Gold-ruthenium alloy target material and preparation method thereof

Abstract

The invention provides a gold-ruthenium alloy target material and a preparation method thereof, and belongs to the technical field of sputtering target materials, and the preparation method comprises the following steps: S1, mixing ammonium chlororuthenate and gold powder, adding a regulating agent, carrying out wet ball milling in a ball mill to obtain composite powder coated with organic molecules, and drying to obtain precursor powder; s2, a template crucible is filled with the precursor powder, segmented heating is conducted in a vacuum induction furnace for smelting, alloy liquid obtained after smelting is completed is poured and solidified, and an alloy ingot is obtained; s3, the alloy ingot is subjected to hot forging and hot rolling treatment, and a target blank is obtained; and S4, the target material blank is annealed, and the gold-ruthenium alloy target material is obtained. According to the scheme, through guiding of the template crucible and coordination of N / P active sites and Ru < 2 + >, the N / P active sites are adsorbed on the surface of a groove and a crystal nucleus interface, dendritic crystal tip growth is inhibited, and the prepared gold-ruthenium alloy target material is small in grain structure, high in alloy density and capable of being applied to the technical field with the high requirement for material functionality.

Description

Technical Field

[0001] The present invention relates to the technical field of sputtering targets, and particularly to a gold-ruthenium alloy target and a preparation method thereof. Background Art

[0002] A sputtering target is a key material in physical vapor deposition technology. During sputtering, high-energy particles (usually ions) bombard the surface of the target, causing target atoms or molecules to fly out from the surface and deposit on the substrate to form a thin film.

[0003] In the forefront exploration of materials science, thin films made of gold-based alloy targets play a crucial role due to their unique physical and chemical properties. Gold-based alloys have excellent electrical conductivity. Electronic components made of this material can ensure efficient signal transmission, greatly improving the operating speed and stability of electronic devices. At the same time, they have excellent chemical stability and can still maintain good performance in complex chemical environments. Their corrosion resistance enables them to work stably for a long time under harsh working conditions. Moreover, gold-based alloy targets have excellent ductility, making it easy to process them into various precise shapes and sizes to meet diverse production requirements.

[0004] Currently, most gold-based alloy targets are mainly used in the production of noble metal surface coatings. In scientific and technological fields such as semiconductor, artificial intelligence chip manufacturing, and high-end optical instruments, which have extremely high requirements for material functionality, their performance is difficult to meet the needs. Taking the semiconductor industry as an example, with the continuous improvement of chip integration and the development of the manufacturing process towards the nanoscale, this requires that the thin films prepared from gold-based alloy targets have extremely high uniformity, density, and precise electrical properties. Existing gold-based alloy targets are difficult to meet such stringent standards.

[0005] In terms of the preparation process, the existing technical means mainly improve the performance of gold-based alloy targets by adding metal-modified quenching agents, metal grain regulators, and rare earth elements. For example, Patent CN115852327A discloses a target for champagne-colored thin films and its preparation method, which reduces the grain length of the target and increases the target density by adding a titanium powder refiner and a quenching modifier prepared from Si and La as raw materials in the raw materials; Patent CN115786860B discloses a target for pink thin films and its preparation method, which refines the grains during melting and sintering by adding a grain regulator prepared from B, Ti, Ge, and La in the raw materials to improve the color uniformity of the product; Patent CN106916991B discloses a purple gold target and its preparation method, which changes the color and hardness of the target by adding Al, Cu, In, and Nd. However, the addition of metal additives or rare earth elements in the above methods may lead to the introduction of a large number of impurities, increasing the brittleness of the alloy material. Although it can change the internal microstructure of the alloy, it is still difficult to meet the application requirements in the scientific and technological fields with extremely high requirements for material functionality. Summary of the Invention

[0006] The purpose of the present invention is to provide a gold-ruthenium alloy target and its preparation method to solve the problems raised in the above background technology.

[0007] To achieve the above purpose, the present invention provides the following technical solutions:

[0008] A preparation method of a gold-ruthenium alloy target, comprising the following steps:

[0009] S1, Mix ammonium ruthenium chloride and gold powder, add a regulator, and perform wet ball milling in a ball mill to obtain a composite powder coated with organic molecules, and dry it to obtain a precursor powder;

[0010] S2, Fill the precursor powder into a template crucible, and perform segmented heating and melting in a vacuum induction furnace. After the melting is completed, the alloy liquid is poured and solidified to obtain an alloy ingot;

[0011] S3, Perform hot forging and hot rolling on the alloy ingot to obtain a target blank;

[0012] S4, Anneal the target blank to obtain a gold-ruthenium alloy target.

[0013] Further, in step S1, the purity of ammonium ruthenium chloride and the purity of gold powder are both not less than 99.99%. The addition amount of ammonium ruthenium chloride is calculated based on Ru, and the atomic ratio with gold powder is Au:Ru = 98 - 98.5:1.5 - 2.

[0014] Further, in step S1, the regulator is phosphorylated serine, and its addition amount is 0.1 - 0.5 wt% of the total amount of Au and Ru.

[0015] Further, in step S1, ethanol is used as the medium and argon is used as the protective gas during the wet ball milling process; the drying process is low-temperature drying, preferably at a temperature of 60 °C, and the particle size of the precursor powder is 20 - 50 μm.

[0016] Further, the preparation method of the template crucible is as follows:

[0017] A1, select a graphite crucible with a purity ≥ 99.99%, and prepare honeycomb micro-nano grooves on the inner wall of the crucible by laser engraving. The groove width is 50 - 200 nm, the depth is 100 - 500 nm, and the spacing is 200 - 800 nm;

[0018] A2, use chemical vapor deposition to coat a single layer of graphene on the surface of the grooves to increase the surface energy gradient;

[0019] A3, anneal the crucible processed in step A2. Under argon protection, heat it to 1200 °C and hold for 2 h to obtain the template crucible.

[0020] Further, in step S2, the step of segmented heating includes:

[0021] Stage 1, under argon protection, heat it to 400 - 600 °C and hold for 1 h to decompose phosphorylated serine to form N / P active sites;

[0022] Stage 2, in an argon-hydrogen mixed atmosphere, heat it to 1200 - 1300 °C and apply a static magnetic field of 0.5 T to promote the directional flow of the melt along the grooves.

[0023] Further, in stage 2, the volume ratio of argon to hydrogen in the argon-hydrogen mixed atmosphere is 4:1.

[0024] Further, in step S3, the temperature of hot forging is 850 - 950 °C, the single-pass deformation amount is 20% - 30%, and the total deformation amount is 60% - 80%; the temperature of hot rolling is 800 - 900 °C, the single-pass deformation amount is 10% - 15%, and the total deformation amount is 70% - 85%; during the whole process of hot forging and hot rolling, argon is used as the protective gas.

[0025] Further, in step S4, the annealing temperature is 500 - 600 °C and the annealing time is 3 - 5 h.

[0026] This solution also discloses a gold ruthenium alloy target prepared by the above preparation method of the gold ruthenium alloy target.

[0027] The beneficial effects of the above technical solution of the present invention are as follows:

[0028] 1. In this solution, honeycomb-like micro-nano grooves are engraved on the inner wall of the crucible, and a single-layer graphene is coated by chemical vapor deposition to form a surface energy gradient. Driven by the difference in hydrophobicity between graphene and the wettability of the molten metal, the melt is induced to flow directionally along the grooves, realizing the oriented growth of crystal grains.

[0029] 2. Using ammonium chlororuthenate as the source of ruthenium metal and adding phosphorylated serine as a regulator, at 500 °C, phosphorylated serine decomposes to form N / P active sites, which preferentially form coordination with ruthenium ions and adsorb on the groove surface and crystal nucleus interface in subsequent steps, inducing the directional deposition of metal atoms and inhibiting the growth of dendrite tips, refining the crystal grains.

[0030] 3. In this solution, the alloy ingot is formed by hot forging and hot rolling, strengthening the directional arrangement of crystal grains, promoting grain boundary migration and pore closure, and increasing the density of the gold-ruthenium alloy target. Description of the Drawings

[0031] Figure 1 It is the Au-Ru binary alloy phase diagram. Specific Embodiments

[0032] The following describes the preferred embodiments of the present invention. It should be understood that the preferred embodiments described herein are only for explaining and illustrating the present invention, and are not used to limit the present invention.

[0033] A method for preparing a gold-ruthenium alloy target, comprising the following steps:

[0034] S1. Mix ammonium chlororuthenate with a purity of 99.99% (calculated as Ru) and gold powder with a purity of 5N in an atomic ratio of Au:Ru = 98 - 98.5:1.5 - 2, and add 0.1 - 0.5 wt% of phosphorylated serine based on the total amount of Au and Ru. Wet ball milling is carried out in a ball mill with ethanol as the medium and argon as the protective gas to obtain a composite powder coated with organic molecules, which is dried at a low temperature of 60 °C, sieved, and a precursor powder with a particle size of 20 - 50 μm is obtained.

[0035] S2. Fill the precursor powder in step S1 into a template crucible with a filling rate of 60 - 70%. In a vacuum induction furnace, under argon protection, slowly heat it from room temperature to 400 - 600 °C at a rate of 5 - 10 °C / min, and keep it warm for 1 h to decompose phosphorylated serine to form N / P active sites. Subsequently, under an argon-hydrogen mixed atmosphere, quickly heat the vacuum induction furnace from room temperature to 1200 - 1300 °C at a rate of 10 - 20 °C / min, and apply a 0.5 T static magnetic field. Through the Lorentz force, promote the directional flow of the melt along the grooves, and make the grains preferentially grow along the magnetic field direction to form directional columnar crystals. Pour and solidify the alloy liquid after melting. Preheat the mold to 200 - 300 °C, and under argon protection, pour the melted alloy liquid into the mold and cool it to 1100 - 1200 °C, keep it warm for 2 h, and then cool it to room temperature at a cooling rate of 5 - 10 °C / min to obtain an alloy ingot.

[0036] S3. Using argon as the protective gas, hot forge the alloy ingot in step S2 at 850 - 950 °C and hot roll it at 800 - 900 °C to obtain a target blank. Among them, the single-pass deformation amount of hot forging is 20% - 30%, and the total deformation amount is 60% - 80%; the single-pass deformation amount of hot rolling is 10% - 15%, and the total deformation amount is 70% - 85%.

[0037] S4. Anneal the target blank obtained in step S3 at 500 - 600 °C for 3 - 5 h to obtain a gold ruthenium alloy target.

[0038] Ammonium chlororuthenate is selected as the raw material, which has appropriate reaction activity in step S2, can fully react with gold powder to form an alloy without excessive side reactions. In addition, high-purity ammonium chlororuthenate can be prepared by chemical synthesis methods to meet the requirements of the gold ruthenium alloy target for the purity of raw materials, reduce the influence of impurities on the alloy performance. During the ball milling process, ammonium chlororuthenate can be well dispersed in the ethanol medium and fully mixed with gold powder.

[0039] Phosphorylated serine is selected as the regulator, which can decompose to form N / P active sites and coordinate with Ru 2+ to form coordination, and adsorb on the surface of the grooves and the interface of crystal nuclei to guide the directional deposition of metal atoms and inhibit the growth of dendrite tips.

[0040] In step S2, in stage 1, ammonium chlororuthenate decomposes and mainly exists in two forms: Ru 2+ and metallic ruthenium. At the same time, phosphorylated serine decomposes to form N / P active sites and preferentially coordinates with Ru 2+A coordination is formed, which plays a role in the early stage of Stage 2 to inhibit the growth of dendrite tips, and ruthenium metal participates in the smelting; in the later stage of Stage 2, ammonium chlororuthenate has been completely decomposed, and under the argon-hydrogen mixed atmosphere, the coordinated ruthenium ions are reduced and continue to participate in the smelting process, while other substances in ammonium chlororuthenate decompose into gases such as HCl, N 2 and ammonia gas, which flow out of the vacuum induction furnace with the protective gas and do not introduce foreign impurities; while the serine main chain (containing the -CH 2 -CH(NH 2 )-COOH structure) is partially carbonized at the high temperature in Stage 2 to form a short-chain carbon skeleton, which covers the grain boundaries and hinders the atomic diffusion path.

[0041] The preparation method of the template crucible is as follows:

[0042] A1, select a graphite crucible with a purity ≥ 99.99%, and prepare honeycomb micro-nano grooves on the inner wall of the crucible by laser engraving. The width of the grooves is 50 - 200 nm, the depth is 100 - 500 nm, and the spacing is 200 - 800 nm;

[0043] A2, use chemical vapor deposition to coat a single layer of graphene on the surface of the grooves to increase the surface energy gradient; among them, the deposition temperature is set at 1000 °C, the pressure is 80 Pa, methane is used as the carbon source, hydrogen is used as the reducing gas, and argon is used as the carrier gas. The volume ratio of the three is CH 4 :H 2 :Ar = 1:50:200;

[0044] A3, anneal the crucible processed in step A2. Under argon protection, heat it up to 1200 °C and keep it warm for 2 h to obtain the template crucible.

[0045] The preparation method of phosphorylated serine is as follows:

[0046] B1, amino and carboxyl protection reaction

[0047] In the reaction flask, dissolve L-serine with N,N-dimethylformamide as the solvent to prepare a 0.5 mol / L solution; then place the reaction flask in an ice-water bath and slowly drop an excess of 20% benzyloxycarbonyl chloride, and at the same time add K with a molar ratio of 1.2:1 to L-serine 2 CO 3 , stir and react for 2 h, remove the ice-water bath, and continue to react at room temperature for 12 h;

[0048] B2, phosphorylation reaction

[0049] Transfer the product after reacting for 12 h in Step B1 to another reaction flask, add pyridine solvent, stir to dissolve to form a 0.3 mol / L solution, then place the reaction flask in a low-temperature bath, cool down to -10 °C, slowly dropwise add phosphorus oxychloride, and the molar ratio of phosphorus oxychloride to L-serine after protection in Step B1 is 1.5:1. After the dropping is completed, raise the reaction temperature to 0 °C and continue to stir and react for 6 h;

[0050] B3, Deprotection reaction

[0051] Transfer the phosphorylated product in Step B2 to a hydrogenation reactor, add methanol to dissolve it, add 5% by mass of Pd / C based on the phosphorylated product to the reactor as a catalyst, introduce hydrogen, and react at normal pressure and room temperature until the reaction is complete;

[0052] B4, Purification

[0053] After the deprotection reaction in Step B3 is completed, filter the product to remove the Pd / C catalyst, distill off methanol under reduced pressure, dissolve the remaining product in deionized water, then extract with ethyl acetate to remove organic impurities. The aqueous phase is a crude product solution containing phosphorylated serine. The crude product solution is subjected to ion exchange chromatography and gel filtration chromatography in sequence. Finally, the product solution after gel filtration chromatography is concentrated under reduced pressure, add an ethanol solution twice the volume of the concentrated solution, stir evenly, stand and crystallize at 4 °C for 24 h, then collect the crystals, wash with a small amount of cold ethanol 2 - 3 times, and dry under vacuum to obtain phosphorylated serine.

[0054] Among them, ion exchange chromatography uses a 0.5 mol / L sodium chloride gradient elution, and gel filtration chromatography uses deionized water as the eluent.

[0055] The gold - ruthenium binary alloy phase diagram is as Figure 1 shown.

[0056] Example 1

[0057] Adopt the preparation method of the above gold - ruthenium alloy target, where:

[0058] S1. Select ammonium chlororuthenate with a purity of 99.99% (calculated as Ru) and gold powder with a purity of 5N, mix them according to an atomic ratio of Au:Ru = 98:2, and add 0.5 wt% of phosphorylated serine based on the total amount of Au and Ru. Perform wet ball milling in a ball mill with ethanol as the medium and argon as the protective gas to obtain a composite powder coated with organic molecules, dry at low temperature, and sieve to obtain a precursor powder with a particle size of 20 μm.

[0059] S2. Fill the precursor powder in step S1 into a template crucible with a filling rate of 60%. In a vacuum induction furnace, under argon protection, slowly heat it up to 600 °C at a rate of 10 °C / min, hold for 1 h to decompose phosphorylated serine to form N / P active sites; then, under an argon-hydrogen mixed atmosphere, quickly heat the vacuum induction furnace to 1300 °C at a rate of 20 °C / min and apply a 0.5 T static magnetic field to promote the directional flow of the melt along the grooves. Pour and solidify the alloy liquid after melting. Preheat the mold to 300 °C, and under argon protection, pour the melted alloy liquid into the mold and cool it to 1200 °C, hold for 2 h, and then cool it to room temperature at a cooling rate of 10 °C / min to obtain an alloy ingot.

[0060] S3. Using argon as the protective gas, hot forge the alloy ingot in step S2 at 850 °C, control the single-pass deformation amount of hot forging to be 20%, and the total deformation amount to be 60%; then perform hot rolling at 800 °C, control the single-pass deformation amount of hot rolling to be 10%, and the total deformation amount to be 70% to obtain a target blank.

[0061] S4. Anneal the target blank obtained in step S3 at 500 °C for 4 h to obtain a gold-ruthenium alloy target.

[0062] The preparation method of the template crucible is as follows:

[0063] A1. Select a graphite crucible with a purity ≥ 99.99%, and prepare honeycomb micro-nano grooves on the inner wall of the crucible by laser engraving. The width of the grooves is 80 nm, the depth is 100 nm, and the spacing is 300 nm.

[0064] A2. Use chemical vapor deposition to coat a single layer of graphene on the surface of the grooves to increase the surface energy gradient; among them, the deposition temperature is set to 1000 °C, the pressure is 80 Pa, methane is used as the carbon source, hydrogen is used as the reducing gas, and argon is used as the carrier gas. The volume ratio of the three is CH 4 :H 2 :Ar = 1:50:200.

[0065] A3. Anneal the crucible processed in step A2. Under argon protection, heat it up to 1200 °C and hold for 2 h to obtain a template crucible.

[0066] Example 2

[0067] Adopt the preparation method of the gold-ruthenium alloy target in the above example, where:

[0068] S1. Select ammonium chlororuthenate with a purity of 99.99% (calculated as Ru) and gold powder with a purity of 5N, mix them according to an atomic ratio of Au:Ru = 98.2:1.8, and add 0.3 wt% of phosphorylated serine based on the total amount of Au and Ru. Use ethanol as the medium and argon as the protective gas in a ball mill for wet ball milling to obtain a composite powder coated with organic molecules. Dry it at a low temperature and sieve it to obtain a precursor powder with a particle size of 35 μm.

[0069] S2. Fill the precursor powder in step S1 into a template crucible with a filling rate of 65%. In a vacuum induction furnace, under argon protection, slowly heat it to 500 °C at a rate of 8 °C / min and hold for 1 h to decompose phosphorylated serine to form N / P active sites; then, in an argon-hydrogen mixed atmosphere, quickly heat the vacuum induction furnace to 1300 °C at a rate of 15 °C / min and apply a 0.5 T static magnetic field to promote the directional flow of the melt along the grooves. Pour and solidify the alloy liquid after melting. Preheat the mold to 300 °C, and under argon protection, pour the melted alloy liquid into the mold and cool it to 1200 °C, hold for 2 h, and then cool it to room temperature at a cooling rate of 10 °C / min to obtain an alloy ingot.

[0070] S3. Using argon as the protective gas, hot forge the alloy ingot in step S2 at 900 °C, control the single-pass deformation amount of hot forging to be 25%, and the total deformation amount to be 70%; then perform hot rolling at 850 °C, control the single-pass deformation amount of hot rolling to be 15%, and the total deformation amount to be 80% to obtain a target blank.

[0071] S4. Anneal the target blank obtained in step S3 at 500 °C for 5 h to obtain a gold-ruthenium alloy target.

[0072] The preparation method of the template crucible is as follows:

[0073] A1. Select a graphite crucible with a purity ≥ 99.99%, and prepare honeycomb micro-nano grooves on the inner wall of the crucible by laser engraving. The groove width is 150 nm, the depth is 300 nm,

[0074] and the spacing is 500 nm;

[0075] A2. Use chemical vapor deposition to coat a single layer of graphene on the surface of the grooves to increase the surface energy gradient; among them, the deposition temperature is set at 1000 °C, the pressure is 80 Pa, using methane as the carbon source, hydrogen as the reducing gas, and argon as the carrier gas, and the volume ratio of the three is CH 4 :H 2 :Ar = 1:50:200;

[0076] A3. Anneal the crucible processed in step A2. Under argon protection, heat it to 1200 °C and hold for 2 h to obtain a template crucible.

[0077] Example 3

[0078] The preparation method of the gold-ruthenium alloy target in the above example is adopted, wherein:

[0079] S1. Ammonium ruthenium chloride with a purity of 99.99% (calculated as Ru) and gold powder with a purity of 5N are selected, mixed according to the atomic ratio Au:Ru = 98.5:1.5, and 0.1 wt% of phosphorylated serine based on the total amount of Au and Ru is added. Wet ball milling is carried out in a ball mill with ethanol as the medium and argon as the protective gas to obtain a composite powder coated with organic molecules. It is dried at low temperature and sieved to obtain a precursor powder with a particle size of 50 μm.

[0080] S2. The precursor powder in step S1 is filled into a template crucible with a filling rate of 70%. In a vacuum induction furnace, under argon protection, it is slowly heated to 400 °C at a rate of 5 °C / min and held for 1 h to decompose phosphorylated serine to form N / P active sites; subsequently, in an argon-hydrogen mixed atmosphere, the vacuum induction furnace is rapidly heated to 1200 °C at a rate of 10 °C / min, and a static magnetic field of 0.5 T is applied to promote the directional flow of the melt along the grooves. The alloy liquid after melting is poured and solidified. The mold is preheated to 200 °C, and under argon protection, the melted alloy liquid is poured into the mold and cooled to 1100 °C, held for 2 h, and then cooled to room temperature at a cooling rate of 5 °C / min to obtain an alloy ingot.

[0081] S3. Using argon as the protective gas, the alloy ingot in step S2 is hot forged at 950 °C, and the single-pass deformation amount of the hot forging is controlled to be 30%, and the total deformation amount is 80%; then it is hot rolled at 900 °C, and the single-pass deformation amount of the hot rolling is controlled to be 15%, and the total deformation amount is 85% to obtain a target blank;

[0082] S4. The target blank obtained in step S3 is annealed at 600 °C for 3 h to obtain a gold-ruthenium alloy target.

[0083] The preparation method of the template crucible is as follows:

[0084] A1. A graphite crucible with a purity ≥ 99.99% is selected, and honeycomb-shaped micro-nano grooves are prepared on the inner wall of the crucible by laser engraving. The groove width is 200 nm, the depth is 500 nm,

[0085] and the spacing is 700 nm;

[0086] A2. Chemical vapor deposition is used to coat a single layer of graphene on the surface of the grooves to increase the surface energy gradient; among them, the deposition temperature is set to 1000 °C, the pressure is 80 Pa, methane is used as the carbon source, hydrogen is used as the reducing gas, and argon is used as the carrier gas. The volume ratio of the three is CH 4 :H 2:Ar = 1:50:200;

[0087] A3. Anneal the crucible processed in step A2. Under argon protection, heat it to 1200 °C and hold for 2 h to obtain a template crucible.

[0088] Comparative Example 1:

[0089] The difference from Example 1 is that:

[0090] In step S2, instead of using a template crucible, a common crucible adapted to a vacuum induction furnace is used.

[0091] Comparative Example 2:

[0092] The difference from Example 1 is that:

[0093] In step S3, instead of hot forging and hot rolling, the alloy ingot is crushed and hot isostatic pressing is carried out. The isostatic pressing temperature is 900 - 1000 °C and the pressure is 150 - 200 Mpa.

[0094] Comparative Example 3:

[0095] The difference from Example 1 is that:

[0096] In step S3, instead of hot forging and hot rolling, it is directly cut into shape and ground and polished.

[0097] Comparative Example 4:

[0098] A comparative experiment is carried out using the technology in the patent document with the application publication number CN115852327A.

[0099] Comparative Example 5:

[0100] A comparative experiment is carried out using the technology in the patent document with the authorization announcement number CN115786860B.

[0101] The relative density is calculated by the following formula:

[0102]

[0103] where ρ is the relative density, ρ a is the actual density, ρ t is the theoretical density, and the theoretical density ρ t can be calculated by the weighted method.

[0104] The test results of Examples 1 - 3 and Comparative Examples 1 - 4 are shown in the following table:

[0105]

[0106]

[0107] 1. It can be seen from the comparison between Examples 1-3 and Comparative Example 1 that the grain size of the gold-ruthenium alloy target prepared without using the template crucible is significantly inferior to that of the examples of this solution. This is because although the N / P active sites of phosphorylated serine can adsorb on the surface of crystal nuclei to inhibit growth, its effect needs to be combined with the physical restriction of the template crucible. The nano-scale spatial constraint of the groove can limit the free expansion of grains, and it is difficult to achieve equivalent grain size control only by chemical regulation.

[0108] 2. It can be seen from the comparison between Examples 1-3 and Comparative Example 2 that in Comparative Example 2, the target blank is subjected to hot isostatic pressing after crushing. Although its density is relatively high, due to the long-time high-temperature treatment, the alloy grains are slightly thickened, and the crushing treatment destroys the directional arrangement of the grains.

[0109] 3. It can be seen from the comparison between Examples 1-3 and Comparative Example 3 that in Comparative Example 3, hot forging and hot rolling treatments are not carried out, and its grain size is large and the density is poor, not meeting the usage requirements. In the examples of the present invention, through hot forging and hot rolling treatments, plastic deformation is carried out on the alloy ingot, so as to introduce dislocations and promote its recrystallization, thereby refining the grains; in addition, the internal pores of the alloy ingot are also eliminated during the hot forging and hot rolling processes, improving its density and reducing its stress.

[0110] 4. It is concluded from the comparison between the examples and Comparative Examples 4-5 that the grain size of the gold-ruthenium alloy target prepared by this solution is significantly better than that of Comparative Example 4 and Comparative Example 5, and it can be applied in scientific and technological fields such as semiconductors.

[0111] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit them. Any other modifications or equivalent replacements made by those of ordinary skill in the art to the technical solutions of the present invention shall be covered by the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a gold-ruthenium alloy target, characterized in that: The following steps are involved: S1, mixing ammonium chlororuthenate and gold powder, adding a regulating agent, and performing wet ball milling in a ball mill to obtain a composite powder coated with organic molecules, and drying to obtain a precursor powder; S2, filling the precursor powder into a template crucible, heating in stages in a vacuum induction furnace for smelting, and pouring and solidifying the alloy liquid after smelting to obtain an alloy ingot; S3, hot forging and hot rolling the alloy ingot to obtain a target material blank; S4, annealing the target material blank to obtain a gold-ruthenium alloy target material.

2. The method for preparing a gold-ruthenium alloy target according to claim 1, characterized in that: In step S1, the purity of the ammonium chlororuthenate and the purity of the gold powder are not less than 99.99%, and the amount of ammonium chlororuthenate added is calculated as Ru, and the atomic ratio of ammonium chlororuthenate to the gold powder is Au:Ru=98~98.5:1.5~2.

3. The method for preparing a gold-ruthenium alloy target according to claim 1, characterized in that: In step S1, the regulator is phosphorylated serine, and the added amount thereof is 0.1-0.5 wt % of the total amount of Au and Ru.

4. The method for preparing a gold-ruthenium alloy target according to claim 1, characterized in that: In step S1, ethanol is used as the medium and argon is used as the protective gas during the wet ball milling process; the drying process is low-temperature drying, and the particle size of the precursor powder is 20 to 50 μm.

5. The method for preparing a gold-ruthenium alloy target according to claim 4, characterized in that: In step S2, the segmented heating step includes: Stage 1: under argon protection, the temperature is raised to 400-600°C and kept for 1 hour to decompose phosphorylated serine to form N / P active sites; In stage 2, the temperature is raised to 1200-1300°C in an argon-hydrogen mixed atmosphere, and a 0.5T static magnetic field is applied to promote the directional flow of the melt along the groove.

6. The method for preparing a gold-ruthenium alloy target according to claim 5, characterized in that: In stage 2, the volume ratio of argon to hydrogen in the argon-hydrogen mixed atmosphere is 4:

1.

7. The method for preparing a gold-ruthenium alloy target according to claim 1, characterized in that: In step S3, the hot forging temperature is 850-950°C, the deformation amount of a single pass is 20%-30%, and the total deformation amount is 60%-80%; the hot rolling temperature is 800-900°C, the deformation amount of a single pass is 10%-15%, and the total deformation amount is 70%-85%; argon is used as the protective gas during the entire process of hot forging and hot rolling.

8. The method for preparing a gold-ruthenium alloy target according to claim 1, characterized in that: In step S4, the annealing temperature is 500-600° C., and the annealing time is 3-5 hours.

9. A gold-ruthenium alloy target, prepared by the method for preparing the gold-ruthenium alloy target according to any one of claims 1 to 8.

10. A method for preparing a template crucible as used in claim 1, A1, select a graphite crucible with a purity of ≥99.99%, and prepare honeycomb micro-nano grooves on the inner wall of the crucible by laser engraving, wherein the grooves have a width of 50 to 200 nm, a depth of 100 to 500 nm, and a spacing of 200 to 800 nm; A2, using chemical vapor deposition to coat a single layer of graphene on the groove surface to increase the surface energy gradient; A3, annealing the crucible treated in step A2, raising the temperature to 1200° C. under argon protection, and keeping the temperature for 2 hours to obtain a template crucible with grooves inside.

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