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WO2003016585A1 - Cible de tungstene fritte destinee a la pulverisation et procede de preparation associe - Google Patents

Cible de tungstene fritte destinee a la pulverisation et procede de preparation associe Download PDF

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Publication number
WO2003016585A1
WO2003016585A1 PCT/JP2002/005545 JP0205545W WO03016585A1 WO 2003016585 A1 WO2003016585 A1 WO 2003016585A1 JP 0205545 W JP0205545 W JP 0205545W WO 03016585 A1 WO03016585 A1 WO 03016585A1
Authority
WO
WIPO (PCT)
Prior art keywords
tungsten
less
sputtering
sintering
powder
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.)
Ceased
Application number
PCT/JP2002/005545
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English (en)
Japanese (ja)
Inventor
Ryo Suzuki
Hirohito Miyashita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Mining Holdings Inc
Original Assignee
Nikko Materials Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nikko Materials Co Ltd filed Critical Nikko Materials Co Ltd
Publication of WO2003016585A1 publication Critical patent/WO2003016585A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals

Definitions

  • the present invention relates to a tungsten sintered compact target for sputtering and a method for producing the same.
  • the present invention relates to a tungsten target used for forming a gate electrode such as IC or LSI or a wiring material by a sputtering method, and a method for manufacturing the same.
  • the electrode materials and wiring materials for this VLSI are generally manufactured by the sputtering method or the CVD method.
  • the sputtering method has a relatively simple structure and operation of the apparatus, can easily form a film, and is low in cost. Therefore, it is more widely used than the CVD method.
  • the tungsten target manufactured by the above-described electron beam melting method or the method of rolling and then sintering tungsten powder under pressure is mechanically brittle because the crystal grains are easily coarsened, and particle defects are generated on the sputtered film.
  • the target of hot rolling after sintering of tungsten powder has a flexural strength of 40 OMPa or less, which is considered to be due to embrittlement peculiar to the rolled structure of the tungsten sintered material.
  • tungsten rolled products Furthermore, a particularly problematic problem with tungsten rolled products is that, starting from a block-shaped sintered material and requiring a step of strong rolling, a thick target or a large target size is required. That requires a large sintered material. Such a large-sized sintered body is liable to cause non-uniform structure and density. Recently, there has been a growing demand for evening gates with a thickness of more than 1 Omm or large evening gates with a 400 mm or more evening get size. There is a problem that it cannot be handled.
  • the CVD-W method shows good sputtering characteristics, it takes a lot of time and money to produce the target, and is inefficient, and at the same time, it has a columnar structure, so its mechanical strength is low. There is also the problem of being low. Disclosure of the invention
  • the present inventors focused on the powder sintering method, which has a relatively simple manufacturing process, and improved the sintering characteristics and manufacturing conditions of the tungsten powder used.
  • the aim is to obtain a method that can manufacture evening targets stably at low cost.
  • the present invention is a.
  • the total amount of alkali metals such as Na and K is 1 ppm or less, the total amount of radioactive elements such as U and Th is 10 ppb or less, the carbon content is 10 ppm or less, Fe, Ni, Cr, 2.
  • Tungsten sintered body for sputtering characterized by sintering using tungsten powder having a powder specific surface area of at least 0. n ⁇ Zg (BET method) and an oxygen content of not more than ⁇ ⁇ ⁇ ⁇ m Manufacturing method
  • the sintering is performed using tungsten powder having a powder specific surface area of 0.6 m 2 / g to 0.8 ⁇ 2 ⁇ (BET method) and an oxygen content of 800 ppm or less.
  • tungsten powder having a purity of 5 N or more has a powder specific surface area of 0.3 m 2 Zg or less.
  • a firing temperature of 2000 ° C. or more is required.
  • crystal grains become coarser than 100 m.
  • Pressure sintering at such a high temperature becomes an important problem, for example, the reaction between the die and the stainless steel in the hot press method or the reaction with the capsule material in the HIP, and the production cost increases.
  • the present inventors have used ammonium metatungstate as a starting material, and have conducted hydrogen purification of tungstate crystals having a purity of 5 N or more obtained by performing high-purity purification to remove hydrogen gas and remove reaction product gas. by accelerating the rate of specific surface area of 0. 4m 2 / g ⁇ 0. 8m 2 / g, particle size 0. 4 ⁇ 0. 8 zm, and oxygen content 10 OO ppm or less, preferably 800 p pm A tungsten powder was prepared and used. If the oxygen content exceeds 1000 ppm, the sinterability deteriorates. Therefore, the lower the oxygen content of the tundastene powder used, the better.
  • the total amount of alkali metals such as Na and K that affect semiconductor characteristics is 1 ppm or less
  • the total amount of radioactive elements such as U and Th is 10 ppb or less
  • the pressure start temperature exceeds 1200 ° C, crystal grains grow and the sinterability deteriorates. Also, it takes 2000 to obtain a closed pore density (93% or more) that enables capsule-free HIP.
  • a hot press temperature of at least ° C is required, and there are problems as described below. Therefore, it is desirable to set the pressurization start temperature at 1200 ° C or less.
  • the hot pressing temperature As described above, setting the hot pressing temperature to 2000 ° C or more is effective for densification, but causes problems such as coarsening of crystal grains and reaction with dies. It is desirable to press.
  • hot pressing the use of carbon sheets on the upper and lower surfaces can promote oxygen dissociation from the material.
  • the HIP treatment is performed at a temperature of 1700 ° C. or more, preferably 1850 ° C. or more, and a pressing force of 1000 kgZcm 2 or more, preferably 1800 kgZcm 2 or more, so that the relative density is 99% or more and the average crystal is Tungsten targets with a grain size of 100 or less and an average grain size of 80 m or less can be obtained.
  • the crystal grain shape is an isotropic shape without random grains unlike a rolled product, and is randomly oriented.
  • the HIP processing can be performed in a capsule-free manner.
  • the specific surface area of the tungsten powder is larger, the density of the tungsten sintered body after hot pressing is higher and the crystal structure is finer, so that the density can be easily increased by the HIP processing and the density after the HIP processing is higher.
  • the occurrence of particle defects was significantly reduced on the film produced using the tungsten target obtained. Examples and comparative examples
  • the relative density of the sintered body after hot pressing was 93.7% to 98.2%.
  • the relative density of the tungsten sintered body after the HIP treatment was 99% to 99.8%.
  • the average crystal grain size of the sintered body obtained as described above was 55 m to 88 / m, and in each case was 100 m or less.
  • the oxygen contents were all 20 ppm or less, and the bending strength was 52 OMPa to 63 OMPa, and was 50 OMPa or more.
  • the number of particles on the film sputtered using this tungsten sintered body was 0.03 to 0.07 cm 2 , which was 0.1 particles / cm 2 or less, and a very good film was obtained.
  • Powder specific surface area saved without exposing the tungsten powder tungsten oxide powder obtained by hydrogen reduction of the atmosphere is 1. 1111 2 8 and 1. 4m 2 / g and the oxygen 790 content, each p pm 890 p pm Except for the use of the tungsten powder (Examples 4 and 5 respectively), the properties of the hot-pressed sintered body and the sintered body after the HIP treatment produced under the same conditions as in Example 1 are also shown in Tables 1 and 2. See Figure 2.
  • Tungsten powder having a specific surface area of 0.78 m 2 Zg and an oxygen content of 840 ppm was used, and the pressing force by hot pressing was set to 150, 200, and 300 kg / cm 2 (Examples 6, 7 and 7, respectively)
  • Table 3 shows the properties of the hot-press sintered body and the sintered body after HIP treatment, which were manufactured under the same conditions as in Example 3 except for 8).
  • the relative density of the obtained sintered body is 99.7% to 99.8%, the average particle size is 67 ⁇ m to 72 m, and the sintered body satisfying the relative density of 99% or more and the average particle size of 100 zm or less I got it.
  • Table 3 The relative density of the obtained sintered body is 99.7% to 99.8%, the average particle size is 67 ⁇ m to 72 m, and the sintered body satisfying the relative density of 99% or more and the average particle size of 100 zm or less I got it.
  • Powder specific surface area used 0.78m 2 / g
  • Table 3 shows the relative density and average crystal grain size of the tungsten sintered body manufactured under the same conditions as in Example 3 except that the hot press firing was performed for 2 hours. In each case, the relative density after HIP treatment was 99% or more, and the average crystal grain size was 100 m or less.
  • the sintered compact hot-pressed at a temperature of 1600 ° C. in Comparative Example 1 and a temperature of 1800 ° C. in Comparative Example 2 had a relative density of 99% or less after HIP treatment, and the number of particles on the film formed by sputtering was 0.6.
  • the pieces were as large as Zcm 2 and 1.7 pieces cm 2, which was not practical.
  • Comparative Example 4 The sintered body of Comparative Example 3 which had been hot-pressed at 2200 ° C had a relative density after HIP treatment of 99%, but had an average crystal grain size of 177 m and was coarse. The number of particles above was also as high as 0.3 / cm 2 . (Comparative Example 4)
  • the specific surface area 1.1111 2 / / 8, with the oxygen content 131 O ppm of tungsten powder was subjected to hot press firing at 1800 ° C and 300 k gZcm 2.
  • a tungsten sintered compact was produced under the same conditions as in Example 3 except that the hot press pressure was set to 120 kgZcm 2 .
  • Table 2 also shows the relative density and average particle size of the obtained sintered body. The average crystal grain size was as fine as 55 jm, but the relative density was as low as 94.7%. (Comparative Example 6)
  • Table 2 shows the relative density and the average crystal grain size of the tungsten sintered body manufactured under the same conditions as in Example 4 except that the pressing start temperature during hot pressing was set at 140 ° C.
  • the average crystal grain size was 98, which was less than 100, but was larger than the average crystal grain size obtained in the other examples, and the relative density was less than 99%. It was unsuitable as a target for performing a film. The invention's effect
  • the tungsten target for sputtering manufactured by the method of the present invention has a feature that the density is higher and the crystal grain size is smaller than that of a tungsten target obtained by a conventional pressure sintering method. This has the effect of significantly reducing the manufacturing cost compared to the conventional CVD-W method.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)
  • Electrodes Of Semiconductors (AREA)

Abstract

L'invention concerne une cible de tungstène fritté destinée à la pulvérisation et caractérisée en ce qu'elle présente une densité relative d'au moins 99 %, un diamètre de grain cristallin moyen d'au plus 100 νm, une teneur en oxygène d'au plus 20 ppm et une force de déflexion d'au moins 500 Mpa ; ainsi qu'un procédé de préparation économique de la cible de tungstène présentant une certaine stabilité et mettant en oeuvre des conditions de production améliorées pour une poudre de tungstène de matériau brut et des conditions de frittage améliorées. La cible de tungstène fritté présente un niveau élevé de densité et un degré élevé de finesse caractéristiques d'une structure cristalline et jamais atteints auparavant par un procédé de frittage sous charge classique et elle présente une nette amélioration au niveau de la force de déflexion, permettant ainsi d'obtenir une réduction importante des occurrences de défauts particulaires.
PCT/JP2002/005545 2001-08-10 2002-06-05 Cible de tungstene fritte destinee a la pulverisation et procede de preparation associe Ceased WO2003016585A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-243120 2001-08-10
JP2001243120A JP2003055758A (ja) 2001-08-10 2001-08-10 スッパタリング用タングステン焼結体ターゲット及びその製造方法

Publications (1)

Publication Number Publication Date
WO2003016585A1 true WO2003016585A1 (fr) 2003-02-27

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Country Link
JP (1) JP2003055758A (fr)
TW (1) TW574377B (fr)
WO (1) WO2003016585A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105345007A (zh) * 2014-08-15 2016-02-24 安泰科技股份有限公司 一种高致密铬钨合金靶材的制备方法
EP3604612A4 (fr) * 2017-03-31 2021-01-27 JX Nippon Mining & Metals Corporation Cible en tungstène
CN113423859A (zh) * 2019-03-15 2021-09-21 三菱综合材料株式会社 氧化钨溅射靶

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005073418A1 (fr) * 2004-01-30 2005-08-11 Nippon Tungsten Co., Ltd. Comprime fritte a base de tungstene et procede pour la production de celui-ci
JP4885305B2 (ja) * 2008-03-17 2012-02-29 Ｊｘ日鉱日石金属株式会社 焼結体ターゲット及び焼結体の製造方法
KR101269787B1 (ko) * 2008-06-02 2013-05-30 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 텅스텐 소결체 스퍼터링 타겟
KR20190112857A (ko) 2009-05-27 2019-10-07 제이엑스금속주식회사 소결체 타겟 및 소결체의 제조 방법
US9388489B2 (en) 2010-09-29 2016-07-12 Ulvac, Inc. Tungsten target and method for producing same
CN103567443B (zh) * 2012-07-25 2015-10-07 宁波江丰电子材料股份有限公司 钨靶材的制作方法
CN103805952B (zh) * 2013-12-12 2016-05-18 株洲硬质合金集团有限公司 一种大尺寸高纯钨靶材及其生产方法
KR102360536B1 (ko) 2015-03-06 2022-02-08 엔테그리스, 아이엔씨. 고체 공급원 전달을 위한 고-순도 텅스텐 헥사카보닐
JP7308013B2 (ja) * 2017-11-10 2023-07-13 Ｊｘ金属株式会社 タングステンスパッタリングターゲット及びその製造方法
CN115415526B (zh) * 2021-05-13 2023-05-19 安泰天龙钨钼科技有限公司 一种超大尺寸钨管及其制备方法
CN113523273B (zh) * 2021-06-17 2022-10-21 北京科技大学 多场耦合下快速制备超细晶纯钨材料的粉末冶金方法
JP7278463B1 (ja) * 2022-06-27 2023-05-19 株式会社アルバック タングステンターゲットおよびその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0593267A (ja) * 1991-10-01 1993-04-16 Hitachi Metals Ltd 半導体用タングステンターゲツトおよびその製造方法
JPH05222525A (ja) * 1992-02-10 1993-08-31 Hitachi Metals Ltd 半導体用タングステンターゲットの製造方法
JPH0776771A (ja) * 1993-09-08 1995-03-20 Japan Energy Corp タングステンスパッタリングターゲット
JP2000256836A (ja) * 1999-03-04 2000-09-19 Japan Energy Corp スパッタリング用タングステンターゲットおよびその製造方法
WO2001023635A1 (fr) * 1999-09-28 2001-04-05 Nikko Materials Company, Limited Cible en tungstene destine a la pulverisation et son procede de preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0593267A (ja) * 1991-10-01 1993-04-16 Hitachi Metals Ltd 半導体用タングステンターゲツトおよびその製造方法
JPH05222525A (ja) * 1992-02-10 1993-08-31 Hitachi Metals Ltd 半導体用タングステンターゲットの製造方法
JPH0776771A (ja) * 1993-09-08 1995-03-20 Japan Energy Corp タングステンスパッタリングターゲット
JP2000256836A (ja) * 1999-03-04 2000-09-19 Japan Energy Corp スパッタリング用タングステンターゲットおよびその製造方法
WO2001023635A1 (fr) * 1999-09-28 2001-04-05 Nikko Materials Company, Limited Cible en tungstene destine a la pulverisation et son procede de preparation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105345007A (zh) * 2014-08-15 2016-02-24 安泰科技股份有限公司 一种高致密铬钨合金靶材的制备方法
EP3604612A4 (fr) * 2017-03-31 2021-01-27 JX Nippon Mining & Metals Corporation Cible en tungstène
US11939647B2 (en) 2017-03-31 2024-03-26 Jx Metals Corporation Tungsten target
CN113423859A (zh) * 2019-03-15 2021-09-21 三菱综合材料株式会社 氧化钨溅射靶

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JP2003055758A (ja) 2003-02-26
TW574377B (en) 2004-02-01

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