JPS62294179A - Production of high-purity metallic body - Google Patents
Production of high-purity metallic bodyInfo
- Publication number
- JPS62294179A JPS62294179A JP13748486A JP13748486A JPS62294179A JP S62294179 A JPS62294179 A JP S62294179A JP 13748486 A JP13748486 A JP 13748486A JP 13748486 A JP13748486 A JP 13748486A JP S62294179 A JPS62294179 A JP S62294179A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- purity
- sheet
- sponge
- substrate
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 230000006698 induction Effects 0.000 claims abstract description 23
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000010894 electron beam technology Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 150000004820 halides Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 abstract description 15
- 238000000151 deposition Methods 0.000 abstract description 6
- 229910010386 TiI4 Inorganic materials 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000004544 sputter deposition Methods 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 85
- 239000010936 titanium Substances 0.000 description 82
- 229910052719 titanium Inorganic materials 0.000 description 77
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 24
- 239000011630 iodine Substances 0.000 description 22
- 229910052740 iodine Inorganic materials 0.000 description 22
- 239000002994 raw material Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101100204059 Caenorhabditis elegans trap-2 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- -1 Inconel Chemical class 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Landscapes
- Chemical Vapour Deposition (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
［発明の目的］
（産業上の利用分野）
本発明は、高純度金属体の製造方法に関し、特にスパッ
タリングターゲット等に適した高純度金属体の製造方法
に係わる。[Detailed Description of the Invention] 3. Detailed Description of the Invention [Object of the Invention] (Industrial Application Field) The present invention relates to a method for manufacturing a high-purity metal body, and particularly relates to a high-purity metal body suitable for sputtering targets, etc. Relates to the manufacturing method.
（従来の技術）
現在、大規模集積回路（ＬＳＩ）の配線、電極用金属に
はアルミニウムが用いられている。しかしながら、今後
さらに高集積化が進むに伴って、構造が微細化し、アル
ミニウム配線中を流れる電流密度は更に大きくなり、神
々の問題を生じる可能性がある。例えば、アルミニウム
原子が電子の運動方向に運ばれるエレクトロマイグレー
ションにより、それが堆積される場所ではアルミニウム
の***が起ったりする。また、その反対側のアルミニウ
ムが欠乏する場所では空孔が発生する。このような欠陥
は、池の配線との短絡や配線抵抗の増大による断線の原
因となる。したがって、今後、高集積化の進行に対応し
てモリブデン、タングステン等の高融点金属又はチタン
の使用が検討されている。特に、チタンはｆｉｌ ！ａ
２的１生質に侵れ、カ０工性も良好であり、しかも耐食
性、ｉ’ｊ１熱性も優れ、エレクトロマイグレーション
も起り難いという特性を有する。このため、高集積化に
よる配線の細線化に充分対応でき、将来の大規模集積回
路用金属材料として有望視されている。(Prior Art) Aluminum is currently used as metal for wiring and electrodes of large-scale integrated circuits (LSI). However, as the degree of integration increases in the future, the structure will become finer and the current density flowing through the aluminum wiring will become even greater, potentially causing problems. For example, electromigration, in which aluminum atoms are transported in the direction of electron movement, can cause aluminum bumps where they are deposited. On the other side, vacancies are generated in places where aluminum is deficient. Such a defect causes a short circuit with the wiring of the pond or disconnection due to an increase in wiring resistance. Therefore, the use of high melting point metals such as molybdenum, tungsten, or titanium is being considered in the future in response to the progress of higher integration. Especially titanium is fil! a
It has the characteristics that it is resistant to 2-1 biochemical properties, has good mechanical properties, has excellent corrosion resistance and i'j1 heat resistance, and is resistant to electromigration. Therefore, it can fully cope with the thinning of wiring due to high integration, and is seen as a promising metal material for future large-scale integrated circuits.
しかしながら、半導体素子に用いられる金属は高純度で
あることが要求され、特に次のような不純物は半導体素
子に悪影響を及ぼす恐れがある。However, metals used in semiconductor devices are required to have high purity, and in particular, the following impurities may have an adverse effect on semiconductor devices.
■、Ｎａ、になどのアルカリ金属は、Ｍ ＯＳ −ＬＳ
Ｉの界面特性の劣化を招く。■Alkali metals such as Na, Ni, etc. are MOS-LS
This leads to deterioration of the interface properties of I.
■、Ｕ、Ｔｈなどの放射性元素は、ソフトエラーを招く
。Radioactive elements such as (2), U, and Th cause soft errors.
■、Ｆｅ、 Ｃｒなどの重金底は、界面接合部のトラブ
ルをひき起こす。■Heavy metal soles such as Fe, Cr, etc. cause problems at interface joints.
■、酵素は、特性劣化を引起こす。■Enzymes cause property deterioration.
ところが、現在、工業的に製造されている純チタンは重
金属元素、ガス成分の他、上述した元素を多量に含有し
ている。これらの元素は、極微量でも素子の性能に悪影
響を及ぼすため、純チタンを更に高純度化する必要があ
る。その一つにハロゲン化物分解法があり、特にヨウ化
物分解法は、チタンの１８ ”ＩＪに用いられている。However, the pure titanium currently produced industrially contains large amounts of the above-mentioned elements in addition to heavy metal elements and gas components. These elements have a negative effect on the performance of the element even in extremely small amounts, so it is necessary to further purify pure titanium. One of them is the halide decomposition method, and in particular the iodide decomposition method is used for titanium 18'' IJ.
ヨウ化物分解法は、化学輸送法の一種であり、チタンを
始めハフニウム、ジルコニウム等活性金届の精製に使用
されている方法である。例えばチタンの精製は、次式（
１）、（２）の反応を利用して行われる。The iodide decomposition method is a type of chemical transport method, and is used to purify active metals such as titanium, hafnium, and zirconium. For example, the refining of titanium is performed using the following formula (
This is carried out using reactions 1) and (2).
Ｔ ｉ ＋２１２→Ｔｉｌ＜ ＜４５０〜６００℃
）・・・（１）Ｔ ｉ １４ −＊’ｒ ｉ
＋ ２ １２ （７７００〜７５００ ℃ ）
−（２）即ら、上記（１）式に示すようにチタン（融点
１８００℃）はヨウ素（融点１１４℃、沸点１８５℃）
と４５０〜６００℃の温度で激しく反応し、Ｔｉｌ＋を
生成する。更に、ＴｉＩ４は１１００〜１５００℃の高
）３で上記（２）式に示すようにチタンとヨウ素に分解
する性質を有する。具体的には、従来、次に説明する第
４図に示す装置によりクリスタルバーチタンを製造して
いた。第４図中の１は、原料であるスポンジチタンとヨ
ウ素とを収容する反応容器である。T i +212→Til<<450~600℃
)...(1)T i 14 -*'r i
+2 12 (7700-7500℃)
-(2) That is, as shown in the above formula (1), titanium (melting point 1800°C) is iodine (melting point 114°C, boiling point 185°C)
It reacts violently with Til+ at a temperature of 450-600°C. Furthermore, TiI4 has the property of decomposing into titanium and iodine at high temperatures of 1100 to 1500° C. as shown in the above formula (2). Specifically, crystal bar titanium has conventionally been produced using an apparatus shown in FIG. 4, which will be described below. Reference numeral 1 in FIG. 4 is a reaction vessel containing titanium sponge and iodine as raw materials.
この容器１は、４５０〜６００℃に加熱された恒温槽（
又恒温炉）２の中に固定されている。前記容器１内には
、例えばＵ７状をなすフィラメント３が吊架されている
。このフィラメント２の両端部は、給電治ＪＱ４ａ、４
ｂにより保持されており、かつ各給電治具４ａ、４ｂは
リード線を介して電源５に接続されている。このような
Ｈａによりクリスタルバーチタンを製造するには、まず
、反応容器１内にスポンジチタン（場合によっては他の
チタン又はチタン合金も使用可能）６とヨウ素７を収容
し、電ａ５から給電治具４ａ、４ｂを通してフィラメン
ト３に通電加熱して１１００〜１５００℃程度に保持す
る。つづいて、反応ｇ器１仝体を恒温槽２により加熱し
て４５０〜６００℃に保持する。原料であるスポンジチ
タン６とヨウ素７は、４５０〜ＧＯＯ℃の低重で反応し
てＴｉ１４８を生成する。生成したＴｉＩ＋８は、高温
のフィラメント３上で分解し１分解生成物のうちＴｉは
フィラメント３に付着し、ヨウ素（Ｉ２）は再び原料の
スポンジチタン６と反応する。つまり、ヨウ素はキャリ
アとしてチタンをフィラメン１へ３上に運ぶ動きをする
このようにしてヨウ素と反応するチタンのみがフィラメ
ント３上に運ばれ、ｆｆ１ｇが行われる。このプロセス
を繰返すことによって、純チタンがフィラメント３上に
威圧する。This container 1 is placed in a constant temperature bath heated to 450 to 600°C (
It is also fixed in a constant temperature furnace (2). In the container 1, a filament 3 having a U7 shape, for example, is suspended. Both ends of this filament 2 are connected to the power supply JQ4a, 4
b, and each power supply jig 4a, 4b is connected to a power source 5 via a lead wire. In order to produce crystal bar titanium using such Ha, first, sponge titanium (other titanium or titanium alloys can be used in some cases) 6 and iodine 7 are placed in a reaction vessel 1, and a power supply from an electric source a5 is carried out. The filament 3 is electrically heated through the tools 4a and 4b and maintained at about 1100 to 1500°C. Subsequently, the reactor 1 was heated in a constant temperature bath 2 and maintained at 450 to 600°C. Sponge titanium 6 and iodine 7, which are raw materials, react at a low gravity of 450 to GOO°C to generate Ti148. The generated TiI+8 is decomposed on the high-temperature filament 3, and among the decomposition products, Ti adheres to the filament 3, and iodine (I2) reacts with the raw material sponge titanium 6 again. In other words, iodine acts as a carrier to transport titanium onto filament 1 and onto filament 3. In this way, only titanium that reacts with iodine is transported onto filament 3, and ff1g is performed. By repeating this process, pure titanium is forced onto the filament 3.
しかしながら、従来の通電加熱方式のみで基体であるフ
ィラメントを加熱する方法ではＴｉ［４の分解速度に限
界があり、ある厚さ以上のチタンを析出するには長時間
を要した。また、ヨウ化物分解法によって高純度チタン
を製造するには人間の電力を消費するため、Ｍｉ＆コス
トが高騰する問題があった。However, in the conventional method of heating a filament, which is a substrate, using only an electrical heating method, there is a limit to the decomposition rate of Ti[4, and it takes a long time to deposit titanium over a certain thickness. In addition, producing high-purity titanium using the iodide decomposition method consumes human power, which poses the problem of rising Mi and cost.
（発明が解決しようとする問題点）
本発明は上記従来の問題点を解決するためになされたも
ので、ハロゲン化物分解法に際し、加熱された基体の表
面に電子ビーム等のエネルギービームを熱中することに
より短時間で所定の厚さの高純度金属を析出し得る高練
喰金属体の製造方法を提供しようとするものである。(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned conventional problems, and in the halide decomposition method, an energy beam such as an electron beam is immersed onto the surface of a heated substrate. The present invention aims to provide a method for producing a highly refined metal body that can deposit a high purity metal of a predetermined thickness in a short period of time.
「発明の構成コ
（問題点を解決するための手段）
本発明は、基体表面にハロゲン化物分解法により直接金
属を析出する高純度金、庇体の製造におぃて、前記基体
を所望のカロ熱手段により加熱し、更に該基体表面にエ
ネルギービームを照射することを特徴とする高純度金属
体の製造方法である。``Structure of the Invention (Means for Solving Problems) The present invention is directed to the production of high-purity gold and eaves bodies in which metal is deposited directly on the surface of the substrate by a halide decomposition method. This is a method for producing a high purity metal body, which is characterized by heating the base body by Calothermal means and further irradiating the surface of the base body with an energy beam.
次に、本発明の高ｆｉｌｌ！度金属体の製造方法を第１
図に示す製造装置を参照して詳細に説明する。Next, the high fill of the present invention! The first method for manufacturing metal objects
This will be explained in detail with reference to the manufacturing apparatus shown in the figures.
第１図中の１１は、原料であるスポンジチタンとヨウ素
とを収容する反応容器である。この容器１１は、４５０
〜６００°Ｃに加熱された恒温槽（又恒温炉）１２の中
に固定されている。前記容器１１内には、基体としての
例えばチタン板１３がその厚さ方向を鉛直方向に対して
直交するように図示しない支持金具により固定されてい
る。また、前記容器１１内には同−鉛直方向面内で渦巻
き状に巻回した誘導加熱コイル１４が配置されている。Reference numeral 11 in FIG. 1 is a reaction vessel containing titanium sponge and iodine as raw materials. This container 11 is 450
It is fixed in a constant temperature bath (or constant temperature furnace) 12 heated to ~600°C. For example, a titanium plate 13 serving as a base is fixed in the container 11 with a support fitting (not shown) so that its thickness direction is perpendicular to the vertical direction. Further, an induction heating coil 14 is arranged inside the container 11 and is spirally wound in the same vertical plane.
つまり、前記誘導加熱コイル１４は前記チタン板１３の
面と平行に配置されている。前記誘導加熱コイル１４は
、高周波用８１５に接続されている。That is, the induction heating coil 14 is arranged parallel to the surface of the titanium plate 13. The induction heating coil 14 is connected to a high frequency 815.
また、前記反応容器１１の側壁には前記チタン板１３の
面にエネルギービーム、例えば電子ビームを照射するた
めの電子ｆｆ１１６が配置されている。Furthermore, an electron ff 116 for irradiating the surface of the titanium plate 13 with an energy beam, for example, an electron beam, is arranged on the side wall of the reaction vessel 11.
更に、前記反応容器１１の上部には排気管１７が連結さ
れている。Furthermore, an exhaust pipe 17 is connected to the upper part of the reaction vessel 11.
上述した製造装置により高純度チタン板を製造するには
、まず、反応容器１１内にスポンジチタン（場合によっ
ては他のチタン又はチタン合金も使用可能）１８とヨウ
素１つを収容し、高置ｅ電源１５から誘導加熱コイル１
４に高周波電力を印加することによって、誘導加熱コイ
ル１４から発生した磁束はチタン板１３の厚さ方向に貫
通し、これにより誘導される電流によってチタン板１３
が１１００〜１５００℃程度に加熱される。つづいて、
反応容器１１全体を恒温槽１２より加熱して４５０〜６
００℃に保持する。原料であるスポンジチタン１８とヨ
ウ素１９は、４５０〜６００℃の低温で前述した（１）
式に示すように反応してＴｉ１４を生成する。生成した
Ｔｉｌ＋は、高温のチタン板１３上で前述した（２式に
示すように分解し、分解生成物のうちＴｉはチタン板１
３に付着し、ヨウ素（Ｉ２）は再び原料のスポンジチタ
ン１８と反応してチタンをチタン板１３上に運ぶ。スポ
ンジチタン中の不純物はヨウ素と反応せず、スポンジチ
タン１８中に残留するため、チタン板１３上に析出する
チタンは純度が高く、その結果、高純度チタン板を製造
できる。このような一連のチタンヨウ化物の生成、分゛
解反応は、基体としてのチタン板１３表面でのヨウ化物
の分解速度が全体の反応に律速しでいる。しかるに、前
記チタン板１３へのチタンの析出過程において、排気管
１７により反応容器１１内を真空排気しながら、チタン
板１３表面に反応容器１１に配置した電子銃１６から電
子ビームを照射し、チタン板１３近傍のチタンヨウ化物
にエネルギーを与え、分解反応を促進することにより、
チタン析出速度を著しく増大させることができ、しかも
充分の厚さにチタンを析出できる。また、誘導加熱コイ
ル１４を同一鉛直方向面内で渦巻き状に巻回した形状と
し、該誘導加熱コイル１４から発生した磁束をチタン板
１３の厚さ方向に貫通させて誘導加熱する方式を床用す
ることによって、高周波電源からの電力の周波数が５０
〜１００００ Ｈ２であり、磁束をチタン板の長さ方向
に貫通させる縦磁束誘導加熱方式に比べて高い周波数を
必要とせず、設備費用の低減、製造コストの低減化を図
ることができる。In order to manufacture a high-purity titanium plate using the above-mentioned manufacturing apparatus, first, titanium sponge (in some cases, other titanium or titanium alloys can be used) 18 and one iodine are placed in the reaction vessel 11, and then Induction heating coil 1 from power source 15
By applying high frequency power to the induction heating coil 14, the magnetic flux generated from the induction heating coil 14 penetrates the titanium plate 13 in the thickness direction, and the current induced thereby causes the titanium plate 13 to
is heated to about 1100 to 1500°C. Continuing,
The entire reaction vessel 11 is heated from the constant temperature bath 12 to 450~6
Maintain at 00°C. The raw materials, sponge titanium 18 and iodine 19, were heated at a low temperature of 450 to 600°C as described above (1).
Ti14 is produced by reacting as shown in the formula. The generated Til+ is decomposed on the high-temperature titanium plate 13 as described above (as shown in equation 2), and among the decomposition products, Ti is
3, the iodine (I2) reacts again with the raw material titanium sponge 18 and transports titanium onto the titanium plate 13. Since impurities in the titanium sponge do not react with iodine and remain in the titanium sponge 18, the titanium deposited on the titanium plate 13 has a high purity, and as a result, a high purity titanium plate can be manufactured. In such a series of titanium iodide production and decomposition reactions, the rate of decomposition of iodide on the surface of the titanium plate 13 serving as a substrate determines the overall reaction rate. However, in the process of depositing titanium onto the titanium plate 13, the surface of the titanium plate 13 is irradiated with an electron beam from the electron gun 16 disposed in the reaction vessel 11 while the interior of the reaction vessel 11 is evacuated through the exhaust pipe 17. By giving energy to the titanium iodide near the plate 13 and promoting the decomposition reaction,
The titanium deposition rate can be significantly increased, and titanium can be deposited to a sufficient thickness. In addition, the induction heating coil 14 is spirally wound in the same vertical plane, and the magnetic flux generated from the induction heating coil 14 is passed through the titanium plate 13 in the thickness direction to perform induction heating. By doing this, the frequency of the power from the high frequency power source becomes 50
~10,000 H2, which does not require a higher frequency than the longitudinal magnetic flux induction heating method in which magnetic flux penetrates the titanium plate in the length direction, and can reduce equipment costs and manufacturing costs.
本発明の高純度金属体を製造する場合、前ｊホした第１
図図示の製造装置の他に例えば第２図又は第３図に示す
製造装置を用いてもよい。なお、前述した第１図と同様
な部材は同符号を付して説明を省略する。When manufacturing the high-purity metal body of the present invention, the first
In addition to the manufacturing apparatus shown in the figure, for example, the manufacturing apparatus shown in FIG. 2 or 3 may be used. Incidentally, the same members as those shown in FIG.
即ち、第２図は真空排気型の製造装置であり、図中の２
０はチタンヨウ化物生成槽である。この生成１１２０は
、ヒータ２１により加熱されろチタンヨウ化物２２が収
容されている。前記生成１曹２０は、供給管２３を介し
て反応容器１１に連結されており、かつ該供給管２３の
反応容器１１側の先端はチタンヨウ化物のガスを高速で
同容器１１内に供給するために細くしである。また、Ｍ
中の２４は冷却槽であり、この冷却槽２４内には排気系
２５により排気されるトラップ２６が挿入されている。That is, Fig. 2 shows a vacuum exhaust type manufacturing equipment, and 2 in the figure
0 is a titanium iodide production tank. This product 1120 is heated by a heater 21 and contains titanium iodide 22 . The produced monocarbonate 20 is connected to the reaction vessel 11 via a supply pipe 23, and the tip of the supply pipe 23 on the reaction vessel 11 side is used to supply titanium iodide gas into the vessel 11 at high speed. It is thin. Also, M
24 is a cooling tank, and a trap 26 is inserted into the cooling tank 24 to be exhausted by an exhaust system 25.
このトラップ２６には、前記反応容器１１に連結した排
気管１７の曲端側が挿入されている。なお、第２図の装
置では、誘導加熱コイル１４は同一水平面内で渦巻き状
に巻回した形状になっており、かつチタン板１３は該コ
イル１４の面に対して平行となるように水平状態に吊架
されている。このような構造の製造装置において、恒温
槽１２により反応容器１１内を４５０〜６００℃に加熱
した状態で、ヒータ２１により生成ｆｆ１２０を加熱し
て該生成槽２０内のチタンヨウ化物２２をガス状態にし
て供給管２３より高速で反応容器１１内に供給しながら
、高周波電源１５から誘導加熱コイル１４に高周波電力
を入力してチタン板１３を誘導加熱し、更にチタン板１
３表面に電子Ｆｃ１６から電子ビームを照射することに
より、チタンヨウ化物から分解した高純度のチタンがチ
タン板１３上に析出される。この時、反応容器１１内の
未分解のＴｉｌ＋及び分解反応により生じたヨウ素は、
排気系２５の作動により排気管１７を通して冷却槽２４
で冷却されたトラップ２６に移行され、このトラップ２
６内で凝固し回収される。The curved end of the exhaust pipe 17 connected to the reaction vessel 11 is inserted into the trap 26 . In the device shown in FIG. 2, the induction heating coil 14 is spirally wound in the same horizontal plane, and the titanium plate 13 is placed in a horizontal state parallel to the surface of the coil 14. It is suspended on a rack. In a manufacturing apparatus having such a structure, the inside of the reaction vessel 11 is heated to 450 to 600° C. by the constant temperature bath 12, and the produced ff120 is heated by the heater 21 to turn the titanium iodide 22 in the generation bath 20 into a gas state. While supplying the titanium plate 13 into the reaction vessel 11 at high speed through the supply pipe 23, high frequency power is inputted from the high frequency power source 15 to the induction heating coil 14 to induction heat the titanium plate 13, and then the titanium plate 1
By irradiating the surface of the titanium plate 13 with an electron beam from the electron Fc 16, high purity titanium decomposed from the titanium iodide is deposited on the titanium plate 13. At this time, undecomposed Til+ in the reaction vessel 11 and iodine generated by the decomposition reaction are
The cooling tank 24 is passed through the exhaust pipe 17 by the operation of the exhaust system 25.
is transferred to the cooled trap 26, and this trap 2
6 and is collected.
なお、反応容器１１（チタン板１３）へのチタンヨウ化
物ガスの供給速度は、ヒータ２１によるチタンヨウ化物
２２の加熱温度を制御することによりｙ４節できる。Note that the supply rate of titanium iodide gas to the reaction vessel 11 (titanium plate 13) can be adjusted to y4 by controlling the heating temperature of the titanium iodide 22 by the heater 21.
第３図は、循環式の製造装置である。この製造装置は、
スポンジチタン１８及びヨウ素１９を収該供給管２３と
反対側の側壁に連結された循環配管２７を前記生成槽２
０に連結すると共に、該配管２７の途中にファン２８を
介装し、更に前記生成槽２０．供給管２３及び循環配管
２７の周囲にヒータ２１′を設けた構造になっている。FIG. 3 shows a circulating manufacturing apparatus. This manufacturing equipment is
A circulation pipe 27 connected to the side wall opposite to the supply pipe 23 containing sponge titanium 18 and iodine 19 is connected to the production tank 2.
0, a fan 28 is interposed in the middle of the piping 27, and the generation tank 20. It has a structure in which a heater 21' is provided around the supply pipe 23 and the circulation pipe 27.
このような構造の製造装置において、まず、排気管１７
により反応容器１１内を真空排気した後、チタンヨウ化
物生成槽２０、供給管２３及び循環配管２７をヒータ２
１′により４５０〜ｅｏｏ℃に加熱する。前記生成＋！
２０では、スポンジチタン１８とヨウ素１９とが反応し
てＴｉ１４を生成する。生成されたＴｉｌ＋はファン２
８により強制的に供給管２３を通して反応容器１１内に
供給され、誘導加熱コイル１４による誘導加熱及び電子
銃１６からの電子ビームが照射されたチタン板１３の表
面上で分解され、高純度のチタンがチタン板１３上に析
出される。未分解のＴｉ１４及び分解反応により生じた
ヨウ素は、循環配管２７を通して再び生成槽２０に送り
込まれ、ヨウ素は生成Ｗｊ２０内のスポンジチタン１８
と反応してＴｉｌ＋を生成し、供給管２３を通して反応
容器１１内に供給される。In a manufacturing apparatus having such a structure, first, the exhaust pipe 17 is
After evacuating the inside of the reaction vessel 11, the titanium iodide production tank 20, the supply pipe 23, and the circulation pipe 27 are connected to the heater 2.
1' to 450-eoo°C. Said generation +!
In 20, sponge titanium 18 and iodine 19 react to produce Ti 14. The generated Til+ is fan 2
8 into the reaction vessel 11 through the supply pipe 23, and is decomposed on the surface of the titanium plate 13, which is induction heated by the induction heating coil 14 and irradiated with the electron beam from the electron gun 16, producing high-purity titanium. is deposited on the titanium plate 13. Undecomposed Ti 14 and iodine generated by the decomposition reaction are sent to the generation tank 20 again through the circulation pipe 27, and the iodine is transferred to the sponge titanium 18 in the generation Wj 20.
Til+ is produced by reacting with Til+, which is supplied into the reaction vessel 11 through the supply pipe 23.
なお、上述した本発明方法に使用する第１図〜第３図図
示の製造装置において、高温のヨウ素雰囲気に曝される
部材はヨウ素に対して耐食性の良好なインコネル、ハス
テロイ、モリブデン等の金属又は銅製のコイル表面にヨ
ウ素に対して耐食性の良好な金、白金、タングステン、
モリブデン等をコーティングしたものを使用することが
必要である。In the manufacturing apparatus shown in FIGS. 1 to 3 used in the method of the present invention described above, the members exposed to the high-temperature iodine atmosphere are made of metals such as Inconel, Hastelloy, and Molybdenum, which have good corrosion resistance against iodine. Gold, platinum, tungsten, which has good corrosion resistance against iodine, is applied to the surface of the copper coil.
It is necessary to use a material coated with molybdenum or the like.
本発明方法に使用する基体の材料は、一般にはその表面
上に析出される高純度金属（例えばチタン、タンタル、
クロム、ジルコニウム、ハフニウム等）と同種のものを
用いるが、ターゲツト材を考慮した場合にはモリブデン
、タングステン等の高融点金属を用い、この基体上に高
純度チタン等を析出してもよい。The material of the substrate used in the method of the invention is generally a high purity metal deposited on its surface (e.g. titanium, tantalum,
However, if the target material is considered, a high melting point metal such as molybdenum or tungsten may be used, and high purity titanium or the like may be deposited on this substrate.
本発明方法は、基体の加熱手段として誘導加熱を採用し
たが、この他に通電加熱等を採用してもよい。また、使
用するハロゲンはヨウ素の他に塩素、臭素などいずれで
もよい。In the method of the present invention, induction heating is used as a heating means for the substrate, but other methods such as electrical heating may also be used. Further, the halogen used may be any of chlorine, bromine, etc. in addition to iodine.
上記基体表面に照射するエネルギービームとして電子ビ
ームを用いたが、この他にレーザビーム等を使用するこ
とができる。Although an electron beam was used as the energy beam to irradiate the surface of the substrate, a laser beam or the like may also be used.
（作用）
本発明によれば、ハロゲン化物分解法により基体表面に
金属を析出するに際し、例えば誘導加熱等により加熱さ
れた基体にエネルギービームを照射することにより該基
体表面上での金属ハロゲン化物の分解速度を著しく促進
できるため、従来法に比べて類時間で高純度の金属を基
体上に析出でき、ひいては高純度金属体を低コストで’
Ｆ７造することができる。(Function) According to the present invention, when depositing metal on the surface of a substrate by a halide decomposition method, the metal halide on the surface of the substrate is irradiated with an energy beam to the substrate heated by, for example, induction heating. Since the decomposition rate can be significantly accelerated, high-purity metal can be deposited on the substrate in a similar amount of time compared to conventional methods, and high-purity metal bodies can be deposited at low cost.
F7 can be built.
（発明の実施例）
以下、本発明の実施例を前述した第１図図示の製造装置
を用いて説明する。(Embodiments of the Invention) Hereinafter, embodiments of the present invention will be described using the above-mentioned manufacturing apparatus shown in FIG.
まず、第１図図示の製造装置におけるハステロイ−Ｂ製
の反応容器１１内に６００９のスポンジチタン１８と２
．５ｇのヨウ素１９を収容し、排気管１７を通して真空
排気した後、反応容器１１全体を約５００℃に加熱した
抵抗加熱方式の縦型恒温炉１２内に装入した。この反応
容器１１内には、直径１５ｃｔｓ、厚さ０．５０のチタ
ン板１３が同一鉛直方向面内で渦巻き状に巻回した金コ
ーティングがなされた水冷同バイブからなる誘導加熱コ
イル１４の面に対して平行となるように図示しないモリ
ブデン製支持金具により近接して固定した。次いで、樅
型恒温炉１２の温度を５００℃に保持しながら、高周波
電源１５から誘導加熱コイル１４に１０ｋ）Ｉｚで３ｋ
Ｗの電力を入力して１４００℃まで加熱すると共に、チ
タン板１３の表面全体に電子銃１６から電圧４００Ｖ、
電流密度１００ｍＡ ／ ｃｔｉの条件で電子ビームを
走査して照射した。First, 6009 titanium sponge 18 and 2
．． After containing 5 g of iodine 19 and evacuating through the exhaust pipe 17, the entire reaction vessel 11 was placed in a resistance heating type vertical constant temperature furnace 12 heated to about 500°C. Inside this reaction vessel 11, a titanium plate 13 with a diameter of 15 cts and a thickness of 0.50 is placed on the surface of an induction heating coil 14 consisting of a water-cooled vibrator coated with gold and spirally wound in the same vertical plane. They were fixed close to each other using molybdenum support fittings (not shown) so as to be parallel to each other. Next, while maintaining the temperature of the fir-shaped constant temperature furnace 12 at 500°C, the induction heating coil 14 is heated with 10 k) of 3 k at Iz from the high frequency power supply 15.
While heating the titanium plate 13 to 1400°C by inputting power of W, a voltage of 400V is applied from the electron gun 16 to the entire surface of the titanium plate 13.
The electron beam was scanned and irradiated at a current density of 100 mA/cti.
上述した条件で１０時間のチタン析出を行なったところ
、厚さ０．５ ａｎのチタン板１３が１．０口に成長し
た。これに対し、チタンの析出時に電子ビームの照射を
行なわない以外、実施例と同様な方法（比較例）では、
厚さ０，５ｃｆＲのチタン板が０．６５ｃｔａまでしか
成長しなかった。When titanium precipitation was carried out for 10 hours under the above-mentioned conditions, the titanium plate 13 with a thickness of 0.5 ann grew to 1.0 ann. On the other hand, in a method similar to the example (comparative example) except that electron beam irradiation is not performed during titanium deposition,
A titanium plate with a thickness of 0.5 cfR grew only to 0.65 cta.
また、本実施例により得たチタン板を分析したところ、
下記第１表に示す結果となった。なお、第１表中には原
料のスポンジチタンの分析結果も併記した。Furthermore, when the titanium plate obtained in this example was analyzed,
The results are shown in Table 1 below. In addition, Table 1 also shows the analysis results of the raw material titanium sponge.
第１表
（準位；冑ｔｐｐｍ）
上記第１表より明らかなように本実施例におけるヨウ化
物分解法によるｒＪ製効果は顕著であり、高純度チタン
板が得られることがわかる。Table 1 (Level: tppm) As is clear from Table 1 above, the effect of producing rJ by the iodide decomposition method in this example is remarkable, and it can be seen that a high purity titanium plate can be obtained.
更に、本実施例及び前記比較例におけるチタン成長速度
を調べたところ、下記第２表に示す結果を得た。Furthermore, when the titanium growth rate in this example and the comparative example was investigated, the results shown in Table 2 below were obtained.
第 ２ 表
上記第２表より明らかなように本実施例の如くチタン板
１３に電子ビームを照射することによりチタンの成長速
度を大きくできることがわかる。Table 2 As is clear from Table 2 above, the growth rate of titanium can be increased by irradiating the titanium plate 13 with an electron beam as in this example.
なお、上記実施例では原料としてスポンジチタンを用い
た場合について説明したが、この代わりに溶融電解法、
帯溶融法、ハロゲン化物分解法により製造した高ＩＴ！
度金属を用いてもよい。このような原料を用いれば、よ
り一層高純度の金属体を得ることができる。In addition, in the above example, the case where sponge titanium was used as the raw material was explained, but instead of this, melting electrolysis method,
High IT manufactured by band melting method and halide decomposition method!
Metal may also be used. If such a raw material is used, a metal body with even higher purity can be obtained.
上記実施例では、高純度チタン板を例にして説明したが
、タンタル、ジルコニウム、ハフニウム、クロム等の高
純度金属体も同様に得ることができた。In the above embodiment, a high-purity titanium plate was used as an example, but high-purity metal bodies such as tantalum, zirconium, hafnium, and chromium could be similarly obtained.
［発明の効果］
以上詳述した如く、本発明によればハロゲン化物分解法
により基体表面に金属を析出するに際し、例えば誘導加
熱等により加熱された基体にエネルギービームを照射す
ることにより該基体表面上での金属ハロゲン化物の分解
速度を著しく促道して短時間で高純度金属を基体上に所
定厚さ析出でき、ひいては大規模集積回路の配線や電極
を形成する際のターゲット等に好適な高純度金属体を低
コストで製造し得る方法を提供できる。[Effects of the Invention] As detailed above, according to the present invention, when depositing metal on the surface of a substrate by a halide decomposition method, the surface of the substrate is irradiated with an energy beam, for example by induction heating, etc. It significantly accelerates the decomposition rate of metal halides on the substrate, allowing high-purity metals to be deposited to a predetermined thickness on the substrate in a short period of time, making it suitable as a target for forming wiring and electrodes in large-scale integrated circuits. A method for manufacturing high-purity metal bodies at low cost can be provided.
第１図は本発明の高純度チタン板を得るための製造装置
の一形態を示す概略図、第２図及び第３図は夫々本発明
の高純度チタン板を得るための製造装置の他の形態を示
す概略図、第４図は従来のクリスタルバーチタンを得る
ための製造装置を示す概略図である。
１１・・・反応容器、１２・・・恒温槽（又は恒温炉）
、１３・・・基体（チタン板）、１４・・・誘導加熱コ
イル、１５・・・高周波Ｎ源、１６・・・電子銃、１７
・・・排気管、１８・・・スポンジチタン、１９・・・
ヨウ素、２０・・・チタンヨウ化物生成槽、２１．２１
′・・・ヒータ、２６・・・トラップ、２７・・・循環
配管、２８・・・ファン。
出願人代理人 弁理士 鈴江武彦
第１図
第３ 図FIG. 1 is a schematic diagram showing one embodiment of the manufacturing apparatus for obtaining the high-purity titanium plate of the present invention, and FIGS. 2 and 3 respectively show other manufacturing apparatuses for obtaining the high-purity titanium plate of the present invention. FIG. 4 is a schematic diagram showing a conventional manufacturing apparatus for obtaining crystal bar titanium. 11... Reaction container, 12... Constant temperature bath (or constant temperature furnace)
, 13... Base (titanium plate), 14... Induction heating coil, 15... High frequency N source, 16... Electron gun, 17
...Exhaust pipe, 18...Sponge titanium, 19...
Iodine, 20...Titanium iodide production tank, 21.21
'...Heater, 26...Trap, 27...Circulation piping, 28...Fan. Applicant's agent Patent attorney Takehiko Suzue Figure 1 Figure 3
Claims (4)
を析出する高純度金属体の製造において、前記基体を所
望の加熱手段により加熱し、更に該基体表面にエネルギ
ービームを照射することを特徴とする高純度金属体の製
造方法。(1) In the production of a high-purity metal body in which metal is deposited directly on the surface of a substrate by a halide decomposition method, the substrate is heated by a desired heating means, and the surface of the substrate is further irradiated with an energy beam. A method for producing a high-purity metal body.
特徴とする特許請求の範囲第１項記載の高純度金属体の
製造方法。(2) The method for manufacturing a high-purity metal body according to claim 1, characterized in that induction heating is used as a heating means for the base body.
徴とする特許請求の範囲第１項記載の高純度金属体の製
造方法。(3) The method for manufacturing a high-purity metal body according to claim 1, wherein the energy beam is an electron beam.
特徴とする特許請求の範囲第１項記載の高純度金属体の
製造方法。(4) The method for manufacturing a high-purity metal body according to claim 1, wherein the energy beam is a laser beam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13748486A JPS62294179A (en) | 1986-06-13 | 1986-06-13 | Production of high-purity metallic body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13748486A JPS62294179A (en) | 1986-06-13 | 1986-06-13 | Production of high-purity metallic body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62294179A true JPS62294179A (en) | 1987-12-21 |
Family
ID=15199713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13748486A Pending JPS62294179A (en) | 1986-06-13 | 1986-06-13 | Production of high-purity metallic body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62294179A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02213490A (en) * | 1989-02-15 | 1990-08-24 | Nippon Mining Co Ltd | Production of high-purity titanium and equipment thereof and high-purity titanium target material |
| FR2649420A1 (en) * | 1989-07-05 | 1991-01-11 | Cezus Co Europ Zirconium | DEVICE FOR OBTAINING MATERIALS COMPRISING A SUBSTRATE AND A PURIFIED TITANIUM COATING OF PLANE SHAPE |
| US5336378A (en) * | 1989-02-15 | 1994-08-09 | Japan Energy Corporation | Method and apparatus for producing a high-purity titanium |
| CN107760886A (en) * | 2017-11-03 | 2018-03-06 | 株洲稀美泰材料有限责任公司 | A kind of equipment for preparing high purity titanium |
-
1986
- 1986-06-13 JP JP13748486A patent/JPS62294179A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02213490A (en) * | 1989-02-15 | 1990-08-24 | Nippon Mining Co Ltd | Production of high-purity titanium and equipment thereof and high-purity titanium target material |
| US5336378A (en) * | 1989-02-15 | 1994-08-09 | Japan Energy Corporation | Method and apparatus for producing a high-purity titanium |
| FR2649420A1 (en) * | 1989-07-05 | 1991-01-11 | Cezus Co Europ Zirconium | DEVICE FOR OBTAINING MATERIALS COMPRISING A SUBSTRATE AND A PURIFIED TITANIUM COATING OF PLANE SHAPE |
| CN107760886A (en) * | 2017-11-03 | 2018-03-06 | 株洲稀美泰材料有限责任公司 | A kind of equipment for preparing high purity titanium |
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