであることがさらに
望ましい。また、平均結晶粒径の下限値が上記範囲に入
っていても、破断面に存在する１０μｍ以下の粒が５０
面積％以下の組織では、硬さ増加による機械加工による
割れ率が上昇する。加えて、破断面に存在する１００μ
ｍ以上の粒が５０面積％であれば抗折力が低下し、スパ
ッタ中に割れる可能性が高まるため、破断面に存在する
１０〜１００μｍの粒が５０面積％以上に規定した。一
方、平均結晶粒径が１００μｍを越えると、ターゲット
材組織の結晶性が向上し熱伝導率は向上するが、抗折力
が低下するため、スパッタ中におけるターゲットの割れ
の原因となる。加えて粗大な結晶粒径を持つターゲット
材は一般に良好な膜が得にくい。したがって、上限を１
００μｍと規定した。The present inventor has studied the relationship between the crystal grain size in the microstructure and the machinability and hardness. If the average grain size of the target material is less than 8 μm, the crack generation rate in the machining sharply increases. , The lower limit of the average crystal grain size is 8μ.
m. In order to stably suppress the generation of cracks, the lower limit of the average crystal grain size is more desirably 10 μm. Further, even if the lower limit of the average crystal grain size falls within the above range, 50 μm or less of grains present in the fractured surface are not present.
In a structure having a surface area of not more than%, the cracking rate due to machining due to an increase in hardness increases. In addition, 100μ
If 50% or more of the particles having a particle size of m or more are used, the transverse rupture strength is reduced and the possibility of cracking during sputtering is increased. On the other hand, if the average crystal grain size exceeds 100 μm, the crystallinity of the target material structure is improved and the thermal conductivity is improved, but the transverse rupture strength is reduced, which causes cracking of the target during sputtering. In addition, it is generally difficult to obtain a good film from a target material having a coarse crystal grain size. Therefore, the upper limit is 1
It was defined as 00 μm.
【００１２】また、本発明のＲｕターゲット材を半導体
用途に適用する場合、純度の低いターゲット材により半
導体薄膜を形成すると、キャパシタ電極間リークや誤動
作が多発するため、Ｒｕターゲット材の純度は高い方が
好ましい。半導体素子の信頼性に悪影響を及ぼすアルカ
リ金属（Ｎａ、Ｋ）遷移金属（Ｆｅ、Ｎｉ、Ｃｒ）放射
性元素（Ｔｈ、Ｕ）などを低減することにより純度を５
Ｎ以上とすることが好ましい。特に上記の不純物元素に
ついては合計で８ｐｐｍ以下であることが好ましい。When the Ru target material of the present invention is applied to semiconductor applications, if a semiconductor thin film is formed from a low-purity target material, leakage between capacitor electrodes and malfunctions occur frequently. Is preferred. Purity is reduced by reducing alkali metal (Na, K) transition metal (Fe, Ni, Cr) and radioactive elements (Th, U) which adversely affect the reliability of semiconductor devices.
It is preferably N or more. In particular, the total amount of the above impurity elements is preferably 8 ppm or less.
【００１３】本発明のＲｕターゲット材は、その硬さが
４００Ｈｖ以下であることが、ターゲット材、特に焼結
ターゲット材としての機械加工性を確保できるため好ま
しい。ターゲット材の純度が低い場合には、不純物元素
の合金強化による硬化、また結晶粒の必要以上の微細化
による硬化が硬さの上昇の原因として挙げられる。本発
明では、高純度化と結晶粒を最適範囲にすることで、硬
さを４００Ｈｖにすることが可能である。さらに好まし
くは３００Ｈｖ以下である。It is preferable that the Ru target material of the present invention has a hardness of 400 Hv or less in order to ensure the machinability of the target material, particularly the sintered target material. When the purity of the target material is low, hardening due to alloy strengthening of the impurity element and hardening due to excessive refinement of crystal grains are cited as causes of the increase in hardness. In the present invention, the hardness can be set to 400 Hv by purifying the crystal and setting the crystal grains in the optimum range. More preferably, it is 300 Hv or less.
【００１４】さらにターゲット材の抗折力が３５０ＭＰ
ａ未満になると、ターゲット材を機械加工する際に割れ
やすくなる。また、スパッタ中の熱衝撃の影響によりタ
ーゲットの割れが発生することにもなる。機械加工性及
びスパッタの安定性を確保するためには３５０ＭＰａ以
上が望ましい。スパッタ効率を向上するために、よりス
パッタのパワーを増加させる傾向がある。したがって、
スパッタ中の熱衝撃も増大するので、割れを防ぐため
に、本発明のＲｕターゲット材の熱伝導率は１２０Ｗ／
ｍＫであることが好ましい。Further, the bending strength of the target material is 350MP.
If the value is less than a, the target material tends to crack when machined. In addition, the target may be cracked due to thermal shock during sputtering. In order to secure the machinability and the stability of sputtering, 350 MPa or more is desirable. In order to improve sputtering efficiency, there is a tendency to increase the power of sputtering. Therefore,
Since thermal shock during sputtering also increases, the thermal conductivity of the Ru target material of the present invention is 120 W /
It is preferably mK.
【００１５】本発明では、純度が５Ｎ以上、平均結晶粒
径が８〜１００μｍであるＲｕターゲット材を製造する
ために、例えば熱プラズマ処理で粉末を高純度化、球状
化した粉末を使って加圧焼結で製造することが可能であ
る。好ましくは平均粒径が５〜１５０μｍである球状化
高純度粉末を採用する。熱プラズマ処理においては高温
領域の通過によって融解し球状化することによって微細
な結晶粒が適度な大きさの結晶粒に調整される。これに
よって作製した高純度粉末はＨＩＰ中の粒成長が抑制さ
れ、８〜１００μｍの最適な平均結晶粒径を持ち、かつ
破断面に存在する１０〜１００μｍの粒が５０面積%以
上であるターゲット材を得ることができる。本発明にお
ける熱プラズマ処理の前処理として、たとえば、スポン
ジ状の多孔体のＲｕ原料をボールミル等により、粗粉砕
しておくことができる。粉砕する場合ボールミル等のメ
ディアや雰囲気からの汚染の可能性があるので粉砕は、
できるだけ短時間がよい。そして、本発明のＲｕターゲ
ット材は、スパッタリング法により、例えば半導体メモ
リのキャパシタ電極膜を形成することが可能である。In the present invention, in order to produce a Ru target material having a purity of 5 N or more and an average crystal grain size of 8 to 100 μm, for example, a powder is purified by a thermal plasma treatment, and the powder is added using a spherical powder. It can be manufactured by pressure sintering. Preferably, a spheroidized high-purity powder having an average particle size of 5 to 150 μm is employed. In the thermal plasma treatment, the fine crystal grains are adjusted to appropriate crystal grains by melting and spheroidizing by passing through a high temperature region. The high-purity powder produced by this method suppresses grain growth in HIP, has an optimal average crystal grain size of 8 to 100 µm, and has a target area in which 10 to 100 µm grains present on the fracture surface are 50% by area or more. Can be obtained. As a pretreatment of the thermal plasma treatment in the present invention, for example, a sponge-like porous Ru material can be roughly pulverized by a ball mill or the like. When crushing, there is a possibility of contamination from media such as a ball mill and the atmosphere.
The shortest possible time is better. The Ru target material of the present invention can form, for example, a capacitor electrode film of a semiconductor memory by a sputtering method.
【００１６】熱プラズマ処理により高純度化したＲｕ粉
末を用いてターゲット材を作製することにより、不純物
およびガス成分がほとんど含まれない高純度のＲｕター
ゲット材を作製することができる。また、熱プラズマ中
に水素ガスを導入すると、不純物の蒸発が促され、高純
度化が促進されるので好ましい。By manufacturing a target material using Ru powder highly purified by thermal plasma processing, a high-purity Ru target material containing almost no impurities and gas components can be manufactured. Further, it is preferable to introduce hydrogen gas into the thermal plasma, since evaporation of impurities is promoted and high purification is promoted.
【００１７】[0017]
【実施例】以下に本発明の具体的な実施例について説明
する。市販の化学的製法によって精製されたスポンジ状
の多孔体であるＲｕ原料（純度３Ｎ５）を１０〜９０分
間、ボールミル粉砕し、原料粉末を粒状化した。ボール
ミル粉砕はＦｅなどの不純物の混入を防ぐために樹脂製
の容器で行った。ボールミルの粉砕時間を表１に示す。
ただし、試料３は熱プラズマ処理を施した試料１と５の
混合によるので粉砕工程はない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention will be described below. Ru raw material (purity 3N5), which is a sponge-like porous material purified by a commercially available chemical manufacturing method, was ball-milled for 10 to 90 minutes to granulate the raw material powder. Ball mill pulverization was performed in a resin container in order to prevent impurities such as Fe from being mixed. Table 1 shows the grinding time of the ball mill.
However, since the sample 3 is obtained by mixing the samples 1 and 5 subjected to the thermal plasma treatment, there is no pulverizing step.
【００１８】[0018]
【表１】 [Table 1]
【００１９】粉砕処理したＲｕ粉末に熱プラズマ処理を
施し、高純度の球状Ｒｕ粉末を得た。熱プラズマには水
素を適宜導入し不純物の蒸発を促した。表１の試料５の
粉末を熱プラズマ処理したＲｕ粉末のグロー放電質量分
析法（ＧＤＭＳ）によって分析した結果を、原料粉末の
分析値と併せて表２に示す。また、表１の試料５以外の
ものもＧＤＭＳ分析を行い、同様に５Ｎ以上の純度のＲ
ｕ粉末となっていることを確認した。The pulverized Ru powder was subjected to a thermal plasma treatment to obtain a high-purity spherical Ru powder. Hydrogen was appropriately introduced into the thermal plasma to promote the evaporation of impurities. Table 2 shows the results of glow discharge mass spectrometry (GDMS) analysis of Ru powder obtained by subjecting the powder of sample 5 in Table 1 to thermal plasma treatment, together with the analysis values of the raw material powder. GDMS analysis was also performed on samples other than sample 5 in Table 1, and R
u powder was confirmed.
【００２０】[0020]
【表２】 [Table 2]
【００２１】上記の方法で、作製した粉末をカプセルに
充填し真空脱気を行った後、圧力１８０ＭＰａ，温度１
３００℃，１時間で熱間静水圧プレス（以下ＨＩＰ）法
で加圧焼結を行い、Ｒｕターゲット材を得た。具体的な
本発明の試料４の２０００倍の破断面組織を図１に示
す。一方 、比較例の試料２の２０００倍の破断面組織
を図２に比較例の試料３の１０００倍の破断面組織を図
３に示す。After the powder thus prepared is filled in a capsule and subjected to vacuum degassing, a pressure of 180 MPa and a temperature of 1
Pressure sintering was performed by a hot isostatic press (hereinafter, HIP) method at 300 ° C. for one hour to obtain a Ru target material. FIG. 1 shows a 2000-fold fracture surface structure of a specific sample 4 of the present invention. On the other hand, FIG. 2 shows a 2000 times fracture surface structure of the comparative sample 2 and FIG. 3 shows a 1000 times fracture surface structure of the comparative example 3 sample.
【００２２】図１に示す如くＨＩＰ後の組織では熱プラ
ズマ処理粉を用いるとＨＩＰにより粒の変形はあるもの
の熱プラズマ処理粉の粒径をほぼ保っていた。一方、比
較例２のような微細な粒径おいても、同様に熱プラズマ
処理粉の粒径をほぼ保っていた。さらに、試料１と５の
熱プラズマ処理粉末を５０：５０混合しＨＩＰした比較
例の試料３においてもＨＩＰにより粒変形は伴うものの
熱プラズマ処理粉末の粒径をほぼ保っていた。したがっ
て、熱プラズマ処理粉末の粒径を制御することで目的の
加圧焼結後の組織を得ることができた。As shown in FIG. 1, in the structure after the HIP, when the thermal plasma-treated powder was used, although the grains were deformed by the HIP, the particle diameter of the thermal plasma-treated powder was almost maintained. On the other hand, even in the case of a fine particle size as in Comparative Example 2, the particle size of the thermal plasma-treated powder was substantially maintained. Furthermore, in the sample 3 of the comparative example in which the thermal plasma-treated powders of the samples 1 and 5 were mixed at 50:50 and HIPed, the particle diameter of the thermal plasma-treated powder was substantially maintained although the particle size was deformed by the HIP. Therefore, the desired structure after pressure sintering could be obtained by controlling the particle size of the thermal plasma treated powder.
【００２３】上記、それぞれの実施例のターゲット材に
ついて、平均粒径と結晶粒径の分布をエッチング等によ
り切断面組織を明らかにし粒径を測定する切断法により
測定し、ビッカース硬度計により硬さ、３点曲げ試験に
より抗折力、レーザーフラッシュ法により熱伝導率をそ
れぞれ測定した。これらの結果を表３に示す。その後、
前記ターゲット材を機械加工により直径２８０ｍｍ，厚
さ５ｍｍの円盤状ターゲットとした。With respect to the target material of each of the above examples, the distribution of the average grain size and the crystal grain size was measured by a cutting method in which the cut surface structure was clarified by etching or the like and the grain size was measured. The bending force was measured by a three-point bending test, and the thermal conductivity was measured by a laser flash method. Table 3 shows the results. afterwards,
The target material was machined into a disk-shaped target having a diameter of 280 mm and a thickness of 5 mm.
【００２４】[0024]
【表３】 [Table 3]
【００２５】比較例である試料１、２、３については、
機械加工中に割れが生じてしまい、加工困難であった。
したがってターゲットとして加工できなかった。また、
試料６，７については、熱伝導率が低下した。原因は明
確ではないが平均粒径が大きいため充分に焼結できなか
ったと推定できる。これらのターゲットを用いてスパッ
タでＲｕ薄膜を成膜した。試料６，７ではスパッタ中に
割れが生じ成膜ができなかった。For samples 1, 2, and 3 as comparative examples,
Cracking occurred during machining, making machining difficult.
Therefore, it could not be processed as a target. Also,
For samples 6 and 7, the thermal conductivity decreased. Although the cause is not clear, it can be presumed that sintering could not be performed sufficiently due to the large average particle size. A Ru thin film was formed by sputtering using these targets. In Samples 6 and 7, cracks occurred during sputtering, and a film could not be formed.
【００２６】[0026]
【発明の効果】本発明により良好な加工性とスパッタ性
を持つＲｕターゲット材となる。良好な機械加工特性に
より安定なターゲット材の製造と、工数、コストの低減
が可能となる。スパッタ中の割れなども低減でき、安定
した薄膜形成が可能となる。According to the present invention, a Ru target material having good workability and sputterability can be obtained. Good machining characteristics make it possible to produce a stable target material and reduce man-hours and costs. Cracks during sputtering can be reduced, and a stable thin film can be formed.
【図１】本発明のＲｕターゲット材の破面のミクロ組織
の一例を示す走査型電子顕微鏡写真である。FIG. 1 is a scanning electron micrograph showing an example of a microstructure of a fracture surface of a Ru target material of the present invention.
【図２】比較例（試料２）のＲｕターゲット材の破面の
ミクロ組織の一例を示す走査型電子顕微鏡写真である。FIG. 2 is a scanning electron micrograph showing an example of a microstructure of a fracture surface of a Ru target material of a comparative example (sample 2).
【図３】比較例（試料３）のＲｕターゲット材の破面の
ミクロ組織の一例を示す走査型電子顕微鏡写真である。FIG. 3 is a scanning electron micrograph showing an example of a microstructure of a fracture surface of a Ru target material of a comparative example (sample 3).
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１３年９月１３日（２００１．９．１
３）[Submission Date] September 13, 2001 (2001.9.1)
3)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Correction target item name] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２４】[0024]
【表３】 [Table 3]
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K018 AA40 BA20 BB01 BC06 EA11 KA29 4K029 BD01 CA05 DC03 DC09 5F083 AD00 FR01 GA27 JA14 JA38 PR22 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K018 AA40 BA20 BB01 BC06 EA11 KA29 4K029 BD01 CA05 DC03 DC09 5F083 AD00 FR01 GA27 JA14 JA38 PR22
Claims (6)
る平均結晶粒径８〜１００μｍであり、かつ破断面に存
在する１０〜１００μｍの粒が５０面積％以上であるこ
とを特徴とするＲｕターゲット材。1. A Ru target material having a relative density of 98% or more, an average crystal grain size in a microstructure of 8 to 100 μm, and particles of 10 to 100 μm present in a fractured surface of 50% by area or more. .
請求項１に記載のＲｕターゲット材。2. The Ru target material according to claim 1, wherein the purity is 5 N or more.
とする請求項１ないし２に記載のＲｕターゲット材。3. The Ru target material according to claim 1, wherein the hardness is 400 Hv or less.
特徴とする請求項１ないし３のいずれかに記載のＲｕタ
ーゲット材。4. The Ru target material according to claim 1, wherein the transverse rupture strength is 350 MPa or more.
ことを特徴とする請求項１ないし４のいずれかに記載の
Ｒｕターゲット材。5. The Ru target material according to claim 1, having a thermal conductivity of 120 W / m · K or more.
状化させたＲｕ粉末を加圧焼結し、焼結体のミクロ組織
における平均結晶粒径８〜１００μｍ、かつ破断面に存
在する１０〜１００μｍの粒を５０面積%以上とするこ
とを特徴とするＲｕターゲット材の製造方法。6. A powder raw material is passed through a thermal plasma, and a spheroidized Ru powder is subjected to pressure sintering. The average crystal grain size in the microstructure of the sintered body is 8 to 100 μm, and the powder is present in a fractured surface. A method for producing a Ru target material, wherein particles having a size of 100 μm to 50 μm are at least 50 area%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001078798A JP2002275625A (en) | 2001-03-19 | 2001-03-19 | Ru TARGET MATERIAL AND PRODUCTION METHOD THEREFOR |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001078798A JP2002275625A (en) | 2001-03-19 | 2001-03-19 | Ru TARGET MATERIAL AND PRODUCTION METHOD THEREFOR |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002275625A true JP2002275625A (en) | 2002-09-25 |
Family
ID=18935360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001078798A Pending JP2002275625A (en) | 2001-03-19 | 2001-03-19 | Ru TARGET MATERIAL AND PRODUCTION METHOD THEREFOR |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002275625A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005031028A1 (en) * | 2003-09-26 | 2005-04-07 | Kabushiki Kaisha Toshiba | Sputtering target and process for producing si oxide film therewith |
| JP2005336583A (en) * | 2004-05-28 | 2005-12-08 | Hitachi Metals Ltd | SINTERED Ru TARGET MATERIAL |
| JP2006138012A (en) * | 2004-10-15 | 2006-06-01 | Hitachi Metals Ltd | Method for producing low oxygen metal powder |
| WO2007097396A1 (en) * | 2006-02-22 | 2007-08-30 | Nippon Mining & Metals Co., Ltd. | Sintered sputtering target made of high-melting metals |
| CN102605332A (en) * | 2012-03-25 | 2012-07-25 | 昆明贵金属研究所 | Ru sputtering target with high purity and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001020065A (en) * | 1999-07-07 | 2001-01-23 | Hitachi Metals Ltd | Sputtering target, method for producing the same, and refractory metal powder material |
-
2001
- 2001-03-19 JP JP2001078798A patent/JP2002275625A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001020065A (en) * | 1999-07-07 | 2001-01-23 | Hitachi Metals Ltd | Sputtering target, method for producing the same, and refractory metal powder material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005031028A1 (en) * | 2003-09-26 | 2005-04-07 | Kabushiki Kaisha Toshiba | Sputtering target and process for producing si oxide film therewith |
| US7998324B2 (en) | 2003-09-26 | 2011-08-16 | Kabushiki Kaisha Toshiba | Sputtering target and process for producing si oxide film therewith |
| JP4791825B2 (en) * | 2003-09-26 | 2011-10-12 | 株式会社東芝 | Sputtering target, Si oxide film using the same, manufacturing method thereof, and display device |
| JP2005336583A (en) * | 2004-05-28 | 2005-12-08 | Hitachi Metals Ltd | SINTERED Ru TARGET MATERIAL |
| JP2006138012A (en) * | 2004-10-15 | 2006-06-01 | Hitachi Metals Ltd | Method for producing low oxygen metal powder |
| WO2007097396A1 (en) * | 2006-02-22 | 2007-08-30 | Nippon Mining & Metals Co., Ltd. | Sintered sputtering target made of high-melting metals |
| US8118984B2 (en) | 2006-02-22 | 2012-02-21 | Jx Nippon Mining & Metals Corporation | Sintered sputtering target made of refractory metals |
| CN102605332A (en) * | 2012-03-25 | 2012-07-25 | 昆明贵金属研究所 | Ru sputtering target with high purity and preparation method thereof |
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