JPH04176887A - Apparatus for producing high-purity y - Google Patents
Apparatus for producing high-purity yInfo
- Publication number
- JPH04176887A JPH04176887A JP30380090A JP30380090A JPH04176887A JP H04176887 A JPH04176887 A JP H04176887A JP 30380090 A JP30380090 A JP 30380090A JP 30380090 A JP30380090 A JP 30380090A JP H04176887 A JPH04176887 A JP H04176887A
- Authority
- JP
- Japan
- Prior art keywords
- electrodeposited
- purity
- bath
- crucible
- electric oven
- 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
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims description 24
- 238000003860 storage Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 230000002285 radioactive effect Effects 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 241000555268 Dendroides Species 0.000 abstract 1
- 229910009523 YCl3 Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 abstract 1
- 238000000034 method Methods 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- -1 Na and carbon Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910013470 LiC1 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
且豆皇垣豆分■
本発明は、高純度金属Ｙの製造方法に関するものであり
、特には半導体デバイス用のＹ酸化物（Ｙ。[Detailed Description of the Invention] The present invention relates to a method for producing high-purity metal Y, particularly Y oxide (Y) for semiconductor devices.
０３）の形成に用いる高純度Ｙの製造方法に関する。The present invention relates to a method for producing high-purity Y used for forming 03).
本発明の金属Ｙは、半導体デバイスに有害な作用を与え
る不純物か極微量まで低減されており、半導体デバイス
におけるキャパシタとして用いられるＹ２Ｏ、の形成に
非常に好適である。The metal Y of the present invention has impurities harmful to semiconductor devices reduced to a trace amount, and is very suitable for forming Y2O used as a capacitor in semiconductor devices.
盗」官ＬΔ
Ｙ金属の製錬方法としては、金属熱還元方法と溶融塩電
解法とか採用されている。Metal thermal reduction method and molten salt electrolysis method are adopted as methods for smelting metals.
前者の金属熱還元法には、フッ化物または塩化物浴をア
ルカリまたはアルカリ土類金属で還元するハロゲン化物
法がある。しかし、反応容器のレトルトか還元生成金属
に侵食されるため、生成金属か汚染されたり或はその材
料の寿命等か極端に短くなり、コストが高くなる等の欠
点があった。そのため、高畦−
゛純度のＹを得ることが困難であった。The former metal thermal reduction method includes a halide method in which a fluoride or chloride bath is reduced with an alkali or alkaline earth metal. However, since the retort of the reaction vessel is corroded by the metal produced by reduction, there are drawbacks such as contamination of the produced metal, extremely shortened life of the material, and increased cost. Therefore, it has been difficult to obtain Y with high purity.
一方、後者の溶融塩電解法においては、−回の電解が終
了した後、電析したＹを溶融塩から引き上げる。その後
、−旦電解炉を冷却してから電解蓋を取外し、大気に触
れさせてカソード棒から電析したＹを脱着する。さらに
、その塩の付着した電析Ｙを真空蒸留していた。このよ
うに、電析したＹの後処理において、−担外気に触れる
と付着した塩が吸湿してしまい、脱塩処理がうまく行か
ないことが多く、残留した浴に含有されている不純物の
影響を受けてしまう。さらにその後のＥＢ溶解において
もスプラッシュが多くなり、歩留も悪かった。また、電
析したＹを取り出すためには溶融塩を一担冷却せねばな
らすバッチ式となり、連続操業ができなかった。On the other hand, in the latter molten salt electrolysis method, the electrodeposited Y is pulled up from the molten salt after -times of electrolysis are completed. Thereafter, the electrolytic furnace is cooled down, and then the electrolytic lid is removed, and the electrodeposited Y is desorbed from the cathode rod by exposing it to the atmosphere. Furthermore, the electrodeposited Y with the salt attached was vacuum distilled. In this way, in the post-treatment of electrodeposited Y, the attached salt absorbs moisture when exposed to the outside air, and the desalting treatment often fails, and the influence of impurities contained in the remaining bath. I end up receiving it. Furthermore, there was a lot of splash in the subsequent EB melting, and the yield was also poor. Furthermore, in order to take out the electrodeposited Y, the molten salt had to be cooled, making it a batch process, which made continuous operation impossible.
そこで、本発明者等が鋭意検討した結果、以下の発明が
なされた。Therefore, as a result of intensive study by the present inventors, the following invention was made.
五里り里疾
溶融塩電解方法により、高純度Ｙを製造する方法におい
て、電析したＹを電解装置の上に設けた電析Ｙ収納装置
に引き上げ、そのまま電析Ｙ収納装置を別の電気炉に移
して、前記電析Ｙ収納装置を含む蒸留装置を真空系に接
続して真空蒸留を行うことを特徴とする高純度Ｙの製造
方法
口の目体的を日
本発明の対象となる粗Ｙは、重金属特にＦｅか１５Ｃ）
−１０００ｐｐｍ、Ｃｒが１１−１Ｏｐｐ、Ｎ］が１〜
１０ ｐ ｐ ｍ 、 Ｃｕが１０〜１０１００ｐ１）
放射性元素は、Ｕが１Ｏ−１００ｐｐｂ、Ｔｈが１０〜
ｌ０００ｐｐｂ含有されている。これら重金属及び放射
性金属の除去には、溶融塩電解精製を実施しなければな
らない。In a method for producing high-purity Y using a molten salt electrolysis method, the deposited Y is pulled up into an electrolytic Y storage device installed on top of an electrolytic device, and the electrodeposited Y storage device is directly transferred to another electrolytic device. A method for producing high-purity Y, which is characterized in that the electrolytic Y is transferred to a furnace, and a distillation apparatus including the electrodeposition Y storage device is connected to a vacuum system to perform vacuum distillation. Y is a heavy metal, especially Fe or 15C)
-1000ppm, Cr is 11-1Opp, N] is 1~
10 p p m, Cu is 10-10100 p1)
The radioactive elements include 1O-100ppb of U and 10~10% of Th.
Contains 1000 ppb. To remove these heavy metals and radioactive metals, molten salt electrolytic refining must be performed.
Ｙ溶融塩電解精製操業に用いられる溶融塩は、安定で、
融点が低くそして導電率の大きな塩化物の混合塩もしく
は塩が単一塩である。例えばＫＣｌ−Ｎａｃｌ、ＬｉＣ
１−ＫＣｌ、ＬｊＣｌ等を溶融塩として使用し、容器に
クラファイトルツボを使用するが、電解装置の上部に接
するような高さにする。クラファイトルツボ及び塩は、
事前に十分真空乾燥脱水し、水分等の除去を行なう。塩
か、溶融した後２Ｎ〜３Ｎの粗Ｙメタルあるいは、より
高純度のものを得たい場合は４Ｎ〜５Ｎのものを投入す
る。さらに、Ａｒカス等の不活性カスと共にＹＣ］、あ
るいはＹＦ、を透明石英管を通して、溶融塩中に吹き込
む。これは、ＹＣ１，等の溶融塩中への分散を良くする
ためであり、かつ溶融塩の脱水もかねている。The molten salt used in Y molten salt electrolytic refining operations is stable,
Mixed salts or salts of chlorides with low melting points and high electrical conductivity are single salts. For example, KCl-Nacl, LiC
1-KCl, LjCl, etc. are used as the molten salt, and a crucible crucible is used as the container, but the height is set so that it touches the top of the electrolyzer. The cruciferous crucible and salt are
Thoroughly vacuum dry and dehydrate in advance to remove moisture, etc. Salt, 2N to 3N crude Y metal after melting, or 4N to 5N if you want to obtain a higher purity product. Further, YC] or YF is blown into the molten salt through a transparent quartz tube together with inert scum such as Ar scum. This is to improve dispersion of YC1, etc. into the molten salt, and also to dehydrate the molten salt.
カソードとしての電極は、Ｎ ｉ 、 Ｗ、 Ｍ ｏ等
である。The electrode as a cathode is Ni, W, Mo, etc.
電解を終了した後、カソードに電着したＹを上部の電析
Ｙ収納装置まで引き上げ、冷却することなく、電析Ｙ収
納装置ごと別の電気炉まで移動する。その後真空系統に
接続し真空蒸留を行なう。真空蒸留の温度は、８０ｏ〜
］２００′Ｃが好マシイ。８０００Ｃ以下では、脱塩処
理か難しく塩が残留してしまい、ＥＢ溶解時のスプラッ
シュの原因となり歩留の低下を招き、好ましくない。１
２００℃以上であると、電気炉の損傷を伴い好ましくな
い。真空度は、１０−’ ｔ ｏ ｒ ｒ以下が好まし
い。これ以上の真空度では、Ｙか酸化してしまい、好ま
しくない。After the electrolysis is finished, the Y electrodeposited on the cathode is pulled up to the upper electrodeposited Y storage device, and the entire electrodeposited Y storage device is moved to another electric furnace without cooling. After that, it is connected to a vacuum system and vacuum distillation is performed. The temperature of vacuum distillation is 80o ~
] 200'C is better. If the temperature is below 8000C, desalting is difficult and salt remains, which causes splash during EB dissolution, leading to a decrease in yield, which is not preferable. 1
If the temperature is 200° C. or higher, the electric furnace may be damaged, which is not preferable. The degree of vacuum is preferably 10-'torr or less. If the degree of vacuum is higher than this, Y will oxidize, which is not preferable.
移動後の電解装置は、直ちにもう一つの電析Ｙ収納装置
とカソード棒を取り付け、前記と同様の電解操業をする
ことができる。After the electrolysis device is moved, another electrodeposition Y storage device and a cathode rod can be immediately attached thereto, and the electrolysis operation can be performed in the same manner as described above.
真空蒸留後、冷却しカソードから電析Ｙを脱着する。After vacuum distillation, it is cooled and the electrodeposited Y is desorbed from the cathode.
より好ましくはＥＢ溶解処理を行ない、Ｎａ、に等のア
ルカリ金属や蒸気圧の高いＭｇ、Ｃａ等の少ない高純度
Ｙを得る。More preferably, EB dissolution treatment is performed to obtain high-purity Y with less alkali metals such as Na and carbon, as well as Mg and Ca having high vapor pressure.
［実施例］
第１図及び第２図に示す溶融塩電解装置を用いて、粗Ｙ
を溶融塩電解精製する実施例を示す。[Example] Using the molten salt electrolyzer shown in Figs. 1 and 2, crude Y
An example is shown in which molten salt electrolytic refining is performed.
Ｎ］製ルツボ３にグラファイトルツボ４を挿入し、その
中に粉状無水塩化リチウム及び塩化カリウムを各々９，
１１ｋｇ入れ、そしてこれを電解槽容器２に入れ、電気
炉４にセットする。A graphite crucible 4 is inserted into a crucible 3 made of N], and powdered anhydrous lithium chloride and potassium chloride are each added at 9,
11 kg was placed in the electrolytic cell container 2 and set in the electric furnace 4.
前操作としてＬｉＣ１，ＫＣｌを真空ポンプで内部を出
ロアより排気しながら約５００ ’Ｃまて加熱した。さ
らに、Ａｒカスを入口６より導入し大気圧以上にする。As a pre-operation, LiC1 and KCl were heated to about 500'C while evacuating the inside from the output lower with a vacuum pump. Furthermore, Ar scum is introduced from the inlet 6 to make the pressure higher than atmospheric pressure.
Ａｒ雰囲気下で表１に示すような粗Ｙメタル１１を約２
ｋｇ挿入し、さらに、Ａｒカスと同時にＹＣ１，を約２
０００ｇ浴中に導入する。この時の電解浴５中のＹ濃度
は約４％であった。導入終了後、浴温を７００′Ｃとし
、さらにＷ電極棒を入れる。初期カソード電流密度を１
．ＯＡ／ｃｍ’とし電解を実施した。約２０ｈｒ通電し
たところで、第一回の電解操作を停止した。電析したＹ
を上部の筒１３の中に引き上げ、上下１４．］、５二つ
のバルブを閉める。筒１３をカソード棒とともに別の電
気炉に移動する。ここで真空系統１６に接続し、真空蒸
留を１０００℃Ｘ２ｈｒ行なう。冷却後取りだした処理
後のＹは、約４００ｇであり、樹枝状結晶であった。Approximately 2 pieces of coarse Y metal 11 as shown in Table 1 was heated under an Ar atmosphere.
Insert about 2 kg of YC1, and then add about 2 kg of YC1 at the same time as
000g into the bath. At this time, the Y concentration in the electrolytic bath 5 was about 4%. After the introduction, the bath temperature is set to 700'C and a W electrode is added. The initial cathode current density is 1
．． Electrolysis was carried out at OA/cm'. After about 20 hours of electricity, the first electrolysis operation was stopped. Electrodeposited Y
into the upper tube 13, and lift it up and down 14. ], 5 Close the two valves. The tube 13 is moved together with the cathode rod to another electric furnace. Here, it is connected to the vacuum system 16 and vacuum distillation is performed at 1000° C. for 2 hours. After cooling, the treated Y was about 400 g and was in the form of dendrites.
その結果得た処理後のＹの純度を表］に示す。The resulting purity of Y after treatment is shown in Table].
表 １
（ｐｐｍ）
１１げ邦弧果
（１）重金属、放射性元素、酸素の少ない高純度のＹが
得られ、半導体デバイスの発展に寄与する。Table 1 (ppm) 11 Results (1) High purity Y with less heavy metals, radioactive elements, and oxygen can be obtained, contributing to the development of semiconductor devices.
（２）溶融塩電解が連続的に操業可能となり、また、真
空蒸留工程も電析Ｙが大気にふれることなく効率的に行
なえる。(2) Molten salt electrolysis can be operated continuously, and the vacuum distillation process can be performed efficiently without exposing the deposited Y to the atmosphere.
第１図は、本発明の高純度Ｙを得るための製造装置の概
略図の一態様でおる。
第２図は、本発明で用いる真空蒸留炉の一態様である。
１・電気炉、２・・・ステンレス製電解槽容器、３・・
Ｎｉ製ルツボ、４ グラファイトルツホ、５・電解浴、
６・−・Ａｒ導入口、７・・排気口、８・カソード電極
棒、１１−Ｙメタル、１３ 電析Ｙ収納装置、１４・上
バルブ１５ 下バルブ、１６・・真空系FIG. 1 is a schematic diagram of one embodiment of a manufacturing apparatus for obtaining high-purity Y of the present invention. FIG. 2 shows one embodiment of the vacuum distillation furnace used in the present invention. 1. Electric furnace, 2.. Stainless steel electrolytic tank container, 3..
Ni crucible, 4 graphite crucible, 5 electrolytic bath,
6--Ar inlet, 7-exhaust port, 8-cathode electrode, 11-Y metal, 13 electrodeposition Y storage device, 14-upper valve 15 lower valve, 16-vacuum system
Claims (1)
て、電析したＹを電解装置の上に設けた電析Ｙ収納装置
に引き上げ、そのまま電析Ｙ収納装置を別の電気炉に移
して、前記電析Ｙ収納装置を含む蒸留装置を真空系に接
続して真空蒸留を行なうことを特徴とする高純度Ｙの製
造方法In a method for producing high-purity Y by a molten salt electrolysis method, the electrodeposited Y is pulled up into a deposited Y storage device provided on an electrolysis device, and the deposited Y storage device is directly transferred to another electric furnace. A method for producing high-purity Y, characterized in that vacuum distillation is performed by connecting a distillation apparatus including the electrodeposited Y storage device to a vacuum system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30380090A JPH04176887A (en) | 1990-11-13 | 1990-11-13 | Apparatus for producing high-purity y |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30380090A JPH04176887A (en) | 1990-11-13 | 1990-11-13 | Apparatus for producing high-purity y |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04176887A true JPH04176887A (en) | 1992-06-24 |
Family
ID=17925454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30380090A Pending JPH04176887A (en) | 1990-11-13 | 1990-11-13 | Apparatus for producing high-purity y |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04176887A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1739196A1 (en) * | 2005-06-29 | 2007-01-03 | Shin-Etsu Chemical Co., Ltd. | Rare earth metal member of high surface purity and making method |
| WO2013001661A1 (en) * | 2011-06-30 | 2013-01-03 | Jx日鉱日石金属株式会社 | High-purity erbium, sputtering target comprising high-purity erbium, metal gate film having high-purity erbium as main component thereof, and production method for high-purity erbium |
| WO2013005349A1 (en) | 2011-07-06 | 2013-01-10 | Jx日鉱日石金属株式会社 | High-purity yttrium, process for producing high-purity yttrium, high-purity yttrium sputtering target, metal gate film deposited with high-purity yttrium sputtering target, and semiconductor element and device equipped with said metal gate film |
| CN103194626A (en) * | 2012-01-06 | 2013-07-10 | 株式会社日立制作所 | Separating and recycling method of rare earth elements |
-
1990
- 1990-11-13 JP JP30380090A patent/JPH04176887A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1739196A1 (en) * | 2005-06-29 | 2007-01-03 | Shin-Etsu Chemical Co., Ltd. | Rare earth metal member of high surface purity and making method |
| US7674427B2 (en) | 2005-06-29 | 2010-03-09 | Shin-Etsu Chemical Co., Ltd. | Rare earth metal member and making method |
| WO2013001661A1 (en) * | 2011-06-30 | 2013-01-03 | Jx日鉱日石金属株式会社 | High-purity erbium, sputtering target comprising high-purity erbium, metal gate film having high-purity erbium as main component thereof, and production method for high-purity erbium |
| US20180087136A1 (en) * | 2011-06-30 | 2018-03-29 | Jx Nippon Mining & Metals Corporation | Method of producing high-purity erbium |
| WO2013005349A1 (en) | 2011-07-06 | 2013-01-10 | Jx日鉱日石金属株式会社 | High-purity yttrium, process for producing high-purity yttrium, high-purity yttrium sputtering target, metal gate film deposited with high-purity yttrium sputtering target, and semiconductor element and device equipped with said metal gate film |
| KR20140012190A (en) | 2011-07-06 | 2014-01-29 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | High-purity yttrium, process for producing high-purity yttrium, high-purity yttrium sputtering target, metal gate film deposited with high-purity yttrium sputtering target, and semiconductor element and device equipped with said metal gate film |
| JPWO2013005349A1 (en) * | 2011-07-06 | 2015-02-23 | Jx日鉱日石金属株式会社 | High purity yttrium, method for producing high purity yttrium, high purity yttrium sputtering target, metal gate film formed using high purity yttrium sputtering target, and semiconductor device and device including the metal gate film |
| US10041155B2 (en) | 2011-07-06 | 2018-08-07 | Jx Nippon Mining & Metals Corporation | High-purity yttrium, process of producing high-purity yttrium, high-purity yttrium sputtering target, metal gate film deposited with high-purity yttrium sputtering target, and semiconductor element and device equipped with the metal gate film |
| CN103194626A (en) * | 2012-01-06 | 2013-07-10 | 株式会社日立制作所 | Separating and recycling method of rare earth elements |
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