TW202446975A - Sputtering target and process for producing the same - Google Patents
Sputtering target and process for producing the same Download PDFInfo
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- TW202446975A TW202446975A TW113114726A TW113114726A TW202446975A TW 202446975 A TW202446975 A TW 202446975A TW 113114726 A TW113114726 A TW 113114726A TW 113114726 A TW113114726 A TW 113114726A TW 202446975 A TW202446975 A TW 202446975A
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 162
- 238000000034 method Methods 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 239000006104 solid solution Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 43
- 238000005245 sintering Methods 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 25
- 230000000930 thermomechanical effect Effects 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 238000005242 forging Methods 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000004663 powder metallurgy Methods 0.000 claims description 7
- 230000016507 interphase Effects 0.000 claims description 3
- 239000013077 target material Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 124
- 239000012071 phase Substances 0.000 description 83
- 239000000463 material Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 12
- 238000001159 Fisher's combined probability test Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000007751 thermal spraying Methods 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 238000005056 compaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000000879 optical micrograph Methods 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 238000004846 x-ray emission Methods 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009694 cold isostatic pressing Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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- 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
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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- 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
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- 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
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- 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
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- B22F3/10—Sintering only
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Abstract
Description
本公開涉及一種濺射靶及製造濺射靶的方法。The present invention relates to a sputtering target and a method for manufacturing the sputtering target.
W-Ni合金 (鎢-鎳合金)是一種高熔點、高硬度、高耐蝕性的合金,廣泛應用於機械、電子、醫療器械、汽車零部件、航太軍工、日用五金零件、工業加工模具等。W-Ni alloy (tungsten-nickel alloy) is an alloy with high melting point, high hardness and high corrosion resistance. It is widely used in machinery, electronics, medical equipment, automotive parts, aerospace and military industries, daily hardware parts, industrial processing molds, etc.
已知由W-Ni混合氧化物組成的電致變色層已有多年。在W合金化的NiO X(W-Ni混合氧化物)中的尤其有利W/Ni原子比率為約0.33。在此比率下,電荷轉移電阻為最佳,以便確保電致變色層的極快速光學轉換行為。將例如由W-Ni合金組成的濺射靶用於以此方式製造的電致變色層,W-Ni合金通過反應性磁控濺鍍在氧下剝蝕形成W-Ni混合氧化物層。氧化靶也從現有技術已知。 Electrochromic layers consisting of W-Ni mixed oxides have been known for many years. A particularly advantageous W/Ni atomic ratio in W-alloyed NiO x (W-Ni mixed oxide) is about 0.33. At this ratio, the charge transfer resistance is optimal in order to ensure a very fast optical switching behavior of the electrochromic layer. For the electrochromic layer produced in this way, a sputtering target consisting, for example, of a W-Ni alloy is used, which is etched under oxygen by reactive magnetron sputtering to form a W-Ni mixed oxide layer. Oxidation targets are also known from the prior art.
此外,W-Ni合金可以用於銅/錫 (Cu/Sn)鍵合應用的阻擋層,具有瞬態Ni緩衝層的亞微米Cu/Sn鍵合在225℃下,可以克服5微米 (μm) Cu/Sn的物理限制,10奈米 (nm) Ni 層在主要鍵合製程之前的步驟中抑制巨大的Cu/Cn相互擴散。當溫度接近Sn熔點時,Ni層溶解,熔化的Sn形成亞微米級Cu/Sn鍵合。該方案出色的機械強度和電氣性能顯示出高密度三維空間 (3D)互連的巨大潛力。同樣地,W-Ni合金也可用於薄膜電晶體 (TFT)與發光二極體晶粒 (LED cell)之間的鍵合層。In addition, W-Ni alloy can be used as a barrier layer for copper/tin (Cu/Sn) bonding applications. Submicron Cu/Sn bonding with a transient Ni buffer layer can overcome the physical limitations of 5 microns (μm) Cu/Sn at 225°C. The 10 nanometer (nm) Ni layer suppresses the huge Cu/Cn interdiffusion in the step before the main bonding process. When the temperature approaches the melting point of Sn, the Ni layer dissolves and the molten Sn forms a submicron Cu/Sn bond. The excellent mechanical strength and electrical properties of this scheme show great potential for high-density three-dimensional (3D) interconnections. Similarly, W-Ni alloy can also be used as a bonding layer between thin-film transistors (TFTs) and light-emitting diode grains (LED cells).
對於由W-Ni合金組成的濺射靶,常規應用採用粉末熱噴塗製程,但是這種製程會導致化學雜質含量高,密度低。化學雜質含量高會導致不同塗佈率,且因此對沉積層的均質性具有不利影響。濺射靶材料的低密度對塗佈率同樣具有不利影響。此外,借助於熱噴塗僅可產生有限材料厚度,其限制靶的材料利用率及使用壽命。For sputtering targets consisting of W-Ni alloys, powder thermal spraying processes are conventionally used, but this process results in a high content of chemical impurities and a low density. The high content of chemical impurities leads to different coating rates and thus has an adverse effect on the homogeneity of the deposited layer. The low density of the sputtering target material also has an adverse effect on the coating rate. In addition, only a limited material thickness can be produced by means of thermal spraying, which limits the material utilization and service life of the target.
如果通過熱噴塗製造如當前所用由W-Ni合金組成的濺射靶,則使用Ni及W粉末作為原始材料製造靶的結果為:展示鐵磁特性的純鎳部分存在於濺射靶中。這些鐵磁性區域不利於磁控濺鍍,因為其導致不同塗佈率,且因此對沉積層的均質性具有不利影響。If a sputtering target consisting of a W-Ni alloy as currently used is produced by thermal spraying, the result of using Ni and W powders as starting materials for the target is that a pure nickel portion exhibiting ferromagnetic properties is present in the sputtering target. These ferromagnetic regions are not conducive to magnetron sputtering, since they lead to different coating rates and therefore have an adverse effect on the homogeneity of the deposited layer.
另外,用熱噴塗法僅可調整有限高的材料密度。濺射靶材料的低密度對塗佈率同樣具有不利影響。此外,借助於熱噴塗僅可產生有限材料厚度,其限制靶的材料利用率及使用壽命。In addition, only limited material densities can be adjusted with thermal spraying. The low density of the sputtering target material also has a negative effect on the coating rate. In addition, only limited material thicknesses can be produced with the aid of thermal spraying, which limits the material utilization and service life of the target.
由製造方法而引起的噴塗粉末中所含有的金屬雜質(其會直接輸送至所產生的濺射靶中)為另一缺點。濺鍍層中的雜質對光學層特性可具有不利影響。Another disadvantage is the presence of metallic impurities in the sprayed powder due to the manufacturing process, which are directly transferred to the resulting sputtering target. Impurities in the sputtered layer can have an adverse effect on the properties of the optical layer.
熱噴塗期間可嵌入濺射靶中的額外的非金屬的、尤其氧化的或絕緣性的夾雜物或相在濺鍍期間導致顆粒數目增加,其又可對濺鍍層的特性(黏著性、特定電阻、層均質性)及塗佈法(高電弧速率)產生不利影響。Additional non-metallic, in particular oxidic or insulating inclusions or phases which can be embedded in the sputtering target during thermal spraying lead to an increase in the number of particles during sputtering, which in turn can have a negative impact on the properties of the sputtered layer (adhesion, specific resistance, layer homogeneity) and the coating process (high arc speed).
為了克服上述熱噴塗帶來的缺陷,WO2015089533A1記載了一種選擇低Ni含量和高W含量的濺射靶。通過其記載的燒結製程,氧含量可以控制在100微克/克 (μg/g)以內,密度可以達到90重量%以上。但是這種製程具有以下缺點:由於低W相作為第二相導致濺射靶表面各部位Ni含量分佈不均勻,純W相的含量過高,而且會使濺射靶包括純Ni相,由此會降低材料的均勻性,還會影響濺射效果。In order to overcome the defects brought by the above-mentioned thermal spraying, WO2015089533A1 records a sputtering target with low Ni content and high W content. Through the sintering process described therein, the oxygen content can be controlled within 100 micrograms/gram (μg/g), and the density can reach more than 90% by weight. However, this process has the following disadvantages: due to the low W phase as the second phase, the Ni content distribution in various parts of the sputtering target surface is uneven, the content of the pure W phase is too high, and the sputtering target includes a pure Ni phase, which reduces the uniformity of the material and affects the sputtering effect.
本公開的目的在於至少部分地克服現有技術的缺陷,提供一種改進的濺射靶及製造濺射靶的方法。The object of the present disclosure is to at least partially overcome the deficiencies of the prior art and to provide an improved sputtering target and a method for manufacturing the sputtering target.
本公開第一方面涉及一種濺射靶,所述濺射靶含有55重量%至80重量%的Ni、餘量W及一般雜質,所述濺射靶含有W相、Ni(W) 固溶相、不含純Ni相且不含或含有以濺射靶截面量測的平均面積比例小於5%的金屬間相。The first aspect of the present disclosure relates to a sputtering target, which contains 55 wt % to 80 wt % Ni, the remainder W and general impurities, and the sputtering target contains a W phase, a Ni(W) solid solution phase, does not contain a pure Ni phase, and does not contain or contains an intermetallic phase with an average area ratio of less than 5% measured by a cross section of the sputtering target.
替代地,所述濺射靶含有60重量%至70重量%的Ni。Alternatively, the sputtering target contains 60 wt % to 70 wt % Ni.
替代地,所述濺射靶含有60重量%至65重量%的Ni。Alternatively, the sputtering target contains 60 wt % to 65 wt % Ni.
替代地,所述濺射靶的氧含量小於50 μg/g。Alternatively, the sputtering target has an oxygen content of less than 50 μg/g.
替代地,所述濺射靶的氧含量小於40 μg/g。Alternatively, the sputtering target has an oxygen content of less than 40 μg/g.
替代地,所述濺射靶的硬度小於500 HV10。Alternatively, the hardness of the sputtering target is less than 500 HV10.
替代地,所述金屬間相選自由以組成的群組中的一種或多種下物質中的任意一種:Ni 4W、WNi、W 2Ni。 Alternatively, the intermetallic phase is any one of one or more of the following substances selected from the group consisting of: Ni 4 W, WNi, W 2 Ni.
替代地,所述濺射靶具有小於40 μm的W相的平均晶粒尺寸。Alternatively, the sputtering target has an average grain size of the W phase less than 40 μm.
替代地,所述濺射靶具有超過90%的相對密度。Alternatively, the sputtering target has a relative density exceeding 90%.
替代地,所述濺射靶具有超過99.5%的相對密度。Alternatively, the sputtering target has a relative density exceeding 99.5%.
本公開的第二方面涉及一種製造本公開的第一方面所述的濺射靶的方法,所述方法經由粉末冶金途徑,包含以下步驟: 實施壓實步驟,其中將W粉末和Ni粉末的粉末混合物通過施加壓力、熱或壓力和熱進行壓實,以得到壓實坯料;以及 實施冷卻步驟,其中以大於3克耳文/分鐘 (K/min)的冷卻速率將所得壓實坯料冷卻到750℃至1000℃的溫度範圍。 The second aspect of the present disclosure relates to a method for manufacturing the sputtering target described in the first aspect of the present disclosure, the method comprising the following steps via a powder metallurgy route: Implementing a compacting step, wherein a powder mixture of W powder and Ni powder is compacted by applying pressure, heat, or pressure and heat to obtain a compacted billet; and Implementing a cooling step, wherein the obtained compacted billet is cooled to a temperature range of 750°C to 1000°C at a cooling rate greater than 3 K/min.
如果通過在1100℃至1450℃溫度下燒結來實現壓實步驟,燒結氣氛與第一氣體和/或真空相結合。較佳地,將燒結氣氛從真空改變為第一氣體,即,燒結在真空和第一氣體下相繼地實施。If the compaction step is achieved by sintering at a temperature of 1100° C. to 1450° C., the sintering atmosphere is combined with the first gas and/or vacuum. Preferably, the sintering atmosphere is changed from vacuum to the first gas, that is, sintering is performed successively under vacuum and the first gas.
替代地,該製程還包括在壓實步驟與冷卻步驟之間進行對坯料的熱機械處理或熱處理。然而,如果這樣的熱機械處理或熱處理在燒結步驟之後進行,則將冷卻步驟中的冷卻速率改變為至少在750℃至900℃的溫度範圍內大於30 K/min。Alternatively, the process further comprises a thermomechanical treatment or heat treatment of the blank between the compacting step and the cooling step. However, if such a thermomechanical treatment or heat treatment is performed after the sintering step, the cooling rate in the cooling step is changed to be greater than 30 K/min at least in the temperature range of 750°C to 900°C.
替代地,該製程還包括在970℃至1450℃範圍內的溫度下進行熱機械處理或熱處理。Alternatively, the process further comprises thermomechanical treatment or heat treatment at a temperature in the range of 970°C to 1450°C.
替代地,所述熱機械處理或熱處理包括至少一個鍛造步驟或輥壓步驟。Alternatively, the thermomechanical treatment or heat treatment comprises at least one forging step or rolling step.
以下,首先對本公開的第一方面涉及的濺射靶進行詳細說明。Hereinafter, the sputtering target according to the first aspect of the present disclosure will be described in detail.
如圖1所示(參見ASM手冊第III卷,合金相圖,1992(ASM Handbook Vol. III, Alloy Phase Diagrams 1992)),濺射靶含有W相、Ni(W) 固溶相、無Ni相,其中Ni(W) 固溶相具有W合金化的Ni混合晶體,較佳為W飽和的Ni混合晶體。As shown in FIG. 1 (see ASM Handbook Vol. III, Alloy Phase Diagrams 1992), the sputtering target contains a W phase, a Ni(W) solid solution phase, and a Ni-free phase, wherein the Ni(W) solid solution phase has a W-alloyed Ni mixed crystal, preferably a W-saturated Ni mixed crystal.
根據本公開的濺射靶較佳含有在靶材料的橫截面處測量的平均小於5面積%的金屬間相。較佳地,根據本公開的濺射靶含有平均小於5面積%的純W相。The sputtering target according to the present disclosure preferably contains an average of less than 5 area % of the intermetallic phase measured at the cross section of the target material. Preferably, the sputtering target according to the present disclosure contains an average of less than 5 area % of the pure W phase.
為了確定根據本公開的濺射靶中存在的金屬間相的比例,在橫截面處分析平均面積比例。為此,生產金相拋光截面並通過光學或電子顯微鏡檢查。金相拋光截面為三維濺射靶的二維截面。面積分析可以通過商業上可獲得的圖像分析軟體在以這種方式產生的顯微圖上進行。這通過圖像分析進行,以便確定上述顯微組織中各個相的比例,通常通過對比待區分的相。借助於適合的蝕刻方法可進一步對比難以區別的相。在此情況下,通過以適合的蝕刻溶液(例如85毫升 (ml)氨溶液及5 ml的30%的過氧化氫溶液)蝕刻,金屬間相可區別於Ni混合晶體(Ni(W)相、W飽和的Ni混合晶體),且可測定面積比例。然而,視微觀結構的狀態而定,替代性的蝕刻溶液及製程也是可以考慮的。平均面積比例計算為以1000倍放大率拍攝的金相拋光截面上的尺寸為100 μm×100 μm的5個影像區域上量測的5個面積比例量測值的算術平均值。小於5%的金屬間相能獲得均勻的濺射表面元素分佈。所製造的濺射靶的Ni含量最大偏差遠低於由WO2015089533A1的方法生產的濺射靶,使得濺射靶不同位置處的Ni均勻性非常高。作為替代方案,可以使用相關JCPDS卡通過X射線衍射 (XRD)(考慮相應的X射線檢測限)輕鬆確認或排除濺射靶中金屬間相的出現。In order to determine the proportions of the intermetallic phases present in the sputtering target according to the present disclosure, the average area ratios are analyzed in cross section. For this purpose, metallographically polished sections are produced and examined by optical or electron microscopy. Metallographically polished sections are two-dimensional sections of a three-dimensional sputtering target. The area analysis can be carried out on the micrographs produced in this way by means of commercially available image analysis software. This is carried out by image analysis in order to determine the proportions of the individual phases in the above-mentioned microstructure, usually by comparing the phases to be differentiated. Phases that are difficult to distinguish can be further compared with the help of suitable etching methods. In this case, the intermetallic phases can be distinguished from the Ni mixed crystals (Ni(W) phase, W-saturated Ni mixed crystals) by etching with a suitable etching solution (e.g., 85 milliliters (ml) of ammonia solution and 5 ml of 30% hydrogen peroxide solution), and the area ratio can be determined. However, depending on the state of the microstructure, alternative etching solutions and processes are also conceivable. The average area ratio is calculated as the arithmetic mean of 5 area ratio measurements measured on 5 image areas of size 100 μm × 100 μm on a metallographic polished section photographed at 1000x magnification. Less than 5% of the intermetallic phase results in a uniform sputtered surface element distribution. The maximum deviation of Ni content in the manufactured sputtering target is much lower than that of the sputtering target produced by the method of WO2015089533A1, making the Ni uniformity at different positions of the sputtering target very high. As an alternative, the presence of intermetallic phases in the sputtering target can be easily confirmed or excluded by X-ray diffraction (XRD) (considering the corresponding X-ray detection limit) using the relevant JCPDS card.
金屬間相例如可選自以下中的任一種:Ni 4W、WNi、W 2Ni。 The intermetallic phase may be selected from any one of the following, for example: Ni 4 W, WNi, W 2 Ni.
從圖1相圖可以看出,當濺射靶中Ni含量大於55重量%時,脆性Ni 4W相優先出現。當鎳含量更高時,能夠出現鐵磁鎳相。 From the phase diagram in Figure 1, it can be seen that when the Ni content in the sputtering target is greater than 55 wt%, the brittle Ni 4 W phase appears first. When the Ni content is higher, the ferromagnetic Ni phase can appear.
本公開的濺射靶含有55重量%至80重量%的Ni、餘量W及不可避免的雜質。術語「不可避免的雜質」是指與生產相關的污染,其具有氣體或伴生元素,它們來源於所用的原料。這些雜質在根據本公開的濺射靶中的比例較佳在氣體(C、H、N、O)低於100 μg/g(對應於ppm)且其他元素低於500 μg/g的範圍內。已知化學元素分析的合適方法取決於待分析的化學元素。本公開的濺射靶通過高Ni含量和低W含量。在由要求保護的濺射靶生產的Ni-W層中,Ni可以作為緩衝層來溶解熔融的Sn,並成功實現亞微米級Cu/Sn鍵合,從而獲得優異的機械強度和電學性能。由該濺射靶生產的Ni-W層可用於TFT電極鍵合和半導體3D集成,其有效解決了現有技術的濺射靶降低材料均勻性、影響濺射效果的技術問題,具有高純度、高密度和良好的應用性能。本公開的濺射靶進一步較佳為含有60重量%至70重量%的Ni,更進一步較佳為含有60重量%至65重量%的Ni,該含量進一步獲得了更好的材料均勻度和應用性能。The sputtering target disclosed herein contains 55 wt % to 80 wt % Ni, the remainder W and inevitable impurities. The term "inevitable impurities" refers to production-related pollution, which has gases or associated elements, which originate from the raw materials used. The proportion of these impurities in the sputtering target according to the present disclosure is preferably in the range of less than 100 μg/g (corresponding to ppm) for gases (C, H, N, O) and less than 500 μg/g for other elements. It is known that the appropriate method for chemical element analysis depends on the chemical element to be analyzed. The sputtering target disclosed herein has a high Ni content and a low W content. In the Ni-W layer produced by the sputtering target to be protected, Ni can be used as a buffer layer to dissolve the molten Sn, and successfully achieve submicron Cu/Sn bonding, thereby obtaining excellent mechanical strength and electrical properties. The Ni-W layer produced by the sputtering target can be used for TFT electrode bonding and semiconductor 3D integration, which effectively solves the technical problem that the sputtering target of the prior art reduces material uniformity and affects the sputtering effect, and has high purity, high density and good application performance. The sputtering target disclosed in the present invention is further preferably Ni containing 60 wt % to 70 wt %, and further preferably Ni containing 60 wt % to 65 wt %, and this content further obtains better material uniformity and application performance.
本公開的濺射靶較佳具有小於50 μg/g的氧含量,特別是較佳小於40 μg/g的氧含量。The sputtering target of the present disclosure preferably has an oxygen content of less than 50 μg/g, and more preferably has an oxygen content of less than 40 μg/g.
可通過感應耦合電漿放射光譜儀 (ICP-OES)用簡單方式測定氧含量。The oxygen content can be determined in a simple manner by inductively coupled plasma optical emission spectroscopy (ICP-OES).
本公開的濺射靶的HV10硬度 (維氏硬度)較佳低於500 HV10。The HV10 hardness (Vickers hardness) of the sputtering target disclosed herein is preferably less than 500 HV10.
已經發現,在HV10硬度小於500 HV10時,可以最佳地確保濺射靶的令人滿意的韌性。這簡化了製造過程中的處理,例如在可選的機械成形步驟中。在使用期間,尤其是作為一個實施例中的單件管狀靶,小於500 HV10的硬度顯著簡化了處理。It has been found that a satisfactory toughness of the sputtering target can be best ensured at an HV10 hardness of less than 500 HV10. This simplifies handling during manufacturing, for example in an optional mechanical forming step. During use, especially as a one-piece tubular target in one embodiment, a hardness of less than 500 HV10 simplifies handling significantly.
對於本發明目的,HV10硬度(維氏硬度) 是由5次硬度測量確定的算術平均值。For the purposes of the present invention, the HV10 hardness (Vickers hardness) is the arithmetic mean determined from 5 hardness measurements.
本公開的濺射靶較佳具有超過90%的相對密度,更佳為超過92%的相對密度,並且最佳為超過99.5%的相對密度。靶的密度越高,其特性越有利。具有低相對密度的靶具有相對高比例的孔隙,其在濺射過程中可能是實際的洩漏和/或雜質和顆粒的來源。此外,具有低密度的濺射靶易於吸收水或其它雜質,這會導致難以控制的製程參數。此外,在濺射過程中,僅緻密化到低程度的材料的燒蝕速率低於具有較高相對密度的材料的燒蝕速率。The sputtering target of the present disclosure preferably has a relative density of more than 90%, more preferably more than 92%, and most preferably more than 99.5%. The higher the density of the target, the more favorable its properties. Targets with low relative density have a relatively high proportion of pores, which may be actual leaks and/or sources of impurities and particles during the sputtering process. In addition, sputtering targets with low density tend to absorb water or other impurities, which can lead to difficult to control process parameters. In addition, during the sputtering process, the erosion rate of materials that are only densified to a low degree is lower than the erosion rate of materials with a higher relative density.
眾所周知,使用阿基米德原理借助於浮力方法,可容易地測定相對密度。It is well known that relative density can be easily determined by the buoyancy method using Archimedes' principle.
由於根據本公開的濺射靶在不同覆層設備中的裝配以及為了對具有不同幾何結構的基板進行覆層而對於根據本公開的濺射靶提出不同的幾何要求。因此,這種靶可呈平面靶形式(例如呈板或盤形式)、呈棒形式、呈管狀靶形式或呈具有其他複雜形狀的主體形式。Due to the assembly of the sputtering target according to the present disclosure in different coating devices and for coating substrates with different geometric structures, different geometric requirements are imposed on the sputtering target according to the present disclosure. Therefore, such a target can be in the form of a planar target (for example in the form of a plate or disk), in the form of a rod, in the form of a tubular target or in the form of a body with another complex shape.
根據本發明的濺射靶較佳地具有W相的平均晶粒尺寸小於40 μm,更佳地小於20 μm。The sputtering target according to the present invention preferably has an average grain size of the W phase of less than 40 μm, more preferably less than 20 μm.
W相的平均晶粒尺寸小於40 μm,更佳地小於20 μm,導致特別均勻的濺射行為,並因此導致具有特別均勻厚度的特別均勻層的沉積。此外,W相的缺口效應以這種方式保持較低,結果是最佳地確保了濺射靶的令人滿意的韌性。The average grain size of the W phase is less than 40 μm, more preferably less than 20 μm, resulting in a particularly uniform sputtering behavior and thus in the deposition of a particularly uniform layer with a particularly uniform thickness. In addition, notch effects of the W phase are kept low in this way, as a result of which a satisfactory toughness of the sputtering target is optimally ensured.
W相的多個晶粒的凝聚物的直徑可以超過40 μm,但在本公開的濺射靶中,不能認為這些凝聚物是W相的單個晶粒。Agglomerates of multiple grains of the W phase may have a diameter exceeding 40 μm, but in the sputtering target disclosed herein, these agglomerates cannot be considered to be single grains of the W phase.
W相的平均晶粒尺寸可以簡單的方式在金相拋光截面上進行線截面來測定。The average grain size of the W phase can be determined in a simple manner by performing a line section on the metallographically polished section.
如上所述,根據本公開第一方面的濺射靶,有效解決降低材料均勻性,影響濺射效果的技術問題,密度高且應用性能好。As described above, the sputtering target according to the first aspect of the present disclosure effectively solves the technical problem of reducing material uniformity and affecting the sputtering effect, and has high density and good application performance.
本公開的這種濺射靶可應用於以下領域: -作為顯示應用中的鍵合解決方案,例如TFT背板上的LED晶片; -作為電致變色裝置或反射隔熱塗層堆疊中的薄層; -作為保護底層金屬線路的覆蓋層,如銅或鋁基層,防止環境暴露和氧化; -作為緩衝層,通過應用特定的厚度(t),如5 nm< t < 50 nm,來控制不同層之間元素的擴散; -作為包裝和焊接中應用的鎳源; -利用反應性濺射製程來沉積氧化物或氮化物 -作為薄膜堆疊中的屏障層,以防止元素的交叉擴散,例如,在薄膜電晶體管金屬化中進入半導體材料和銅金屬線,這將降低電氣性能。 The sputtering target disclosed herein can be applied in the following fields: - As a bonding solution in display applications, such as LED chips on TFT backplanes; - As a thin layer in electrochromic devices or reflective insulation coating stacks; - As a capping layer to protect underlying metal lines, such as copper or aluminum base layers, from environmental exposure and oxidation; - As a buffer layer to control the diffusion of elements between different layers by applying a specific thickness (t), such as 5 nm < t < 50 nm; - As a nickel source for packaging and welding applications; - Deposition of oxides or nitrides using a reactive sputtering process - Acts as a barrier layer in the thin film stack to prevent cross-diffusion of elements, e.g. into semiconductor materials and copper metal lines in thin film transistor metallization, which would degrade electrical performance.
以下對本公開第二方面的濺射靶的製造方法進行說明。The following is a description of a method for manufacturing a sputtering target according to the second aspect of the present disclosure.
本公開第二方面經由粉末冶金途徑的製造本公開的第一方面所述的濺射靶方法的特徵在於其包含至少以下步驟: 實施壓實步驟,其中將W粉末和Ni粉末的粉末混合物通過施加壓力、熱或壓力和熱進行壓實,以得到壓實坯料;以及 實施冷卻步驟,其中以大於3 K/min的冷卻速率將所得壓實坯料冷卻到750℃至1000℃的溫度範圍。 The second aspect of the present disclosure is characterized in that the method for manufacturing the sputtering target described in the first aspect of the present disclosure via a powder metallurgy route comprises at least the following steps: A compacting step is performed, wherein a powder mixture of W powder and Ni powder is compacted by applying pressure, heat, or pressure and heat to obtain a compacted billet; and A cooling step is performed, wherein the obtained compacted billet is cooled to a temperature range of 750°C to 1000°C at a cooling rate greater than 3 K/min.
作為根據本發明的用於製造W-Ni濺射靶的方法的一部分的壓實步驟導致通過施加壓力、熱或壓力和熱來壓實和緻密化適當的粉末混合物以形成坯料。這可以通過各種工藝步驟進行,例如通過壓制和燒結、冷等靜壓、熱等靜壓、熱壓或放電等離子燒結(SPS)或這些方法的組合或壓實粉末混合物的其它方法。The compaction step as part of the method for manufacturing a W-Ni sputtering target according to the invention results in compacting and densifying a suitable powder mixture by applying pressure, heat or pressure and heat to form a blank. This can be done by various process steps, for example by pressing and sintering, cold isostatic pressing, hot isostatic pressing, hot pressing or discharge plasma sintering (SPS) or a combination of these methods or other methods of compacting the powder mixture.
可用於根據本公開方法的粉末混合物的製造較佳通過適當量W粉末及Ni粉末的秤重以及將其在適合混合設備中,直至確保粉末混合物中組分均質分佈來實現。對於本公開的目的,表述粉末混合物可包括含有組分W、Ni和X的預合金或部分合金粉末。The preparation of a powder mixture that can be used according to the method of the present disclosure is preferably achieved by weighing appropriate amounts of W powder and Ni powder and placing them in a suitable mixing device until a homogeneous distribution of the components in the powder mixture is ensured. For the purposes of this disclosure, the expression powder mixture may include a pre-alloyed or partially alloyed powder containing the components W, Ni and X.
將以此方式產生的粉末混合物較佳填充至模具中以便實施壓實步驟。這裡合適的模具是冷等靜壓機的模具或柔性管、熱壓機或放電等離子燒結設備的模具,或者在熱等靜壓的情況下是罐。The powder mixture produced in this way is preferably filled into a mold for the pressing step. Suitable molds here are molds or flexible tubes of a cold isostatic press, molds of a hot press or discharge plasma sintering equipment or, in the case of hot isostatic pressing, cans.
冷卻步驟中坯料以大於3 K/min的冷卻速率將所得坯料冷卻到750℃至1000℃的溫度範圍,該冷卻步驟作為根據本公開的製造W-Ni濺射靶方法的一部分避免不期望的金屬間相的出現。在一個較佳的實施例中,坯料在該溫度範圍內保持15分鐘至3小時,更佳為45分鐘至2小時,更進一步較佳為45分鐘至90分鐘。借助於本公開的方法製造的W-Ni濺射靶中的過高比例金屬間相可首先導致濺鍍速率不同於剩餘靶,且因此導致濺射靶上的非均一剝蝕,且從而使沉積層厚度有所波動。此外,濺射靶的微觀結構中的脆性金屬間相可導致電弧作用或增加的顆粒形成。另一方面,由於金屬間相的低韌性,更加難以操作此類濺射靶。In the cooling step, the blank is cooled to a temperature range of 750° C. to 1000° C. at a cooling rate of more than 3 K/min, and the cooling step avoids the appearance of undesirable intermetallic phases as part of the method for producing a W—Ni sputtering target according to the present disclosure. In a preferred embodiment, the blank is kept in this temperature range for 15 minutes to 3 hours, more preferably 45 minutes to 2 hours, and more preferably 45 minutes to 90 minutes. An excessively high proportion of intermetallic phases in the W—Ni sputtering target produced by the method of the present disclosure can firstly lead to a sputtering rate that is different from the remaining target, and thus to non-uniform erosion on the sputtering target, and thus to fluctuations in the thickness of the deposited layer. Furthermore, brittle intermetallic phases in the microstructure of the sputtering target can lead to arcing or increased particle formation. On the other hand, due to the low toughness of the intermetallic phases, it is more difficult to handle such sputtering targets.
如上所述,如果熱機械處理或熱處理在壓實步驟之後進行,例如燒結步驟,將冷卻速率改變為大於30 K/min至750℃至900℃的溫度範圍內。更佳地,在所得坯料的此類冷卻步驟中,以大於50 K/min的冷卻速率將所得坯料降溫到750℃至900℃的溫度範圍,因為由此能以尤其最佳的方式設定靶的所述材料特性及微觀結構。可例如通過在空氣、水或油狀物中冷卻來實現此類型冷卻步驟。此類冷卻步驟確保:最佳地避免金屬間相形成,且使得通過該方法製造的濺射靶具有微結構及機械特性的最佳可能組合。As mentioned above, if a thermomechanical treatment or heat treatment is carried out after the compaction step, for example a sintering step, the cooling rate is changed to a temperature range of 750° C. to 900° C. at a rate of more than 30 K/min. More preferably, in such a cooling step of the resulting blank, the resulting blank is cooled to a temperature range of 750° C. to 900° C. at a cooling rate of more than 50 K/min, since the material properties and the microstructure of the target can thereby be set in a particularly optimal manner. Such a cooling step can be achieved, for example, by cooling in air, water or oil. Such a cooling step ensures that the formation of intermetallic phases is optimally avoided and that the sputtering target produced by the method has the best possible combination of microstructure and mechanical properties.
較佳為通過在1100℃至1450℃溫度下燒結來實現所述壓實步驟,此時的燒結氣氛與第一氣體和/或真空相結合。在一個較佳實施例中,在燒結過程中使用第一氣體和真空兩者。已經發現,在根據本公開的用於製造W-Ni濺射靶的方法中,通過在1100℃至1450℃的溫度下燒結來實現壓實步驟是特別有利的。這裡,燒結是一種稱為在小於2 MPa的壓力下,優選在低於大氣壓的壓力下無壓燒結的燒結方法。Preferably, the compacting step is achieved by sintering at a temperature of 1100° C. to 1450° C., the sintering atmosphere at this time being combined with the first gas and/or vacuum. In a preferred embodiment, both the first gas and the vacuum are used during the sintering process. It has been found that in the method for manufacturing a W—Ni sputtering target according to the present disclosure, it is particularly advantageous to achieve the compacting step by sintering at a temperature of 1100° C. to 1450° C. Here, sintering is a sintering method called pressureless sintering at a pressure of less than 2 MPa, preferably at a pressure lower than atmospheric pressure.
在這些溫度下的壓實最佳地確保了在存在的粉末混合物中發生固相燒結至非常高的相對密度。在低於1100℃下壓實時,可獲得的密度可能太低,而在高於1450℃的溫度下,可能發生濺射靶的機械穩定性的降低。在所示溫度範圍內進行壓實的情況下,確保了所實現的高密度和最佳機械性能的最佳組合。由於生產的濺射靶中Ni含量較高,常規製程難以將O含量控制在較低值並達到閉孔條件下的密度。如果在1100℃至1450℃的溫度下進行燒結,並且燒結氣氛與第一氣體和/或真空結合,則可以顯著降低氧含量。第一氣體較佳為以氫氣為主體的混合氣體,混合氣體中例如還可以包括氬氣,但並不限於此,也可以是其他適當的氣體。Compacting at these temperatures optimally ensures that solid phase sintering to a very high relative density occurs in the powder mixture present. In the case of compacting below 1100°C, the achievable density may be too low, while at temperatures above 1450°C a reduction in the mechanical stability of the sputtering target may occur. In the case of compaction within the temperature range indicated, an optimal combination of high density achieved and optimal mechanical properties is ensured. Due to the high Ni content in the produced sputtering targets, conventional processes have difficulty controlling the O content to low values and achieving densities in closed-pore conditions. If sintering is carried out at temperatures between 1100°C and 1450°C and the sintering atmosphere is combined with a first gas and/or a vacuum, the oxygen content can be significantly reduced. The first gas is preferably a mixed gas mainly composed of hydrogen. The mixed gas may also include argon, but is not limited to this and may also be other appropriate gases.
在根據本公開的製造W-Ni濺射靶的方法中,所得坯料的熱機械處理或熱處理較佳在壓實步驟與冷卻步驟之間進行。此類熱機械處理或熱處理可產生有利特性,例如密度進一步增加及/或微觀結構的進一步均質化。In the method for producing a W-Ni sputtering target according to the present disclosure, the thermomechanical treatment or heat treatment of the obtained blank is preferably performed between the compaction step and the cooling step. Such thermomechanical treatment or heat treatment can produce advantageous properties, such as further increase in density and/or further homogenization of the microstructure.
較佳地,借助於此類熱機械處理或熱處理,可能仍存在的任何較小比例金屬間相可在濺射靶的微觀結構中均質分佈且因此使這些相的副作用降至最小。通過此精細分佈確保:在濺鍍期間無凹凸形成地均一剝蝕。Preferably, by means of such a thermomechanical treatment or heat treatment, any relatively small proportions of intermetallic phases which may still be present can be homogeneously distributed in the microstructure of the sputtering target and thus the adverse effects of these phases can be minimized. This fine distribution ensures uniform etching without the formation of irregularities during sputtering.
在製造W/Ni濺射靶的方法中,所用熱機械處理或熱處理在970℃至1450℃範圍內的溫度下進行為佳。In the method of manufacturing a W/Ni sputtering target, the thermomechanical treatment or heat treatment is preferably performed at a temperature in the range of 970°C to 1450°C.
在指示溫度範圍內在兩相區域W(Ni)+Ni(W)中進行熱機械處理或熱處理,且在較佳情況下使得不形成或基本上不形成其他不期望的脆性金屬間相。在最佳情況下,在壓實後可存在的金屬間相可很大程度上通過此類熱機械處理或熱處理溶解。Thermomechanical treatment or heat treatment is carried out in the two-phase region W(Ni)+Ni(W) within the indicated temperature range and preferably in such a way that no or substantially no other undesirable brittle intermetallic phases are formed. In the best case, intermetallic phases that may be present after compaction can be largely dissolved by such thermomechanical treatment or heat treatment.
通過此類不期望的脆性金屬間相的盡可能的避免,使借助於本公開的方法製造的W-Ni濺射靶尤其良好地成型。此舉又簡化較大形式濺射靶(及尤其較長及較佳為一件式管狀靶)的製造,且亦對與可達成的最終幾何結構的接近度具有有利影響。The avoidance of such undesirable brittle metal interphases as far as possible makes the W—Ni sputtering target produced by means of the disclosed method particularly well formed. This in turn simplifies the production of larger sputtering targets (and in particular longer and preferably one-piece tubular targets) and also has a favorable effect on the closeness to the final geometry that can be achieved.
較佳地,熱機械處理或熱處理包括至少一個鍛造步驟或輥壓步驟。Preferably, the thermomechanical treatment or heat treatment comprises at least one forging step or a rolling step.
在本公開的範圍內,熱機械處理或熱處理可以單階段或多階段方法進行。多種合適方法的組合也是可能的。因此,熱機械處理或熱處理可含有一個或多個分步驟,其不包含或基本上不包含濺射靶的變型。Within the scope of the present disclosure, the thermomechanical treatment or heat treatment can be performed as a single-stage or multi-stage method. A combination of multiple suitable methods is also possible. Thus, the thermomechanical treatment or heat treatment can contain one or more sub-steps that do not or substantially do not include a modification of the sputtering target.
在根據本公開的製造W-Ni濺射靶的方法中,熱機械處理或熱處理含有至少一個輥壓步驟或鍛造步驟為尤其有利的。In the method for producing a W—Ni sputtering target according to the present disclosure, the thermomechanical treatment or the heat treatment containing at least one rolling step or forging step is particularly advantageous.
可通過含有至少一個輥壓步驟或鍛造步驟的熱機械處理或熱處理以尤其具有目標性的方式將經定義的變形度引入濺射靶中。這樣,例如可以避免過度的加強,並因此避免超過可以施加的變形力。A defined degree of deformation can be introduced into the sputtering target in a particularly targeted manner by a thermomechanical treatment or heat treatment including at least one rolling step or forging step. In this way, for example, excessive reinforcement and thus deformation forces that exceed the applicable value can be avoided.
可借助於含有至少一個輥壓步驟或鍛造步驟的熱機械處理或熱處理以目標性方式將織構設置在濺射靶中,且這些又可對濺射靶的機械特性及濺鍍特性兩者施加積極影響。The structure can be introduced into the sputtering target in a targeted manner by means of a thermomechanical treatment or a heat treatment which comprises at least one rolling step or a forging step, and these in turn can exert a positive influence both on the mechanical properties of the sputtering target and on the sputtering properties.
此外,一個或多個輥壓步驟或鍛造步驟可使得在成型材料長度上改變其厚度且以具有目標性的方式設定此厚度。Furthermore, one or more rolling or forging steps make it possible to vary the thickness of the formed material over its length and to set this thickness in a targeted manner.
另外,借助於輥壓或鍛造,可確保對於濺射靶的進一步機械處理或進一步熱機械處理或熱處理有利且均一的表面品質、高直度及良好圓度。In addition, by means of rolling or forging, a favorable and uniform surface quality, high straightness and good roundness can be ensured for further mechanical treatment or further thermomechanical treatment or heat treatment of the sputtering target.
較佳地,借助於根據本公開的製造W-Ni濺射靶的方法製造含有55重量%至80重量%的Ni、餘量W及一般雜質的濺射靶。在此情況下,使用本公開方法確保所得W-Ni濺射靶含有W相、Ni(W) 固溶相、不含Ni相且不含或含有以濺射靶截面量測的平均面積比例小於5%的金屬間相。在此,面積比例理解為平均面積比例,其計算為在具有100 μm×100 μm尺寸金相拋光截面的5個影像部分上量測的5個面積比例量測值的算術平均值,以1000倍放大率記錄。Preferably, a sputtering target containing 55 wt % to 80 wt % Ni, the remainder W and general impurities is produced by means of the method for producing a W-Ni sputtering target according to the present disclosure. In this case, the method of the present disclosure is used to ensure that the resulting W-Ni sputtering target contains a W phase, a Ni (W) solid solution phase, does not contain a Ni phase, and does not contain or contains an intermetallic phase with an average area ratio of less than 5% measured on a cross section of the sputtering target. Here, the area ratio is understood to be the average area ratio, which is calculated as the arithmetic mean of 5 area ratio measurement values measured on 5 image portions of a metallographic polished cross section with a size of 100 μm×100 μm, recorded at a magnification of 1000 times.
根據本公開的製造W-Ni濺射靶的方法可確保在借此方法製造的W-Ni濺射靶中相對密度超過90%,更佳為超過92%,最佳為超過99.5%。通過根據本公開用於製造W-Ni濺射靶的方法,還優化了所得濺射靶的純度及機械性能。The method for manufacturing a W-Ni sputtering target according to the present disclosure can ensure that the relative density in the W-Ni sputtering target manufactured by the method exceeds 90%, more preferably exceeds 92%, and most preferably exceeds 99.5%. The purity and mechanical properties of the obtained sputtering target are also optimized by the method for manufacturing a W-Ni sputtering target according to the present disclosure.
因此,根據本公開的方法在由此製造的濺射靶中產生極低含量雜質,例如較佳氧含量小於50 μg/g,特別較佳小於40 μg/g。實質上避免脆性金屬間相的形成亦較佳促使借助於本公開的方法製造的W-Ni濺射靶的硬度得以最優化。Therefore, the method according to the present disclosure produces extremely low impurity content in the sputtering target produced thereby, for example, preferably less than 50 μg/g oxygen content, particularly preferably less than 40 μg/g. Substantially avoiding the formation of brittle metal interphases also preferably promotes the optimization of the hardness of the W-Ni sputtering target produced by the method of the present disclosure.
較佳地,借助於本公開的方法達成小於500HV10的硬度。Preferably, a hardness of less than 500 HV10 is achieved by means of the method disclosed herein.
在這種情況下,通過根據本公開的方法實現的W相的平均晶粒尺寸小於40 μm,較佳小於20 μm。In this case, the average grain size of the W phase achieved by the method according to the present disclosure is less than 40 μm, preferably less than 20 μm.
以下借助於實施例說明本公開。The present disclosure is explained below with the help of embodiments.
實例Examples
實例1:Example 1:
將具有根據費雪法測定的4 μm粒徑的W金屬粉末及具有根據費雪法量測的4.2 μm粒徑的Ni金屬粉末用作原料。40重量%的鎢粉末和60重量%的鎳粉末在混合機中混合,且在轉速為12每分鐘轉速 (rpm)下混合1小時。W metal powder having a particle size of 4 μm measured by the Fisher method and Ni metal powder having a particle size of 4.2 μm measured by the Fisher method were used as raw materials. 40 wt% of tungsten powder and 60 wt% of nickel powder were mixed in a mixer and mixed at a rotation speed of 12 rpm for 1 hour.
將粉末混合物引入到橡膠中,該橡膠在其開口端通過橡膠帽封閉。封閉的橡膠定位於等靜壓機中,且在200 MPa壓力下壓制,保壓時間為1分鐘,以提供具有67%相對密度及23 mm厚度、158 mm寬度及748 mm長度的生坯。The powder mixture was introduced into a rubber which was closed at its open end by a rubber cap. The closed rubber was positioned in an isostatic press and pressed at a pressure of 200 MPa with a dwell time of 1 minute to provide a green body having a relative density of 67% and a thickness of 23 mm, a width of 158 mm and a length of 748 mm.
先將生坯在真空中以3℃/min的升溫速率燒結到1350℃,在1350℃保溫1小時,然後將燒結氣氛換為第一氣體繼續保溫3個小時,然後以8℃/min的速度冷卻到980℃,再將燒結氣氛變化為H 2氣氛保溫1小時,然後以10℃/min的速度冷卻至室溫。燒結之後,燒結坯料具有20 mm的厚度、144 mm的寬度、665 mm的長度、90.6%的相對密度、23.6 μg/g的氧含量。 The green body was first sintered to 1350°C in vacuum at a heating rate of 3°C/min, kept at 1350°C for 1 hour, then the sintering atmosphere was changed to the first gas and kept for 3 hours, then cooled to 980°C at a rate of 8°C/min, and then the sintering atmosphere was changed to H2 atmosphere and kept for 1 hour, and then cooled to room temperature at a rate of 10°C/min. After sintering, the sintered green body had a thickness of 20 mm, a width of 144 mm, a length of 665 mm, a relative density of 90.6%, and an oxygen content of 23.6 μg/g.
燒結之後,以機械方式加工該生坯以提供15 mm厚度、128 mm寬度、620 mm長度的尺寸。實例1中燒結後的濺射靶的均勻性非常高,其中在濺射靶的不同長度位置處的Ni含量百分比的最大偏差僅為0.1%至0.3%。After sintering, the green body was machined to provide dimensions of 15 mm thickness, 128 mm width, and 620 mm length. The uniformity of the sputtering target after sintering in Example 1 was very high, with the maximum deviation of the Ni content percentage at different length positions of the sputtering target being only 0.1% to 0.3%.
對燒結後的濺射靶的不同長度位置的Ni含量的百分比(分別為1/4長度和1/2長度和3/4長度這三個位置)進行X射線螢光光譜(XRF)檢測且計算最大偏差。同時也對由WO2015089533A1的方法製造的濺射靶(對比例5)在相同位置進行檢測以進行對比,該濺射靶具有40重量%的W和60重量%的Ni。根據檢測結果進行驗證。
可見,實例1中所製造的濺射靶的Ni含量的最大偏差遠低於對照組,最大偏差很低,僅為0.28%,從而在不同位置的Ni的均勻性非常高。此外,還分別對實例1和對比例5兩者分別進行了XRD測量,在實例1中所製造的濺射靶中未發現純Ni相,而在對照組中所製造的濺射靶中發現有局部純Ni相存在。It can be seen that the maximum deviation of the Ni content of the sputtering target manufactured in Example 1 is much lower than that of the control group, and the maximum deviation is very low, only 0.28%, so the uniformity of Ni at different positions is very high. In addition, XRD measurements were performed on Example 1 and Comparative Example 5, respectively. No pure Ni phase was found in the sputtering target manufactured in Example 1, while local pure Ni phase was found in the sputtering target manufactured in the control group.
圖2A、圖2B分別顯示了實例1的光學顯微鏡圖像和SEM(掃描電子顯微鏡)圖像中的微觀結構。在光學顯微鏡下,Ni(W)固溶相呈淺灰色。純W相呈圖案化深灰色。孔隙(由粉末冶金生產方法產生)和/或其他製品(由製備產生)呈現黑色。在 SEM 圖像中,淺灰色顯示 Ni(W) 固溶相、孔隙和/或偽影呈黑色,純W相呈白色。Figures 2A and 2B show the microstructure in the optical microscope image and SEM (scanning electron microscope) image of Example 1, respectively. Under the optical microscope, the Ni(W) solid solution phase is light gray. The pure W phase is patterned dark gray. Pores (generated by the powder metallurgy production method) and/or other products (generated by the preparation) appear black. In the SEM image, the light gray shows the Ni(W) solid solution phase, pores and/or pseudo-images are black, and the pure W phase is white.
對比例5(由WO2015089533A1的方法製備的實例,也參見WO2015089533A1的表1、實例4):Comparative Example 5 (an example prepared by the method of WO2015089533A1, see also Table 1 and Example 4 of WO2015089533A1):
使用費雪法測定的粒徑為4 μm的W金屬粉末和篩分至粒徑小於160 μm的Ni金屬粉末作為原料。43重量%的鎢粉末和57重量%的鎳粉末在混合機中混合。在200 MPa的壓力下進行冷等靜壓,得到直徑25 mm、厚度13.5 mm的生坯。然後通過在2小時內加熱至1350℃然後在該溫度下保持4小時並在2小時內冷卻來燒結該生坯。燒結坯料的相對密度為73.7%,氧含量為268 μg/g。通過XRD測量,可以檢測到金屬間相。W metal powder with a particle size of 4 μm measured by the Fisher method and Ni metal powder sieved to a particle size of less than 160 μm were used as raw materials. 43 wt% of tungsten powder and 57 wt% of nickel powder were mixed in a mixer. Cold isostatic pressing was performed at a pressure of 200 MPa to obtain a green body with a diameter of 25 mm and a thickness of 13.5 mm. The green body was then sintered by heating to 1350°C within 2 hours, then maintaining at this temperature for 4 hours and cooling within 2 hours. The relative density of the sintered body was 73.7% and the oxygen content was 268 μg/g. Intermetallic phases can be detected by XRD measurement.
實例2:Example 2:
將具有根據費雪法測定的4 μm粒徑的W金屬粉末及具有根據費雪法量測的4.2 μm粒徑的Ni金屬粉末用作原料。35重量%的鎢粉末和65重量%的鎳粉末在混合機中混合,且在12 rpm轉速下混合1小時。W metal powder having a particle size of 4 μm measured by the Fisher method and Ni metal powder having a particle size of 4.2 μm measured by the Fisher method were used as raw materials. 35 wt% of tungsten powder and 65 wt% of nickel powder were mixed in a mixer and mixed at a rotation speed of 12 rpm for 1 hour.
將粉末混合物引入到橡膠中,該橡膠在其開口端通過橡膠帽封閉。封閉的橡膠定位於等靜壓機中,且在200MPa壓力下壓制,保壓時間為1分鐘,以提供具有66%相對密度及25 mm厚度、160 mm寬度及750mm長度的生坯。The powder mixture was introduced into a rubber which was closed at its open end by a rubber cap. The closed rubber was positioned in an isostatic press and pressed at a pressure of 200 MPa with a dwell time of 1 minute to provide a green body having a relative density of 66% and a thickness of 25 mm, a width of 160 mm and a length of 750 mm.
先將生坯在真空中以 3℃ /min 的升溫速率燒結到1350℃,在1350℃保溫1小時,然後將燒結氣氛換為第一氣體繼續保溫3個小時,然後以8℃/min的速度冷卻到980℃,再將燒結氣氛變化為H 2氣氛保溫1小時,然後以10℃/min的速度冷卻至室溫。燒結之後,燒結坯料具有22 mm的厚度、142 mm的寬度、667 mm的長度、90.8%的相對密度、29.8 μg/g的氧含量。實例2中燒結後的濺射靶的均勻性非常高,在濺射靶的不同長度位置的Ni含量的百分比的最大偏差僅為0.1%至0.3%。 First, the green body is sintered to 1350°C in vacuum at a heating rate of 3°C/min, kept at 1350°C for 1 hour, then the sintering atmosphere is changed to the first gas and kept for 3 hours, then cooled to 980°C at a rate of 8°C/min, and then the sintering atmosphere is changed to H2 atmosphere and kept for 1 hour, and then cooled to room temperature at a rate of 10°C/min. After sintering, the sintered blank has a thickness of 22 mm, a width of 142 mm, a length of 667 mm, a relative density of 90.8%, and an oxygen content of 29.8 μg/g. The uniformity of the sputtering target after sintering in Example 2 is very high, and the maximum deviation of the percentage of Ni content at different length positions of the sputtering target is only 0.1% to 0.3%.
對燒結後的濺射靶的不同長度位置的Ni含量的百分比(分別為1/4長度和1/2長度和3/4長度這三個位置)進行X射線螢光光譜(XRF)檢測且計算最大偏差。同時也對由WO2015089533A1的方法製造的濺射靶(對比例6)在相同位置進行檢測以進行對比,該濺射靶具有35重量%W和65重量%Ni。根據檢測結果進行驗證。
可見,實例2中所製造的濺射靶的Ni含量的最大偏差遠低於對照組,最大偏差很低,僅為0.15%,從而在不同位置的Ni的均勻性非常高。此外,還分別對實例2和對比例6兩者分別進行了XRD測量,在實例2中所製造的濺射靶中未發現純Ni相,而在對照組中所製造的濺射靶中發現有局部純Ni相存在。在實例2中,通過XRD測量沒有檢測到金屬間相或純W。It can be seen that the maximum deviation of the Ni content of the sputtering target manufactured in Example 2 is much lower than that of the control group, and the maximum deviation is very low, only 0.15%, so the uniformity of Ni at different positions is very high. In addition, XRD measurements were performed on both Example 2 and Comparative Example 6, respectively. No pure Ni phase was found in the sputtering target manufactured in Example 2, while local pure Ni phase was found in the sputtering target manufactured in the control group. In Example 2, no intermetallic phase or pure W was detected by XRD measurement.
圖2C、圖2D分別顯示了實例2的光學顯微鏡圖像和掃描電子顯微鏡(SEM)圖像中的微觀結構。在光學顯微鏡下,Ni(W)固溶相呈淺灰色。孔隙(由粉末冶金生產方法產生)和/或其他製品(由製備產生)呈現黑色。該圖像中未顯示純W相。在 SEM 圖像中,淺灰色顯示 Ni(W) 固溶相、孔隙和/或偽影呈黑色。儘管該圖像中顯示了白色的純W相,但是在該實例的XRD中沒有檢測到W相,即W相低於檢測限。Figure 2C and Figure 2D show the microstructure in the optical microscope image and scanning electron microscope (SEM) image of Example 2, respectively. Under the optical microscope, the Ni(W) solid solution phase is light gray. The pores (produced by the powder metallurgy production method) and/or other products (produced by the preparation) appear black. The pure W phase is not shown in this image. In the SEM image, the light gray shows the Ni(W) solid solution phase, and the pores and/or pseudo-images are black. Although the white pure W phase is shown in the image, the W phase is not detected in the XRD of this example, that is, the W phase is below the detection limit.
對比例6(由WO2015089533A1的方法製備的實例):Comparative Example 6 (Example prepared by the method of WO2015089533A1):
使用費雪法測定的粒徑為4 μm的W金屬粉末和篩分至粒徑小於160 μm的Ni金屬粉末作為原料。35重量%的鎢粉末和65重量%的鎳粉末在混合機中混合。在200 MPa的壓力下進行冷等靜壓,得到直徑25 mm、厚度14.1 mm的生坯。然後通過在2小時內加熱至1350℃然後在該溫度下保持4小時並在2小時內冷卻來燒結該生坯。燒結坯料的相對密度為85.2%,氧含量為82 μg/g。W metal powder with a particle size of 4 μm measured by the Fisher method and Ni metal powder sieved to a particle size of less than 160 μm were used as raw materials. 35 wt% of tungsten powder and 65 wt% of nickel powder were mixed in a mixer. Cold isostatic pressing was performed at a pressure of 200 MPa to obtain a green body with a diameter of 25 mm and a thickness of 14.1 mm. The green body was then sintered by heating to 1350°C within 2 hours, then maintaining at this temperature for 4 hours and cooling within 2 hours. The relative density of the sintered body was 85.2% and the oxygen content was 82 μg/g.
實例3:Example 3:
將具有根據費雪法測定的4 μm粒徑的W金屬粉末及具有根據費雪法量測的4.2 μm粒徑的Ni金屬粉末用作原料。30重量%的鎢粉末和70重量%的鎳粉末在混合機中混合,且在12 rpm轉速下混合1小時。W metal powder having a particle size of 4 μm measured by the Fisher method and Ni metal powder having a particle size of 4.2 μm measured by the Fisher method were used as raw materials. 30 wt % of tungsten powder and 70 wt % of nickel powder were mixed in a mixer and mixed at a rotation speed of 12 rpm for 1 hour.
將粉末混合物引入到柔性橡膠管中,該橡膠管在其開口端通過橡膠帽封閉。封閉的橡膠定位於等靜壓機中,且在200 MPa壓力下壓制,保壓時間為1分鐘,以提供具有67%相對密度及尺寸為Ø 15毫米x50毫米的生坯。The powder mixture was introduced into a flexible rubber tube which was closed at its open end by a rubber cap. The closed rubber was positioned in an isostatic press and pressed at a pressure of 200 MPa with a dwell time of 1 minute to provide a green body with a relative density of 67% and dimensions of Ø 15 mm x 50 mm.
先將生坯在真空中以 3℃/min 的升溫速率燒結到1350℃,在1350℃保溫1小時,然後將燒結氣氛換為第一氣體繼續保溫3個小時,然後以8℃/min的速度冷卻到980℃,再將燒結氣氛變化為H 2氣氛保溫1小時,然後以10℃/min的速度冷卻至室溫。燒結之後的生坯尺寸為Ø 13毫米x44毫米的長度,相對密度為92%,氧含量為32 μg/g。實例3中燒結後的濺射靶的均勻性非常高,在濺射靶的不同長度位置的Ni含量的百分比的最大偏差僅為0.1%至0.3%。 The green body was first sintered to 1350°C in vacuum at a heating rate of 3°C/min, kept at 1350°C for 1 hour, then the sintering atmosphere was changed to the first gas and kept for 3 hours, then cooled to 980°C at a rate of 8°C/min, then the sintering atmosphere was changed to H2 atmosphere and kept for 1 hour, and then cooled to room temperature at a rate of 10°C/min. The size of the green body after sintering was Ø 13 mm x 44 mm in length, the relative density was 92%, and the oxygen content was 32 μg/g. The uniformity of the sputtering target after sintering in Example 3 was very high, and the maximum deviation of the percentage of Ni content at different length positions of the sputtering target was only 0.1% to 0.3%.
對燒結後的濺射靶的不同長度位置的Ni含量的百分比(分別為1/4長度和1/2長度和3/4長度這三個位置)進行X射線螢光光譜(XRF)檢測且計算最大偏差。同時也對由WO2015089533A1的方法製造的濺射靶(對比例7)在相同位置進行檢測以進行對比,該濺射靶具有30重量%W和70重量%Ni。根據檢測結果進行驗證。
可見,實例3中所製造的濺射靶的Ni含量的最大偏差遠低於對照組,最大偏差很低,僅為0.15%,從而在不同位置的Ni的均勻性非常高。此外,還分別對實例3和對比例7兩者分別進行了XRD測量,在實例3中所製造的濺射靶中未發現純Ni相,而在對照組中所製造的濺射靶中發現有局部純Ni相存在。在實例3中,通過XRD測量沒有檢測到金屬間相或純W。It can be seen that the maximum deviation of the Ni content of the sputtering target manufactured in Example 3 is much lower than that of the control group, and the maximum deviation is very low, only 0.15%, so the uniformity of Ni at different positions is very high. In addition, XRD measurements were performed on both Example 3 and Comparative Example 7, respectively. No pure Ni phase was found in the sputtering target manufactured in Example 3, while local pure Ni phase was found in the sputtering target manufactured in the control group. In Example 3, no intermetallic phase or pure W was detected by XRD measurement.
圖2E、圖2F分別顯示了實例3的光學顯微鏡圖像和掃描電子顯微鏡(SEM)圖像中的微觀結構。在光學顯微鏡下,Ni(W)固溶相呈淺灰色。孔隙(由粉末冶金生產方法產生)和/或其他製品(由製備產生)呈現黑色。該圖像中未檢測到純W相。在 SEM 圖像中,淺灰色顯示 Ni(W) 固溶相、孔隙和/或偽影呈黑色。儘管該圖像中顯示了小的白色純W相,但是在該實例的XRD中沒有檢測到W相,即W相低於檢測限。Figure 2E and Figure 2F show the microstructure in the optical microscope image and scanning electron microscope (SEM) image of Example 3, respectively. Under the optical microscope, the Ni(W) solid solution phase is light gray. The pores (produced by the powder metallurgy production method) and/or other products (produced by the preparation) appear black. No pure W phase was detected in this image. In the SEM image, the light gray shows the Ni(W) solid solution phase, pores and/or pseudo-images are black. Although a small white pure W phase is shown in the image, no W phase was detected in the XRD of this example, that is, the W phase is below the detection limit.
對比例7(由WO2015089533A1的方法製備的實例):Comparative Example 7 (prepared by the method of WO2015089533A1):
使用費雪法測定的粒徑為4 μm的W金屬粉末和篩分至粒徑小於160 μm的Ni金屬粉末作為原料。30重量%的鎢粉末和70重量%的鎳粉末在混合機中混合。在200 MPa的壓力下進行冷等靜壓,得到直徑25 mm、厚度14.6 mm的生坯。然後通過在2小時內加熱至1350℃然後在該溫度下保持4小時並在2小時內冷卻來燒結該生坯。燒結坯料的相對密度為85.7%,氧含量為120 μg/g。W metal powder with a particle size of 4 μm measured by the Fisher method and Ni metal powder sieved to a particle size of less than 160 μm were used as raw materials. 30 wt% of tungsten powder and 70 wt% of nickel powder were mixed in a mixer. Cold isostatic pressing was performed at a pressure of 200 MPa to obtain a green body with a diameter of 25 mm and a thickness of 14.6 mm. The green body was then sintered by heating to 1350°C within 2 hours, then maintaining at this temperature for 4 hours and cooling within 2 hours. The relative density of the sintered body was 85.7% and the oxygen content was 120 μg/g.
實例4Example 4
將具有根據費雪法測定的4 μm粒徑的W金屬粉末及具有根據費雪法量測的4.2 μm粒徑的Ni金屬粉末用作原料。35重量%的鎢粉末和65重量%的鎳粉末在混合機中混合,且在12 rpm轉速下混合1小時。W metal powder having a particle size of 4 μm measured by the Fisher method and Ni metal powder having a particle size of 4.2 μm measured by the Fisher method were used as raw materials. 35 wt% of tungsten powder and 65 wt% of nickel powder were mixed in a mixer and mixed at a rotation speed of 12 rpm for 1 hour.
將粉末混合物引入到橡膠中,該橡膠在其開口端通過橡膠帽封閉。 封閉的橡膠定位於等靜壓機中,且在200 MPa壓力下壓制,保壓時間為1分鐘,以提供具有22mm厚度的生坯。先將生坯在真空中以3℃/min 的升溫速率燒結到1350℃,在1350℃保溫1小時,然後將燒結氣氛換為第一氣體繼續保溫3個小時,然後以8℃/min的速度冷卻到980℃,再將燒結氣氛變化為H 2氣氛保溫1小時,然後以10℃/min的速度冷卻至室溫。燒結之後,燒結坯料具有22mm的厚度、142 mm的寬度、667 mm的長度。燒結後進行2道次輥壓,得到15 mm的厚度。然後將輥壓塊在1300℃下退火半小時,並再次進行2道次輥壓以獲得10mm的厚度。然後用平整機加工,最後在1200℃退火半小時。退火後,在900至750°C的溫度範圍內實現至少34 K/min的冷卻速率。該工藝之後的生坯的相對密度為99.8%,氧含量為15.9 μg/g。 The powder mixture is introduced into a rubber which is closed at its open end by a rubber cap. The closed rubber is positioned in an isostatic press and pressed at a pressure of 200 MPa for a holding time of 1 minute to provide a green body having a thickness of 22 mm. The green body is first sintered to 1350°C at a heating rate of 3°C/min in a vacuum, kept at 1350°C for 1 hour, then the sintering atmosphere is changed to the first gas for a continuous holding time of 3 hours, then cooled to 980°C at a rate of 8°C/min, then the sintering atmosphere is changed to a H2 atmosphere for a holding time of 1 hour, and then cooled to room temperature at a rate of 10°C/min. After sintering, the sintered blank has a thickness of 22 mm, a width of 142 mm and a length of 667 mm. After sintering, two roll pressing passes are carried out to obtain a thickness of 15 mm. The rolled block is then annealed at 1300°C for half an hour and rolled again in two passes to obtain a thickness of 10 mm. It is then processed with a flattening machine and finally annealed at 1200°C for half an hour. After annealing, a cooling rate of at least 34 K/min is achieved in the temperature range of 900 to 750°C. The relative density of the green body after this process is 99.8% and the oxygen content is 15.9 μg/g.
根據本公開的第二方面的製造濺射靶的方法,有效解決降低材料均勻性,影響濺射效果的技術問題,密度高且應用性能好。The method for manufacturing a sputtering target according to the second aspect of the present disclosure effectively solves the technical problem of reducing material uniformity and affecting the sputtering effect, and has high density and good application performance.
圖3A顯示了實例4的光學顯微鏡圖像的微觀結構,其中顯示了晶粒的取向以及材料的高密度。FIG. 3A shows the microstructure of an optical microscope image of Example 4, showing the orientation of the grains and the high density of the material.
圖3B和圖3C分別顯示了實例4的光學顯微鏡圖像和掃描電子顯微鏡(SEM)圖像中的微觀結構。在光學顯微鏡下,Ni(W)固溶相呈淺灰色。由於這種材料的高密度,該圖像中幾乎沒有顯示任何孔隙。該圖像中未檢測到純W相。SEM圖像顯示了晶粒在縱向上的取向。在此圖像中仍然可以找到一個單一的純W晶粒,但這低於XRD的檢測水準。Figures 3B and 3C show the microstructure in an optical microscope image and a scanning electron microscope (SEM) image of Example 4, respectively. Under the optical microscope, the Ni(W) solid solution phase appears light gray. Due to the high density of this material, there are almost no pores in this image. No pure W phase is detected in this image. The SEM image shows the orientation of the grains in the longitudinal direction. A single pure W grain can still be found in this image, but this is below the detection level of XRD.
同樣在該實例4中,沒有檢測到純Ni、沒有純W以及沒有金屬間相。Also in Example 4, no pure Ni, no pure W, and no intermetallic phase were detected.
純Ni由於具有鐵磁性質,會影響磁控濺射的正常運行,因此WO2015089533A1中記載的技術方案才採用了較低Ni含量的WNi比例。同時,在本領域一般認為,如果需要增加材料元素分佈的均勻性,需要降低所需合金元素的含量,也就是說要增加Ni分佈的均勻性需要進一步降低Ni的含量。Pure Ni has ferromagnetic properties, which will affect the normal operation of magnetron sputtering. Therefore, the technical solution described in WO2015089533A1 adopts a WNi ratio with a lower Ni content. At the same time, it is generally believed in this field that if the uniformity of material element distribution needs to be increased, the content of the required alloying elements needs to be reduced, that is, to increase the uniformity of Ni distribution, the Ni content needs to be further reduced.
但是本公開的發明人們通過研究發現,如果按照現有的認識,進一步降低Ni的含量會產生如下問題:由於Ni相區域偏少,作為第二相的W-Ni相導致濺射靶各部位Ni元素含量分佈不均勻。However, the inventors of the present disclosure have found through research that further reducing the Ni content according to existing knowledge will cause the following problems: due to the small amount of Ni phase area, the W-Ni phase as the second phase causes the Ni element content in various parts of the sputtering target to be unevenly distributed.
本公開採用了與WO2015089533A1相反的技術方案,使用了較高的Ni含量,但是這本身也會導致產生如下問題:1)高Ni含量可能會導致材料純Ni相產生而產生磁性,不利於磁控濺射的進行,2)由於Ni元素的氧親和力比較強,可能會導致材料的氧含量增加。也就是說,高Ni含量的WNi濺射靶難以達到無純Ni相材料的結果,如何控制純Ni相的產生成為需要克服的技術難題。本公開的發明人們正是通過上述第一實施例和第二實施例中記載的改進後的技術,克服了上述技術難題,才能夠有效解決降低材料均勻性,影響濺射效果的技術問題,密度高且應用性能好。The present disclosure adopts a technical solution opposite to WO2015089533A1, using a higher Ni content, but this itself will also lead to the following problems: 1) High Ni content may lead to the generation of pure Ni phase in the material and produce magnetism, which is not conducive to the conduct of magnetron sputtering, 2) Since the Ni element has a strong oxygen affinity, it may lead to an increase in the oxygen content of the material. In other words, it is difficult for a WNi sputtering target with a high Ni content to achieve the result of a material without a pure Ni phase, and how to control the generation of a pure Ni phase becomes a technical problem that needs to be overcome. The inventors of the present disclosure have overcome the above technical difficulties through the improved technology described in the first and second embodiments above, and can effectively solve the technical problems of reducing material uniformity and affecting the sputtering effect, with high density and good application performance.
根據本公開所涉及的濺射靶以及製造濺射靶的方法,有效解決降低材料均勻性、影響濺射效果的技術問題,獲得密度高且應用性能好的濺射靶。According to the sputtering target and the method for manufacturing the sputtering target involved in the present disclosure, the technical problem of reducing material uniformity and affecting the sputtering effect is effectively solved, and a sputtering target with high density and good application performance is obtained.
雖然通過參照本公開的某些較佳實施方式,已經對本公開進行了圖示和描述,但本領域的普通技術人員應該明白,可以在形式上和細節上對其作各種改變,而不偏離本公開的精神和範圍。Although the present disclosure has been illustrated and described with reference to certain preferred embodiments thereof, it will be apparent to those skilled in the art that various changes may be made in form and detail without departing from the spirit and scope of the present disclosure.
無without
圖1示出了Ni-W系統的相圖,其中標記了根據本公開第一方面的濺射靶的組成範圍。 圖2A和2B示出了在本公開第二方面的濺射靶的製造方法的實例1中製造的濺射靶(WNi 40/60)的顯微鏡圖,圖2C和2D示出了在本公開第二方面的濺射靶的製造方法的實例2中製造的濺射靶(WNi 35/65)的顯微鏡圖,圖2E和2F示出了在本公開第二方面的濺射靶的製造方法的實例3中製造的濺射靶(WNi 30/70)的顯微鏡圖。 圖3A示出了在本公開第二方面的濺射靶的製造方法的實例4中製造的濺射靶的顯微鏡圖。 圖3B和3C分別示出了在本公開第二方面的濺射靶的製造方法的實例4中製造的濺射靶(WNi 35/65 rolled)的光學顯微鏡圖(light optical microscope)和SEM圖。 FIG1 shows a phase diagram of the Ni-W system, in which the composition range of the sputtering target according to the first aspect of the present disclosure is marked. FIGS. 2A and 2B show microscopic images of a sputtering target (WNi 40/60) manufactured in Example 1 of the method for manufacturing a sputtering target according to the second aspect of the present disclosure, FIGS. 2C and 2D show microscopic images of a sputtering target (WNi 35/65) manufactured in Example 2 of the method for manufacturing a sputtering target according to the second aspect of the present disclosure, and FIGS. 2E and 2F show microscopic images of a sputtering target (WNi 30/70) manufactured in Example 3 of the method for manufacturing a sputtering target according to the second aspect of the present disclosure. FIG. 3A shows a microscopic image of a sputtering target manufactured in Example 4 of the method for manufacturing a sputtering target according to the second aspect of the present disclosure. Figures 3B and 3C respectively show the optical microscope image (light optical microscope) and SEM image of the sputtering target (WNi 35/65 rolled) manufactured in Example 4 of the method for manufacturing the sputtering target of the second aspect of the present disclosure.
無without
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