A pvd hard coating magnetron sputtering target material, and a preparation method and application thereof

Abstract

The application discloses a PVD hard coating magnetron sputtering target material and a preparation method and application thereof, and the preparation method comprises the following steps: (1) providing a substrate and performing sand blasting cleaning; (2) sequentially depositing a base layer, a transition layer, a functional layer and a surface layer on the surface of the substrate from inside to outside; the transition layer is a W-Si composite layer, wherein the content of tungsten is 70wt%-99wt%, and the content of silicon is 1wt%-30wt%; the content of tungsten in the functional layer is greater than or equal to 90wt%; the surface layer is a WSi2 enrichment layer; before deposition, tungsten powder and silicon powder are respectively screened to 50-400 meshes, and then mixed for 6-8 hours before being sent into a plasma flame for spraying deposition; and (3) performing vacuum heat treatment after deposition is completed. Through the specific particle size screening and mixing process, the technical problems of large density difference and large melting point difference of the W-Si system are overcome, the obtained target material is uniform in composition, high in surface smoothness and high in bonding strength, and is suitable for the magnetron sputtering preparation of hard coatings of cutters, molds and the like.

Description

Technical Field

[0001] This invention relates to the field of magnetron sputtering target preparation technology, specifically to a PVD hard-coated magnetron sputtering target, its preparation method, and its application. Background Technology

[0002] Magnetron sputtering targets are key consumables in physical vapor deposition (PVD) processes, widely used in semiconductors, flat panel displays, solar cells, and hard coatings. Among them, tungsten-silicon (W-Si) targets have broad application prospects in tool coatings, mold coatings, and decorative coatings due to the high hardness, good wear resistance, and high-temperature oxidation resistance of the coatings they produce.

[0003] Currently, the preparation of tungsten-silicon targets mainly adopts the powder metallurgy route, which involves mixing tungsten powder and silicon powder in a certain proportion and then forming the target blank through hot pressing sintering or hot isostatic pressing. For example, existing technologies disclose a method for preparing tungsten-silicon targets by mixing tungsten powder and silicon powder in a certain proportion and then hot pressing sintering. However, the above-mentioned powder metallurgy route has the following inherent drawbacks: (1) The density difference between tungsten powder (density 19.25 g / cm³) and silicon powder (density 2.33 g / cm³) is significant (approximately 8 times). When mixing the powders using a conventional ball mill, the two powders are prone to segregation and stratification during mixing and feeding due to the density difference, making it difficult to obtain a uniformly mixed powder. Even by extending the mixing time, it is difficult to fundamentally solve the problem of uneven mixing caused by the density difference.

[0004] (2) The melting point of tungsten (3422℃) is very different from that of silicon (1414℃). During the hot pressing sintering process, silicon melts first while tungsten remains solid, which easily causes liquid phase segregation and uneven structure, ultimately affecting the sputtering performance of the target material and the coating quality.

[0005] (3) Both tungsten and silicon are easily oxidized at high temperatures. Tungsten is oxidized to WO3 and silicon is oxidized to SiO2, which has an adverse effect on the purity of the target material and the performance of the subsequent sputtered thin film.

[0006] In addition, there are reports of using plasma spraying technology to prepare targets. However, existing plasma spraying techniques for preparing targets usually use premixed powder as the spraying material. For the W-Si system, due to the significant difference in density between W and Si, the dynamic segregation and delamination caused by the density difference are particularly prominent during the transportation of premixed powder in the powder feeding tank, powder feeding pipeline and inside the spray gun. It is also difficult to achieve continuous and precise control of the coating composition, which ultimately leads to significant inhomogeneity of the target composition and structure at both the macroscopic and microscopic scales. Summary of the Invention

[0007] This invention addresses the technical challenges of component segregation and uneven microstructure caused by the large density and melting point differences between W and Si in the preparation of tungsten-silicon sputtering targets. It provides a method for preparing PVD hard-coated magnetron sputtering targets. This method involves constructing a target layer with a specific structure on the substrate surface and combining it with a powder pretreatment process to obtain W-Si magnetron sputtering targets with uniform composition, high density, and high bonding strength.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution: A method for preparing a PVD hard-coated magnetron sputtering target includes the following steps: (1) Provide a substrate and clean the surface of the substrate by sandblasting; (2) A base layer, a transition layer, a functional layer and a surface layer are deposited sequentially from the inside to the outside on the surface of the substrate, and the deposition is carried out under vacuum conditions; The underlying layer is a NiCrAlY or a pure Mo layer; The transition layer is a W-Si composite layer, in which the tungsten content is 70wt%-99wt% and the silicon content is 1wt%-30wt%. The functional layer is a high W content layer, with a W content ≥ 90 wt%; The surface layer is a WSi2 enriched layer; Before deposition, tungsten powder and silicon powder are screened separately, and powders with a particle size of 50 to 400 mesh are selected. Then, the screened tungsten powder and silicon powder are mixed for 6-8 hours to obtain a mixed powder. The mixed powder is then sent into a plasma flame for spray deposition. (3) After deposition, vacuum heat treatment is performed.

[0009] This invention effectively controls the particle size distribution range of tungsten powder and silicon powder by strictly screening their particle size (50 mesh to 400 mesh) and setting a specific mixing time (6-8 hours). By controlling the particle size of tungsten powder and silicon powder within a similar fineness range, their acceleration and flight velocity in gas transport and plasma flow tend to be consistent, reducing the difference in settling velocity caused by particle size differences. This minimizes segregation caused by significant density differences during the mixing stage. Simultaneously, limiting the mixing time to 6-8 hours ensures uniform mixing of the two powders at both the macroscopic and microscopic scales while avoiding powder agglomeration or the introduction of impurities due to excessively long mixing times. This invention limits the tungsten content in the transition layer to 70wt%-99wt% and the silicon content to 1wt%-30wt%. Within this range, sufficient hardness, wear resistance, and high-temperature oxidation resistance of the target material are ensured, while the addition of silicon improves the density of the coating and its bonding strength with the substrate. If the silicon content is too high (>30wt%), the coating becomes more brittle and its high-temperature oxidation resistance decreases; if the tungsten content is too low (<70wt%), the coating hardness is insufficient and cannot meet the requirements for hard coating applications. After deposition, surface polishing is performed to obtain a finished target material with a surface finish that meets the requirements for magnetron sputtering.

[0010] Further, in step (2), the deposition is carried out using plasma spraying with a power of 80-150kW, a spraying distance of 200-400mm, a substrate temperature controlled at ≤200℃, a working pressure of 80 Pa to 120 Pa, and a powder feeding rate of 2-3RPM. The deposition atmosphere is a mixture of H2 and Ar, with an Ar flow rate of 2300NL / H and an H2 flow rate of 200-240vL / H. Plasma spraying technology uses a high-temperature plasma jet (flame temperature can reach over 10000℃) to heat the coating material to a molten or semi-molten state and spray it onto the substrate surface at high speed to form a coating. This technology is suitable for spraying high-melting-point materials such as tungsten and can be carried out under vacuum or a protective atmosphere, effectively suppressing the oxidation of W and Si.

[0011] Furthermore, in step (2), the side of the functional layer away from the transition layer is a high W content layer; its function is to optimize sputtering performance and improve hardness. More preferably, the W content is ≥90wt% and the thickness is 100-500μm.

[0012] Further, in step (2), the WSi2 enriched layer is a coating with tungsten disilicide (WSi2) as the main component. Preferably, the mass percentage of the WSi2 phase in the WSi2 enriched layer is ≥80wt%, and the thickness of the surface layer is 10-50μm. This invention, by setting a WSi2 enriched layer on the outermost layer of the target material, utilizes the high hardness, high melting point, and excellent high-temperature oxidation resistance of WSi2 to impart good wear resistance and oxidation resistance to the target material surface. During subsequent sputtering, a dense SiO2 protective film can be formed in situ on the surface of the WSi2 enriched layer, effectively inhibiting the oxidation of W and Si inside the coating and maintaining the stability of the target material composition. Simultaneously, the WSi2 enriched layer can act as a diffusion barrier layer during magnetron sputtering, suppressing adverse reactions between W in the functional layer and the sputtering atmosphere, and improving the quality and uniformity of the sputtered film.

[0013] Furthermore, in step (2), the underlayer is a NiCrAlY or pure Mo layer, taking advantage of the fact that the thermal expansion coefficient of the underlayer is between that of the substrate (stainless steel approximately 16 × 10⁻⁶). -6 / K) and W-Si coating (W: 4.5×10 -6 / K, Si: 2.6×10 -6 The properties between / K) effectively alleviate thermal stress caused by the difference in thermal expansion coefficients. Meanwhile, the thermal expansion coefficient of molybdenum is approximately 5.2 × 10⁻⁶. -6 / K, and the coefficient of thermal expansion of tungsten (4.5×10) -6 The molybdenum and tungsten elements are close in size (e.g., molybdenum / tungsten), and both belong to Group VIB, allowing them to form an infinite solid solution. This facilitates a gradient transition in thermal expansion coefficients and interfacial metallurgical bonding. Compared to alloy underlayers such as NiCrAlY, a pure molybdenum layer avoids the problem of interfacial thermal stress concentration caused by excessive differences in thermal expansion coefficients. More preferably, the thickness of the underlayer is 5-100 μm.

[0014] Furthermore, after deposition, a vacuum heat treatment is performed at a temperature of 1000-1200℃ for 2-4 hours, with a vacuum degree of 10. - ² Pa ~ 10 - ³ Pa. The subsequent vacuum heat treatment at a specific temperature utilizes the characteristic that silicon's melting point is much lower than tungsten's to melt silicon and promote its diffusion reaction with tungsten particles, generating high-hardness phases such as WSi2 in situ, thus achieving densification and sintering of the coating. On the other hand, this heat treatment process, in conjunction with the gradient structure, allows the surface layer to be naturally enriched with WSi2 phase, while the transition layer forms intermediate phases such as W5Si3, thereby constructing a composite coating with gradient changes in composition and structure, significantly alleviating internal stress and improving bonding strength.

[0015] Furthermore, in step (3), the vacuum heat treatment is carried out under an inert atmosphere with a heating rate of 5-15℃ / min. The purpose of the vacuum heat treatment in this application is twofold: firstly, to promote the diffusion reaction between W and Si at the interface, generating target phases such as WSi2, thereby improving the density and phase uniformity of the coating; secondly, to eliminate the internal stress generated during plasma spraying, improving the bonding strength between the coating and the substrate, and forming a good metallurgical bond with the substrate. Vacuum heat treatment causes the coating to undergo densification sintering, resulting in a target material relative density of over 95% and a porosity reduced to below 5%, significantly superior to the performance of the sprayed target material.

[0016] As another feasible molding method, the invention can also employ hot isostatic pressing (HIP) to prepare the target material. Specifically, tungsten powder and silicon powder are sieved to 50-400 mesh and then mixed uniformly in a target ratio (tungsten content 70wt%-99wt%, silicon content 1wt%-30wt%). This mixture is then filled into a casing and coated onto the outside of the substrate. After degassing, it is subjected to HIP molding. The HIP process parameters are: temperature 1100-1300℃, pressure 80-120 MPa, and holding time 1-3 hours. Preferably, the HIP process is 1200℃ / 100 MPa / 2h, resulting in a coating porosity of <2% after densification. HIP molding can obtain a target coating with high density and high bonding strength, making it suitable for applications requiring higher target density.

[0017] Another objective of this application is to provide a PVD hard-coated magnetron sputtering target, which is prepared by the above-described method for preparing a PVD hard-coated magnetron sputtering target, comprising: a substrate, and an underlayer, a transition layer, a functional layer and a surface layer sequentially disposed on the substrate.

[0018] The third objective of this application is to provide an application of the above-mentioned PVD hard-coated magnetron sputtering target in PVD hard-coated magnetron sputtering, which can be widely used in the manufacture of magnetron sputtering targets in fields such as tool coating, mold coating, and decorative coating, and has good industrial applicability.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention effectively overcomes the technical challenges of component segregation and narrow process windows caused by the large density difference in the W-Si system through specific particle size screening and mixing processes, resulting in a high-performance target material with uniform composition. By limiting the tungsten content in the transition layer to 70wt%-99wt% and the silicon content to 1wt%-30wt%, the target material is ensured to have both high hardness, good wear resistance, and high-temperature oxidation resistance. The gradient transition design between the underlayer and the transition layer effectively alleviates the thermal stress caused by the difference in thermal expansion coefficients and improves the bonding strength between the layers of the target material. Surface polishing treatment ensures that the surface finish of the target material meets the requirements for magnetron sputtering. Detailed Implementation

[0020] The present invention will be further described in detail below with reference to embodiments, but the embodiments of the present invention are not limited thereto. The raw materials used in the following embodiments are all commercially available products, wherein the purity of tungsten powder is ≥99.9%, the purity of silicon powder is ≥99.9%, and the particle size of the powder is 300 mesh.

[0021] Example 1 This embodiment provides a method for preparing a PVD hard-coated magnetron sputtering target, including the following steps: (1) Provide a 304 stainless steel substrate and use white corundum abrasive to sandblast the surface of the substrate. The sandblasting pressure is 0.6 MPa and the surface roughness Ra of the substrate after sandblasting is 5-8 μm. After sandblasting, the substrate is ultrasonically cleaned in anhydrous ethanol for 10 min and dried at 100℃ for later use.

[0022] (2) Preparation of coating powder: Tungsten powder and silicon powder are sieved separately, and powders with a particle size of 200 to 300 mesh are selected. The sieved tungsten powder and silicon powder are mixed in a mixer at a tungsten content of 90 wt% and a silicon content of 10 wt%, respectively, and mixed for 7 hours to obtain a mixed powder.

[0023] A plasma spraying system is used to feed the mixed powder into a plasma flame, and deposit the underlayer, transition layer, functional layer and surface layer sequentially from the inside to the outside on the pretreated substrate surface. Deposition was carried out under vacuum conditions, with a plasma spraying power of 120kW, a spraying distance of 300mm, a substrate temperature controlled at ≤200℃ by compressed air cooling, a stable working pressure of 100 Pa, and a powder feed rate of 2RPM. The deposition atmosphere was a mixture of H2 and Ar, with an Ar flow rate of 2300NL / H and an H2 flow rate of 220sL / H.

[0024] The base coat uses NiCrAlY powder (NiCrAlY alloy powder, Ni balance, Cr: 20-25wt%, Al: 8-12wt%, Y: 0.5-1.5wt%) as the spraying material, with a deposition thickness of 50μm; The transition layer uses the mixed powder (W:Si=90wt%:10wt%) as the spraying material, and the deposition thickness is 500μm.

[0025] The functional layer uses pure tungsten powder as the coating material, with a deposition thickness of 300μm and a W content of ≥99wt%.

[0026] The surface layer uses WSi2 composite powder (W to Si atomic ratio of 1:2) as the coating material, with a deposition thickness of 30μm.

[0027] (3) Vacuum heat treatment After deposition, the resulting target material was placed in a vacuum heat treatment furnace and subjected to vacuum heat treatment under an argon protective atmosphere. The temperature was increased to 1100℃ at a heating rate of 10℃ / min and held for 3 hours, followed by cooling to room temperature in the furnace at a rate of 8℃ / min.

[0028] Performance testing The performance of the target material obtained in this embodiment was tested: Relative density: determined using Archimedes' displacement method, the result was 95.8%; Porosity: Determined using image analysis, the result was 4.2%; Bond strength: The bond strength between the underlayer and the substrate was determined by tensile testing and was 50 MPa. Surface roughness: measured using a stylus profilometer, Ra=0.6μm; Compositional uniformity: EDS line scanning analysis showed that the distribution of W and Si in the transition layer was in good agreement with the design values, and no obvious segregation was observed.

[0029] Example 2 The difference between this embodiment and Embodiment 1 is that: In step (2), tungsten powder and silicon powder are sieved separately, and powders with a particle size of 50 to 100 mesh are selected. The mixing time is 6 hours.

[0030] In step (2), the screened tungsten powder and silicon powder are mixed according to a tungsten content of 70wt% and a silicon content of 30wt%.

[0031] In step (2), the plasma spraying power is 80kW, the spraying distance is 400mm, the working pressure is stable at 120 Pa, and the powder feeding rate is 3RPM.

[0032] The bottom layer is a pure Mo layer with a thickness of 100 μm.

[0033] The transition layer thickness is 800 μm.

[0034] The functional layer is 500 μm thick, and the surface layer is 50 μm thick.

[0035] After surface polishing in step (3), the surface roughness Ra ≤ 0.8 μm.

[0036] The target material obtained in this embodiment has a relative density of 94.5%, a porosity of 5.1%, a bonding strength of 44 MPa, and a surface roughness Ra=0.7 μm, according to the test results.

[0037] Example 3 The difference between this embodiment and Embodiment 1 is that: In step (2), tungsten powder and silicon powder are sieved separately, and powders with a particle size of 300 to 400 mesh are selected. The mixing time is 8 hours.

[0038] In step (2), the screened tungsten powder and silicon powder are mixed according to a tungsten content of 99 wt% and a silicon content of 1 wt%.

[0039] In step (2), the plasma spraying power is 150kW, the spraying distance is 200mm, the working pressure is stable at 80Pa, and the powder feeding rate is 2.5RPM.

[0040] The bottom layer is a NiCrAlY layer with a thickness of 5μm.

[0041] The transition layer thickness is 200 μm.

[0042] The functional layer is 100 μm thick, and the surface layer is 10 μm thick.

[0043] After surface polishing in step (3), the surface roughness Ra ≤ 0.8 μm.

[0044] The target material obtained in this embodiment has a relative density of 96.2%, a porosity of 3.8%, a bonding strength of 54 MPa, and a surface roughness Ra=0.5 μm, according to the test results.

[0045] Example 4 This embodiment provides a method for preparing PVD hard-coated magnetron sputtering targets using hot isostatic pressing (HIP), including the following steps: (1) Provide a 304 stainless steel substrate and use white corundum abrasive to sandblast the surface of the substrate. The sandblasting pressure is 0.6 MPa and the surface roughness Ra of the substrate after sandblasting is 5-8 μm. After sandblasting, the substrate is ultrasonically cleaned in anhydrous ethanol for 10 min and dried at 100℃ for later use.

[0046] (2) Powder preparation: Tungsten powder and silicon powder are sieved separately, and powders with a particle size of 200 to 300 mesh are selected. The sieved tungsten powder and silicon powder are mixed in a mixer at a tungsten content of 90 wt% and a silicon content of 10 wt%, respectively, and mixed for 7 hours to obtain mixed powder.

[0047] The resulting mixed powder was filled into a casing and wrapped around the pretreated matrix. After vacuum degassing, the casing was sealed.

[0048] (3) The sealed casing is placed in a hot isostatic pressing (HIP) apparatus and hot isostatic pressing is performed under the condition that argon is used as the pressure transmission medium. The hot isostatic pressing process is 1200℃ / 100 MPa / 2h, that is: the temperature is raised to 1200℃ at a heating rate of 10℃ / min, and the pressure is raised to 100MPa at the same time. The temperature and pressure are maintained for 2h to allow the powder to solidify on the outer surface of the substrate. Then, the furnace is cooled to room temperature and the pressure is released. The casing is then removed, and the target blank is obtained after removing the casing.

[0049] (4) Surface polishing treatment: The surface of the target material is polished by mechanical polishing to make the surface roughness Ra≤0.8μm.

[0050] Performance testing Relative density: determined using Archimedes' displacement method, the result was 99.1%; Porosity: determined using image analysis, the result was 0.9%; Bond strength: The bond strength between the coating and the substrate was determined by tensile testing to be 82 MPa. Surface roughness: measured using a stylus profilometer, Ra=0.6μm; Compositional uniformity: EDS line scanning analysis showed that the distribution of W and Si in the coating was in good agreement with the design values, with no obvious segregation. After hot isostatic pressing, the target material porosity was <2%, indicating a significant densification effect.

[0051] Comparative Example 1 The difference between this comparative example and Example 1 is that it does not use a multi-layer structure with an underlayer, transition layer, functional layer, and surface layer; instead, it uses a single-component target material layer. The remaining steps are the same as in Example 1.

[0052] Testing revealed that the W and Si distribution in the target material obtained in Comparative Example 1 was severely uneven, with obvious component segregation. The target material had a relative density of 82.3% and a porosity of 15.1%.

[0053] Comparative Example 2 The difference between this comparative example and Example 1 is that in step (2), the tungsten powder and silicon powder were not screened for particle size of 50 to 400 mesh, but were directly mixed using the original powder (with a wide particle size distribution, including a large amount of fine and coarse powder), and the mixing time was still 7 hours. The remaining steps are the same as in Example 1.

[0054] Testing revealed that the W and Si distribution in the target material obtained in Comparative Example 2 was uneven. Due to the difference in particle size, segregation occurred during the mixing and powder feeding process. The composition of the transition layer deviated from the design value, with a relative density of 85.7% and a porosity of 12.4%.

[0055] Performance Tests and Results The performance of the targets prepared in Examples 1-4 and Comparative Examples 1-2 was tested, and the results are as follows: Table 1. Comparison of target material performance between the examples and comparative examples

[0056] The above results demonstrate that this invention, through specific particle size screening and mixing processes, effectively overcomes the technical challenges of component segregation and narrow process windows caused by the large density difference in the W-Si system, resulting in a high-performance target material with uniform composition. By controlling the tungsten content within the range of 70wt%-99wt% and the silicon content within the range of 1wt%-30wt%, the obtained target material exhibits excellent hardness, wear resistance, and high-temperature oxidation resistance. Surface polishing ensures that the surface finish of the target material meets the requirements for magnetron sputtering applications.

[0057] Furthermore, by employing hot isostatic pressing (Example 4), a target coating with high density (relative density 99.1%) and high bonding strength (82MPa) can be obtained, and the porosity can be reduced to below 2% (0.9%), making it suitable for application scenarios with higher requirements for target density.

[0058] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a PVD hard-coated magnetron sputtering target, characterized in that: Includes the following steps: (1) Provide a substrate and clean the surface of the substrate by sandblasting; (2) A base layer, a transition layer, a functional layer and a surface layer are deposited sequentially from the inside to the outside on the surface of the substrate, and the deposition is carried out under vacuum conditions; The transition layer is a W-Si composite layer, and the mass ratio of tungsten powder to silicon powder in the transition layer is (70%-99%):(1%-30%). The tungsten powder and silicon powder are sieved to a particle size range of 50 mesh to 400 mesh. Then, the sieved tungsten powder and silicon powder are mixed for 6-8 hours to obtain a mixed powder. The mixed powder is then sent into a plasma flame for spraying and deposition. The functional layer is a high W content layer, with a W content ≥ 90 wt%; The surface layer is a WSi2 enriched layer; (3) After deposition, vacuum heat treatment is performed.

2. The method for preparing a PVD hard-coated magnetron sputtering target according to claim 1, characterized in that, In step (2), the deposition is carried out by plasma spraying with a power of 80-150kW, a spraying distance of 200-400mm, and the substrate temperature is controlled at ≤200℃.

3. The method for preparing a PVD hard-coated magnetron sputtering target according to claim 1, characterized in that, In step (2), the deposition atmosphere is a mixture of H2 and Ar, with an Ar flow rate of 2300 NL / H and an H2 flow rate of 200-240 vL / H.

4. The method for preparing a PVD hard-coated magnetron sputtering target according to claim 1, characterized in that, In step (2), the powder feeding rate is 2-3 RPM.

5. The method for preparing a PVD hard-coated magnetron sputtering target according to claim 1, characterized in that, The substrate layer is a NiCrAlY or pure Mo layer, and the thickness of the substrate layer is 5-100 μm.

6. The method for preparing a PVD hard-coated magnetron sputtering target according to claim 1, characterized in that, In step (3), the vacuum heat treatment temperature is 1000-1200℃, and the temperature is maintained for 2-4 hours.

7. The method for preparing a PVD hard-coated magnetron sputtering target according to claim 1, characterized in that, In step (3), the vacuum heat treatment is carried out under an inert atmosphere and the heating rate is 5-15℃ / min.

8. The method for preparing a PVD hard-coated magnetron sputtering target according to claim 1, characterized in that, The thickness of the functional layer is 100-500 μm; The thickness of the transition layer is 200-800 μm; The thickness of the surface layer is 10-50 μm.

9. A PVD hard-coated magnetron sputtering target, prepared by the method for preparing the PVD hard-coated magnetron sputtering target according to any one of claims 1-8, characterized in that, include: The substrate, and the base layer, transition layer, functional layer and surface layer sequentially disposed on the substrate.

10. The application of the PVD hard-coated magnetron sputtering target as described in claim 9 in PVD hard-coated magnetron sputtering.

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