Low-hydrogen low-oxygen high-density molybdenum-titanium alloy target material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of alloy target materials, and particularly relates to a low-hydrogen low-oxygen high-density molybdenum-titanium alloy target material and a preparation method and application thereof. The preparation raw materials of the low-hydrogen low-oxygen high-density molybdenum-titanium alloy target material comprise molybdenum powder and titanium powder; the titanium powder comprises spherical titanium powder and activated titanium powder; wherein the activated titanium powder is activated titanium powder subjected to hydrogenation-dehydrogenation treatment; the atomic percent content of the titanium powder is 10%-90%; the mass ratio of the spherical titanium powder to the activated titanium powder is 1: (1-2). According to the low-hydrogen low-oxygen high-density molybdenum-titanium alloy target material, the activated titanium powder subjected to hydrogenation-dehydrogenation treatment is adopted and has very high surface activity, in the target material preparation process, mixing and densification are more uniform, degassing is easy, and the prepared molybdenum-titanium alloy target material has the beneficial effects of being low in oxygen, low in hydrogen, high in density and good in plasticity.

Description

Technical Field

[0001] This invention belongs to the field of alloy target technology, specifically relating to a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target. Background Technology

[0002] Molybdenum-titanium alloy sputtering targets are sputtering targets made by powder metallurgy and processing molybdenum powder and titanium powder in a specific ratio. Based on high-purity molybdenum, the addition of titanium significantly improves the material's mechanical properties and thin film characteristics, making it an upgraded solution to replace pure molybdenum sputtering targets.

[0003] Molybdenum-titanium alloy sputtering targets are used as barrier layer materials in TFT-LCD and semiconductor interconnect processes. While existing powder metallurgy methods (CIP, vacuum sintering, HIP, etc.) can produce highly dense sputtering targets, they often face challenges in the fabrication of large-size targets: ① Oxygen / hydrogen content on the titanium powder surface affects mechanical plasticity and densification; ② Insufficient powder mixing uniformity leads to component segregation; ③ If hydrogen or adsorbed oxygen is present after HIP, brittle phases or cracks may form during subsequent rolling, reducing yield. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target, its preparation method, and its applications. This addresses at least one aspect of solving the above-mentioned technical problems.

[0005] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, the raw materials for which are prepared include molybdenum powder and titanium powder; Titanium powder includes spherical titanium powder and activated titanium powder; The activated titanium powder is activated titanium powder that has undergone hydrogenation-dehydrogenation treatment; The atomic percentage content of the titanium powder is 10%~90%; The mass ratio of the spherical titanium powder to the activated titanium powder is 1:(1~2).

[0006] In some possible implementations, the average particle size of the molybdenum powder is 2 μm to 10 μm.

[0007] In some possible implementations, the purity of the molybdenum powder is above 99.9%.

[0008] In some possible implementations, the average particle size of the spherical titanium powder is 20 μm to 150 μm.

[0009] In some possible implementations, the average particle size of the activated titanium powder is 20 μm to 150 μm.

[0010] In some possible implementations, the atomic percentage content of the titanium powder is 40% to 65%.

[0011] In some possible implementations, the relative density of the molybdenum-titanium alloy target is above 98.5%.

[0012] In some possible implementations, the hydrogen content of the molybdenum-titanium alloy target is below 3 ppm.

[0013] In some possible implementations, the oxygen content of the molybdenum-titanium alloy target is below 800 ppm.

[0014] Secondly, the present invention provides a method for preparing the above-mentioned low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target, comprising the following steps: After the raw material for preparing low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy targets is made into a green blank, it is subjected to hot isostatic pressing and vacuum heating dehydrogenation-degassing treatment. The raw materials used in the preparation include molybdenum powder, spherical titanium powder, and activated titanium powder.

[0015] In some possible implementations, the preparation of the green body includes the following steps: Under an inert atmosphere, molybdenum powder, spherical titanium powder and activated titanium powder are mixed and sheared at high speed according to a preset ratio, and then subjected to cold isostatic pressing.

[0016] In some possible implementations, the hot isostatic pressing process includes the following steps: The green blanks are sintered under high pressure.

[0017] In some possible implementations, the vacuum heating dehydrogenation-degassing process includes the following steps: Under vacuum, the green compact after hot isostatic pressing is heated to the dehydrogenation-degassing temperature and then held at that temperature.

[0018] In some possible implementations, the preparation of the activated titanium powder includes the following steps: The titanium powder to be activated is subjected to hydrogenation-dehydrogenation treatment.

[0019] In some possible implementations, the relative density of the green body is 60% to 80% of the theoretical density.

[0020] In some possible implementations, the inert atmosphere used in the preparation of the green body includes at least one of argon and helium.

[0021] In some possible implementations, the high-speed mixing shearing rate during the preparation of the green body is 2000 rpm to 6000 rpm.

[0022] In some possible implementations, the high-speed mixing and shearing time during the preparation of the green body is 5 min to 60 min.

[0023] In some possible implementations, the high-speed mixing and shearing time in the preparation of the green body is 10 min to 30 min.

[0024] In some possible implementations, the pressure during the cold isostatic pressing process in the preparation of the green blank is 100 MPa to 200 MPa.

[0025] In some possible implementations, the high-pressure sintering in the hot isostatic pressing process includes the following steps: Under high pressure and an inert atmosphere, the green blank is heated to the sintering temperature and then sintered.

[0026] In some possible implementations, the pressure of the high pressure is 50 MPa to 300 MPa.

[0027] In some possible implementations, the pressure of the high pressure is 100MPa to 200MPa.

[0028] In some possible implementations, the heating rate is 5°C / min to 20°C / min.

[0029] In some possible implementations, the sintering temperature is 1000℃~1400℃.

[0030] In some possible implementations, the sintering temperature is 1000℃~1300℃.

[0031] In some possible implementations, the sintering time is 2h to 8h.

[0032] In some possible implementations, the vacuum degree in the vacuum heating dehydrogenation-degassing process is ≤1×10⁻⁶. - 2 Pa.

[0033] In some possible implementations, the heating rate in the vacuum heating dehydrogenation-degassing process is 1℃ / min to 10℃ / min.

[0034] In some possible implementations, the dehydrogenation-degassing process under vacuum heating is carried out at a temperature of 700°C to 1200°C.

[0035] In some possible implementations, the holding time in the vacuum heating dehydrogenation-degassing treatment is 1h to 12h.

[0036] In some possible implementations, the holding time in the vacuum heating dehydrogenation-degassing treatment is 2h to 6h.

[0037] In some possible implementations, the hydrogenation-dehydrogenation treatment in the preparation of the activated titanium powder includes the following steps: The titanium powder to be activated is hydrogenated in a hydrogen atmosphere and then dehydrogenated by heating in a vacuum or inert atmosphere.

[0038] In some possible implementations, the hydrogenation time in the hydrogenation-dehydrogenation process is 1 to 3 hours.

[0039] In some possible implementations, the hydrogenation temperature in the hydrogenation-dehydrogenation process is 300°C to 400°C.

[0040] In some possible implementations, the temperature for heating and dehydrogenation in the hydrogenation-dehydrogenation process is 550°C to 650°C.

[0041] In some possible implementations, the heating dehydrogenation time in the hydrogenation-dehydrogenation process is 1h to 3h.

[0042] Thirdly, the present invention provides an application of the above-mentioned low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target in the fields of semiconductors, new energy, or aerospace.

[0043] The low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material provided by this invention has at least the following beneficial technical effects compared with the prior art: The low-hydrogen, low-oxygen, and high-density molybdenum-titanium alloy target material provided by this invention uses activated titanium powder that has undergone hydrogenation-dehydrogenation treatment. This activated titanium powder has high surface activity, and during the target material preparation process, the mixing and densification are more uniform and degassing is easier. The resulting molybdenum-titanium alloy target material has the characteristics of low oxygen, low hydrogen, high density, and good plasticity.

[0044] The method for preparing low-hydrogen, low-oxygen, and high-density molybdenum-titanium alloy targets provided by this invention has at least the following beneficial technical effects compared with the prior art: The present invention provides a method for preparing a low-hydrogen, low-oxygen, and high-density molybdenum-titanium alloy target. First, a green billet is subjected to cold isostatic pressing (COP) to form a shape, followed by hot isostatic pressing (HIP) to densify the billet. Finally, a vacuum heating dehydrogenation-degassing treatment is performed, significantly reducing the hydrogen content and further decreasing the effective oxygen content in the target, while simultaneously eliminating brittle phases formed or remaining during HIP. The molybdenum-titanium alloy target prepared by the method provided in this invention exhibits characteristics of low oxygen, low hydrogen, high density, and good plasticity. Attached Figure Description

[0045] To more clearly illustrate the technical solutions in the embodiments of this drawing or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this drawing. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0046] Figure 1 This is a SEM image of the molybdenum-titanium alloy target provided in Embodiment 1 of the present invention; Figure 2 The image shows a SEM image of the molybdenum-titanium alloy target provided in Comparative Example 1 of this invention. Figure 3a SEM image of the molybdenum-titanium alloy target provided in Comparative Example 2 of this invention; Figure 3b This is a SEM elemental distribution mapping image of molybdenum in the molybdenum-titanium alloy target provided in Comparative Example 2 of the present invention. Figure 4 This is a physical image of the molybdenum-titanium alloy target provided in Comparative Example 3 of the present invention.

[0047] The purpose, features, and advantages of this accompanying drawing will be further explained in conjunction with the embodiments and with reference to the accompanying drawing. Detailed Implementation

[0048] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described and illustrated below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments provided by this invention without inventive effort are within the scope of protection of this invention.

[0049] Obviously, the following description is merely some examples or embodiments of the present invention. Those skilled in the art can apply the present invention to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this invention, modifications to design, manufacturing, or production based on the technical content disclosed in this invention are merely conventional technical means and should not be construed as insufficient disclosure of the present invention.

[0050] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand the invention and is not intended to limit the subject matter of the claims.

[0051] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present invention can be combined with each other to form new technical solutions.

[0052]

Low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy sputtering target

[0053] The low-hydrogen, low-oxygen, and high-density molybdenum-titanium alloy target material provided in this invention uses activated titanium powder that has undergone hydrogenation-dehydrogenation treatment. This activated titanium powder has high surface activity, and during the target material preparation process, the mixing and densification are more uniform and degassing is easier. The resulting molybdenum-titanium alloy target material has the characteristics of low oxygen, low hydrogen, high density, and good plasticity.

[0054] In some embodiments, the average particle size of the molybdenum powder is 2 μm to 10 μm.

[0055] In some embodiments, the purity of the molybdenum powder is 99.9% or higher.

[0056] In some embodiments, the average particle size of the spherical titanium powder is 20 μm to 150 μm.

[0057] In some embodiments, the average particle size of the activated titanium powder is 20 μm to 150 μm.

[0058] In some embodiments, the atomic percentage content of titanium powder is 40% to 65%.

[0059] In some embodiments, the relative density of the molybdenum-titanium alloy target is above 98.5%.

[0060] In some embodiments, the hydrogen content of the molybdenum-titanium alloy target is less than 3 ppm.

[0061] In some embodiments, the oxygen content of the molybdenum-titanium alloy target is below 800 ppm.

[0062] Preparation method of low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material A second aspect of this invention provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target, comprising the following steps: S10. After the raw material for preparing low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target is made into a green blank, it is subjected to hot isostatic pressing and vacuum heating dehydrogenation-degassing treatment. The raw materials used in the preparation include molybdenum powder, spherical titanium powder, and activated titanium powder.

[0063] The method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target provided in this invention involves first performing cold isostatic pressing on a green billet, followed by hot isostatic pressing to densify the billet; finally, a vacuum heating dehydrogenation-degassing treatment is performed to significantly reduce the hydrogen content and further reduce the effective oxygen content in the target, while simultaneously eliminating brittle phases formed or remaining during the hot isostatic pressing (HIP) process. The molybdenum-titanium alloy target prepared by the method provided in this invention exhibits characteristics of low oxygen, low hydrogen, high density, and good plasticity.

[0064] In some embodiments, the preparation of the green blank in step S10 above includes the following steps: S101. Under an inert atmosphere, molybdenum powder, spherical titanium powder and activated titanium powder are mixed and sheared at high speed according to a preset ratio, and then subjected to cold isostatic pressing treatment.

[0065] In the preparation of the green body described above, the raw materials are subjected to high-speed mixing and shearing. The high shear rate reduces the agglomeration of the raw materials and achieves uniform distribution in a short time, while also reducing the probability of oxygen absorption during the mixing process, resulting in high uniformity and low oxygen adsorption in the raw materials. The raw materials are then subjected to cold isostatic pressing to form the desired shape.

[0066] In some embodiments, in step S101 above, the inert atmosphere includes at least one of argon and helium.

[0067] In some embodiments, the preparation of activated titanium powder in step S101 above includes the following steps: S1011. Perform hydrogenation-dehydrogenation treatment on the titanium powder to be activated.

[0068] In the preparation of the activated titanium powder described above, the hydrogenation-dehydrogenation treatment reduces the oxygen in the titanium powder, thereby reducing the oxygen in the molybdenum-titanium alloy target.

[0069] In some embodiments, in step S1011 above, the hydrogenation-dehydrogenation process includes the following steps: S10111. After the titanium powder to be activated is hydrogenated in a hydrogen atmosphere, it is dehydrogenated by heating in a vacuum or inert atmosphere.

[0070] In the above hydrogenation-dehydrogenation process, hydrogenation makes the titanium metal hydrogen embrittled, making it easier to crush and pulverize, and also facilitates the subsequent removal of oxygen from the titanium powder. Dehydrogenation removes oxygen and organic matter from the titanium powder and enriches the surface activity of the powder, making subsequent mixing and densification more uniform and easier to degas.

[0071] In some embodiments, in step S10111 above, the hydrogenation time is 1h to 3h.

[0072] In some embodiments, in step S10111 above, the hydrogenation temperature is 300°C to 400°C.

[0073] In some embodiments, in step S10111 above, the temperature for heating and dehydrogenation is 550°C to 650°C.

[0074] In some embodiments, in step S10111 above, the heating time for dehydrogenation is 1h to 3h.

[0075] In some embodiments, in step S10111 above, the vacuum level is <10. -3 Pa.

[0076] In some embodiments, in step S101 above, the shearing rate of the high-speed hybrid shearing is 2000 rpm to 6000 rpm.

[0077] In some embodiments, in step S101 above, the high-speed mixing and shearing time is 5 min to 60 min.

[0078] In some preferred embodiments, the high-speed mixing and shearing time in step S101 above is 10 min to 30 min.

[0079] In some embodiments, during the cold isostatic pressing process in step S101, the pressure is 100MPa~200MPa.

[0080] In some embodiments, in step S10 above, the relative density of the green blank is 60% to 80% of the theoretical density.

[0081] In some embodiments, in step S10 above, the hot isostatic pressing process includes the following steps: S102. The green body is subjected to high-pressure sintering.

[0082] In some embodiments, in step S102 above, high-pressure sintering includes the following steps: S1021. Under high pressure and an inert atmosphere, the green blank is heated to the sintering temperature and then sintered.

[0083] In some embodiments, in step S1021 above, the pressure of the high pressure is 50MPa~300MPa.

[0084] In some preferred embodiments, in step S1021 above, the high pressure is 100MPa~200MPa.

[0085] In some embodiments, in step S1021 above, the heating rate is 5°C / min to 20°C / min.

[0086] In some embodiments, in step S1021 above, the sintering temperature is 1000℃~1400℃.

[0087] In some preferred embodiments, the sintering temperature in step S1021 is 1000℃~1300℃.

[0088] In some preferred embodiments, the sintering time in step S1021 above is 2h to 8h.

[0089] In some embodiments, in step S10 above, the vacuum heating dehydrogenation-degassing treatment includes the following steps: S103. Under vacuum, the green compact after hot isostatic pressing is heated to the dehydrogenation-degassing temperature and then held at that temperature.

[0090] In some embodiments, in step S103 above, the vacuum degree is ≤1×10 -2 Pa.

[0091] In some embodiments, in step S103 above, the heating rate is 1℃ / min to 10℃ / min.

[0092] In some embodiments, in step S103 above, the dehydrogenation-degassing temperature is 700°C to 1200°C.

[0093] In some embodiments, the heat preservation time in step S103 is 1h to 12h.

[0094] In some preferred embodiments, the heat preservation time in step S103 is 2h to 6h.

[0095] In some embodiments, a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target is provided, which further includes the following steps: S20. Post-processing.

[0096] In some embodiments, in step S20 above, the post-processing includes the following steps: S201. According to the preset target size, the molten billet obtained by vacuum heating dehydrogenation-degassing treatment is rolled and annealed.

[0097] In some embodiments, in step S201 above, the rolling temperature of the rolling process is 600°C to 1000°C.

[0098] In some preferred embodiments, in step S201 above, the rolling temperature of the rolling process is 700°C to 900°C.

[0099] In some preferred embodiments, the total reduction rate of the rolling process in step S201 above is 30% to 50%.

[0100] In some embodiments, the annealing process in step S201 above includes vacuum annealing.

[0101] In some embodiments, the annealing temperature for vacuum annealing is 400°C to 700°C.

[0102] In some embodiments, the vacuum annealing time is 0.5h to 3h.

[0103] In some embodiments, the annealing process in step S201 above further includes high-temperature annealing under vacuum. In this case, high-temperature annealing can obtain the desired recrystallized structure and stress relief.

[0104] In some embodiments, the high-temperature annealing temperature is 800℃~1400℃.

[0105] In some embodiments, the high-temperature annealing time is 2h to 12h.

[0106] In some preferred embodiments, the high-temperature annealing time is 2h to 6h.

[0107] The following description, in conjunction with specific embodiments, provides further details.

[0108] Example 1 Example 1 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, prepared from molybdenum powder and titanium powder; The titanium powder is a mixture of spherical titanium powder and activated titanium powder that has undergone hydrogenation-dehydrogenation treatment; The molybdenum powder has an average particle size of 4μm and a purity of over 99.9%.

[0109] The atomic percentage content of titanium powder is 40%; The average particle size of the spherical titanium powder is 40 μm; The average particle size of the activated titanium powder is 45 μm; The mass ratio of spherical titanium powder to activated titanium powder is 1:1.

[0110] This embodiment also provides a method for preparing the low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material of this embodiment, the steps of which are as follows: E10. Preparation of activated titanium powder After the activated titanium powder is hydrogenated in a hydrogen atmosphere, it is heated under vacuum to remove hydrogen, thus obtaining activated titanium powder. The hydrogenation temperature was 350℃ and the time was 2 hours. The vacuum level is 10. -3 Pa, the temperature for dehydrogenation is 600℃ and the time is 2h.

[0111] E20. Preparation of green body Under an argon atmosphere, molybdenum powder, spherical titanium powder and activated titanium powder are mixed and sheared at high speed according to a preset ratio, and then subjected to cold isostatic pressing. Among them, the high-speed hybrid shearing has a shearing rate of 4000 rpm and a time of 10 min; In cold isostatic pressing, the pressure is 150 MPa, and the relative density of the green body is 70% of the theoretical density.

[0112] E30. Hot Isostatic Pressing Treatment Under high pressure and argon atmosphere, the green compact is heated to the sintering temperature and then sintered; The high pressure is 150 MPa, the heating rate is 10℃ / min, the sintering temperature is 1100℃, and the time is 4h.

[0113] E40. Vacuum heating dehydrogenation-degassing treatment In a vacuum ≤ 1 × 10 -2 Under Pa conditions, the green billet after hot isostatic pressing is heated to a dehydrogenation-degassing temperature of 900℃ at a heating rate of 5℃ / min and held for 4 hours to obtain a cooked billet.

[0114] E50. Post-processing According to the preset target size, the billet is rolled, vacuum annealed and high-temperature annealed in vacuum to obtain the low-hydrogen, low-oxygen and high-density molybdenum-titanium alloy target provided in this embodiment. The rolling process involves a rolling temperature of 800℃ and a total reduction rate of 40%. The vacuum annealing temperature was 600℃ and the time was 1 hour; The high-temperature annealing temperature is 1000℃ and the time is 5 hours.

[0115] Example 2 Example 2 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, prepared from molybdenum powder and titanium powder; The titanium powder is a mixture of spherical titanium powder and activated titanium powder that has undergone hydrogenation-dehydrogenation treatment; The molybdenum powder has an average particle size of 2μm and a purity of over 99.9%.

[0116] The titanium powder has an atomic percentage content of 50% and an average particle size of 100μm. The average particle size of the activated titanium powder is 120 μm; The mass ratio of spherical titanium powder to activated titanium powder is 1:2.

[0117] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target. The steps are basically the same as those in Example 1, except that the proportion of raw materials used in the preparation is the same as that provided in this embodiment.

[0118] Example 3 Example 3 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, prepared from molybdenum powder and titanium powder; The titanium powder is a mixture of spherical titanium powder and activated titanium powder that has undergone hydrogenation-dehydrogenation treatment; The molybdenum powder has an average particle size of 10 μm and a purity of over 99.9%.

[0119] The titanium powder has an atomic percentage content of 65% and an average particle size of 20μm. The average particle size of the activated titanium powder is 20 μm; The mass ratio of spherical titanium powder to activated titanium powder is 1:1.5.

[0120] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target. The steps are basically the same as those in Example 1, except that the proportion of raw materials used in the preparation is the same as that provided in this embodiment.

[0121] Example 4 Example 4 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, prepared from molybdenum powder and titanium powder; The titanium powder is a mixture of spherical titanium powder and activated titanium powder that has undergone hydrogenation-dehydrogenation treatment; The molybdenum powder has an average particle size of 10 μm and a purity of over 99.9%.

[0122] The titanium powder has an atomic percentage content of 10% and an average particle size of 150μm; The average particle size of the activated titanium powder is 150 μm; The mass ratio of spherical titanium powder to activated titanium powder is 1:1.

[0123] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target. The steps are basically the same as those in Example 1, except that the proportion of raw materials used in the preparation is the same as that provided in this embodiment.

[0124] Example 5 Example 5 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, prepared from molybdenum powder and titanium powder; The titanium powder is a mixture of spherical titanium powder and activated titanium powder that has undergone hydrogenation-dehydrogenation treatment; The molybdenum powder has an average particle size of 10 μm and a purity of over 99.9%.

[0125] The titanium powder has an atomic percentage content of 90% and an average particle size of 20μm. The average particle size of the activated titanium powder is 20 μm; The mass ratio of spherical titanium powder to activated titanium powder is 1:1.

[0126] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target. The steps are basically the same as those in Example 1, except that the proportion of raw materials used in the preparation is the same as that provided in this embodiment.

[0127] Example 6 Example 6 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, with the raw materials and proportions being basically the same as in Example 1.

[0128] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target, the steps of which are basically the same as those in Example 1, except that: In step E20, the high-speed mixing shearing has a shearing rate of 2000 rpm and a time of 60 min; In cold isostatic pressing, the pressure is 200 MPa, and the relative density of the green body is 80% of the theoretical density.

[0129] Example 7 Example 7 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, with the same raw materials and proportions as in Example 1.

[0130] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target, the steps of which are basically the same as those in Example 1, except that: In step E20, the high-speed mixing shearing has a shearing rate of 6000 rpm and a time of 5 min; In cold isostatic pressing, the pressure is 100 MPa, and the relative density of the green body is 60% of the theoretical density.

[0131] Example 8 Example 8 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, with the raw materials and proportions being basically the same as in Example 1.

[0132] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target, the steps of which are basically the same as those in Example 1, except that: In step E40, the heating rate is 1℃ / min, the dehydrogenation-degassing temperature is 700℃, and the holding time is 12h.

[0133] Example 9 Example 9 provides a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target material, with the same raw materials and proportions as in Example 1.

[0134] This embodiment also provides a method for preparing a low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target, the steps of which are basically the same as those in Example 1, except that: In step E40, the heating rate is 10℃ / min, the dehydrogenation-degassing temperature is 1200℃, and the holding time is 2h.

[0135] Comparative Example 1 Comparative Example 1 provides a molybdenum-titanium alloy target material, which is prepared from molybdenum powder and spherical titanium powder; The molybdenum powder has an average particle size of 10 μm and a purity of over 99.9%.

[0136] The atomic percentage content of the spherical titanium powder is 40%; the average particle size is 20μm.

[0137] This comparative example also provides a method for preparing a molybdenum-titanium alloy target. The steps are basically the same as those in Example 1, except that the proportion of raw materials used in the preparation is the same as that provided in this comparative example, and the preparation of activated titanium powder in step E10 is not performed.

[0138] Comparative Example 2 Comparative Example 2 provides a method for preparing a molybdenum-titanium alloy target, the steps of which are basically the same as those in Example 1, except that: In step E20, molybdenum powder, spherical titanium powder and activated titanium powder are mixed using a V-type batching machine and then subjected to cold isostatic pressing.

[0139] Comparative Example 3 Comparative Example 3 provides a method for preparing a molybdenum-titanium alloy target, the steps of which are basically the same as those in Example 1, except that: In step E40, vacuum dehydrogenation-degassing was not performed.

[0140] To verify the advancements of the low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target and its preparation method provided in this invention, the relative density, oxygen content, and hydrogen content of the molybdenum-titanium alloy targets prepared in the embodiments and comparative examples of this invention were measured. The results are shown in Table 1 below. SEM images of the molybdenum-titanium alloy targets from Examples 1 and Comparative Examples 1 to 3 are provided as follows. Figures 1-4 As shown.

[0141]

[0142] From Table 1 above, at least the following conclusions can be drawn: In Comparative Example 1, spherical titanium powder was used exclusively, resulting in a lower density after mixing molybdenum and titanium powders, leading to defects in the microstructure, such as... Figure 2 As shown.

[0143] Due to the significant difference in particle size between titanium powder and molybdenum powder, in Comparative Example 2, the fine molybdenum powder easily agglomerates within the gaps between the coarse titanium powder after mixing using the conventional method (V-type batcher), resulting in molybdenum segregation white spots appearing on the surface of the molybdenum-titanium target (e.g., Figure 3a and Figure 3b As shown in the figure, it affects the subsequent vacuum deoxidation and sputtering film performance.

[0144] In Comparative Example 3, hydrogen and oxygen accumulated at the phase interface of the molybdenum-titanium target material that had not undergone vacuum dehydrogenation-degassing treatment, leading to phase interface embrittlement and cracking during subsequent rolling. Figure 4 As shown.

[0145] The low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target provided in this invention uses a mixture of two titanium powders with different morphologies: spherical titanium powder and hydrogenated / dehydrogenated titanium powder. This increases the contact area between the powders and improves the relative density of the subsequent molybdenum-titanium target. In the preparation method of the low-hydrogen, low-oxygen, high-density molybdenum-titanium alloy target provided in this invention, high-speed shear mixing can fully mix the molybdenum powder and titanium powder, eliminating molybdenum powder agglomeration. The resulting molybdenum-titanium alloy target microstructure contains almost no lattice defects (such as...). Figure 1 As shown in the figure, no molybdenum segregation white spots will appear on the surface of the target material, and no cracking will occur during the subsequent rolling process.

[0146] It should be noted that the present invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments that have the same structure and perform the same effects as the technical concept within the scope of the present invention are included within the scope of the present invention. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of the present invention, are also included within the scope of the present invention.

Claims

1. A low hydrogen low oxygen high density molybdenum titanium alloy target material, characterized by, The preparation raw material includes molybdenum powder and titanium powder; The titanium powder includes spherical titanium powder and activated titanium powder; The activated titanium powder is activated titanium powder treated by hydrogenation-dehydrogenation; The atomic percentage content of the titanium powder is 10%-90%; The mass ratio of the spherical titanium powder to the activated titanium powder is 1:1-2.

2. The low hydrogen low oxygen high density molybdenum titanium alloy target material of claim 1, wherein, At least one of the following (1)-(8) characteristics is satisfied: (1) The average particle size of the molybdenum powder is 2-10 μm; (2) The purity of the molybdenum powder is higher than 99.9%; (3) The average particle size of the spherical titanium powder is 20-150 μm; (4) The average particle size of the activated titanium powder is 20-150 μm; (5) The atomic percentage content of the titanium powder is 40%-65%; (6) The relative density of the molybdenum-titanium alloy target material is higher than 98.5%; (7) The hydrogen content of the molybdenum-titanium alloy target material is lower than 3 ppm; (8) The oxygen content of the molybdenum-titanium alloy target material is lower than 800 ppm.

3. A method of producing a low-hydrogen low-oxygen high-density molybdenum-titanium alloy target material as claimed in claim 1 or 2, characterized by, The method includes the following steps: After the preparation raw material of the low-hydrogen low-oxygen high-density molybdenum-titanium alloy target material is made into a green body, the green body is treated by hot isostatic pressing and vacuum heating dehydrogenation-deaeration; The preparation raw material includes molybdenum powder, spherical titanium powder and activated titanium powder.

4. The method of claim 3, wherein the molybdenum-titanium alloy target having low hydrogen and low oxygen and high density is prepared by the steps of: preparing a molybdenum-titanium alloy ingot by vacuum melting; and performing a heat treatment on the molybdenum-titanium alloy ingot. At least one of the following (1)-(5) characteristics is satisfied: (1) The preparation of the green body includes the following steps: The molybdenum powder, the spherical titanium powder and the activated titanium powder are mixed and sheared at high speed in an inert atmosphere according to a preset ratio, and then the green body is treated by cold isostatic pressing; (2) The hot isostatic pressing treatment includes the following steps: The green body is sintered at high pressure; (3) The vacuum heating dehydrogenation-deaeration treatment includes the following steps: The green body treated by hot isostatic pressing is heated to a dehydrogenation-deaeration temperature and kept for a period of time in a vacuum; (4) The preparation of the activated titanium powder includes the following steps: The titanium powder to be activated is treated by hydrogenation-dehydrogenation; (5) The relative density of the green body is 60%-80% of the theoretical density.

5. The method of claim 4, wherein the molybdenum-titanium alloy target having low hydrogen and low oxygen and high density is prepared by the steps of: preparing a molybdenum-titanium alloy ingot by vacuum melting; and performing a heat treatment on the molybdenum-titanium alloy ingot. In the preparation of the green body, at least one of the following (1)-(5) characteristics is satisfied: (1) The inert atmosphere includes at least one of argon and helium; (2) The shearing rate of the high-speed mixing and shearing is 2000-6000 rpm; (3) The time of the high-speed mixing and shearing is 5-60 min; (4) The time of the high-speed mixing and shearing is 10-30 min; (5) In the cold isostatic pressing treatment, the pressure is 100-200 MPa.

6. The method of claim 4, wherein the molybdenum-titanium alloy target having low hydrogen and low oxygen and high density is prepared by the steps of: preparing a molybdenum-titanium alloy ingot by vacuum melting; and performing a heat treatment on the molybdenum-titanium alloy ingot. In the hot isostatic pressing treatment, the high-pressure sintering includes the following steps: The green body is sintered at high pressure and in an inert atmosphere after being heated to a sintering temperature.

7. The method of claim 6, wherein the molybdenum-titanium alloy target having low hydrogen and low oxygen and high density is prepared by the steps of: preparing a molybdenum-titanium alloy ingot by vacuum melting; and performing a heat treatment on the molybdenum-titanium alloy ingot. At least one of the following (1)-(6) characteristics is satisfied: (1) The pressure of the high pressure is 50-300 MPa; (2) The pressure of the high pressure is 100-200 MPa; (3) The heating rate is 5-20 ℃ / min; (4) The sintering temperature is 1000-1400 ℃; (5) The sintering temperature is 1000-1300 ℃; (6) The sintering time is 2-8 h.

8. The method of claim 4, wherein the molybdenum-titanium alloy target having low hydrogen and low oxygen and high density is prepared by the steps of: preparing a molybdenum-titanium alloy ingot by vacuum melting; and performing a heat treatment on the molybdenum-titanium alloy ingot. In the vacuum heating dehydrogenation-deaeration treatment, at least one of the following (1)-(5) characteristics is satisfied: (1) the vacuum degree is ≤ 1 x 10 -2 Pa; (2) the temperature rising rate is 1℃ / min~10℃ / min; (3) the dehydrogenation-dedusting temperature is 700℃~1200℃; (4) the holding time is 1h~12h; (5) the holding time is 2h~6h.

9. The method of claim 4, wherein the molybdenum-titanium alloy target having low hydrogen and low oxygen and high density is prepared by the steps of: preparing a molybdenum-titanium alloy ingot by vacuum melting; and performing a heat treatment on the molybdenum-titanium alloy ingot. In the preparation of the activated titanium powder, at least one of the following (1)~(5) characteristics is met: (1) the hydrogenation-dehydrogenation treatment comprises the following steps: After the titanium powder to be activated is hydrogenated under a hydrogen atmosphere, it is heated and dehydrogenated under vacuum or an inert atmosphere; (2) the hydrogenation time is 1h~3h; (3) the hydrogenation temperature is 300℃~400℃; (4) the heating and dehydrogenation temperature is 550℃~650℃; (5) the heating and dehydrogenation time is 1h~3h.

10. Application of the low-hydrogen low-oxygen high-density molybdenum-titanium alloy target material as claimed in claim 1 or 2 in the fields of semiconductors, new energy or aerospace.

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