JPH03197640A - High purity tantalum material and its production and tantalum target using the same - Google Patents
High purity tantalum material and its production and tantalum target using the sameInfo
- Publication number
- JPH03197640A JPH03197640A JP33480589A JP33480589A JPH03197640A JP H03197640 A JPH03197640 A JP H03197640A JP 33480589 A JP33480589 A JP 33480589A JP 33480589 A JP33480589 A JP 33480589A JP H03197640 A JPH03197640 A JP H03197640A
- Authority
- JP
- Japan
- Prior art keywords
- tantalum
- target
- high purity
- purity
- film
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 17
- 229910052715 tantalum Inorganic materials 0.000 title claims description 48
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010894 electron beam technology Methods 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000010408 film Substances 0.000 description 20
- 239000012535 impurity Substances 0.000 description 10
- 229910021332 silicide Inorganic materials 0.000 description 10
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000005546 reactive sputtering Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- MISXNQITXACHNJ-UHFFFAOYSA-I tantalum(5+);pentaiodide Chemical compound [I-].[I-].[I-].[I-].[I-].[Ta+5] MISXNQITXACHNJ-UHFFFAOYSA-I 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【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、半導体装置に使用される高純度タンタルとそ
の製造方法及びそれを用いたスパッタターゲットに関す
る。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to high-purity tantalum used in semiconductor devices, a manufacturing method thereof, and a sputter target using the same.
（従来の技術）
現在、ＶＬＳＩの蓄積キャパシタ材料として、ＳｉＯ□
に代わり酸化タンタル（ｒａ２ｏｓ）薄膜が検討されて
いる。Ｔａ、０．はＳｉＯ□に比べ約６倍の比誘電率を
持つので、キャパシタ面積を小さくすることができる。(Prior art) Currently, SiO□ is used as storage capacitor material for VLSI.
Instead, tantalum oxide (RA2OS) thin films are being considered. Ta, 0. has a dielectric constant about six times that of SiO□, so the capacitor area can be reduced.
しかしＴａ、 Ｏ，はＳｉｎ、に比ベリーク電流が大き
い、あるいは薄膜化したときに実効的な比誘電率が下が
ってしまう５等の理由から、これまで使われなかった。However, Ta, O, and O have not been used until now because they have a larger leakage current than Sin, or because the effective dielectric constant decreases when the film is made thinner.
このＴａ２Ｏ，薄膜は反応性スパッタリング法、ＣＶ
Ｄ法などにより成膜されるが、反応性スパッタリングの
場合には、タンクルターゲットを用いてアルゴン、酸素
混合気体中スパッタリングを行ない成膜される。This Ta2O thin film was produced by reactive sputtering method, CV
The film is formed by method D or the like, but in the case of reactive sputtering, the film is formed by sputtering in a mixed gas of argon and oxygen using a tank target.
一方ＶＬＳＩの電極材料として、Ｍｏ、 Ｗなどの高融
点金属シリサイドが使われてきているが、次期の電極材
料としてＴａシリサイドが検討されてきているｅＴａシ
リサイド膜を形成するには、いくつかの方法があるが、
多結晶シリコン上にＴａ膜をつけ、その後シリコンとＴ
ａを反応させ自己整合的にＴａシサイドを形成する際に
は、純Ｔａターゲットが使われる。On the other hand, high melting point metal silicides such as Mo and W have been used as electrode materials for VLSIs, but Ta silicide is being considered as the next electrode material.There are several methods to form eTa silicide films. There is, but
A Ta film is applied on polycrystalline silicon, and then silicon and T
A pure Ta target is used when reacting a to form Ta oxide in a self-aligned manner.
一般にＶＬＳＩに用いられる金属材料中の次のような不
純物は素子に悪影響を及ぼすので、高純度であることが
要求される。Generally, the following impurities in metal materials used in VLSI devices have a negative effect on the device, so they are required to be highly pure.
ａ、 Ｎａ、 Ｋ等のアルカリ金属（界面特性の劣化）
ｂ、Ｕ、Ｔｈ等の放射性元素（ソフトエラー）ｃ、 Ｆ
ｅ、 Ｃｒ等の重金属（界面接合のトラブル）ところで
、現在工業的に製造されているタンタルターゲットは、
電解法などにより精製したタンタルを溶解してタンタル
インゴットとし、それをターゲットに加工している。し
かしながら、上述の元素を多量に含有しているためＬＳ
Ｉ用としては使用できない。これらの元素は極微量でも
素子の特性に悪影響を及ぼすので、さらにタンタルを高
純度化し、これを用いたタンタルターゲットを製造ｍす
る必要があった。Alkali metals such as a, Na, and K (deterioration of interfacial properties)
b, radioactive elements such as U, Th (soft errors) c, F
Heavy metals such as e, Cr (problems with interfacial bonding) By the way, the tantalum targets currently manufactured industrially are:
Tantalum refined by electrolytic methods is melted into tantalum ingots, which are then used as targets for processing. However, because it contains large amounts of the above-mentioned elements, LS
It cannot be used for I. Since even trace amounts of these elements adversely affect the characteristics of the device, it was necessary to further purify tantalum and manufacture tantalum targets using it.
（発明が解決しようとする課題）
従来の技術で製造したタンタルは不純物濃度が高く、Ｌ
ＳＩ用材料として使用できない。そこで、本発明では半
導体装置に使用可能な高純度タンタル材とその製造方法
及びそれを用いたタンタルターゲットを提供することを
目的とする。(Problem to be solved by the invention) Tantalum manufactured using conventional technology has a high impurity concentration and
Cannot be used as SI material. Therefore, an object of the present invention is to provide a high-purity tantalum material that can be used in semiconductor devices, a method for manufacturing the same, and a tantalum target using the same.
（課題を解決するための手段）
すなわち、本発明は、酸素含有量が５０ｐｐｍ以下、鉄
、ニッケル、クロムの各元素の含有量が０、０５ｐｐｍ
以下であることを特徴とする高純度タンタル材及びこれ
を用いたタンクルターゲットである。(Means for Solving the Problems) That is, the present invention has an oxygen content of 50 ppm or less, and a content of each element of iron, nickel, and chromium of 0.05 ppm.
A high purity tantalum material and a tankle target using the same, characterized by the following:
さらに本発明は、この高純度タンタル材の製造方法であ
って、ヨウ化物分解法により精製したタンタルを５×１
０″” ｍｂａｒ以下の真空中で溶解することを特徴と
する高純度タンタル材の製造方法である。Furthermore, the present invention provides a method for producing this high-purity tantalum material, in which tantalum purified by an iodide decomposition method is
This is a method for producing high-purity tantalum material, which is characterized by melting in a vacuum of 0"" mbar or less.
（作用）
ＬＳＩの集積度の上昇、素子の微細化に対応して、電気
抵抗の増大による信号遅延が問題になってきている。こ
のようなことを背景に、次期電極材料は、電気抵抗が低
いことが求められる。ところで、高融点金属シリサイド
膜中の酸素は、電気抵抗を増加させる。特に近年、成膜
プロセス中の汚染が非常に少なくなり、ターゲット中の
不純物がそのまま膜中の不純物濃度に反映するようにな
ってきている。そこで我々は、Ｔａターゲット中の酸素
濃度と反応性Ｔａシリサイド膜の比抵抗の関係を詳細に
調べた。(Function) In response to the increase in the degree of integration of LSIs and the miniaturization of elements, signal delay due to an increase in electrical resistance has become a problem. Against this background, next-generation electrode materials are required to have low electrical resistance. By the way, oxygen in the high melting point metal silicide film increases electrical resistance. Particularly in recent years, contamination during the film formation process has become extremely low, and impurities in the target are now directly reflected in the impurity concentration in the film. Therefore, we investigated in detail the relationship between the oxygen concentration in the Ta target and the resistivity of the reactive Ta silicide film.
まず多結晶シリコン上に０．１−のＴａ−一一一一膜を
成膜し１０００℃でランプアニールしＴａシリサイド膜
を形成した。Ｔａターゲットの酸素濃度は、それぞれ３
０ｐｐｍ、 ５０ｐｐｍ、 １１００ｐｐ、 ２５０ｐ
ｐｍ、 ４００ｐｐｍである。他の不純物は、はぼ同等
の濃度である。このようにして成膜したＴａシリサイド
膜の比抵抗と酸素濃度の関係を示したのが、第１図であ
る。この結果から明らかなように酸素を１００ｐｐ＋ｍ
以上含むと比抵抗が酸素濃度の増加とともに高くなる。First, a 0.1 - Ta-1111 film was formed on polycrystalline silicon and lamp annealed at 1000° C. to form a Ta silicide film. The oxygen concentration of the Ta target is 3
0ppm, 50ppm, 1100pp, 250p
pm, 400 ppm. Other impurities are at approximately equivalent concentrations. FIG. 1 shows the relationship between the resistivity and oxygen concentration of the Ta silicide film formed in this manner. As is clear from this result, oxygen was added at 100pp+m
If it is included above, the specific resistance increases as the oxygen concentration increases.
このように、反応性Ｔａシリサイド膜の比抵抗を低く抑
えるには、Ｔａターゲット中の酸素濃度は、５０ｐｐｍ
以下でなければならない。In this way, in order to keep the specific resistance of the reactive Ta silicide film low, the oxygen concentration in the Ta target should be 50 ppm.
Must be less than or equal to
一方Ｓｉｎ、に代わる蓄積キャパシタ材料としてＴａ２
Ｏ，を用いる場合、最も大きい問題は、リーク電流が大
きい点である。最近リーク電流がターゲット中の不純物
濃度と関連のあることがわかってきた。特に膜厚が非常
に薄くなってきた場合に、微量不純物の影響が顕著にな
ってくる。そこでリーク電流に与える重金属不純物の影
響について調べるため、製造プロセスの異なる３種類の
ターゲットを用いて反応性スパッタによりＴａ、Ｏｓ薄
膜を作製した。それぞれの鉄、ニッケル、クロムの濃度
を第１表に示す。On the other hand, Ta2 is used as a storage capacitor material instead of Sin.
The biggest problem when using O, is that the leakage current is large. Recently, it has been found that leakage current is related to the impurity concentration in the target. Particularly when the film thickness becomes very thin, the influence of trace impurities becomes noticeable. Therefore, in order to investigate the influence of heavy metal impurities on leakage current, Ta and Os thin films were fabricated by reactive sputtering using three types of targets with different manufacturing processes. Table 1 shows the respective concentrations of iron, nickel, and chromium.
第１表 この第１表に示した以外の元素の濃度はＡ、Ｂ。Table 1 The concentrations of elements other than those shown in Table 1 are A and B.
Ｃ共にほぼ同等である。またその膜厚は、すべて約１５
ｎｍとした。このそれぞれの膜の電界とリーク電流密度
の関係を第２図に示す。鉄、ニッケル。Both C and C are almost equivalent. The thickness of all films is approximately 15
It was set as nm. FIG. 2 shows the relationship between the electric field and leakage current density of each film. iron, nickel.
クロムの濃度が最も低いターゲットＡを用いて成膜した
Ｔａ２Ｏ，は、ターゲットＢ、Ｃを用いたものに比べて
リーク電流が極めて低く重金属元素の低減が、リーク電
流を抑えるのに有効であり、それぞれの濃度を０．０５
ＰＰＩｌ以下とする必要がある。The Ta2O film formed using target A, which has the lowest concentration of chromium, has an extremely low leakage current compared to those using targets B and C. Reduction of heavy metal elements is effective in suppressing leakage current. Each concentration is 0.05
It is necessary to keep it below PPIl.
このようにＶＬＳＩ用のタンタルターゲットは、ナトリ
ウム、カリウムおよびウラン、トリウムの低減も重要で
あるが、酸素９重金属元素の濃度も低くしなければなら
ない、こうした仕様を満たす高純度ターゲットは以下の
ようなプロセスにより製造することができる。In this way, it is important for tantalum targets for VLSI to reduce sodium, potassium, uranium, and thorium, but it is also important to reduce the concentration of oxygen9 heavy metal elements.High-purity targets that meet these specifications are as follows. It can be manufactured by a process.
上述のような高純度タンクルターゲットは、ヨウ化物分
解法と電子ビーム溶解を組み合わせることにより製造し
た高純度タンタル材より得ることができる。このヨウ化
物分解法は化学輸送法の一種であり、タンタルをはじめ
チタ、ン、ジルコニウム、ハフニウム等の活性金属の精
製に使用される方法である。精製は次式〇、■の反応を
利用して行われる。A high-purity tantalum target as described above can be obtained from a high-purity tantalum material produced by a combination of iodide decomposition and electron beam melting. This iodide decomposition method is a type of chemical transport method, and is a method used for purifying active metals such as tantalum, titanium, zirconium, hafnium, etc. Purification is carried out using the reactions of the following formulas 〇 and ②.
Ｔａ ＋ ５／２ Ｉ２ → Ｔａｌ５ （３
００〜７００℃） ■Ｔａｌ５ →Ｔａ ＋ ５／
２ Ｉ２ （８０（１〜１５００℃） ■すなわち、タ
ンタルはヨウ素と３００〜７００℃の温度でＴａＩ、を
生成する（０式）、さらにＴａＩ、は８００〜１５００
℃の高温で前記０式に示すようにタンタルとヨウ素に分
解する性質を有する。第３図は、このヨウ化物分解法に
よる高純度タンタルの製造装置の一例である図中の１は
、原料のタンタル４とヨウ素５を収容する反応容器であ
る。２はフィラメントであり、７ａ、７ｂの接続子を介
して電源６に接続され、通電加熱により８００〜１５０
０℃の温度に加熱される。反応容器全体は恒温槽３の中
に入れられ、３００〜７００℃に保持される。この温度
範囲においては、前述のように０式の反応によって、タ
ンタルとヨウ素が反応してＴａ１．を生成する。 Ｔａ
ｌ５はフィラメント上で０式に従いヨウ素とタンタルに
分解し、フィラメント上にタンタルが析出し、ヨウ素は
再び原料のタンタルと反応してタンタルをフィラメント
上に運ぶ。この際に、原料のタンタル中の不純物はタン
タルよりヨウ素との反応性が低いため原料中に残存し、
原理的には純粋なタンタルのみがフィラメント上に運ば
れる２ヨウ化物分解法による高純度タンタルは、このよ
うな原理で精製が行われる。各種金属ヨウ化物の蒸気圧
は温度に大きく依存し、タンタルヨウ化物の生成温度（
３００〜７００℃）においてはＮａ ＋ Ｋ ＊ Ｕ
＋丁り、 Ｆｅ。Ta + 5/2 I2 → Tal5 (3
00~700℃) ■Tal5 → Ta + 5/
2 I2 (80 (1 to 1500°C)) ■That is, tantalum produces TaI with iodine at a temperature of 300 to 700°C (formula 0), and TaI is 800 to 1500°C.
It has the property of decomposing into tantalum and iodine at a high temperature of °C as shown in the above formula 0. FIG. 3 shows an example of an apparatus for producing high-purity tantalum using this iodide decomposition method. Reference numeral 1 in the figure is a reaction vessel containing tantalum 4 and iodine 5 as raw materials. 2 is a filament, which is connected to the power source 6 through the connectors 7a and 7b, and is heated to a temperature of 800 to 150 by heating with electricity.
It is heated to a temperature of 0°C. The entire reaction vessel is placed in a constant temperature bath 3 and maintained at a temperature of 300 to 700°C. In this temperature range, as mentioned above, tantalum and iodine react by the reaction of equation 0, resulting in Ta1. generate. Ta
l5 decomposes into iodine and tantalum on the filament according to the formula 0, tantalum is precipitated on the filament, and the iodine reacts with the raw material tantalum again to transport tantalum onto the filament. At this time, impurities in the raw material tantalum remain in the raw material because they have lower reactivity with iodine than tantalum.
High-purity tantalum is purified by the diiodide decomposition method, in which only pure tantalum is transported onto the filament, based on this principle. The vapor pressure of various metal iodides greatly depends on temperature, and the formation temperature of tantalum iodide (
300-700℃), Na + K * U
+Ding, Fe.
Ｃｒのヨウ化物の蒸気圧は非常に低くこれより精製効果
が高くなる。The vapor pressure of Cr iodide is very low and the purification effect is higher than this.
一方、電子ビーム溶解法は、蒸気圧の差を利用して不純
物を分離する方法である。特に蒸気圧の高いナトリウム
、カリウムなどは精製効果が高い。On the other hand, the electron beam melting method is a method of separating impurities using a difference in vapor pressure. Particularly effective in refining substances such as sodium and potassium, which have high vapor pressure.
前述したヨウ化物分解法で精製されたチタンは、電子ビ
ーム溶解によりさらに精製される。溶解は。Titanium purified by the iodide decomposition method described above is further purified by electron beam melting. As for dissolution.
５ Ｘ １０−’＋ｍｂａｒ以下の高真空中で行われる
ため酸素や窒素による汚染も少なく高純度のタンタルイ
ンドに仕上げる。Since the process is carried out in a high vacuum of 5 x 10-'+mbar or less, there is little contamination by oxygen or nitrogen, resulting in highly pure tantalum ind.
（実施例）
第３図に示すハステロイ製の反応容器内に原料として市
販のタンタルとヨウ素を入れ、約５５０℃に加熱した恒
温槽の中にいれた。直径２．０ｍのタンタル製フィラメ
ントを直接通電加熱により約１０００℃に加熱しフィラ
メント上にタンタルを析出させた。１０５時間後フィラ
メントが直径２５ａｍまで成長した。このようにして製
造した高純度タンタルをＩ Ｘ １０−’ｍｂａｒの真
空中で電子ビーム溶解を行ないさらに精製した。その後
鍛造９撮械加工によりターゲットに仕上げた。原料、ヨ
ウ化物分解法後、電子ビーム溶解後の分析値を第２表に
示す。(Example) Commercially available tantalum and iodine as raw materials were placed in a Hastelloy reaction vessel shown in FIG. 3, and placed in a constant temperature bath heated to about 550°C. A tantalum filament with a diameter of 2.0 m was heated to about 1000° C. by direct current heating to precipitate tantalum on the filament. After 105 hours, the filament had grown to a diameter of 25 am. The high purity tantalum thus produced was further purified by electron beam melting in a vacuum of I x 10 mbar. After that, it was finished into a target by forging 9-photo machining. Table 2 shows the analytical values for the raw materials, after iodide decomposition, and after electron beam melting.
（以下余白）
この表に示されているように、ヨウ化物分解法と電子ビ
ーム溶解とを組合わせることにより、各々の元素の含有
量を大幅に低減することができる。(Left below) As shown in this table, by combining the iodide decomposition method and electron beam melting, the content of each element can be significantly reduced.
次いでこのターゲットを用いて多結晶シリコン上に０．
１ｚのＴａ薄膜をスパッタリング法により成膜し１００
０℃でランプアニールしＴａシリサイド膜を作製した。This target is then used to deposit 0.00% on polycrystalline silicon.
A Ta thin film of 1z was deposited by sputtering method.
A Ta silicide film was produced by lamp annealing at 0°C.
４端子法により膜の比抵抗を測定したところ３５．２μ
辞房省であった。The specific resistance of the membrane was measured using the 4-terminal method and was 35.2μ.
It was the Ministry of Education.
また、上述のターゲットを用いて反応性スパッタにより
Ｔａ、 Ｏ，膜を成膜し、電界をかけてその時のリーク
電流を測定したところ、２．５μ■の時ＩＸ １０−”
Ａ−Ｃａｌ−７のリーク電流密度であった。In addition, when a Ta, O, film was formed by reactive sputtering using the above-mentioned target, and the leakage current was measured by applying an electric field, it was found that IX 10-'' at 2.5μ■
It was the leakage current density of A-Cal-7.
本発明によれば、ヨウ化物分解法によりタンタルを電子
ビーム溶解することにより、従来よりさらに高純度なタ
ンタル材を製造することができ、これより高純度のタン
タルターゲットが得られる。According to the present invention, by electron beam melting tantalum using an iodide decomposition method, it is possible to produce a tantalum material with higher purity than in the past, and a tantalum target with higher purity can be obtained.
第１図は反応性Ｔａシリサイド膜比抵抗とＴａターゲッ
ト中の酸素濃度の関係を示す特性図、第２図はＴａ、
０．薄膜のリーク電流の電界強さ依存性を示す特性図、
第３図は従来のヨウ化物分解法の製造装置の概略図であ
る。
１・・・反応容器、 ２・・・フィラメント３・
・・恒温槽、 ４・・・タンタル５・・・ヨウ
素、 ６・・・電源７ａ、 ７ｂ・・・接続子Figure 1 is a characteristic diagram showing the relationship between the specific resistance of the reactive Ta silicide film and the oxygen concentration in the Ta target.
0. Characteristic diagram showing the dependence of thin film leakage current on electric field strength,
FIG. 3 is a schematic diagram of a production apparatus for a conventional iodide decomposition method. 1... Reaction container, 2... Filament 3.
... Constant temperature chamber, 4 ... Tantalum, 5 ... Iodine, 6 ... Power supply 7a, 7b ... Connector
Claims (4)
クロムの各元素の含有量が０．０５ｐｐｍ以下であるこ
とを特徴とする高純度タンタル材。(1) Oxygen content is 50 ppm or less, iron, nickel,
A high-purity tantalum material characterized in that the content of each element of chromium is 0.05 ppm or less.
１０＾−＾５ｍｂａｒ以下の真空中で溶解することを特
徴とする請求項１記載の高純度タンタル材の製造方法。(2) Tantalum purified by iodide decomposition method 5x
2. The method for producing high-purity tantalum material according to claim 1, characterized in that the melting is carried out in a vacuum of 10^-^5 mbar or less.
する請求項２記載の高純度タンタル材の製造方法。(3) The method for producing high-purity tantalum material according to claim 2, characterized in that the melting is performed by an electron beam melting method.
ことを特徴とするタンタルターゲット。(4) A tantalum target characterized by using the high-purity tantalum material according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1334805A JP3031474B2 (en) | 1989-12-26 | 1989-12-26 | Method for manufacturing high-purity tantalum material, tantalum target, thin film, and semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1334805A JP3031474B2 (en) | 1989-12-26 | 1989-12-26 | Method for manufacturing high-purity tantalum material, tantalum target, thin film, and semiconductor device |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29470698A Division JP3207393B2 (en) | 1989-12-26 | 1998-10-02 | High-purity tantalum material, tantalum target using the same, thin film and semiconductor device formed using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03197640A true JPH03197640A (en) | 1991-08-29 |
| JP3031474B2 JP3031474B2 (en) | 2000-04-10 |
Family
ID=18281427
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1334805A Expired - Lifetime JP3031474B2 (en) | 1989-12-26 | 1989-12-26 | Method for manufacturing high-purity tantalum material, tantalum target, thin film, and semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3031474B2 (en) |
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