JP2000119707A - Production of high purity ruthenium fine powder - Google Patents
Production of high purity ruthenium fine powderInfo
- Publication number
- JP2000119707A JP2000119707A JP10296301A JP29630198A JP2000119707A JP 2000119707 A JP2000119707 A JP 2000119707A JP 10296301 A JP10296301 A JP 10296301A JP 29630198 A JP29630198 A JP 29630198A JP 2000119707 A JP2000119707 A JP 2000119707A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- electron beam
- purity
- fine powder
- ground
- 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.)
- Withdrawn
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、平均粒径：１０
μｍ以下の高純度Ｒｕ微粉末の製造方法に関するもので
ある。[0001] The present invention relates to a method for producing a fine powder having an average particle size of 10
The present invention relates to a method for producing a high-purity Ru fine powder of μm or less.
【０００２】[0002]
【従来の技術】従来、高集積度の半導体メモリーのキャ
パシタの電極にはスパッタリングにより形成されたＰｔ
膜が使用されていた。しかし、Ｐｔ膜はドライエッチン
グによる加工性が悪いことおよび誘電体である（Ｂａ，
Ｓｒ）ＴｉＯ3 のＴｉとＳｉ基板のＳｉがＰｔ膜に拡散
して複合化合物を形成し、キャパシタ特性を変化させる
などの欠点がある。そのために、近年、半導体メモリー
のキャパシタ用電極にＲｕ膜を使用することが検討され
はじめている。2. Description of the Related Art Conventionally, Pt formed by sputtering is applied to the electrodes of a capacitor of a highly integrated semiconductor memory.
A membrane was used. However, the Pt film has poor workability by dry etching and is a dielectric (Ba,
There is a drawback that Ti of Sr) TiO 3 and Si of the Si substrate diffuse into the Pt film to form a composite compound and change the capacitor characteristics. Therefore, in recent years, the use of a Ru film for a capacitor electrode of a semiconductor memory has begun to be studied.
【０００３】このキャパシタ用電極のＲｕ膜は、市販の
Ｒｕ粉末をホットプレスして得られたホットプレスＲｕ
ターゲットをスパッタリングすることにより形成されて
おり、この市販のＲｕ粉末は、白金精鉱の残査からさら
にＡｇ，Ｐｔ，Ｐｄなどを取り除いたＩｒ，Ｏｓ，Ｒｕ
含有の残査をＫＯＨおよびＫＮＯ3 と共に溶融し、水を
加えて溶液を取りだし、この溶液に塩素ガスを吹き込ん
でＲｕＯ4 とし、さらに塩酸およびメチルアルコールを
添加してＲｕＯＣｌ2 とし、これを焙焼して再びＲｕＯ
4 とし、水素雰囲気中で均熱して還元することにより金
属Ｒｕを製造し、得られた金属Ｒｕを粉砕またはアトマ
イズすることにより製造している。The Ru film of the capacitor electrode is formed by hot pressing Ru obtained by hot pressing commercially available Ru powder.
This commercially available Ru powder is formed by sputtering a target, and is made of Ir, Os, and Ru obtained by further removing Ag, Pt, Pd, and the like from the residue of platinum concentrate.
The contained residue was melted together with KOH and KNO 3 , water was added to take out the solution, chlorine gas was blown into this solution to make RuO 4 , hydrochloric acid and methyl alcohol were added to make RuOCl 2, and this was roasted. And then RuO again
The metal Ru is manufactured by reducing the temperature by soaking in a hydrogen atmosphere, and the obtained metal Ru is manufactured by grinding or atomizing.
【０００４】[0004]
【発明が解決しようとする課題】このようにして得られ
る市販のＲｕ粉末は、アルカリ金属、アルカリ土類金
属、Ａｌ，Ｔｉ，Ｓｉなどの不純物が多く含まれてお
り、その純度は低く、３Ｎ〜４Ｎ（９９．９〜９９．９
９％）が限度であって、キャパシタ用電極のＲｕ膜形成
用ターゲットの原料粉末としては少なくとも５Ｎ（９
９．９９９％）の高純度Ｒｕ粉末が求められている。ま
た市販のＲｕ粉末は、平均粒径が２８μｍ以上であって
粒度が粗いためにホットプレス温度を１４００℃以上に
上げないと所定の焼結密度にすることができず、ホット
プレス温度を１４００℃以上に上げるとホットプレスＲ
ｕターゲットと治具とが反応してＲｕターゲットの純度
が一層低下する。かかる治具との反応を起こすことなく
高純度のホットプレスＲｕターゲットを製造するために
は原料粉末として一層微細な粒度のＲｕ粉末が求められ
ていた。この発明は、従来よりも高純度でかつ微細な粒
度のＲｕ粉末を提供することを目的とするものである。The commercially available Ru powder thus obtained contains a large amount of impurities such as alkali metals, alkaline earth metals, Al, Ti, and Si, and its purity is low and 3N. ~ 4N (99.9-99.9
9%), and the raw material powder of the target for forming the Ru film of the capacitor electrode is at least 5N (9%).
(9,999%). Further, since commercially available Ru powder has an average particle size of 28 μm or more and a coarse particle size, a predetermined sintering density cannot be achieved unless the hot press temperature is raised to 1400 ° C. or more. Hot press R
The u target reacts with the jig to further reduce the purity of the Ru target. In order to produce a high-purity hot press Ru target without causing a reaction with such a jig, a Ru powder having a finer particle size has been required as a raw material powder. An object of the present invention is to provide a Ru powder having a higher purity and a finer particle size than before.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、従来より
も一層高純度で微細なＲｕ粉末を得るべく研究を行った
結果、（ａ）市販のＲｕ粉末をプレスして得られたプレ
ス成形体を電子ビーム溶解すると、純度を５Ｎまで向上
させることができる、（ｂ）プレス成形体を電子ビーム
溶解して得られた電子ビーム溶解品を砥石を用いて研削
すると、従来よりも微細な平均粒径：１０μｍ以下のＲ
ｕ微粉末が得られる。（ｃ）砥石研削して得られたＲｕ
粉末には砥粒が含まれているところから、砥粒を分離除
去し、さらに化学洗浄処理する必要がある、などの知見
を得たのである。The present inventors have conducted research to obtain finer and finer Ru powder with higher purity than before, and as a result, (a) a press obtained by pressing a commercially available Ru powder. The purity can be improved to 5N by electron beam melting the molded product. (B) When the electron beam melted product obtained by electron beam melting the press molded product is ground using a grindstone, finer than before can be obtained. Average particle size: R of 10 μm or less
u fine powder is obtained. (C) Ru obtained by grinding the grinding wheel
From the fact that the powder contains abrasive grains, it has been found that it is necessary to separate and remove the abrasive grains and further perform a chemical cleaning treatment.
【０００６】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）市販のＲｕ粉末をプレスして得
られたプレス成形体を電子ビーム溶解して電子ビーム溶
解品を作製し、得られた電子ビーム溶解品を砥石を用い
て研削し、研削により得られたＲｕの研削粉末から砥粒
を分離除去し、さらに化学洗浄処理する高純度Ｒｕ微粉
末の製造方法、に特徴を有するものである。The present invention has been made based on such knowledge, and (1) an electron beam melted product is produced by pressing a commercially available Ru powder to obtain a pressed compact obtained by electron beam melting. The method for producing a high-purity Ru fine powder in which the obtained electron beam melted product is ground using a grindstone, abrasive grains are separated and removed from the Ru ground powder obtained by the grinding, and further subjected to chemical cleaning treatment. Things.
【０００７】電子ビーム溶解品の表面は溶解組織を有し
ており、硬さが不足する。したがって、Ｒｕの電子ビー
ム溶解品をそのまま砥石を用いて研削すると、最初の研
削時にチップ状の研削粉末が生成して平均粒径：１０μ
ｍ以下の研削微粉末とならないことがある。そのため、
Ｒｕの電子ビーム溶解品を加工硬化させたのち砥石を用
いて研削することが好ましい。Ｒｕ金属は極めて加工硬
化しやすい金属であるところから、Ｒｕの電子ビーム溶
解品の表面の薄皮を研削するだけで加工硬化する。[0007] The surface of the electron beam melted product has a melted structure and is insufficient in hardness. Therefore, when the Ru electron beam melted product is ground as it is using a grindstone, a chip-shaped ground powder is generated at the first grinding, and the average particle size is 10 μm.
m or less may not be obtained. for that reason,
After work hardening the Ru electron beam melted product, it is preferable to grind it with a grindstone. Since Ru metal is a metal that is extremely easy to work harden, work hardening is performed only by grinding a thin skin on the surface of a Ru electron beam melted product.
【０００８】Ｒｕの電子ビーム溶解品を薄皮研削して得
られた研削初期の研削粉末にはチップ状の研削粉末が含
まれている恐れがあるところからこれを除去し、薄皮研
削終了後の電子ビーム溶解品を研削して得られたＲｕの
研削粉末を採取し、これから砥粒を分離除去し、さらに
化学洗浄処理することが好ましい。[0008] The initial grinding powder obtained by thin-grinding the electron beam-melted product of Ru is removed from the area where chip-like grinding powder may be contained, which is removed. It is preferable to collect Ru ground powder obtained by grinding the beam melted product, separate and remove abrasive grains therefrom, and further perform a chemical cleaning treatment.
【０００９】なお、研削前に電子ビーム溶解品にショッ
トピーニング、鍛造または圧延などの塑性加工を施す
と、薄皮を含むＲｕの電子ビーム溶解品全体が加工硬化
し、この加工硬化した電子ビーム溶解品を研削して得ら
れた研削粉末にはチップ状の研削粉末を含むことがなく
なるところから、一層効率良く高純度のＲｕ微粉末を製
造することができる。If the electron beam melted product is subjected to plastic working such as shot peening, forging or rolling before grinding, the entire Ru electron beam melted product including the thin skin is work hardened, and the work hardened electron beam melted product is processed. Since the ground powder obtained by grinding the powder no longer contains chip-shaped ground powder, it is possible to more efficiently produce high-purity Ru fine powder.
【００１０】したがって、この発明は、（２）市販のＲ
ｕ粉末をプレスして得られたプレス成形体を電子ビーム
溶解して電子ビーム溶解品を作製し、前記電子ビーム溶
解品を加工硬化させたのち砥石を用いて研削し、研削し
て得られたＲｕの研削粉末から砥粒を分離除去し、さら
に化学洗浄処理する高純度Ｒｕ微粉末の製造方法、に特
徴を有するものである。Therefore, the present invention relates to (2) a commercially available R
The pressed compact obtained by pressing the u powder was subjected to electron beam melting to produce an electron beam melted product, and the electron beam melted product was worked and hardened, then ground using a grindstone, and then ground. The present invention is characterized in that a method for producing a high-purity Ru fine powder in which abrasive grains are separated and removed from the Ru ground powder and further subjected to a chemical cleaning treatment.
【００１１】この発明の高純度Ｒｕ微粉末の製造方法で
用いる砥石は、アルミナ、シリカ、ジルコニヤ、マグネ
タイトなどの酸化物系砥石、またはＷＣ、ＳｉＣ、Ｔｉ
Ｃなどの炭化物系砥石を用いることができるが、最も軽
量なアルミナ砥石を用いることが研削粉末からＲｕ粉末
と砥粒を最も分離しやくなるので最も好ましい。The grindstone used in the method for producing high-purity Ru fine powder of the present invention is an oxide grindstone such as alumina, silica, zirconia or magnetite, or WC, SiC or Ti.
A carbide-based grindstone such as C can be used, but the use of the lightest alumina grindstone is most preferable because the Ru powder and the abrasive grains are most easily separated from the grinding powder.
【００１２】前記（１）または（２）製造方法で作製し
た高純度Ｒｕ微粉末の平均粒径は１０μｍ以下の微細な
Ｒｕ粉末が得られる。したがって、この発明は、前記
（１）または（２）製造方法で作製した平均粒径：１０
μｍ以下の高純度Ｒｕ微粉末、に特徴を有するものであ
る。A fine Ru powder having an average particle diameter of 10 μm or less can be obtained from the high-purity Ru fine powder produced by the above-mentioned method (1) or (2). Therefore, the present invention provides a method for producing a composite material according to the above (1) or (2), wherein the average particle size is 10
It is characterized by a high-purity Ru fine powder of not more than μm.
【００１３】[0013]
【発明の実施の形態】実施例 市販のＲｕ粉末を用意し、このＲｕ粉末の成分組成を分
析したところ、純度が９９．９１２７３％であり、粒度
を測定したところ、平均粒径：３８μｍであった。この
市販のＲｕ粉末をプレスすることによりプレス成形体を
作製し、このプレス成形体を１×１０-5Ｔｏｒｒの高真
空の電子ビーム溶解炉で溶解して直径：３００ｍｍ×厚
さ：１０ｍｍの寸法を有する電子ビーム溶解品を作製し
た。得られた電子ビーム溶解品の純度は９９．９９９９
２％であった。EXAMPLES A commercially available Ru powder was prepared, and the composition of the Ru powder was analyzed. The purity was 99.9273%, and the particle size was measured. The average particle size was 38 μm. Was. A pressed compact is prepared by pressing this commercially available Ru powder, and the pressed compact is melted in a high vacuum electron beam melting furnace of 1 × 10 −5 Torr and has a diameter of 300 mm × thickness of 10 mm. Was prepared. The purity of the obtained electron beam melted product is 99.99999.
2%.
【００１４】この高純度電子ビーム溶解品を＃１８０の
アルミナ砥石で電子ビーム溶解品の表面の皮を全体にわ
たって研削し、この時研削して得られた研削粉末を取り
除き、次に、前記皮研削を行った電子ビーム溶解品を前
記アルミナ砥石で研削し、得られた研削粉末を磁性流体
を用いた比重差分離によりＲｕ粉末と砥粒とを分離し、
分離して得られたＲｕ粉末をＮａＯＨ溶液中で煮沸後水
洗し、さらにＨＣｌ溶液中で煮沸後乾燥することにより
本発明Ｒｕ粉末を作製した。この様にして得られた本発
明Ｒｕ粉末の粒度を測定したところ、平均粒径：３μｍ
であった。この本発明Ｒｕ粉末をホットプレスすること
によりＲｕターゲットを作製したところ、１３６０℃で
所定の密度にホットプレスすることができ、純度：９
９．９９９８６％の高純度Ｒｕターゲットが得られた。The high purity electron beam melted product is ground over the entire surface of the electron beam melted product with a # 180 alumina grindstone. At this time, the ground powder obtained by the grinding is removed. The obtained electron beam melted product is ground with the alumina grindstone, and the obtained ground powder is separated into Ru powder and abrasive grains by specific gravity difference separation using a magnetic fluid,
The Ru powder obtained by separation was boiled in a NaOH solution, washed with water, further boiled in an HCl solution, and dried to prepare a Ru powder of the present invention. When the particle size of the Ru powder of the present invention thus obtained was measured, the average particle size was 3 μm.
Met. When a Ru target was produced by hot-pressing the Ru powder of the present invention, the Ru target could be hot-pressed to a predetermined density at 1360 ° C. and the purity: 9
A high purity Ru target of 9.99986% was obtained.
【００１５】従来例 実施例で用意した市販のＲｕ粉末をそのままホットプレ
スすることによりＲｕターゲットを作製したが、所定の
密度にするためにはホットプレス温度を１４５０℃以上
でホットプレスしなければならず、かかる高温でホット
プレスすることにより得られたＲｕターゲットは治具と
反応して純度が低下し、市販のＲｕ粉末の純度よりも低
い純度：９９．８９９８６％のＲｕターゲットが得られ
た。Conventional Example A commercially available Ru powder prepared in Example was directly hot-pressed to produce a Ru target. However, in order to obtain a predetermined density, hot pressing must be performed at a hot pressing temperature of 1450 ° C. or more. Instead, the Ru target obtained by hot pressing at such a high temperature reacted with the jig to reduce the purity, and a Ru target having a purity: 99.89986% lower than the purity of a commercially available Ru powder was obtained.
【００１６】[0016]
【発明の効果】上述のように、この発明は、従来よりも
高純度で微細な粒度のＲｕ微粉末を提供することができ
るので、従来よりも低い温度でホットプレスすることに
より従来よりも高純度のＲｕターゲットを提供すること
ができ、特に半導体産業の発展に大いに貢献しうるもの
である。As described above, the present invention can provide a Ru fine powder having a higher purity and a finer particle size than the conventional one. It can provide a pure Ru target, and can greatly contribute to the development of the semiconductor industry in particular.
Claims (3)
レス成形体を電子ビーム溶解して電子ビーム溶解品を作
製し、得られた電子ビーム溶解品を砥石を用いて研削
し、研削により得られたＲｕの研削粉末から砥粒を分離
除去し、さらに化学洗浄処理することを特徴とする高純
度Ｒｕ微粉末の製造方法。1. A pressed compact obtained by pressing a commercially available Ru powder is melted with an electron beam to produce an electron beam melted product, and the obtained electron beam melted product is ground by using a grindstone, and then ground. A method for producing a high-purity Ru fine powder, comprising separating and removing abrasive grains from the obtained Ru ground powder and further subjecting the resultant to a chemical cleaning treatment.
のち砥石を用いて研削することを特徴とする請求項１記
載の高純度Ｒｕ微粉末の製造方法。2. The method for producing a high-purity Ru fine powder according to claim 1, wherein the electron beam melted product is hardened and then ground using a grindstone.
平均粒径：１０μｍ以下の高純度Ｒｕ微粉末。3. A high-purity Ru fine powder having an average particle size of 10 μm or less produced by the method according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10296301A JP2000119707A (en) | 1998-10-19 | 1998-10-19 | Production of high purity ruthenium fine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10296301A JP2000119707A (en) | 1998-10-19 | 1998-10-19 | Production of high purity ruthenium fine powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000119707A true JP2000119707A (en) | 2000-04-25 |
Family
ID=17831788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10296301A Withdrawn JP2000119707A (en) | 1998-10-19 | 1998-10-19 | Production of high purity ruthenium fine powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000119707A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014194085A (en) * | 2007-12-19 | 2014-10-09 | Quantam Global Technologies Llc | Method for cleaning process kit and chamber, and method for recovering ruthenium |
| CN110893467A (en) * | 2019-12-24 | 2020-03-20 | 湖南欧泰稀有金属有限公司 | Grinding tank and preparation method of high-purity superfine ruthenium powder |
| JP2021520453A (en) * | 2018-04-04 | 2021-08-19 | メタル パウダー ワークス， エルエルシーＭｅｔａｌ Ｐｏｗｄｅｒ Ｗｏｒｋｓ， Ｌｌｃ | Systems and methods for powder production |
-
1998
- 1998-10-19 JP JP10296301A patent/JP2000119707A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014194085A (en) * | 2007-12-19 | 2014-10-09 | Quantam Global Technologies Llc | Method for cleaning process kit and chamber, and method for recovering ruthenium |
| JP2021520453A (en) * | 2018-04-04 | 2021-08-19 | メタル パウダー ワークス， エルエルシーＭｅｔａｌ Ｐｏｗｄｅｒ Ｗｏｒｋｓ， Ｌｌｃ | Systems and methods for powder production |
| JP7335321B2 (en) | 2018-04-04 | 2023-08-29 | メタル パウダー ワークス， エルエルシー | Systems and methods for powder manufacturing |
| CN110893467A (en) * | 2019-12-24 | 2020-03-20 | 湖南欧泰稀有金属有限公司 | Grinding tank and preparation method of high-purity superfine ruthenium powder |
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