JPS62174373A - Chromium target material and its production - Google Patents
Chromium target material and its productionInfo
- Publication number
- JPS62174373A JPS62174373A JP23220486A JP23220486A JPS62174373A JP S62174373 A JPS62174373 A JP S62174373A JP 23220486 A JP23220486 A JP 23220486A JP 23220486 A JP23220486 A JP 23220486A JP S62174373 A JPS62174373 A JP S62174373A
- Authority
- JP
- Japan
- Prior art keywords
- less
- target material
- purity
- powder
- chromium
- 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
- 239000013077 target material Substances 0.000 title claims abstract description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 38
- 239000011651 chromium Substances 0.000 title claims description 31
- 229910052804 chromium Inorganic materials 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002775 capsule Substances 0.000 claims abstract description 26
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000010959 steel Substances 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 239000004033 plastic Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001513 hot isostatic pressing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 abstract description 10
- 238000007740 vapor deposition Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract 3
- 230000002706 hydrostatic effect Effects 0.000 abstract 2
- 238000012856 packing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 239000013078 crystal Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000005056 compaction Methods 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は乾式クロム蒸着被覆に使用する素材及びその製
造方法、いわゆるスパッタリング、イオン蒸着などのタ
ーゲツト材及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a material used for dry chromium vapor deposition coating and a method for producing the same, a target material for so-called sputtering, ion vapor deposition, etc. and a method for producing the same.
エレクトロニクス産業において、クロム蒸着薄膜はＬＳ
Ｉ製造時のマスキング用、磁気ハードディスクの基盤コ
ーティング用などにスパッタリング法、イオンブレーテ
ィング法などにより製作し、盛んに利用されている。In the electronics industry, chromium-deposited thin films are LS
It is manufactured by sputtering method, ion blating method, etc., and is widely used for masking during I manufacturing and for base coating of magnetic hard disks.
このクロムターゲット材はその要求特性として高純度の
もの、少なくとも、９９．５％以上のものが要求されて
おり、それぞれの用途、装置に応じて９９．９％以上、
９９．９９％以上などの基準のものもある。This chromium target material is required to have high purity, at least 99.5% or higher, depending on the application and equipment.
There are also standards such as 99.99% or higher.
このような高純度クロムの製造法としては、クロム酸溶
液の電気分解法、クロム酸溶液から不純物の有機溶媒抽
出による精製クロム酸化物の水素還元法、電気分解相ク
ロムを沃素化し、これを熱分解する沃素法、または金属
カルシウム蒸気によるＣａ還元法などがある。電解クロ
ムは酸素、水素などのガス含有量が多い。沃素法は、８
００℃付近で沃素と反応させ、生成沃化物を昇華させて
１１００〜１３００℃のフィラメント上に熱分解させる
法でＣ１０、Ｎなどの非金属元素をとくに低くすること
ができる。Ｃａ還元法は高真空容器内で金属Ｃａと粗ク
ロムとを１０００℃前後に加熱するとＣａが蒸発し、蒸
気圧２０ｎｗｎｌ（ｇとなり、粗クロムを還元する。一
方、この蒸気は反応管中の低温域に蒸着する。このよう
にしてＣａ蒸気と接することによりクロム中の酸素を還
元するものであるがＣａＯなどが混在する。Methods for producing such high-purity chromium include electrolysis of a chromic acid solution, hydrogen reduction of purified chromium oxide by organic solvent extraction of impurities from a chromic acid solution, and iodine of electrolytic phase chromium, which is then heated. Examples include the decomposition iodine method and the Ca reduction method using metallic calcium vapor. Electrolytic chromium has a high content of gases such as oxygen and hydrogen. The iodine method is 8
The content of nonmetallic elements such as C10 and N can be particularly reduced by reacting with iodine at around 00°C, sublimating the produced iodide, and thermally decomposing it on a filament at 1100 to 1300°C. In the Ca reduction method, metallic Ca and crude chromium are heated to around 1000°C in a high-vacuum container, and the Ca evaporates, giving a vapor pressure of 20 nwnl (g) and reducing the crude chromium. In this way, oxygen in chromium is reduced by contacting with Ca vapor, but CaO and the like are mixed therein.
このようにして得られた高純度クロムは粒状。The high-purity chromium obtained in this way is in granular form.
板状、粉状であり、ターゲット用として使用するときは
溶解鋳造、圧縮、焼結などによって成形する必要があり
、それぞれ次のような問題点がある。They are in the form of plates or powders, and when used as targets, they must be formed by melting casting, compression, sintering, etc., and each has the following problems.
クロムを溶解するには真空中または不活性ガス雰囲気中
で１８８０℃以上の高温加熱をする必要がある。酸素と
の反応性が強いため、高級ルツボ材、たとえばジルコニ
ア質、アルミナ質でなげねばならず、それでもなお酸素
を取り込む。すなわちルツボ材により汚染される結果と
なる。また、他方溶解鋳造は凝固収縮を生ずるため押湯
は不可欠であり、総じて全部の歩留は７０％以下である
。To melt chromium, it is necessary to heat it to a high temperature of 1880° C. or higher in a vacuum or an inert gas atmosphere. Because of its strong reactivity with oxygen, it must be treated with high-grade crucible materials such as zirconia and alumina, which still absorb oxygen. In other words, this results in contamination by the crucible material. On the other hand, since melt casting causes solidification shrinkage, a riser is indispensable, and the overall yield is generally less than 70%.
さらに紡造品は鋳造結晶粒が粗大化しやすく、そのまま
では熱間、温間、冷間の塑性加工は不可能であり、鋼製
またはステンレス製のカプセルにて包み、これと−緒に
塑性加工をおこなえば、小物についてはどうにか塑性加
工が可能であるが、鋳造インゴット肉厚が７０Ｉｌ１１
１程度以上になると非常に困難である。このため、従来
はターゲツト材の製品は、鋳造インゴットそのものから
切出していたために必然的に歩留は相当劣るものであっ
た。Furthermore, the cast crystal grains of textile products tend to become coarse, and hot, warm, and cold plastic processing is impossible if they are left untreated, so they are wrapped in a steel or stainless steel capsule, and plastic processing is carried out along with them. If you do this, it is possible to plastically process small items, but the thickness of the cast ingot is 70Il11.
It is extremely difficult when the value exceeds about 1. For this reason, in the past, target material products were cut from the cast ingot itself, which inevitably resulted in a considerably poor yield.
他方圧縮成形後、焼結する方法も提案されている。圧縮
成形をおこなう場合、潤滑剤などに起因する汚染防止、
さらに１５００℃以上にもおよぶ焼結温度に起因する酸
化防止のための高純度水素の利用、および還元ガス中に
生ずる水蒸気の急速な排出法が必要である。すなわち雰
囲気中の水蒸気分圧の厳重な調整を必要とする。On the other hand, a method of sintering after compression molding has also been proposed. When performing compression molding, prevent contamination caused by lubricants, etc.
Furthermore, there is a need for the use of high purity hydrogen to prevent oxidation due to the sintering temperatures of over 1500° C., and a method for rapidly discharging the water vapor generated in the reducing gas. In other words, strict adjustment of the water vapor partial pressure in the atmosphere is required.
かくして得られた焼結晶はなお焼結粒間に若干の細孔が
残り、顕微鏡下でａｍされる。そのために熱間、温間、
冷間の塑性加工が回連であり、前述のようにステンレス
などのカプセルに収納して熱間加工をしてもカプセル中
で破砕し、加工は不可能に近いものであった。さらにか
かる圧縮成形−水素気流中焼結という方法では、圧縮成
形の際残留応力の不均一のために変形、亀裂などの問題
が発生するため、等方加圧法ラバープレスなどの利用も
報告されている（特公昭６０−４２４１号）が、この場
合も焼結後焼結粒間に細孔が残り、ターゲット部品を作
製する場合は塑性加工が不可能なため焼結晶より直接切
出し１機械加工仕上に依らざるを得なかった。The thus obtained sintered crystals still have some pores between the sintered grains and are examined under a microscope. For that purpose, hot, warm,
Cold plastic working is repeated, and as mentioned above, even if it was placed in a capsule made of stainless steel or the like and hot worked, it would fracture in the capsule, making processing nearly impossible. Furthermore, with this method of compression molding and sintering in a hydrogen stream, problems such as deformation and cracking occur due to non-uniform residual stress during compression molding, so the use of isostatic pressure method rubber press etc. has also been reported. (Japanese Patent Publication No. 60-4241), but in this case as well, pores remain between the sintered grains after sintering, and plastic working is not possible when producing target parts, so the sintered crystal is directly cut out and machined. I had no choice but to rely on it.
更に以上のような問題点を解決する高クロム合金材の製
造法として特開昭５５−１５４５５１号に、特定条件下
で原料粉末をカプセルに封入し、次いで熱間等方静水圧
成形、熱間加工する発明が開示されている。Furthermore, as a manufacturing method for high chromium alloy materials that solves the above-mentioned problems, Japanese Patent Application Laid-Open No. 55-154551 describes a method in which raw material powder is encapsulated in capsules under specific conditions, followed by hot isostatic pressing and hot isostatic pressing. An invention for processing is disclosed.
本発明者らは１以上の公知技術を基に研究を行なった結
果、クロムターゲット材として最適の製造方法、および
蒸着性の優れたクロムターゲット材の発明に至ったもの
である。As a result of research conducted by the present inventors based on one or more known techniques, they have arrived at the invention of an optimal manufacturing method for a chromium target material and a chromium target material with excellent vapor deposition properties.
本発明は、純度９９．５％以下で、炭素、窒素をそれぞ
れ０．０５％以下、残部不可避的不純物よりなり、粒度
２０メツシュ以下が９０％、残部１０メツシュ以下であ
る高純度金属クロム粉末を熱間等方静水圧成形したこと
を特徴とするクロムターゲット材、および純度９９．５
％以上で炭素、窒素をそれぞれ０．０５％以下、残部不
可避的不純物よりなり、粒度２０メツシュ以下が９０％
、残部１０メツシュ以下である高純度金属クロム粉末を
鋼またはステンレス鋼カプセルに充填し、 １１０−３
ｎｎＨ以下で真空密封したのち、１０００℃以上、５０
０ｋｇｆ／ｃｍ２以上の圧力で３０分以上熱間等方静水
圧成形することを特徴とするクロムターゲット材の製造
方法である。なお、本願発明方法において前記熱間等方
静水圧成形後に７００−１２００℃の温度範囲で熱間加
工をする、更に引き続いて５０％以下の加工率で塑性加
工、望ましくは２５０℃以上で温間加工をし、最終的に
６００〜１１００℃の範囲で２０分以上加熱処理して焼
なまし処理する態様で実施することが望ましい。The present invention provides high-purity metallic chromium powder with a purity of 99.5% or less, carbon and nitrogen content of 0.05% or less each, and the balance consisting of unavoidable impurities, 90% of which has a particle size of 20 mesh or less, and the remainder 10 mesh or less. A chromium target material characterized by hot isostatic pressing, and a purity of 99.5
% or more, carbon and nitrogen are each 0.05% or less, the balance is unavoidable impurities, and 90% has a particle size of 20 mesh or less.
, filling a steel or stainless steel capsule with high-purity metallic chromium powder with a balance of 10 mesh or less, 110-3
After vacuum sealing at nnH or less, 1000℃ or more, 50
This is a method for producing a chromium target material, characterized by hot isostatic pressing at a pressure of 0 kgf/cm2 or more for 30 minutes or more. In addition, in the method of the present invention, after the hot isostatic pressing, hot working is performed in a temperature range of 700-1200°C, and subsequently, plastic working is performed at a working rate of 50% or less, preferably warm at 250°C or higher. It is desirable to carry out the process in such a manner that the material is processed and finally annealed by heat treatment in the range of 600 to 1100° C. for 20 minutes or more.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
まず、ターゲツト材について説明する。First, the target material will be explained.
純度を９９．５％以上としたのは、これ以下の純度では
ターゲツト材としては不向であるためである。The reason why the purity is set to 99.5% or more is because if the purity is lower than this, it is not suitable as a target material.
また、Ｃ，Ｎの濃度を５００ＰＰｏ＋以下としたのはＣ
１Ｎはクロムの延伸性に関係深く、含有量が多くなると
硬さも高くなり脆化して来る。このため、蒸着薄膜の剥
離がおこる。そのために５００ＰＰｍを越えることは好
ましくない。In addition, the concentration of C and N was set to 500 PPo+ or less because C
1N is closely related to the extensibility of chromium, and as the content increases, the hardness increases and the chromium becomes brittle. For this reason, peeling of the deposited thin film occurs. Therefore, it is not preferable to exceed 500 PPm.
また、使用する高純度金属クロム粉末の粒度を２０メツ
シュ以下９０％以上、残部１０メツシュ以下としたのは
、それ以上の粗粒が混じると熱間加工時に破砕するため
である。Furthermore, the particle size of the high-purity metal chromium powder used is set to 90% or less of 20 mesh or less, and the remainder to 10 mesh or less, because if larger coarse particles are mixed in, they will be crushed during hot working.
次に本発明ターゲツト材の製造方法について説明する。Next, a method for manufacturing the target material of the present invention will be explained.
使用する高純度金属クロム粉末については上述の通りで
ある。The high purity metallic chromium powder used is as described above.
前記高純度金属クロム粉末を鋼またはステンレス製カプ
セルに１０’ ｎｎ１１ｇ以下の真空条件下で密封する
が、これは１０すｍｍ１ｇを越えると、原料粉末に付着
しているガスや水分等の除去が十分に行なわれないため
である。この際カプセルの肉厚は４ｍｍ以下が望ましい
。The high-purity metal chromium powder is sealed in a steel or stainless steel capsule under vacuum conditions with a weight of 10 mm or less, but if it exceeds 10 mm or 1 g, gases, moisture, etc. attached to the raw material powder can be removed sufficiently. This is because it will not be done. In this case, the wall thickness of the capsule is preferably 4 mm or less.
次に高純度金属クロム粉末を充填したこのカプセルを熱
間等方静水圧圧密装置ｉ！（ＨＩＰ）により、１０００
℃以上で圧力５００ｋｇｆ／ａｄで０．５時間以上圧密
する。Next, this capsule filled with high-purity metal chromium powder is placed in a hot isostatic pressure compaction machine i! (HIP), 1000
Consolidation is performed at a temperature of 500 kgf/ad or more at a temperature of 0.5 hours or more.
この方法によるとたとえば２００ ｍｍφ程度の素材の
中心にても十分圧密効果が及んでおり、顕微鏡観察によ
っても、粒子間に細孔は検知されない。According to this method, the compaction effect is sufficient even in the center of a material of, for example, about 200 mmφ, and no pores are detected between the particles even by microscopic observation.
また密度もほぼ理論密度に到達している。Moreover, the density has almost reached the theoretical density.
かくして得られた圧密品をカプセルのまま８５０〜１１
５０℃で熱間加工を行なえば容易に板状のもの。The compressed product obtained in this way is 850 to 11
It can be easily made into a plate by hot working at 50°C.
棒状のものを作り得る。加熱温度を８５０〜１１５０℃
とするのは、８５０℃未満では加工時割れが生ずる危険
があり、また１１５０℃を越えると熱間加工が困難なた
めである。You can make stick-shaped things. Heating temperature 850-1150℃
This is because if the temperature is lower than 850°C, there is a risk of cracking during processing, and if the temperature exceeds 1150°C, hot working is difficult.
このように８５０〜１１５０℃にて熱間加工を行なえば
。If hot working is performed at 850 to 1150°C in this way.
その後さらに塑性加工が可能となる。特に、加工率５０
％以下、２５０℃以上の温間にて加工すると、結晶粒が
繊細になり、靭性が向上し、このため研削などの機械加
工が容易となる。さらにカプセルの肉厚の検知を可能に
し、目標寸法に精度よく仕上げることができるようにな
る。そのため製品歩留が向上する。After that, further plastic working becomes possible. In particular, the processing rate is 50
% or less, and when processed at a temperature of 250° C. or higher, the crystal grains become finer and the toughness improves, making machining such as grinding easier. Furthermore, it becomes possible to detect the wall thickness of the capsule, allowing it to be finished to target dimensions with high accuracy. Therefore, product yield is improved.
この温間加工前の焼なましは必ずしも必要でなく、加工
率、硬さなどにより決める。This annealing before warm working is not necessarily necessary, and is determined depending on the processing rate, hardness, etc.
最終的には、結晶粒を微細化させない温度域、時間で焼
なましを行なう。Finally, annealing is performed within a temperature range and for a time that does not cause grain refinement.
以上の工程が終了したら最終的にはカプセル部は除去さ
れる。カプセル部を研削除去して、希望とする寸法のも
のに作ることができ、塩酸または王水でエッチすればク
ロム質と容易に区別することができる。After the above steps are completed, the capsule portion is finally removed. It can be made into desired dimensions by removing the capsule, and can be easily distinguished from chromium by etching with hydrochloric acid or aqua regia.
このようにして作ったターゲツト材は使用中にガスを発
生することもなく、蒸着クロムの厚さの不均一、またタ
ーゲツト板の肌荒れ、消耗の不均一などの欠陥は全くな
い。鋳造のままのターゲツト材では結晶粒の粗大不揃い
のためにピット発生、また焼結晶ターゲットではガス気
孔に由来すると考えられるピット発生のトラブルが発生
して再研磨は不可避であったが、Ｉ（ＩＰｍによるター
ゲツト材ではこれらはなくなった。なお、最終時の焼な
ましは残留応力の除去のためで、これが残留すると機械
加工後、またはスパッタリング使用時変形を起こすため
である。The target material produced in this manner does not generate gas during use and has no defects such as uneven thickness of deposited chromium, rough surface of the target plate, or uneven wear. In the as-cast target material, pits occur due to coarse and irregular crystal grains, and in the case of fired crystal targets, pits occur due to gas pores, making re-polishing unavoidable. These problems disappeared in the target material produced by the method.Final annealing was performed to remove residual stress, which would cause deformation after machining or during sputtering.
実施例１
純度９９．６％、Ｃ１２０ｐｐｍ、 Ｎ ８０ｐｐｍ、
０４００ｐｐｍの純クロム粉末で、９０％以上が４８
メツシュ以下で残部１０メツシュ以下の粒度のものを鋼
製のカプセル（径６０φ、長さ２８０ｍｍ、肉厚２ ｒ
ｍ ）に１０−’ ＋ｍＨｇの真空下で密封した。これ
を１１８０℃で１００１００Ｏ／ａｉｒの圧力で１時間
ＨＩ Ｐにて圧密した。圧密化後の純度、Ｃ，Ｎ、Ｏ量
は粉末時と変動がなかった（以下の実施例も同様）。こ
れより直径１０ｍｍφ、長１０ｎｗｎの鍛造試験片を切
出し、鍛造試験機により高温で衝撃エネルギーを加えて
変形率と亀裂の発生の有無を調べた。結果を図に示す。Example 1 Purity 99.6%, C 120 ppm, N 80 ppm,
0400ppm pure chromium powder, more than 90% is 48
A steel capsule (diameter 60 φ, length 280 mm, wall thickness 2 r
m) was sealed under a vacuum of 10-' + mHg. This was consolidated by HIP at 1180° C. and a pressure of 100,100 O/air for 1 hour. The purity, C, N, and O content after compaction did not vary from that of the powder (the same applies to the following examples). From this, a forged test piece with a diameter of 10 mmφ and a length of 10 nwn was cut out, and impact energy was applied at high temperature using a forging tester to examine the deformation rate and the presence or absence of cracks. The results are shown in the figure.
７００〜１０５０℃の範囲では３５〜４５％の変形率ま
で亀裂のないことがわかった。It was found that there was no cracking in the range of 700 to 1050°C up to a deformation rate of 35 to 45%.
変形率とは、（Ｑｌ−Ｑ□）ｘｔＯＯ／Ｑ□で表わす。The deformation rate is expressed as (Ql-Q□)xtOO/Q□.
Ｑ□、Ｑ２は鍛造前後の長さを示す。Q□ and Q2 indicate the length before and after forging.
実施例２
純度９９．９９％、Ｃ１８ｐｐｍ、 Ｎ １０ｐｐｍ、
０３０ｐｐｍの沃化物分解法によって製造した純クロ
ム粒を粉砕し９０％以上を２８メツシュ以下、残部１０
メツシュ以下として、これを５ＵＳ３０４ステンレス製
のカプセル（内径２４０ｎｗｎφ、高さ４０ｎｖｎ、肉
厚３ｍ）に充填し、１０’ ｎ＋ｍＨｇにて真空吸引し
て密封した。このカプセルをＨＩＰにて１２００℃、１
００１００Ｏ／ａ＋ｆにて１時間圧密したのち、カプセ
ルに包んだまま９５０〜１１５０℃の範囲にて熱間加工
し、全体を１２ｍの板にしたのち、ステンレスカプセル
を取除いて９ｍｍのクロム板を作った。９５０℃にて１
時間加熱徐冷して焼なまししたのち、スパッタリング用
ターゲットに切削加工仕上した。Example 2 Purity 99.99%, C18ppm, N 10ppm,
Pure chromium grains produced by the iodide decomposition method at 0.30 ppm are crushed, 90% or more are 28 mesh or less, and the remainder is 10
The mixture was packed into a 5US304 stainless steel capsule (inner diameter 240nwnφ, height 40nvn, wall thickness 3m) and sealed by vacuum suction at 10'n+mHg. This capsule was heated at 1200℃ in HIP for 1
After consolidating at 00100O/a+f for 1 hour, hot working in the range of 950 to 1150℃ while still encased in the capsule, the whole was made into a 12m plate, and the stainless steel capsule was removed to make a 9mm chrome plate. Ta. 1 at 950℃
After being annealed by heating and slowly cooling for a period of time, it was finished by cutting into a sputtering target.
スパッタリング性の評価をおこなったが、作業は安定し
ていて、結晶粒間ピッティングも少なく。We evaluated the sputtering properties and found that the work was stable and there was little pitting between grains.
使用中も肌荒れなどなく蒸着膜も均等であり良好な膜が
得られた。鋳造品、焼結晶の切出法によるターゲツト材
では、５０時間のスパッタ一時間毎に平面研削が必要で
あるのに対し、本ターゲットでは肌荒れもなく、研削も
不必要であった。Even during use, there was no roughening of the skin, and the deposited film was uniform and good. Target materials made by cutting out cast products or fired crystals require surface grinding every hour of sputtering for 50 hours, but this target did not have rough surfaces and did not require grinding.
実施例３
Ｃｒ純度９９．７％、Ｃ８００ｐｐｍ、 Ｎ ５００ｐ
ｐｍの純Ｃｒ粉を−２８メツシュ９５％に粉砕し、 Ｓ
ＵＳ３０４ｍカプセル（１８０ｘ４０ｎｍ）に１０−ｓ
ｍｍＨｇの真空下で充填し、これを１１８０℃１０１０
００）ｃ／ｄの圧力下で圧密した。次いでこれを実施例
２と同様な方法で圧延し、１５３φＸ８＋＋ｗ＋＋ｔの
ターゲットを作った。Example 3 Cr purity 99.7%, C800ppm, N 500p
pm pure Cr powder is crushed to -28 mesh 95%, S
10-s in US304m capsule (180x40nm)
Filled under a vacuum of mmHg and heated to 1180℃1010
00) Consolidated under pressure of c/d. This was then rolled in the same manner as in Example 2 to produce a target of 153φX8++w++t.
スパッタリング方式により、１２００人の薄膜を作製し
てフレメンステストにより剥離性を比較した。Thin films were prepared by 1200 people using the sputtering method, and their removability was compared using the Flemens test.
５０ｇ荷重で実施した結果、剥離が生じた。一方。As a result of carrying out the test with a load of 50 g, peeling occurred. on the other hand.
実施例２のターゲットから得られた薄膜では１２００人
にて６０ｇの荷重にても全く剥離は認められなかった・
実施例４
実施例２と同様にして全体を１２ｎｗａの板とし、さら
に８８０℃にて１時間加熱焼なましをしたのち、６００
°Ｃにて温間加工を行ない、１０ｎｗｎの板厚とした。In the thin film obtained from the target of Example 2, no peeling was observed at all even under a load of 60 g by 1200 people. Example 4 A 12 nwa plate was formed as a whole in the same manner as Example 2, and further heated to 880°C. After heating and annealing for 1 hour,
Warm working was performed at °C to give a plate thickness of 10 nwn.
これを８５０℃で３０分焼なまししたのち、カプセルを
削除して８．４冊のクロム板を作った。組織は、細長く
伸びた結晶粒と一部再結晶した混合組織となっており、
硬さはｔ（ｖ１５０であった。ターゲツト材に機械加工
したが、ｅｄｇｅの欠けなどのトラブルがなく、靭性が
高く取扱い易いものであった６実施例５
Ｃｒ純度９９０ｇ％、Ｃ１７０ｐｐｍ、 Ｎ ３３０ｐ
ｐｍ、 ０４００ｐｐｍの水素還元法で得られたクロム
を粉砕し、２８メツシュ以下のものを９５％、残部１０
メツシュ以下として、これを内径１６０１ｗｗφ、高さ
４０＋＋ｗ＋＋のステンレス製カプセルに充填し、１０
’ ｎｗＨＨの真空中で密封し、これを１２００℃、１
０００気圧にて１．５時間、ＨＩＰ！＠にて圧密した。After annealing this at 850°C for 30 minutes, the capsules were removed and 8.4 chrome plates were made. The structure is a mixed structure with elongated crystal grains and some recrystallization.
The hardness was t(v150). Although the target material was machined, there were no problems such as edge chipping, and it had high toughness and was easy to handle.6 Example 5 Cr purity 990g%, C170ppm, N 330p
pm, 0400 ppm chromium obtained by hydrogen reduction method is crushed, 95% is less than 28 mesh, and the remainder is 10
Fill it into a stainless steel capsule with an inner diameter of 1601wwφ and a height of 40++w++, and
' nwHH sealed in vacuum and heated at 1200°C for 1
HIP! for 1.5 hours at 000 atm! Consolidated at @.
これをステンレス製カプセルのまま８５０〜１０５０℃
の範囲内にて熱間加工して２０ｍｍ板厚とした。さらに
これを冷間で１６ｍｍの板厚まで加工し、８５０℃にて
１時間焼なましをおこない、冷間で１３ｍｍの板厚に仕
上げた。途中カプセルの亀裂、その他のトラブルはなか
った。さらに８５０℃にて焼なまししたのち、カプセル
を切削除去して９■厚の純クロム製スパッタリングター
ゲットを作製した。スパッタリング性の評価、蒸着膜の
耐剥離性などをおこない、満足すべき結果が得られた。This is kept in a stainless steel capsule at 850-1050℃.
The plate was hot worked within the range of 20 mm in thickness. Further, this was cold worked to a thickness of 16 mm, annealed at 850° C. for 1 hour, and finished to a thickness of 13 mm by cold working. There were no cracks in the capsule or other troubles during the flight. After further annealing at 850°C, the capsule was cut and removed to produce a pure chromium sputtering target with a thickness of 9 cm. Satisfactory results were obtained by evaluating the sputtering properties and peeling resistance of the deposited film.
以上説明のように本発明によれば、蒸着性の良好なりロ
ムターゲットを高歩留で製造することが可能であり工業
上有益である。As described above, according to the present invention, it is possible to produce a ROM target with good vapor deposition properties at a high yield, which is industrially useful.
第り図は実施例１における鍛造試験結果である。各温度
において、亀裂の発生をみない変形率の限度を示したも
のである。これにより区域Ａは亀裂の発生しない範囲を
示すものである。
第 ｌ 図
加Ｍ温泉℃Figure 2 shows the forging test results in Example 1. This shows the limit of the deformation rate without cracking at each temperature. As a result, area A indicates a range in which no cracks occur. Figure l KaM hot spring ℃
Claims (1)
５％以下、残部不可避的不純物からなり、粒度２０メッ
シュ以下が９０％以上、残部１０メッシュ以下である高
純度金属クロム粉末を熱間等方静水圧成形したことを特
徴とするクロムターゲット材。 ２ 純度９９．５％以上で炭素、窒素をそれぞれ０．０
５％以下、残部不可避的不純物からなり、粒度２０メッ
シュ以下が９０％以上、残部１０メッシュ以下である高
純度金属クロム粉末を鋼またはステンレス鋼カプセルに
充填し、１０＾−＾３ｍｍＨｇ以下で真空密封したのち
１０００℃以上、５００ｋｇｆ／ｃｍ＾２以上の圧力で
３０分以上熱間等方静水圧成形することを特徴とするク
ロムターゲット材の製造方法。 ３ 熱間等方静水圧成形後、７００〜１２００℃の温度
範囲で熱間加工する特許請求の範囲第２項記載のクロム
ターゲット材の製造方法。 ４ 熱間等方静水圧成形後、７００〜１２００℃の温度
範囲で熱間加工し、さらに５０％以下の加工率で塑性加
工を行なう特許請求の範囲第２項記載のクロムターゲッ
ト材の製造方法。 ５ 塑性加工が５０％以下の加工率、２５０℃以上の温
度で実施される特許請求の範囲第４項記載のクロムター
ゲット材の製造方法。 ６ 塑性加工後、６００〜１１００℃の範囲で２０分以
上加熱して焼なまし処理する特許請求の範囲第４項ない
し第５項のいずれかに記載のクロムターゲット材の製造
方法。[Claims] 1. Purity of 99.5% or more and 0.0% carbon and 0.0% nitrogen each
A chromium target material obtained by hot isostatically forming a high-purity metallic chromium powder having a particle size of 5% or less, the remainder consisting of unavoidable impurities, 90% or more having a particle size of 20 mesh or less, and the remainder 10 mesh or less. 2. Purity 99.5% or higher, carbon and nitrogen each 0.0
Fill a steel or stainless steel capsule with high-purity metallic chromium powder, which consists of 5% or less, the balance being unavoidable impurities, 90% or more having a particle size of 20 mesh or less, and the remainder 10 mesh or less, and vacuum-sealing at 10^-^3mmHg or less. A method for producing a chromium target material, which is then subjected to hot isostatic pressing at a temperature of 1000° C. or higher and a pressure of 500 kgf/cm^2 or higher for 30 minutes or longer. 3. The method for producing a chromium target material according to claim 2, wherein hot isostatic pressing is followed by hot working in a temperature range of 700 to 1200°C. 4. The method for producing a chromium target material according to claim 2, wherein after hot isostatic pressing, hot working is performed in a temperature range of 700 to 1200°C, and further plastic working is performed at a working rate of 50% or less. . 5. The method for producing a chromium target material according to claim 4, wherein the plastic working is performed at a working rate of 50% or less and a temperature of 250° C. or more. 6. The method for producing a chromium target material according to any one of claims 4 to 5, which comprises annealing by heating at a temperature of 600 to 1100° C. for 20 minutes or more after plastic working.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-221457 | 1985-10-04 | ||
| JP22145785 | 1985-10-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62174373A true JPS62174373A (en) | 1987-07-31 |
| JPH032230B2 JPH032230B2 (en) | 1991-01-14 |
Family
ID=16767023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23220486A Granted JPS62174373A (en) | 1985-10-04 | 1986-09-30 | Chromium target material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62174373A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03150356A (en) * | 1989-11-02 | 1991-06-26 | Hitachi Metals Ltd | Tungsten or molybdenum target and production thereof |
| EP1746173A2 (en) * | 2005-07-22 | 2007-01-24 | Heraeus, Inc. | Enhanced sputter target manufacturing method |
| EP1923481A2 (en) * | 2005-07-22 | 2008-05-21 | Heraeus, Inc. | Enhanced sputter target manufacturing method |
| CN103785838A (en) * | 2012-11-01 | 2014-05-14 | 宁波江丰电子材料有限公司 | Chromium target production method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126451A (en) * | 1977-03-30 | 1978-11-21 | Airco, Inc. | Manufacture of plates by powder-metallurgy |
| JPS55154551A (en) * | 1979-05-18 | 1980-12-02 | Mitsubishi Metal Corp | Manufacture of high chromium alloy material |
| JPS5792103A (en) * | 1980-10-04 | 1982-06-08 | Heraeus Gmbh W C | Manufacture of target from chromium or chromium base alloy |
| JPS5855502A (en) * | 1981-09-28 | 1983-04-01 | Toyo Soda Mfg Co Ltd | Preparation of metal chromium plate |
| JPS604241A (en) * | 1983-06-22 | 1985-01-10 | Nec Corp | Semiconductor device |
-
1986
- 1986-09-30 JP JP23220486A patent/JPS62174373A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4126451A (en) * | 1977-03-30 | 1978-11-21 | Airco, Inc. | Manufacture of plates by powder-metallurgy |
| JPS55154551A (en) * | 1979-05-18 | 1980-12-02 | Mitsubishi Metal Corp | Manufacture of high chromium alloy material |
| JPS5792103A (en) * | 1980-10-04 | 1982-06-08 | Heraeus Gmbh W C | Manufacture of target from chromium or chromium base alloy |
| JPS5855502A (en) * | 1981-09-28 | 1983-04-01 | Toyo Soda Mfg Co Ltd | Preparation of metal chromium plate |
| JPS604241A (en) * | 1983-06-22 | 1985-01-10 | Nec Corp | Semiconductor device |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03150356A (en) * | 1989-11-02 | 1991-06-26 | Hitachi Metals Ltd | Tungsten or molybdenum target and production thereof |
| EP1746173A2 (en) * | 2005-07-22 | 2007-01-24 | Heraeus, Inc. | Enhanced sputter target manufacturing method |
| EP1746173A3 (en) * | 2005-07-22 | 2007-05-09 | Heraeus, Inc. | Enhanced sputter target manufacturing method |
| EP1923481A2 (en) * | 2005-07-22 | 2008-05-21 | Heraeus, Inc. | Enhanced sputter target manufacturing method |
| EP1923481A3 (en) * | 2005-07-22 | 2008-06-18 | Heraeus, Inc. | Enhanced sputter target manufacturing method |
| CN103785838A (en) * | 2012-11-01 | 2014-05-14 | 宁波江丰电子材料有限公司 | Chromium target production method |
| CN103785838B (en) * | 2012-11-01 | 2016-06-01 | 宁波江丰电子材料股份有限公司 | The making method of chromium target |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH032230B2 (en) | 1991-01-14 |
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