Nickel-vanadium alloy target material as well as preparation method and application thereof

Abstract

The invention discloses a nickel-vanadium alloy target as well as a preparation method and application thereof, and belongs to the technical field of alloy targets. According to the nickel-vanadium alloy target material, the nickel-vanadium alloy cast ingot is subjected to forging, static pressure upsetting, first rolling, second rolling and annealing treatment in sequence, the deformation rate in the static pressure upsetting process, the temperature ranges of the first rolling and the second rolling and the temperature rising rate range in the annealing process are controlled, and grains can be effectively refined; and the defect degree is reduced, so that the prepared nickel-vanadium alloy target material is fine and uniform in crystal grain and high in density.

Description

Technical Field

[0001] The invention belongs to the technical field of alloy target materials, and in particular relates to a nickel-vanadium alloy target material and a preparation method and application thereof. Background Art

[0002] In the production of integrated circuits, pure gold is generally used as the surface conductive layer, but gold and silicon wafers are prone to generate AuSi low melting point compounds, resulting in weak adhesion between the gold and silicon interfaces. People have proposed adding a bonding layer on the surface of gold and silicon wafers. Pure nickel is often used as the bonding layer, but diffusion will also form between the nickel layer and the gold conductive layer, so a barrier layer is needed to prevent diffusion between the gold conductive layer and the nickel bonding layer. The barrier layer needs to use a metal with a high melting point and must withstand a large current density. High-purity metal vanadium can meet this requirement. Nickel sputtering targets, vanadium sputtering targets, and gold sputtering targets are used in the production of integrated circuits. Nickel-vanadium sputtering targets are made by adding vanadium to the nickel melt during the preparation of nickel-vanadium and gold, so that the prepared alloy is more conducive to magnetron sputtering. Combining the advantages of nickel sputtering targets and vanadium sputtering targets, the nickel layer (bonding layer) and vanadium layer (barrier layer) can be sputtered at one time. Nickel-vanadium alloy is non-magnetic, which is conducive to magnetron sputtering.

[0003] In CN111004985A "A method for preparing a nickel-vanadium sputtering target", the nickel-vanadium ingot is subjected to hot forging, annealing, cold deformation and secondary annealing in sequence; 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 grain size of the obtained nickel-vanadium sputtering target is ≤150μm. The nickel-vanadium target prepared by this method has coarse grains, which affects the deposition rate of the sputtering coating and the coating quality.

[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 the present invention is to overcome the deficiencies of the above-mentioned prior art and to provide a nickel-vanadium alloy target material with fine and uniform grains, no defects, high density, and a preparation method and application thereof.

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

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

[0008] (2) statically press roughening the forged target blank to obtain a statically pressed roughened target blank;

[0009] (3) subjecting the target blank after static pressing roughening to a first rolling and a second rolling in sequence, and then cooling the target blank to obtain a rolled target blank;

[0010] (4) annealing the rolled target blank to obtain a nickel-vanadium alloy target;

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

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

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

[0014] The nickel-vanadium alloy target provided by the present invention is prepared by sequentially subjecting the nickel-vanadium alloy ingot to forging, static pressing roughening, first rolling, second rolling and annealing treatment, and controlling the deformation rate during static pressing roughening, the temperature range of the first rolling and the second rolling, and the heating rate during annealing, so as to effectively refine the grains and reduce the defect degree, thereby making the prepared nickel-vanadium alloy target have fine and uniform grains and high density.

[0015] Exemplarily, in step (2), the deformation rate of static pressing can be any point value between 10-30% or any two point range value, for example, it can be 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, etc.

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

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

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

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

[0020] As a preferred embodiment of the preparation method of the present invention, the insulation temperature is 900-1200° C. and the time is 1-3 hours.

[0021] As a preferred embodiment of the preparation method of the present invention, the heat treatment temperature is 800-1100° C. and the time is 1-2 h.

[0022] As a preferred embodiment of the preparation method of the present invention, the number of upsetting and drawing is 2-4 times, and the steel is returned to the furnace for heat preservation during the upsetting and drawing process, and the time for returning to the furnace for heat preservation is 20-40 minutes.

[0023] The present invention has found that the forging method used to forge the nickel-vanadium alloy ingot can break up the coarse columnar crystals in the ingot and refine the grains; and through heat preservation, heat treatment and remelting during the roughing and drawing process, the plastic deformation ability of the ingot can be improved, the coarse grains can be destroyed in all directions, the risk of cracking can be reduced, and the defect rate of the target material can be reduced.

[0024] Preferably, the cooling is water cooling or air cooling. Subsequent treatment after cooling can reduce dynamic recrystallization and reduce the tendency of grain growth.

[0025] As a preferred embodiment of the preparation method of the present invention, in the step (2), the static pressure roughening pressure is 500-2000 tons.

[0026] The present invention has found that when the deformation rate of static pressure upsetting is within the range given by the present invention and the pressure of static pressure upsetting is within the above range, the grains can be more excellently refined, the target blank thickness can be reduced, the rolling folding curve can be compensated, and the defect rate can be reduced.

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

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

[0029] The present invention has been found that the target blank subjected to static pressure roughening treatment is subjected to the first rolling and the second rolling in sequence, which can further refine the grains; specifically, when the first rolling is firstly carried out within a specific temperature range and the total deformation rate and the single-pass deformation rate of the first rolling are controlled within the above range, the grains can be effectively refined; and then when the second rolling is carried out within the specific temperature range and the total deformation rate and the single-pass deformation rate of the second rolling are controlled within the above range, the target blank can be plastically deformed at the crystallization temperature, dynamic recrystallization can be reduced, and the grains can be refined.

[0030] Preferably, in step (3), cooling is performed by water cooling or air cooling. The second post-rolling cooling can reduce the tendency of grain growth.

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

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

[0033] The present invention has found that by heating the temperature within the above-mentioned heating rate range to the annealing temperature range and maintaining it for a certain time, the grains can be further controlled to be finer and more uniform.

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

[0035] The nickel-vanadium alloy target material provided by the present invention has excellent comprehensive performance, specifically, has good density and fine and uniform grain structure, and can be effectively applied to subsequent semiconductor sputtering.

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

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The nickel-vanadium alloy target provided by the present invention is prepared by sequentially subjecting the nickel-vanadium alloy ingot to forging, static pressing roughening, first rolling, second rolling and annealing treatment, and controlling the deformation rate during the static pressing roughening process, the temperature range of the first rolling and the second rolling, and the range of the heating rate during the annealing process, so that the grains can be effectively refined and the defect degree can be reduced, so that the prepared nickel-vanadium alloy target has fine and uniform grains and high density. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a microscopic morphology of the nickel-vanadium alloy target prepared in Example 1. DETAILED DESCRIPTION

[0040] In order to better illustrate the purpose, technical solutions 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 the present invention are all conventional reagents, methods and equipment in the art; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch of raw materials.

[0042] Example 1

[0043] An embodiment of the present invention provides a nickel-vanadium alloy target material, and a method for preparing the nickel-vanadium alloy target material comprises the following steps:

[0044] (1) A nickel-vanadium alloy ingot (with a purity of 99.99% and a mass percentage of vanadium of 7%) is heated to 1100° C. and kept warm for 2 h, and then subjected to three times of roughing and drawing, during which the ingot is returned to the furnace for keeping warm for 30 min, and after the three times of roughing and drawing, it is heat treated at 900° C. for 1 h; then heated to 1100° C. and kept warm for 2 h, and then subjected to three times of roughing and drawing, during which the ingot is returned to the furnace for keeping warm for 30 min, and after the three times of roughing and drawing, it is heat treated at 900° C. for 1 h; wherein the total deformation rate of roughing is 50%, and the total deformation rate of drawing is 70%; after forging, it is air-cooled to obtain a forged target blank;

[0045] (2) placing the forged target blank under 1000 tons for static press roughening until the deformation rate is 15%, thereby obtaining a target blank after static press roughening;

[0046] (3) The target blank after static pressing roughening is subjected to the first rolling (temperature of 1000°C, single-pass deformation rate of 5%, total deformation rate of 70%) and the second rolling (temperature of 450°C, single-pass deformation rate of 3%, total deformation rate of 20%) in sequence, wherein the first rolling and the second rolling adopt a cross-rolling method, and water cooling is performed after the second rolling is completed to obtain the rolled target blank;

[0047] (4) The rolled target blank is annealed by heating the temperature to 550° C. at a heating rate of 10° C. / min and keeping the temperature for 3 h; after the insulation, a nickel-vanadium alloy target is obtained.

[0048] Example 2

[0049] An embodiment of the present invention provides a nickel-vanadium alloy target material, and a method for preparing the nickel-vanadium alloy target material comprises the following steps:

[0050] (1) A nickel-vanadium alloy ingot (with a purity of 99.99% and a mass percentage of vanadium of 6.5%) is heated to 900° C. and kept warm for 3 h, and then subjected to three times of roughing and drawing, during which the ingot is returned to the furnace for keeping warm for 20 min, and after the three times of roughing and drawing, it is heat treated at 800° C. for 2 h; then heated to 900° C. and kept warm for 3 h, and then subjected to three times of roughing and drawing, during which the ingot is returned to the furnace for keeping warm for 20 min, and after the three times of roughing and drawing, it is heat treated at 800° C. for 2 h; wherein the total deformation rate of roughing is 30%, and the total deformation rate of drawing is 50%; after forging, it is air-cooled to obtain a forged target blank;

[0051] (2) placing the forged target blank under 500 tons for static press roughening until the deformation rate is 20%, thereby obtaining a target blank after static press roughening;

[0052] (3) The target blank after static pressing roughening is subjected to the first rolling (temperature of 900°C, single-pass deformation rate of 10%, total deformation rate of 60%) and the second rolling (temperature of 550°C, single-pass deformation rate of 1%, total deformation rate of 15%) in sequence, wherein the first rolling and the second rolling adopt a cross-rolling method, and water cooling is performed after the second rolling is completed to obtain the rolled target blank;

[0053] (4) The rolled target blank is annealed by heating the temperature to 650° C. at a heating rate of 20° C. / min and keeping the temperature for 2 h; after the insulation is completed, a nickel-vanadium alloy target is obtained.

[0054] Example 3

[0055] An embodiment of the present invention provides a nickel-vanadium alloy target material, and a method for preparing the nickel-vanadium alloy target material comprises the following steps:

[0056] (1) A nickel-vanadium alloy ingot (with a purity of 99.99% and a mass percentage of vanadium of 7.5%) is heated to 1200° C. and kept warm for 1 hour, and then subjected to three times of roughing and drawing, during which the ingot is returned to the furnace for keeping warm for 30 minutes, and after the three times of roughing and drawing, it is heat treated at 1100° C. for 1 hour; then heated to 1200° C. and kept warm for 1 hour, and then subjected to three times of roughing and drawing, during which the ingot is returned to the furnace for keeping warm for 30 minutes, and after the three times of roughing and drawing, it is heat treated at 1100° C. for 1 hour; wherein the total deformation rate of roughing is 15%, and the total deformation rate of drawing is 30%; after forging, it is air-cooled to obtain a forged target blank;

[0057] (2) placing the forged target blank under 2000 tons for static press roughening until the deformation rate is 15%, thereby obtaining a target blank after static press roughening;

[0058] (3) The target blank after static pressing roughening is subjected to the first rolling (temperature of 1000°C, single-pass deformation rate of 8%, total deformation rate of 65%) and the second rolling (temperature of 450°C, single-pass deformation rate of 5%, total deformation rate of 30%) in sequence, wherein the first rolling and the second rolling adopt a cross-rolling method, and water cooling is performed after the second rolling is completed to obtain the rolled target blank;

[0059] (4) The rolled target blank is annealed by heating the temperature to 750° C. at a heating rate of 5° C. / min and keeping the temperature for 4 h; after the insulation is completed, a nickel-vanadium alloy target is obtained.

[0060] Example 4

[0061] The embodiment of the present 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 embodiment 1 is that in step (1), the deformation rate of roughening is 10%, and the deformation rate of elongation is 20%.

[0062] Example 5

[0063] The embodiment of the present 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 embodiment 1 is that in step (1), the deformation rate of roughening is 60%, and the deformation rate of elongation is 80%.

[0064] Example 6

[0065] The embodiment of the present 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 embodiment 1 is that in step (2), the deformation rate of static pressure roughening is 10%.

[0066] Example 7

[0067] The embodiment of the present 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 embodiment 1 is that in step (2), the deformation rate of static pressure roughening is 30%.

[0068] Example 8

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

[0070] Example 9

[0071] The embodiment of the present 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 embodiment 1 is that in step (3), the temperature of the first rolling is 1100°C and the temperature of the second rolling is 600°C.

[0072] Example 10

[0073] The embodiment of the present invention provides a nickel-vanadium alloy target. The only difference between the preparation method of the nickel-vanadium alloy target and that of embodiment 1 is that in step (4), the temperature is increased to 450° C. at a heating rate of 1° C. / min and kept at this temperature for 3 h.

[0074] Comparative Example 1

[0075] The comparative example of the present 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 the step (2) of static pressure roughening is omitted.

[0076] Comparative Example 2

[0077] The comparative example of the present 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 step (3) the first rolling step is omitted.

[0078] Comparative Example 3

[0079] The comparative example of the present 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 step (3) the second rolling step is omitted.

[0080] Comparative Example 4

[0081] The comparative example of the present 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 pressure roughening is 5%.

[0082] Comparative Example 5

[0083] The comparative example of the present 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 pressure roughening is 35%.

[0084] Comparative Example 6

[0085] The comparative example of the present 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 temperature of the first rolling is 600°C.

[0086] Comparative Example 7

[0087] The comparative example of the present 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 temperature of the second rolling is 800°C.

[0088] Comparative Example 8

[0089] The comparative example of the present 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 increased to 800° C. at a heating rate of 25° C. / min and kept at this temperature for 1 hour.

[0090] Effect example

[0091] The effect examples of the present 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 by Archimedes drainage method;

[0093] 2. Average grain size: Use a metallographic microscope and analysis software to measure and record the average grain size;

[0094] The obtained results are shown in Table 1;

[0095] Table 1

[0096]

[0097]

[0098] It can be seen from Table 1 that the nickel-vanadium alloy target prepared by the technical solution provided by the present invention has excellent comprehensive performance. Specifically, the density of the prepared nickel-vanadium alloy target 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 is better. Specifically, the density can reach 100%, and the average grain size is between 30-40 μm. The nickel-vanadium alloy target prepared in Example 1 is observed by microscopic morphology, and the obtained figure is as follows: Figure 1 As shown, from Figure 1 It can be seen that the prepared nickel-vanadium alloy target has a fine and uniform particle size structure.

[0099] It can be seen from Example 1 and Comparative Example 1 that when the static pressure roughening step is missing, the density of the obtained product shows a significant downward trend; it can be seen from Example 1 and Comparative Examples 2-3 that 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 downward trend; it can be seen from Example 1 and Comparative Examples 4-8 that the preparation parameters of the nickel-vanadium alloy target material of the present invention will 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 downward trend.

[0100] Finally, it should be noted that the above embodiments are intended to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing a nickel-vanadium alloy target, characterized in that: The preparation method comprises the following steps: (1) forging a nickel-vanadium alloy ingot to obtain a forged target blank; (2) statically press roughening the forged target blank to obtain a statically pressed roughened target blank; (3) subjecting the target blank after static pressing roughening to a first rolling and a second rolling in sequence, and then cooling the target blank to obtain a rolled target blank; (4) annealing the rolled target blank to obtain a nickel-vanadium alloy target; In the step (2), the deformation rate of static pressing roughening is 10-30%; In the step (3), the temperature of the first rolling is 800-1100° C., and the temperature of the second rolling is 400-600° C.; In the step (4), the heating rate of annealing is ≤20°C / min.

2. The preparation method according to claim 1, characterized in that: In the step (1), the forging process is: after heat preservation, roughing and drawing are performed, followed by heat treatment, which is repeated 1-3 times and then cooled; the deformation rate of roughing is 15-50%, and the deformation rate of drawing is 30-70%.

3. The preparation method according to claim 2, characterized in that: The insulation temperature is 900-1200℃ and the time is 1-3h; and / or, the heat treatment temperature is 800-1100° C. and the time is 1-2 h; And / or, the times of upsetting and drawing are 2-4 times, and the steel is returned to the furnace for heat preservation during the upsetting and drawing process, and the time of returning to the furnace for heat preservation is 20-40 minutes.

4. The preparation method according to claim 1, characterized in that: In the step (2), the static pressure upsetting pressure is 500-2000 tons.

5. The preparation method according to claim 1, characterized in that: In the step (3), the total deformation rate of the first rolling is 60-75%, and the deformation rate of a single pass is 5-10%.

6. The preparation method according to claim 1, characterized in that: In the step (3), the total deformation rate of the second rolling is 15-30%, and the deformation rate of a single pass is 1-5%.

7. The preparation method according to claim 1, characterized in that: In the step (4), the annealing temperature is 500-750° C. and the time is 2-4 hours.

8. The preparation method according to claim 1, characterized in that: In the step (4), the heating rate during the annealing process is 5-20°C / min.

9. A nickel-vanadium alloy target, characterized in that: The nickel-vanadium alloy target is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the nickel-vanadium alloy target material as claimed in claim 9 in semiconductor sputtering.

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