Nickel-vanadium alloy target material, method for preparing the same and use thereof

Abstract

The application discloses a nickel-vanadium alloy target material and a preparation method and application thereof, and belongs to the technical field of alloy target materials.The nickel-vanadium alloy target material is prepared by sequentially performing forging, static pressure roughing, first rolling, second rolling and annealing treatment on a nickel-vanadium alloy ingot, and by controlling the deformation rate in the static pressure roughing process and the temperature range of the first rolling and the second rolling and the temperature rising rate range in the annealing process, so that the grains can be effectively refined, the defect degree is reduced, and thus the prepared nickel-vanadium alloy target material has fine and uniform grains and high density.

Description

Technical Field

[0001] This invention belongs to the field of alloy target technology, and particularly relates to a nickel-vanadium alloy target, its preparation method and application. Background Technology

[0002] In integrated circuit fabrication, pure gold is typically used as the surface conductive layer. However, gold readily forms low-melting-point AuSi compounds with silicon wafers, leading to weak bonding at the gold-silicon interface. To address this, a bonding layer has been added to the surface of the gold and silicon wafers, often using pure nickel. However, diffusion can occur between the nickel layer and the gold conductive layer, necessitating a barrier layer to prevent this diffusion. This barrier layer requires a high-melting-point metal and must withstand high current densities; high-purity vanadium meets these requirements. Nickel, vanadium, and gold sputtering targets are used in integrated circuit fabrication. Nickel-vanadium sputtering targets are created by adding vanadium to the molten nickel during the preparation of nickel, vanadium, and gold, resulting in an alloy more suitable for magnetron sputtering. This combination of advantages allows for the simultaneous sputtering of both the nickel (bonding layer) and vanadium (barrier layer) layers in a single process. The non-magnetic nature of nickel-vanadium alloys further facilitates magnetron sputtering.

[0003] CN111004985A, "A Method for Preparing a Nickel-Vanadium Sputtering Target," describes a method for sequentially hot-forging, annealing, cold-deformation, and secondary annealing of nickel-vanadium ingots. The V content in the nickel-vanadium sputtering target is 7±0.7%, and the purity of the nickel-vanadium ingot is 99.9%-99.995%. The resulting nickel-vanadium sputtering target has a grain size ≤150μm. However, the coarse grains in the nickel-vanadium target prepared by this method affect the deposition rate and quality of the sputtered coating.

[0004] Therefore, how to prepare a nickel-vanadium alloy target with fine and uniform grains has become a research hotspot. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a nickel-vanadium alloy target material with fine, uniform, defect-free, and high density, as well as its preparation method and application.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a method for preparing a nickel-vanadium alloy target, the method comprising the following steps:

[0007] (1) Forging a nickel-vanadium alloy ingot to obtain a forged target blank;

[0008] (2) The forged target billet is statically uptaken to obtain the statically uptaken target billet;

[0009] (3) The target billet after static upsetting is subjected to first rolling and second rolling in sequence, and then cooled to obtain the rolled target billet.

[0010] (4) Anneal the rolled target billet to obtain a nickel-vanadium alloy target material;

[0011] In step (2), the deformation rate of the static pressure upsetting is 10-30%;

[0012] In step (3), the temperature of the first rolling is 800-1100℃, and the temperature of the second rolling is 400-600℃;

[0013] In step (4), the annealing heating rate is ≤20℃ / min.

[0014] The nickel-vanadium alloy target material provided by this invention involves sequentially forging, static upsetting, first rolling, second rolling, and annealing a nickel-vanadium alloy ingot. By controlling the deformation rate during static upsetting, the temperature range of the first and second rolling processes, and the heating rate during annealing, the grain size can be effectively refined and the defect rate reduced. As a result, the prepared nickel-vanadium alloy target material has fine, uniform grains and high density.

[0015] For example, in step (2), the deformation rate of the static pressure pier can be any point value or any two-point range value between 10% and 30%, such as 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc.

[0016] Preferably, in step (2), the deformation rate of the static pressure upsetting is 15-20%.

[0017] For example, in step (3), the temperature of the first rolling can be any point value or any two-point range value between 800-1100℃, such as 800℃, 850℃, 900℃, 950℃, 1000℃, 1050℃, 1100℃, etc.; the temperature of the second rolling can be any point value or any two-point range value between 400-600℃, such as 400℃, 450℃, 500℃, 550℃, 600℃, etc.

[0018] Preferably, in step (3), the temperature of the first rolling is 900-1000℃ and the temperature of the second rolling is 450-550℃.

[0019] As a preferred embodiment of the preparation method of the present invention, in step (1), the forging process is as follows: after heat preservation, upsetting and drawing are performed, followed by heat treatment, repeated 1-3 times and then cooled; the deformation rate of upsetting is 15-50%, and the deformation rate of drawing is 30-70%.

[0020] As a preferred embodiment of the preparation method described in this invention, the heat preservation temperature is 900-1200℃ and the time is 1-3h.

[0021] In a preferred embodiment of the preparation method described in this invention, the heat treatment temperature is 800-1100℃ and the time is 1-2h.

[0022] As a preferred embodiment of the preparation method described in this invention, the upsetting and drawing process is carried out 2-4 times, and the material is kept in the furnace for 20-40 minutes during the upsetting and drawing process.

[0023] This invention has found that forging nickel-vanadium alloy ingots using the above-mentioned forging method can break up the coarse columnar crystals in the ingots and refine the grains. Furthermore, by using heat preservation, heat treatment, and heat preservation in the furnace during the upsetting and drawing process, the plastic deformation capacity of the ingots can be improved, the coarse grains can be destroyed in all directions, and the risk of cracking can be reduced, thus lowering the defect rate of the target material.

[0024] Preferably, the cooling is water cooling or air cooling. Cooling before subsequent processing can reduce dynamic recrystallization and decrease the tendency for grain growth.

[0025] In a preferred embodiment of the preparation method described in this invention, the static pressure for roughing in step (2) is 500-2000 tons.

[0026] The present invention has found that when the deformation rate of static upsetting is within the range given in the present invention, and the pressure of static upsetting is within the above range, it is possible to refine the grains more effectively, reduce the target billet thickness, compensate for the rolling fold curve, and reduce the defect rate.

[0027] In a preferred embodiment of the preparation method of the present invention, in step (3), the total deformation rate of the first rolling is 60-75%, and the deformation rate per pass is 5-10%.

[0028] In a preferred embodiment of the preparation method of the present invention, in step (3), the total deformation rate of the second rolling is 15-30%, and the deformation rate per pass is 1-5%.

[0029] This invention has found that sequentially performing a first rolling and a second rolling on a target billet that has undergone static upsetting treatment can further refine the grains. Specifically, performing the first rolling within a specific temperature range and controlling the total deformation rate and single-pass deformation rate of the first rolling within the aforementioned range can effectively refine the grains. Then, performing the second rolling within a specific temperature range and controlling the total deformation rate and single-pass deformation rate of the second rolling within the aforementioned range can cause the target billet to undergo plastic deformation at the crystallization temperature, reducing dynamic recrystallization and refining the grains.

[0030] Preferably, in step (3), cooling is performed by water cooling or air cooling. Secondary cooling after rolling can reduce the tendency for grain growth.

[0031] In a preferred embodiment of the preparation method of the present invention, in step (4), the annealing temperature is 500-750℃ and the time is 2-4h.

[0032] In a preferred embodiment of the preparation method of the present invention, in step (4), the heating rate of the annealing process is 5-20℃ / min.

[0033] The present invention has found that heating to the annealing temperature range within the above-mentioned heating rate range and holding for a certain period of time can further control the grain size, making it finer and more uniform.

[0034] In a second aspect, the present invention provides a nickel-vanadium alloy target material, which is prepared by the preparation method described in the present invention.

[0035] The nickel-vanadium alloy target provided by this invention has excellent comprehensive performance. Specifically, it has good density and fine and uniform grain structure, and can be effectively applied in subsequent semiconductor sputtering.

[0036] In a third aspect, the present invention provides the application of the described nickel-vanadium alloy target in semiconductor sputtering.

[0037] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0038] The nickel-vanadium alloy target material provided by this invention involves sequentially forging, static upsetting, first rolling, second rolling, and annealing a nickel-vanadium alloy ingot. By controlling the deformation rate during static upsetting, the temperature range during the first and second rolling processes, and the heating rate range during annealing, the grain size can be effectively refined and the defect rate reduced. As a result, the prepared nickel-vanadium alloy target material has fine, uniform grains and high density. Attached Figure Description

[0039] Figure 1 This is a microscopic morphology diagram of the nickel-vanadium alloy target material prepared in Example 1. Detailed Implementation

[0040] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0041] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch.

[0042] Example 1

[0043] This invention provides a nickel-vanadium alloy target material, the preparation method of which includes the following steps:

[0044] (1) The nickel-vanadium alloy ingot (purity of 99.99% and vanadium mass percentage of 7%) was heated to 1100℃ and held for 2 hours. Then, it was upsetting and drawing was performed three times. During the upsetting and drawing, it was reheated and held in the furnace for 30 minutes. After the three upsetting and drawing were completed, it was heat-treated at 900℃ for 1 hour. Then, it was heated to 1100℃ and held for 2 hours. Then, it was upsetting and drawing was performed three times. During the upsetting and drawing, it was reheated and held in the furnace for 30 minutes. After the three upsetting and drawing were completed, it was heat-treated at 900℃ for 1 hour. The total deformation rate of upsetting was 50%, and the total deformation rate of drawing was 70%. After forging, it was air-cooled to obtain the forged target billet.

[0045] (2) The forged target blank is subjected to static pressure upsetting at 1000 tons until the deformation rate is 15%, thus obtaining the target blank after static pressure upsetting.

[0046] (3) The target billet after static pressure upsetting is subjected to first rolling (temperature 1000℃, single-pass deformation rate 5%, total deformation rate 70%) and second rolling (temperature 450℃, single-pass deformation rate 3%, total deformation rate 20%). The first rolling and the second rolling adopt cross rolling method. After the second rolling is completed, water cooling is performed to obtain the rolled target billet.

[0047] (4) The rolled target billet is annealed, specifically heated to 550°C at a heating rate of 10°C / min and held for 3 hours; after the holding period, nickel-vanadium alloy target material is obtained.

[0048] Example 2

[0049] This invention provides a nickel-vanadium alloy target material, the preparation method of which includes the following steps:

[0050] (1) The nickel-vanadium alloy ingot (purity of 99.99%, vanadium mass percentage of 6.5%) was heated to 900℃ and held for 3 hours. Then, it was upsetting and drawing was carried out three times. During the upsetting and drawing, it was reheated and held in the furnace for 20 minutes. After the three upsetting and drawing were completed, it was heat-treated at 800℃ for 2 hours. Then, it was heated to 900℃ and held for 3 hours. Then, it was upsetting and drawing was carried out three times. During the upsetting and drawing, it was reheated and held in the furnace for 20 minutes. After the three upsetting and drawing were completed, it was heat-treated at 800℃ for 2 hours. The total deformation rate of upsetting was 30%, and the total deformation rate of drawing was 50%. After forging, it was air-cooled to obtain the forged target billet.

[0051] (2) The forged target billet is subjected to static pressure upsetting at 500 tons until the deformation rate is 20%, thus obtaining the target billet after static pressure upsetting.

[0052] (3) The target billet after static upsetting is subjected to first rolling (temperature 900℃, single-pass deformation rate 10%, total deformation rate 60%) and second rolling (temperature 550℃, single-pass deformation rate 1%, total deformation rate 15%). The first rolling and the second rolling adopt a cross rolling method. After the second rolling is completed, the target billet is water-cooled to obtain the rolled target billet.

[0053] (4) The rolled target billet is annealed, specifically heated to 650°C at a heating rate of 20°C / min and held for 2 hours; after the holding period, nickel-vanadium alloy target material is obtained.

[0054] Example 3

[0055] This invention provides a nickel-vanadium alloy target material, the preparation method of which includes the following steps:

[0056] (1) The nickel-vanadium alloy ingot (purity of 99.99% and vanadium mass percentage of 7.5%) was heated to 1200℃ and held for 1 hour. Then, it was upsetting and drawing was performed three times. During the upsetting and drawing, it was reheated in the furnace for 30 minutes. After the three upsetting and drawing, it was heat-treated at 1100℃ for 1 hour. Then, it was heated to 1200℃ and held for 1 hour. Then, it was upsetting and drawing was performed three times. During the upsetting and drawing, it was reheated in the furnace for 30 minutes. After the three upsetting and drawing, it was heat-treated at 1100℃ for 1 hour. The total deformation rate of upsetting was 15%, and the total deformation rate of drawing was 30%. After forging, it was air-cooled to obtain the forged target billet.

[0057] (2) The forged target blank is subjected to static pressure upsetting at 2000 tons until the deformation rate is 15%, thus obtaining the target blank after static pressure upsetting.

[0058] (3) The target billet after static upsetting is subjected to first rolling (temperature 1000℃, single-pass deformation rate 8%, total deformation rate 65%) and second rolling (temperature 450℃, single-pass deformation rate 5%, total deformation rate 30%). The first rolling and the second rolling adopt a cross rolling method. After the second rolling is completed, the target billet is water-cooled to obtain the rolled target billet.

[0059] (4) The rolled target billet is annealed, specifically heated to 750°C at a heating rate of 5°C / min and held for 4 hours; after the holding period, nickel-vanadium alloy target material is obtained.

[0060] Example 4

[0061] This invention provides a nickel-vanadium alloy target material. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (1), the deformation rate of upsetting is 10% and the deformation rate of elongation is 20%.

[0062] Example 5

[0063] This invention provides a nickel-vanadium alloy target material. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (1), the deformation rate of upsetting is 60% and the deformation rate of elongation is 80%.

[0064] Example 6

[0065] This invention provides a nickel-vanadium alloy target material. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (2), the deformation rate of static upsetting is 10%.

[0066] Example 7

[0067] This invention provides a nickel-vanadium alloy target material. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (2), the deformation rate of the static upsetting is 30%.

[0068] Example 8

[0069] This invention provides a nickel-vanadium alloy target material. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (3), the first rolling temperature is 800°C and the second rolling temperature is 400°C.

[0070] Example 9

[0071] This invention provides a nickel-vanadium alloy target material. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (3), the first rolling temperature is 1100°C and the second rolling temperature is 600°C.

[0072] Example 10

[0073] This invention provides a nickel-vanadium alloy target material. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (4), the temperature is raised to 450°C at a heating rate of 1°C / min and held for 3 hours.

[0074] Comparative Example 1

[0075] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that step (2) static pressure upsetting is omitted.

[0076] Comparative Example 2

[0077] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that step (3) the first rolling step is omitted.

[0078] Comparative Example 3

[0079] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that the second rolling step (3) is omitted.

[0080] Comparative Example 4

[0081] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (2), the deformation rate of static upsetting is 5%.

[0082] Comparative Example 5

[0083] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (2), the deformation rate of static upsetting is 35%.

[0084] Comparative Example 6

[0085] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (3), the temperature of the first rolling is 600°C.

[0086] Comparative Example 7

[0087] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (3), the second rolling temperature is 800°C.

[0088] Comparative Example 8

[0089] The present invention provides a nickel-vanadium alloy target material in a comparative example. The only difference between the preparation method of the nickel-vanadium alloy target material and that of Example 1 is that in step (4), the temperature is raised to 800°C at a heating rate of 25°C / min and held for 1 hour.

[0090] Example of effect

[0091] The effectiveness examples of this invention verify the performance of the nickel-vanadium alloy targets prepared in Examples 1-10 and Comparative Examples 1-8, including the following aspects:

[0092] 1. Density: Tested using Archimedes' displacement method;

[0093] 2. Average grain size: The average grain size was measured and recorded using a metallographic microscope and analysis software;

[0094] The results are shown in Table 1.

[0095] Table 1

[0096]

[0097]

[0098] As can be seen from Table 1, the nickel-vanadium alloy target material prepared using the technical solution provided by this invention has excellent comprehensive performance. Specifically, the density of the prepared nickel-vanadium alloy target material is above 99.5%, and the average grain size is below 94 μm. When the parameters are further selected within the preferred range, the comprehensive performance of the obtained nickel-vanadium alloy target material is even better; specifically, the density can reach 100%, and the average grain size is between 30-40 μm. The microstructure of the nickel-vanadium alloy target material prepared in Example 1 was observed, and the results are shown in the figure below. Figure 1 As shown, from Figure 1 As can be seen, the prepared nickel-vanadium alloy target material has a fine and uniform particle size distribution.

[0099] As can be seen from Example 1 and Comparative Example 1, when the static pressure upsetting step is missing, the density of the obtained product shows a significant decreasing trend. As can be seen from Example 1 and Comparative Examples 2-3, when only the first rolling or the second rolling is performed, the average grain size of the obtained product is above 100 μm, and the density also shows a significant decreasing trend. As can be seen from Example 1 and Comparative Examples 4-8, the preparation parameters of the nickel-vanadium alloy target material of the present invention also have a significant impact on the product. When the preparation parameters are not within the scope of the present invention, the average grain size of the obtained product is above 100 μm, and the density shows a significant decreasing trend.

[0100] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a nickel-vanadium alloy target, characterized in that, The preparation method includes the following steps: (1) Forging a nickel-vanadium alloy ingot to obtain a forged target blank; (2) The forged target blank is statically upset to obtain the statically upset target blank; (3) The target billet after static upsetting is subjected to first rolling and second rolling in sequence, and then cooled to obtain the rolled target billet; (4) Anneal the rolled target billet to obtain a nickel-vanadium alloy target material; In step (1), the forging process is as follows: after heat treatment, upsetting and drawing are performed, followed by heat treatment, repeated 1-3 times and then cooled; the deformation rate of upsetting is 15-50%, and the deformation rate of drawing is 30-70%; In step (2), the deformation rate of static upsetting is 10-30%, and the pressure of static upsetting is 500-2000 tons; In step (3), the temperature of the first rolling is 800-1100℃, and the temperature of the second rolling is 400-600℃; the total deformation rate of the first rolling is 60-75%, and the single-pass deformation rate is 5-10%; the total deformation rate of the second rolling is 15-30%, and the single-pass deformation rate is 1-5%. In step (4), the annealing heating rate is ≤20℃ / min.

2. The preparation method according to claim 1, characterized in that, The insulation temperature is 900-1200℃, and the time is 1-3 hours; And / or, the heat treatment temperature is 800-1100℃ and the time is 1-2h; And / or, the upsetting and drawing process is repeated 2-4 times, and the material is kept in the furnace for 20-40 minutes during the upsetting and drawing process.

3. The preparation method according to claim 1, characterized in that, In step (4), the annealing temperature is 500-750℃ and the time is 2-4h.

4. The preparation method according to claim 1, characterized in that, In step (4), the annealing process has a heating rate of 5-20℃ / min.

5. A nickel-vanadium alloy target material, characterized in that, The nickel-vanadium alloy target is prepared by the preparation method described in any one of claims 1-4.

6. The application of the nickel-vanadium alloy target as described in claim 5 in semiconductor sputtering.

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