WO2024075547A1 - Ｎｉ合金膜およびＮｉ合金膜形成用スパッタリングターゲット材 - Google Patents

Ｎｉ合金膜およびＮｉ合金膜形成用スパッタリングターゲット材 Download PDF

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WO2024075547A1
WO2024075547A1 PCT/JP2023/034499 JP2023034499W WO2024075547A1 WO 2024075547 A1 WO2024075547 A1 WO 2024075547A1 JP 2023034499 W JP2023034499 W JP 2023034499W WO 2024075547 A1 WO2024075547 A1 WO 2024075547A1
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alloy film
atomic
alloy
sputtering target
film
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English (en)
French (fr)
Japanese (ja)
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英夫 村田
萌美 多久和
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Proterial Ltd
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Proterial Ltd
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Priority to KR1020257010970A priority Critical patent/KR20250053965A/ko
Priority to JP2024555715A priority patent/JPWO2024075547A1/ja
Priority to CN202380070409.8A priority patent/CN119998475A/zh
Publication of WO2024075547A1 publication Critical patent/WO2024075547A1/ja
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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
    • C23C14/06—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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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
    • 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

Definitions

  • the present invention relates to Ni alloy films with high-temperature oxidation resistance that are used in applications where oxidation resistance at high temperatures is required, such as protective films for internal electrodes of electronic components and oxidation prevention films for equipment components used in semiconductor manufacturing equipment and baking furnaces, and to sputtering target materials for forming such films.
  • Ni, Cu, and their alloys have been used in thin films used for internal electrodes of electronic components that require small size and weight reduction, and there is a demand for thin films that can maintain oxidation resistance even in a film formation process that involves high-temperature heating of 600°C or higher in the atmosphere.
  • Cr films, Ni films, and Ni-Cr alloy films in which Cr is added to Ni have been known as thin films with high oxidation resistance.
  • These thin films are formed by plating or PVD (Physical Vapor Deposition) methods such as vacuum deposition and sputtering.
  • a CVD (Chemical Vapor Deposition) method in order to obtain an insulating protective film made of an oxide, nitride, or the like formed by a CVD (Chemical Vapor Deposition) method, corrosive gases, etc., may be used as the raw material gas, and the components constituting the chamber and device in which the gas is decomposed and deposited in plasma are also required to have oxidation resistance at high temperatures. Furthermore, oxidation resistance at high temperatures is also required for components such as chambers, adhesion protection plates, and trays in sintering furnaces used in sintering ionic active substances in an oxygen atmosphere, which affect the performance of large-capacity batteries that are essential for mobile products.
  • CVD Chemical Vapor Deposition
  • Patent Document 1 proposes a Ni-based alloy that contains, by mass%, 3.6-4.4% Al, 0.1-2.5% Si, 0.8-4.0% Cr, and one or more of 0.1-1.5% Mn, with the remainder being Ni and unavoidable impurities.
  • Patent Document 2 also proposes a Ni-based alloy that contains, by mass%, Al: 0.05-2.5%, Si: 0.3-2.5%, Cr: 0.5-3.0%, Mn: 0.5-1.8%, with Si/Cr ⁇ 1.1 or less, and the remainder being Ni and unavoidable impurities, and has excellent heat resistance and corrosion resistance.
  • Patent Document 3 also proposes a component in which a Ni-Al alloy layer is formed by calorizing the surface of a substrate made of pure Ni or a Ni-Cr-Fe alloy.
  • Patent No. 3814822 Japanese Patent Application Laid-Open No. 2-163336 JP 2012-219369 A
  • the object of the present invention is to provide a Ni alloy film that has high oxidation resistance at high temperatures even without containing Cr, and a sputtering target material for forming the film.
  • the inventors conducted extensive research into new alloys that would provide high oxidation resistance at high temperatures. As a result, they discovered that high oxidation resistance at high temperatures could be achieved by incorporating a specified amount of Al and V into Ni, and thus arrived at the present invention.
  • the present invention relates to a Ni alloy film containing 9.0 to 25.0 atomic % of Al, 1.0 to 8.0 atomic % of V, and the remainder being Ni and unavoidable impurities.
  • the Ni alloy film of the present invention preferably contains Al and V in a total amount of 11.0 to 30.0 atomic %.
  • the Ni alloy film of the present invention preferably contains 10.0 to 18.0 atomic % of Al. More preferably, the Ni alloy film of the present invention contains 11.0 to 16.0 atomic % of Al and 2.5 to 3.5 atomic % of V.
  • the present invention also relates to a sputtering target material for forming a Ni alloy film having a Curie point at or below room temperature, the Ni alloy film containing 9.0 to 25.0 atomic % Al, 1.0 to 8.0 atomic % V, and the remainder being Ni and unavoidable impurities.
  • the sputtering target material for forming a Ni alloy film of the present invention preferably contains Al and V in a total amount of 11.0 to 30.0 atomic %.
  • the sputtering target material for forming a Ni alloy film preferably contains 10.0 to 18.0 atomic % of Al.
  • the sputtering target material for forming a Ni alloy film of the present invention more preferably contains 11.0 to 16.0 atomic % of Al and 2.5 to 3.5 atomic % of V.
  • the present invention can provide a Ni alloy film that suppresses surface and internal oxidation of the Ni alloy film itself and exhibits excellent oxidation resistance at high temperatures, even when it does not contain Cr and undergoes a high-temperature heating process of 600°C or more in air. Therefore, the present invention can contribute to the miniaturization and weight reduction of various electronic components, the high integration, and the large capacity of batteries, as well as reducing the environmental impact at the time of disposal.
  • FIG. 1 is a schematic cross-sectional view of a Ni alloy film according to the present invention.
  • the Ni alloy film 2 of the present invention is formed, for example, on the surface of a substrate 1.
  • the Ni alloy film of the present invention is characterized in that it has a thin film thickness and achieves oxidation resistance at high temperatures without containing Cr, which has been an essential additive element in conventional oxidation-resistant alloys.
  • the "oxidation resistance” can be confirmed by the discoloration of the Ni alloy film caused by surface oxidation when heated in an oxygen-containing atmosphere, and can be quantitatively evaluated, for example, by reflectance.
  • the "internal oxidation” means that oxidation progresses from the surface to the inside of the Ni alloy film.
  • the electrical resistance value may increase in the case of the internal electrode, and the strength of the device member may decrease.
  • the adhesion of the Ni alloy film may decrease and the film may fall off, resulting in the loss of the oxidation prevention function. For this reason, even if the Ni alloy film is thin, it is necessary to prevent oxidation from progressing to the interface with the internal electrode or the device member, i.e., to suppress internal oxidation.
  • the "internal oxidation" of the Ni alloy film can be confirmed, for example, by forming a Ni alloy film on a transparent glass substrate and heating it in the atmosphere, and by observing discoloration or loss of metallic color when the Ni alloy film is viewed from the glass surface side, and can also be quantitatively evaluated by reflectance.
  • the Ni alloy film of the present invention contains 9.0 to 25.0 atomic % of Al, 1.0 to 8.0 atomic % of V, and the remainder being Ni and unavoidable impurities.
  • Both Al and V are elements that are more easily oxidized than Ni.
  • Al is the element that is most easily oxidized and is most easily diffused in Ni. When heated in the air, Al diffuses into the surface layer of the thin film to form an oxide layer.
  • V is an element that is less susceptible to oxidation than Al and diffuses slower in Ni than Al. When V is added alone to Ni, it has the effect of improving the oxidation resistance more than Al at temperatures of 300° C.
  • Ni alloy film of the present invention When the Ni alloy film of the present invention is heated in the atmosphere, Al, which diffuses quickly and is easily oxidized, forms an oxide layer at the surface, and a V layer, which diffuses slowly and is less likely to oxidize than Al, is formed underneath the oxide layer, thereby suppressing the diffusion of oxygen from the surface.
  • the Al content is set to 9.0 atomic % or more in order to stably generate an Al oxide layer on the surface layer and suppress internal oxidation.
  • the Al content in order to ensure adhesion to the substrate glass, Si wafer, metal foil, and various metal members, the Al content must be 9.0 atomic % or more.
  • the Al content of the Ni alloy film of the present invention is set to 25.0 atomic % or less.
  • the Al content of the Ni alloy film of the present invention is preferably set to 23.0 atomic % or less.
  • the V content is set to 1.0 atomic % or more in order to obtain the effect of suppressing internal oxidation by generating V between the Al oxide layer and the Ni alloy matrix during heating.
  • the V content exceeds 8.0 atomic %, the oxidation of V itself is promoted, and the oxidation resistance may decrease.
  • the V content of the Ni alloy film of the present invention is set to 8.0 atomic % or less.
  • the Ni alloy film according to the embodiment of the present invention can fully suppress internal oxidation by making the total content of Al and V 11.0 atomic % or more.
  • the Ni alloy film of the present invention contains a total of 11.0 to 30.0 atomic % of Al and V.
  • the Ni alloy film of the present invention contains a total of 11.0 to 28.0 atomic % of Al and V.
  • the Al content is set to 10.0 atomic % or more or 18.0 atomic % or less, so that discoloration due to surface oxidation of the Ni alloy film itself can be suppressed. Therefore, the Ni alloy film of the present invention preferably contains Al at 10.0 to 18.0 atomic %.
  • the content of Al in order to suppress the surface oxidation of the Ni alloy film itself at high temperatures, it is more preferable that the content of Al is 11.0 to 16.0 atomic % and the content of V is 2.5 to 3.5 atomic %.
  • the content of Al is preferably made larger than the content of V, and is preferably made 1.5 times or more the content of V.
  • the Ni alloy film of the present invention is composed of Ni and unavoidable impurities, with the remainder being other than Al and V.
  • the content of unavoidable impurities is small, and unavoidable impurities such as gas components oxygen, nitrogen and carbon, and transition metals Cr, Fe, Cu, etc. may be included within a range that does not impair the action of the present invention.
  • the gas components oxygen and nitrogen are each 1000 mass ppm or less
  • carbon is 200 mass ppm or less
  • Cr, Fe, Cu are each 200 mass ppm or less
  • the purity excluding gas components is 99.9 mass% or more.
  • a sputtering method using a sputtering target material is suitable.
  • a method of forming the film using a sputtering target having the same composition as the composition of the Ni alloy film, or a method of forming the film by co-sputtering using a sputtering target material consisting of a Ni-Al alloy and a Ni-V alloy can be applied. From the viewpoint of ease of setting sputtering conditions and ease of obtaining a Ni alloy film of a desired composition, it is optimal to form the film by sputtering using a sputtering target having the same composition as the composition of the Ni alloy film.
  • the sputtering target material of the present invention contains 9.0 to 25.0 atomic % Al, 1.0 to 8.0 atomic % V, and the remainder is composed of Ni and unavoidable impurities.
  • the sputtering target material according to the embodiment of the present invention preferably contains Al and V in a total amount of 11.0 to 30.0 atomic %.
  • the sputtering target material according to the embodiment of the present invention preferably contains 10.0 to 18.0 atomic % of Al.
  • the sputtering target material according to the embodiment of the present invention more preferably contains 11.0 to 16.0 atomic % Al and 2.5 to 3.5 atomic % V.
  • the sputtering target material for forming a Ni alloy film of the present invention is composed of Ni and inevitable impurities, except for Al and V.
  • the content of inevitable impurities is small, and inevitable impurities such as oxygen, nitrogen, and carbon, which are gas components, and Cr, Fe, and Cu, which are transition metals, may be contained within a range that does not impair the action of the present invention.
  • the gas components oxygen and nitrogen are each 1000 mass ppm or less, carbon is 200 mass ppm or less, and Cr, Fe, and Cu are each 200 mass ppm or less, and the purity excluding gas components is 99.9 mass% or more.
  • the sputtering target material of the present invention has a Curie point below room temperature.
  • the sputtering target material In order to efficiently form a Ni alloy film in a magnetron sputtering method, the sputtering target material must be nonmagnetic at room temperature, that is, have a Curie point below room temperature.
  • room temperature here refers to the range of 5 to 35°C as specified in JIS Z 8703.
  • Ni which is the main constituent element of the Ni alloy film of the present invention, is a magnetic material, and in order to set the Curie point below room temperature, it is important to alloy Ni with Al and V, which are non-magnetic elements that make up the composition of the Ni alloy film of the present invention.
  • This sputtering target material can be produced, for example, by a method of machining an ingot produced by melting raw materials adjusted to a predetermined composition, or by a powder sintering method.
  • a powder sintering method it is possible to produce alloy powder by a gas atomizing method and use it as the raw material powder, or to use a mixed powder in which multiple alloy powders or pure metal powders are mixed to achieve the final composition of the present invention as the raw material powder.
  • a sputtering target material was prepared. After weighing the raw materials to obtain a non-magnetic binary composition of Ni-13.0 atomic % Al, Ni-7.0 atomic % V, Ni-10.0 atomic % V, Ni-10.0 atomic % Cr, and Ni-10.0 atomic % Si, and a ternary composition of Ni-14.0 atomic % Al-3.5 atomic % V, ingots were produced by melting and casting in a vacuum melting furnace.
  • the sputtering target material of Ni-50.0 atomic % Al was obtained by producing an ingot by sintering alloy powder of the same composition.
  • Each of the above ingots was processed into a plate shape by hot plastic working, and after heat treatment for removing distortion, it was machined to produce a disk-shaped sputtering target material having a diameter of 100 mm and a thickness of 5 mm.
  • a SmCo magnet was brought close to each of the sputtering target materials obtained above, the magnet was not attracted, and it was confirmed that the sputtering target materials were non-magnetic at room temperature.
  • Each sputtering target material was brazed to a copper backing plate with In, and then attached to a sputtering device (model number: CS-200) manufactured by ULVAC, Inc.
  • a sputtering test was carried out under conditions of an Ar atmosphere, a pressure of 0.5 Pa, and a power of 500 W. It was found that all of the sputtering target materials were able to be sputtered.
  • the sputtering target materials obtained above were combined and various Ni alloy films were formed on a glass substrate (Corning Eagle-XG) with a thickness of 500 nm by a co-sputtering method for simultaneous film formation.
  • the Ni alloy films formed on polyimide films under the same conditions as above were dissolved in a dissolving solution containing hydrofluoric acid, and the component composition was analyzed by ICP emission spectrometry.
  • the reflectance of each of the Ni alloy films prepared above was measured after heat treatment in the atmosphere at 600° C. and 700° C.
  • the reflectance was measured using a spectrophotometric colorimeter CM-2500d manufactured by Konica Minolta.
  • the internal oxidation was evaluated by the reflectance and color when the Ni alloy film was viewed from the transparent glass side after heating at 700°C. If the film had a metallic color, the internal oxidation was suppressed, and if the film was discolored, the entire film was oxidized, and it was judged that internal oxidation had occurred.
  • the measurement results are shown in Table 1.
  • Ni alloy films of Samples No. 1 to No. 10 which are examples of the present invention and contain a predetermined amount of Al and V, were observed from the glass surface side after heating at 700°C. It was confirmed that the Ni alloy films maintained their metallic color, had a high reflectance of 50% or more, and had suppressed internal oxidation.
  • sample No. 11 which is a comparative example containing Cr, also had a metallic color on the glass surface side after heating at 700° C.
  • the reflectance of the Ni alloy film surface side at the time of film formation was 54 to 58% in all cases.
  • the Ni alloy film of sample No. 11 containing Cr as a comparative example had a reflectance lowered to less than 20% after heating at 600°C and 700°C, and it was confirmed that the oxidation resistance of the Ni alloy film surface was low.
  • Sample No. 1 to Sample No. 10 which contain Ni with Al and V within the range of the present invention, have a high reflectance exceeding 25% even after heating at 700°C, and that the oxidation resistance of the Ni alloy film surface is also high.
  • the Ni alloy films of Samples No. 3, 4, 6, 7, and 8, which are examples of the present invention have a high reflectance of 55% or more even after heating at 700°C, and further have excellent high-temperature oxidation resistance.
  • Example 2 Using the Ni-14.0 atomic % Al-3.5 atomic % V and Ni-10.0 atomic % Cr target materials prepared in Example 1, an Ni alloy film having a film thickness of 100 to 500 nm was formed on a glass substrate in an Ar atmosphere under a pressure of 0.5 Pa and a power of 500 W by adjusting the film formation time in the same manner as in Example 1.
  • a pure Ni target material was prepared and formed on a glass substrate to obtain a pure Ni film as a comparative example.
  • Each of the Ni alloy films and the pure Ni film obtained above was subjected to a heat treatment at 700° C. in the atmosphere, and then the reflectance was measured in the same manner as in Example 1. The results are shown in Table 2.
  • the reflectance of the pure Ni film could not be measured because the entire film was oxidized and peeled off.
  • the reflectance on the glass surface side was high at 50% or more when the film thickness was 150 nm or more, suppressing internal oxidation, but the reflectance on the Ni alloy film surface side dropped to 30% or less when the film thickness was in the range of 100 to 500 nm after heating at 700°C, confirming that the oxidation resistance was poor.
  • the Ni-14.0 atomic % Al-3.5 atomic % V example of the present invention like Ni-10.0 atomic % Cr, has a reflectance on the glass surface side that exceeds 50% at a film thickness of 150 nm or more, suppressing internal oxidation, while the reflectance on the Ni alloy film surface side exceeds 30% at a film thickness of 150 nm or more, with the reflectance increasing as the film thickness increases, and it has been confirmed that it has better oxidation resistance than Ni-10.0 atomic % Cr.
  • the Ni alloy of the present invention does not contain Cr, it can suppress internal oxidation in the same manner as Ni-10 atomic % Cr, and has a high reflectance even on the Ni alloy film side, confirming that it is a Ni alloy film with high oxidation resistance.

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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)
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PCT/JP2023/034499 2022-10-07 2023-09-22 Ｎｉ合金膜およびＮｉ合金膜形成用スパッタリングターゲット材 Ceased WO2024075547A1 (ja)

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KR1020257010970A KR20250053965A (ko) 2022-10-07 2023-09-22 Ni 합금막 및 Ni 합금막 형성용 스퍼터링 타겟재
JP2024555715A JPWO2024075547A1 (https=) 2022-10-07 2023-09-22
CN202380070409.8A CN119998475A (zh) 2022-10-07 2023-09-22 Ni合金膜及Ni合金膜形成用溅射靶材

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008158479A (ja) * 2006-11-30 2008-07-10 Sumitomo Metal Mining Co Ltd 耐熱遮光フィルムとその製造方法、及びそれを用いた絞り又は光量調整装置
JP2010054543A (ja) * 2008-08-26 2010-03-11 Sumitomo Metal Mining Co Ltd 吸収型多層膜ｎｄフィルター
JP2018009233A (ja) * 2016-07-15 2018-01-18 三菱マテリアル株式会社 Ｎｉ−Ｖ合金スパッタリングターゲット
JP2021075749A (ja) * 2019-11-07 2021-05-20 三井金属鉱業株式会社 スパッタリングターゲット
CN114318255A (zh) * 2021-12-09 2022-04-12 贵研铂业股份有限公司 一种由易氧化金属镀膜保护制备的高致密NiV合金溅射靶材及其制备方法

Family Cites Families (3)

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Publication number Priority date Publication date Assignee Title
JPH02163336A (ja) 1988-12-15 1990-06-22 Toshiba Corp 耐粒界腐食Ｎｉ基合金および腐食試験方法
JP3814822B2 (ja) 2002-03-08 2006-08-30 三菱マテリアル株式会社 高温熱交換器用フィンおよびチューブ
JP2012219369A (ja) 2011-04-14 2012-11-12 Mmc Superalloy Corp 皮膜形成処理装置用部材

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008158479A (ja) * 2006-11-30 2008-07-10 Sumitomo Metal Mining Co Ltd 耐熱遮光フィルムとその製造方法、及びそれを用いた絞り又は光量調整装置
JP2010054543A (ja) * 2008-08-26 2010-03-11 Sumitomo Metal Mining Co Ltd 吸収型多層膜ｎｄフィルター
JP2018009233A (ja) * 2016-07-15 2018-01-18 三菱マテリアル株式会社 Ｎｉ−Ｖ合金スパッタリングターゲット
JP2021075749A (ja) * 2019-11-07 2021-05-20 三井金属鉱業株式会社 スパッタリングターゲット
CN114318255A (zh) * 2021-12-09 2022-04-12 贵研铂业股份有限公司 一种由易氧化金属镀膜保护制备的高致密NiV合金溅射靶材及其制备方法

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