High-strength and high-toughness molybdenum-niobium alloy target material, preparation method and application thereof

Abstract

The application relates to the alloy technical field, in particular to a high-strength and high-toughness molybdenum-niobium alloy target material and a preparation method and application thereof, the alloy target material comprises the following components in parts by weight: 12.23-24.55% of niobium, 2.87-6.54% of chromium, 3.45-6.58% of titanium, 4.12-7.52% of silicon, 5.32-12.14% of zirconium, 14.12-22.45% of aluminum hydroxide doped carbon nanotubes, and the balance is molybdenum. The molybdenum-niobium alloy target material provided by the application has excellent mechanical properties, and the electrical performance is greatly improved.

Description

Technical Field

[0001] This invention belongs to the field of alloy technology, and particularly relates to a high-strength, high-toughness molybdenum-niobium alloy target material, its preparation method, and its applications. Background Technology

[0002] Alloy sputtering targets are key materials used as the source of atoms or molecules in film deposition processes such as physical vapor deposition (PVD) and chemical vapor deposition (CVD). They are made from two or more metals, or metals and non-metals, through processes such as melting and sintering. For example, molybdenum-niobium alloy sputtering targets are alloy materials composed of molybdenum (Mo) and niobium (Nb), playing an important role in many fields. They possess advantages such as high melting point, high density, and high purity. For instance, the high melting point allows them to remain stable at high temperatures, resisting melting or deformation, making them suitable for preparing high-temperature thin films or devices that need to withstand high-temperature environments. The high density facilitates more efficient energy release during sputtering, improving sputtering efficiency. They also possess better hardness and wear resistance, allowing them to withstand high-intensity sputtering processes and extending their service life, demonstrating significant advantages in preparing high-adhesion thin films. Their purity typically reaches over 99.9%, with some products even reaching 99.99% or higher, indicating extremely low impurity content. This allows for the release of purer atoms or molecules during sputtering, contributing to the formation of higher-quality and more stable thin films on the substrate. However, molybdenum-niobium alloy sputtering targets also have some drawbacks. For example, while the atomic radii of molybdenum and niobium are similar, their weights differ significantly, and their grain structures are also different. During alloying, when niobium atoms replace molybdenum atoms, the molybdenum atoms are subjected to pressure, while the niobium atoms are subjected to controlling forces. This easily leads to lattice distortion, and the resulting internal stress from this lattice distortion is substantial, easily causing significant alloy segregation. This results in poor grain structure integration, making the alloy highly unstable and brittle, affecting subsequent hot working. This non-uniform composition means that during sputtering, the uneven distribution of molybdenum and niobium in the film leads to differences in the electrical, optical, and mechanical properties of the film. Furthermore, compositional inhomogeneity can cause structural defects in the film, such as porosity and cracks, reducing the film's density and integrity.

[0003] For example, CN118951014A discloses a molybdenum-niobium alloy sintered billet, its preparation method, a molybdenum-niobium alloy target material, and its applications. The preparation method includes the following steps: sintering a molybdenum-niobium alloy compact to obtain a sintered billet; wherein the compact includes molybdenum powder and niobium hydride powder; the sintering step includes vacuum sintering followed by hydrogen atmosphere sintering; the vacuum sintering temperature is 1300℃~1500℃; the hydrogen atmosphere sintering temperature is 2000℃-2250℃. The sintered billet has a microstructure free of defects such as pores, cracks, delamination, and inclusions, with a density of over 99%, an oxygen content of less than 100ppm, and a hydrogen content of less than 10ppm. The sintered billet has uniform grains with an average grain size of less than 55μm. This application improves the average grain quality of the sintered billet through multiple sintering processes, but the performance of the molybdenum-niobium alloy itself is not improved.

[0004] For example, CN104550979A discloses a method for preparing a molybdenum-niobium alloy target plate. Molybdenum powder is placed in an air jet mill, argon gas is introduced, and the gas pressure is adjusted to obtain molybdenum powder with three particle size distributions. Niobium powder is also placed in an air jet mill, argon gas is introduced, and the gas pressure is adjusted to obtain niobium powder with three particle size distributions. The molybdenum powder and niobium powder are mixed separately to obtain molybdenum-niobium alloy powder with three particle size distributions. The molybdenum-niobium alloy powder is pressed into a billet and sintered in a medium-frequency furnace with hydrogen to obtain the molybdenum-niobium alloy target plate. This method for preparing the molybdenum-niobium alloy target plate is simple to operate and low in cost. High-quality molybdenum-niobium alloy target plates can be directly sintered using powder metallurgy. However, this application only changes the grain quality of the molybdenum-niobium alloy and cannot change the alloy's electrical conductivity or mechanical properties.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a high-strength and high-toughness molybdenum-niobium alloy target, its preparation method, and its application. The molybdenum-niobium alloy target provided by this invention has excellent mechanical properties and significantly improved electrical properties.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] In a first aspect, embodiments of the present invention provide a high-strength, high-toughness molybdenum-niobium alloy target material, comprising the following components by weight: 7.23%-19.55% niobium, 2.87%-6.54% chromium, 3.45%-6.58% titanium, 4.12%-7.52% silicon, 5.32%-12.14% zirconium, 14.12%-22.45% aluminum hydroxide-doped carbon nanotubes, with the balance being molybdenum.

[0009] In a preferred embodiment, the alloy target material comprises the following components by weight: 12%-19% niobium, 3.5%-5.5% chromium, 4%-5.5% titanium, 5%-6% silicon, 7%-10% zirconium, 16%-20% aluminum hydroxide-doped carbon nanotubes, and the balance being molybdenum.

[0010] In this invention, the mechanical and electrical properties of the alloy are effectively improved by the combination of multiple elements, and the combination of multiple metal elements improves the uniformity of the alloy.

[0011] In improving the mechanical properties of alloys, niobium and molybdenum can combine to form a series of intermetallic compounds, such as NbMo and Nb3Mo. These compounds possess extremely high hardness and good thermal stability. Distributed in a fine, dispersed state within the alloy matrix, they strongly hinder dislocation movement, making the alloy less prone to plastic deformation and thus significantly improving its strength. Furthermore, during the solidification and crystallization process, zirconium atoms act as heterogeneous nucleation sites, greatly increasing the number of crystal nuclei and refining the grains. Fine grains mean more grain boundaries, which effectively hinder dislocation slip, disperse stress concentration, and prevent premature crack initiation and propagation, thereby enhancing the alloy's toughness. In addition, chromium and titanium have different atomic radii than molybdenum. When they dissolve into the molybdenum lattice, they form substitutional solid solutions by replacing the positions of molybdenum atoms, inducing lattice distortion. This distortion significantly increases the external force required for dislocation slip, leading to an increase in the alloy's yield strength and tensile strength, meeting the basic mechanical performance requirements of high-strength structural components. Silicon atoms, being relatively small, can enter the interstitial sites of the molybdenum lattice, forming interstitial solid solutions. This causes partial compression of the crystal structure, increasing dislocation slip resistance and strengthening the alloy. Furthermore, the integration of silicon atoms into the lattice also stabilizes the lattice structure, making the alloy more stable under stress. The silicides formed by the reaction of silicon with other elements in the alloy, such as MoSi2 and NbSi2, have high melting points. At high temperatures, these silicides remain solid, providing a stable internal framework for the alloy, inhibiting grain growth at high temperatures, and preventing a decrease in toughness due to coarse grains. This allows the alloy to maintain good toughness even under high-temperature conditions. Chromium forms a dense Cr2O3 oxide film on the alloy surface, which not only resists high-temperature oxidation but also reduces surface defects and stress concentration caused by oxidation corrosion, ensuring that the toughness of the alloy does not significantly decrease due to oxidation damage during long-term high-temperature service.

[0012] In terms of improving electrical performance, molybdenum itself has good conductivity, and the addition of niobium can fine-tune the electronic structure of the alloy. The interaction between niobium atoms and molybdenum atoms moderately alters the electron cloud distribution, optimizes electron migration paths, and reduces electron scattering, thereby maintaining or even improving the overall conductivity of the alloy. This is crucial for manufacturing electronic circuits, electrodes, and other components requiring efficient current transmission. Silicon, when incorporated into the alloy, stabilizes the crystal lattice structure to a certain extent, reducing interference as electrons move within the lattice. When silicon and molybdenum form an interstitial solid solution, it reduces electron traps caused by lattice defects, allowing electrons to move more smoothly and ensuring stable conductivity. Furthermore, chromium has strong oxidation resistance and readily forms a dense oxide film on the alloy surface, typically Cr2O3. This oxide film not only protects the alloy from corrosion but also acts as an insulating layer, precisely controlling the charge distribution on the alloy surface, reducing surface leakage, disordered charge dissipation, and other undesirable electrical behaviors, thus improving electrical stability. Additionally, zirconium can adsorb impurities in the alloy, reducing the interference of impurity atoms on electron conduction. Furthermore, zirconium refines the grains during alloy solidification, resulting in a more uniform microstructure and more consistent surface electrical properties, thus preventing malfunctions caused by localized electrical differences. The remaining elements, combined with titanium, regulate the alloy's crystal and electronic structures, suppressing excessive magnetic domain wall movement and making electromagnetic properties more controllable and predictable. This allows the alloy to operate stably in complex electromagnetic environments, meeting the specific electromagnetic requirements of various electrical devices. Further, the combination of silicon, zirconium, molybdenum, and niobium can improve the alloy's thermoelectric effect under specific temperature gradients. The presence of silicides and zirconium compounds influences electron and phonon transport, optimizing carrier concentration and mobility.

[0013] In terms of providing alloy homogeneity, zirconium atoms can act as heterogeneous nucleation sites when the alloy melt begins to solidify. Due to the difference in crystal structure between zirconium and other elements in the alloy, it preferentially crystallizes, providing numerous uniformly distributed attachment sites for subsequently solidifying metal atoms. This allows the alloy grains to grow in a refined and uniform direction from the beginning, avoiding localized grain coarsening, greatly reducing compositional segregation, and improving overall homogeneity. Silicon lowers the alloy's melting point, altering the viscosity of the molten alloy during solidification and enhancing its fluidity. This allows atoms of various elements more time in the liquid state to disperse uniformly with the help of convection, stirring, and other external forces, rather than being fixed in localized areas during rapid solidification, laying the foundation for uniform solidification into an alloy. Chromium and titanium integrate with molybdenum to form solid solutions, and niobium also dissolves with molybdenum. The formation of solid solutions involves atomic transposition and rearrangement; during this process, the atoms of various elements continuously mix, gradually eliminating concentration differences and strengthening the compositional homogeneity within the alloy. Furthermore, niobium and molybdenum are fine and dispersed throughout the alloy, fixing interstitial atoms such as carbon and nitrogen and preventing them from segregating and agglomerating at grain boundaries during the later stages of solidification. This avoids disrupting alloy homogeneity due to localized enrichment of interstitial atoms and maintains compositional stability from the center to the edges. Additionally, chromium forms a dense oxide film on the alloy surface, blocking oxygen from entering the alloy interior and reducing internal oxidation. Uneven distribution of oxidation products can easily lead to impurity segregation, but chromium's antioxidant protection makes the alloy system purer, ensuring uniform elemental distribution unaffected by oxidation impurities.

[0014] In a preferred embodiment, the aluminum hydroxide-doped carbon nanotubes are prepared as follows:

[0015] Carbon nanotubes were acidified with a solvent, washed and dried, and then mixed with a 30 wt% hydrogen peroxide aqueous solution for a first reaction. After washing and drying, the resulting solid was dispersed in ethanol, and aluminum chloride hexahydrate was added for a second reaction. After filtration, washing and drying, the mixture was subjected to a third reaction to obtain aluminum hydroxide-doped carbon nanotubes.

[0016] In a preferred embodiment, the carbon nanotubes have a particle size of 100-200 nm.

[0017] In a preferred embodiment, the solvent is a mixture of concentrated sulfuric acid and concentrated nitric acid, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1.

[0018] In a preferred embodiment, the mass ratio of the solvent to the carbon nanotubes is (100-200):1.

[0019] In a preferred embodiment, the acidification treatment takes 1-3 hours.

[0020] In a preferred embodiment, the mass ratio of the carbon nanotubes to the 30wt% hydrogen peroxide aqueous solution is 1:(100-150).

[0021] In a preferred embodiment, the conditions for the primary reaction are: reaction time of 16-24 hours and reaction temperature of 25°C-30°C.

[0022] In a preferred embodiment, the mass ratio of the solid, ethanol and aluminum chloride hexahydrate is 1:(50-100):(2-3).

[0023] In a preferred embodiment, the conditions for the secondary reaction are: reaction time of 1-3 hours and reaction temperature of 25°C-30°C.

[0024] In a preferred embodiment, the conditions for the three reactions are: thermal decomposition at 200℃-300℃ for 4-10 hours.

[0025] This invention improves the dispersion performance of carbon nanotubes in alloys by using self-made aluminum hydroxide-doped carbon nanotubes, and also synergistically enhances the electrical properties of the alloys with the addition of these nanotubes and other elements.

[0026] In terms of improving dispersion performance, aluminum hydroxide particles can act as an insulator between carbon nanotubes, preventing them from approaching each other and agglomerating. When aluminum hydroxide is uniformly distributed in the alloy system, it occupies a certain space, separating the carbon nanotubes within these spaces. This increases the distance between the carbon nanotubes, reduces the likelihood of them agglomerating due to interactions such as van der Waals forces, and improves the dispersibility of carbon nanotubes in the alloy. Furthermore, aluminum hydroxide can modify the surface of carbon nanotubes, altering their surface properties. On one hand, aluminum hydroxide may chemically react with the hydroxyl groups on the surface of carbon nanotubes to form chemical bonds, giving the carbon nanotube surface better compatibility with the alloy matrix. On the other hand, aluminum hydroxide adsorbs on the surface of carbon nanotubes, forming a protective film that reduces the surface energy of the carbon nanotubes and decreases their interaction with surrounding substances, thus making it easier for the carbon nanotubes to disperse uniformly in the alloy. Aluminum hydroxide can also improve the wettability between carbon nanotubes and the alloy matrix. Wettability refers to the ability of a liquid to spread on a solid surface; good wettability helps carbon nanotubes to better bond and disperse with the alloy matrix. The addition of aluminum hydroxide reduces the surface tension of the alloy melt, making it easier to wet the surface of carbon nanotubes, thereby enabling the carbon nanotubes to better integrate into the alloy matrix and improve their dispersion performance.

[0027] Carbon nanotubes possess excellent electrical properties, such as high conductivity and carrier mobility, for improving the electrical performance of alloys. They can form unique conductive networks within the alloy, providing channels for rapid electron transport and thus improving the overall conductivity of the alloy. The aluminum hydroxide-doped carbon nanotubes (ANH3-doped carbon nanotubes) of this invention not only prevent carbon nanotube aggregation but also provide a certain supporting effect, making the conductive network formed by the carbon nanotubes more stable and uniform, thereby improving the stability and consistency of the alloy's electrical performance. Furthermore, niobium can alter the electronic structure of the alloy; when acting in conjunction with ANH3-doped carbon nanotubes, it further optimizes the electron transport path in the conductive network, reduces electron scattering, and improves conductivity. The oxide film formed by chromium on the alloy surface protects the alloy from corrosion, maintaining the long-term stability of the alloy's electrical performance. Simultaneously, ANH3-doped carbon nanotubes can form a good transition layer between the oxide film and the alloy matrix, enhancing the bonding force between the oxide film and the matrix, further improving the electrical stability of the alloy. When ANH3-doped carbon nanotubes synergistically interact with titanium, they improve the electrical performance of the alloy by regulating electron spin and distribution. Furthermore, silicon can improve the crystal structure of the alloy, making it more uniform and dense. When combined with aluminum hydroxide-doped carbon nanotubes, it can optimize the alloy's microstructure, reduce the obstruction of electron transport by crystal defects, and improve electrical conductivity. Similarly, zirconium can adsorb impurities in the alloy, reducing their interference with electron conduction. The synergy between aluminum hydroxide-doped carbon nanotubes and zirconium can further purify the alloy's microenvironment, allowing electrons to transport more smoothly in the conductive network and improving the alloy's electrical properties. Furthermore, molybdenum itself has good conductivity; the synergy between aluminum hydroxide-doped carbon nanotubes and molybdenum can form more efficient conductive channels in the alloy, enhancing its conductivity. Simultaneously, the addition of molybdenum may affect the alloy's crystal structure and electronic states, working in conjunction with the effects of carbon nanotubes and aluminum hydroxide to further improve the alloy's electrical properties. More importantly, aluminum hydroxide-doped carbon nanotubes can improve the interfacial bonding with elements such as niobium, chromium, titanium, silicon, zirconium, and molybdenum, reducing interfacial resistance. Good interfacial bonding facilitates electron transport between different phases, reducing electron scattering and energy loss at the interface, thereby improving the overall electrical properties of the alloy. Furthermore, by altering the charge distribution at the interface, aluminum hydroxide-doped carbon nanotubes can influence the movement and distribution of electrons in the alloy, thereby optimizing the alloy's electrical properties.

[0028] Secondly, embodiments of the present invention provide a method for preparing a high-strength, high-toughness molybdenum-niobium alloy target as described above, comprising the following steps:

[0029] Niobium powder, chromium powder, titanium powder, silicon powder, zirconium powder, and molybdenum powder are ball-milled once under an argon atmosphere. Then, aluminum hydroxide-doped carbon nanotubes are added and ball-milled a second time under an argon atmosphere. After sieving, the mixed powder is fed into a spray gun and sprayed onto the surface of the target substrate tube to obtain an alloy target.

[0030] In a preferred embodiment, the conditions for the first ball milling are as follows: add 2-4 wt% ethanol to the raw material powder and ball mill at 500-800 rpm for 30-60 min.

[0031] In a preferred embodiment, the conditions for the secondary ball milling are as follows: add 2-4 wt% ethanol to the raw material powder and ball mill at 500-800 rpm for 15-30 min.

[0032] In a preferred embodiment, the sieve used for sieving is 200-400 mesh.

[0033] In this invention, the addition of ethanol ensures uniform mixing of all components, and in particular, disperses aluminum hydroxide-doped carbon nanotubes in the alloy powder, thus guaranteeing uniform and consistent electrical properties of the alloy target material.

[0034] Thirdly, the present invention provides an application of the high-strength and high-toughness molybdenum-niobium alloy target as described above in the preparation of conductive or barrier layers.

[0035] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0036] 1. In this invention, the mechanical and electrical properties of the alloy are effectively improved by the combination of multiple elements, and the combination of multiple metal elements improves the uniformity of the alloy.

[0037] 2. This invention improves the dispersion performance of carbon nanotubes in alloys by using self-made aluminum hydroxide-doped carbon nanotubes, and also improves the electrical properties of the alloys in synergy with the elements.

[0038] 3. In this invention, the addition of ethanol ensures that the various components are mixed evenly. In particular, it disperses aluminum hydroxide-doped carbon nanotubes in the alloy powder, thus ensuring that the electrical properties of the alloy target material are uniform and consistent. Detailed Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Unless otherwise specified, all raw materials and reagents used in this invention are commercially available.

[0041] Niobium powder, with a purity of 99.9 wt.% and an average particle size of 100 nm, was purchased from Beijing Xingrongyuan Technology Co., Ltd.

[0042] Chromium powder, purity 99.8 wt.%, average particle size 200 nm, purchased from Hebei Hongyuan Alloy Welding Materials Co., Ltd.

[0043] Titanium powder, with a purity of 99.9 wt.% and an average particle size of 400 nm, was purchased from Weifang Kaihong Metal Products Co., Ltd.

[0044] Silicon powder, with a purity of 99.9 wt.% and an average particle size of 200 nm, was purchased from Shanghai Lidian Silicon Powder Materials Co., Ltd.

[0045] Zirconium powder, with a purity of 99.5 wt.% and an average particle size of 100 nm, was purchased from Beijing Xingrongyuan Technology Co., Ltd.

[0046] Molybdenum powder, with a purity of 99.8 wt.% and an average particle size of 200 nm, was purchased from Beijing Xingrongyuan Technology Co., Ltd.

[0047] Carbon nanotubes with an average particle size of 150 nm were purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0048] Example 1

[0049] This embodiment provides a method for preparing a high-strength, high-toughness molybdenum-niobium alloy target, comprising the following steps:

[0050] Preparation of aluminum hydroxide-doped carbon nanotubes:

[0051] By mass, one part of carbon nanotubes with an average particle size of 150 nm was acidified for 2 h using 150 parts of solvent, which was a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1. After washing and drying, one part of carbon nanotubes was mixed with 120 parts of 30 wt% hydrogen peroxide aqueous solution and reacted at 25 °C for 18 h. After washing and drying, one part of the resulting solid was dispersed in 65 parts of ethanol, and 2.2 parts of aluminum chloride hexahydrate were added. The mixture was then reacted at 25 °C for 1.5 h. After filtration, washing and drying, the resulting mixture was thermally decomposed at 220 °C for 6 h to obtain aluminum hydroxide-doped carbon nanotubes.

[0052] Preparation of molybdenum-niobium alloy targets:

[0053] By weight, 12 parts niobium powder, 3.5 parts chromium powder, 4 parts titanium powder, 5 parts silicon powder, 7 parts zirconium powder, and 53.5 parts molybdenum powder were mixed with 3 wt% ethanol of the raw material powder under an argon atmosphere and ball-milled at 600 rpm for 45 min. Then, 15 parts aluminum hydroxide-doped carbon nanotubes were added, and 3 wt% ethanol of the raw material powder was added again under an argon atmosphere and ball-milled at 600 rpm for 20 min. The mixture was then passed through a 300-mesh sieve. The mixed powder was then fed into a spray gun and sprayed onto the surface of the target substrate tube to obtain an alloy target.

[0054] Example 2

[0055] This embodiment provides a method for preparing a high-strength, high-toughness molybdenum-niobium alloy target, comprising the following steps:

[0056] Preparation of aluminum hydroxide-doped carbon nanotubes:

[0057] By mass, one part of carbon nanotubes with an average particle size of 150 nm was acidified for 2 h using 180 parts of solvent, which was a mixture of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3:1. After washing and drying, one part of carbon nanotubes was mixed with 140 parts of 30 wt% hydrogen peroxide aqueous solution and reacted at 25 °C for 20 h. After washing and drying, one part of the resulting solid was dispersed in 80 parts of ethanol, and 2.8 parts of aluminum chloride hexahydrate were added. The mixture was then reacted at 25 °C for 2 h. After filtration, washing and drying, the resulting mixture was thermally decomposed at 250 °C for 6 h to obtain aluminum hydroxide-doped carbon nanotubes.

[0058] Preparation of molybdenum-niobium alloy targets:

[0059] By weight, 19 parts niobium powder, 5.5 parts chromium powder, 5.5 parts titanium powder, 6 parts silicon powder, 10 parts zirconium powder, and 34 parts molybdenum powder were mixed with 3 wt% ethanol of the raw material powder under an argon atmosphere and ball-milled at 600 rpm for 45 min. Then, 20 parts aluminum hydroxide-doped carbon nanotubes were added, and 3 wt% ethanol of the raw material powder was added again under an argon atmosphere and ball-milled at 600 rpm for 20 min. The mixture was then passed through a 300-mesh sieve. The mixed powder was then fed into a spray gun and sprayed onto the surface of the target substrate tube to obtain an alloy target.

[0060] Comparative Example 1

[0061] The difference between this comparative example and Example 1 is that chromium powder is not added, and the mass fraction of molybdenum powder is changed to 57 parts.

[0062] Comparative Example 2

[0063] The difference between this comparative example and Example 1 is that titanium powder is not added, and the mass fraction of molybdenum powder is changed to 57.5 parts.

[0064] Comparative Example 3

[0065] The difference between this comparative example and Example 1 is that silicon powder is not added, and the mass fraction of molybdenum powder is changed to 58.5 parts.

[0066] Comparative Example 4

[0067] The difference between this comparative example and Example 1 is that zirconium powder is not added, and the mass fraction of molybdenum powder is changed to 60.5 parts.

[0068] Comparative Example 5

[0069] The difference between this comparative example and Example 1 is that aluminum hydroxide-doped carbon nanotubes are not added, and the mass fraction of molybdenum powder is changed to 68.5 parts.

[0070] Comparative Example 6

[0071] The difference between this comparative example and Example 1 is that aluminum hydroxide-doped carbon nanotubes are replaced with carbon nanotubes.

[0072] Comparative Example 7

[0073] The difference between this comparative example and Example 1 is that the aluminum hydroxide-doped carbon nanotubes are replaced with a simple mixture of carbon nanotubes and aluminum hydroxide.

[0074] Performance testing

[0075] 1. The alloy target materials obtained in the above examples and comparative examples were subjected to coating experiments to test the sputtering performance of the target materials. The substrate was cemented carbide (WC-8%Co), with dimensions of 10×10×8mm. After grinding, mirror polishing, ultrasonic cleaning, and hot air drying, it was ready for use.

[0076] Select the same coating experiment parameters: base vacuum degree 5×10 -4 The substrate was heated to 500°C and then filled with pure N2 at a pressure of 3.5 Pa. The substrate bias was -100 V, and the power density was 17 W / cm². 2 By adjusting the deposition time, a coating with a thickness of approximately 3 μm was obtained. The sputtering performance of the target material is shown in Table 1.

[0077] The discharge stabilization time refers to the dry-sputtering time, which is the time during which the target material is left to sputter before reaching the required deposition rate (discharge frequency reaches a certain value). A longer discharge stabilization time indicates more defects such as pores, inclusions, and non-conductive oxides within the target material, resulting in poorer phase and microstructure uniformity. A shorter discharge stabilization time indicates higher target material density and better microstructure uniformity.

[0078] The surface roughness of the coating was measured using a surface profilometer or an atomic force microscope.

[0079] The coating hardness was measured using a microhardness tester with a load of 0.05 kgf.

[0080] 2. The tensile strength of the coating formed by the above-mentioned coating at 25℃ and 600℃ was tested using GB / T 228.1-2010.

[0081] Table 1. Sputtering performance test results of target material

[0082] Discharge stabilization time / min Coating roughness / nm <![CDATA[Hardness / HV 0.05 > Example 1 29 69 3124 Example 2 34 75 3208 Comparative Example 1 24 58 2988 Comparative Example 2 26 60 2992 Comparative Example 3 25 59 3014 Comparative Example 4 23 61 3047 Comparative Example 5 14 44 2874 Comparative Example 6 18 48 2931 Comparative Example 7 20 52 2955

[0083] Table 2 Test results of mechanical properties of the target material

[0084]

[0085]

[0086] As can be seen from the above performance test results, the mechanical and electrical properties of Examples 1-2 are significantly improved, especially the comprehensive performance of Example 2 is the most outstanding. This is mainly because the synergistic effect between the various elements compounded in this invention and the aluminum hydroxide-doped carbon nanotubes effectively improves the mechanical and electrical properties of the alloy target material.

[0087] The comparative example, however, did not employ the necessary technical solutions, resulting in significantly worse performance than the embodiment in the corresponding tests. This further demonstrates the irreplaceable nature of the specific technical solution in this application for achieving the technical effect and solving the technical problem.

[0088] The above description represents the preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high-strength, high-toughness molybdenum-niobium alloy target material, characterized in that, It comprises the following components by weight: niobium 7.23%-19.55%, chromium 2.87%-6.54%, titanium 3.45%-6.58%, silicon 4.12%-7.52%, zirconium 5.32%-12.14%, aluminum hydroxide-doped carbon nanotubes 14.12%-22.45%, and the balance being molybdenum; The method for preparing the aluminum hydroxide-doped carbon nanotubes is as follows: Carbon nanotubes were acidified with a solvent, washed and dried, and then mixed with a 30 wt% hydrogen peroxide aqueous solution for a first reaction. After washing and drying, the resulting solid was dispersed in ethanol, and aluminum chloride hexahydrate was added for a second reaction. After filtration, washing and drying, the mixture was subjected to a third reaction to obtain aluminum hydroxide-doped carbon nanotubes. The carbon nanotubes have a particle size of 100-200 nm; And / or, the solvent is a mixture of concentrated sulfuric acid and concentrated nitric acid, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1; And / or, the mass ratio of the solvent to carbon nanotubes is (100-200):1; The acidification treatment time is 1-3 hours; And / or, the mass ratio of the carbon nanotubes to the 30wt% hydrogen peroxide aqueous solution is 1:(100-150); The conditions for the first reaction are: reaction time 16-24h, reaction temperature 25℃-30℃; And / or, the mass ratio of the solid, ethanol and aluminum chloride hexahydrate is 1:(50-100):(2-3); The conditions for the secondary reaction are: reaction time 1-3 hours, reaction temperature 25℃-30℃; And / or, the conditions for the three reactions are: thermal decomposition at 200℃-300℃ for 4-10 hours.

2. The high-strength, high-toughness molybdenum-niobium alloy target material according to claim 1, characterized in that, The alloy target material comprises the following components by weight: 12%-19% niobium, 3.5%-5.5% chromium, 4%-5.5% titanium, 5%-6% silicon, 7%-10% zirconium, 16%-20% aluminum hydroxide-doped carbon nanotubes, and the balance being molybdenum.

3. A method for preparing a high-strength, high-toughness molybdenum-niobium alloy target as described in any one of claims 1-2, characterized in that, Includes the following steps: Niobium powder, chromium powder, titanium powder, silicon powder, zirconium powder, and molybdenum powder are ball-milled once under an argon atmosphere. Then, aluminum hydroxide-doped carbon nanotubes are added and ball-milled a second time under an argon atmosphere. After sieving, the mixed powder is fed into a spray gun and sprayed onto the surface of the target substrate tube to obtain an alloy target.

4. The method for preparing the high-strength, high-toughness molybdenum-niobium alloy target according to claim 3, characterized in that, The conditions for the first ball milling are as follows: add 2-4 wt% ethanol to the raw material powder and ball mill at 500-800 rpm for 30-60 min; And / or, the conditions for the secondary ball milling are: adding 2-4 wt% ethanol to the raw material powder and ball milling at 500-800 rpm for 15-30 min; And / or, the sieve used for sieving is 200-400 mesh.

5. The application of a high-strength, high-toughness molybdenum-niobium alloy target as described in any one of claims 1-2 in the preparation of a conductive layer or a barrier layer.

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