Method for preparing molybdenum alloy tube target material, molybdenum alloy tube target material and its use

Abstract

The present application relates to a method for preparing a molybdenum alloy tube target material, a molybdenum alloy tube target material, and its applications, which belong to the powder metallurgy technical field. The target is prepared by cold isostatic pressing, cladding, hot isostatic pressing, extrusion, annealing, etc. of raw material powder, and the prepared target material contains, in mass%, Ni: 10-30%, Ti: 5-25%, Re: 0.5-5%, and M: 0-15%, where M is at least one of Cr, Zr, Ta, and Nb, M is used to replace a part of Ti, and the remainder is Mo and unavoidable impurities, and the mass% content of Mo in the molybdenum alloy tube target material is 50% or more. The prepared target material has good ductility and toughness, good deformation ability, and fine and uniform crystal grains. The prepared target material is used to deposit a thin film by sputtering, and the thickness distribution is more uniform, and the metal coating layer is formed by sputtering and attached to the main conductive layer of a laminated wiring film for electronic components, which can be used in flat displays, thin film solar energy, semiconductor devices, etc.

Description

[Technical field]

[0001] The present invention belongs to the field of powder metallurgy technology, and particularly relates to a method for preparing a molybdenum alloy tube target material, a molybdenum alloy tube target material and its application. [Background technology]

[0002] With technological advances in flat display devices such as liquid crystal displays and display panels, it is necessary to reduce the resistance of wiring films. At the same time, relatively low film resistance levels are also required with the trend toward larger screens, higher resolution, faster response times, and larger flexible panels for flat display devices.

[0003] Thin film transistors (TFTs) are the driving elements of display panels, and use Al or Cu as the main wiring material. However, if Al or Cu comes into direct contact with Si, thermal diffusion will occur due to heat processing during preparation, which will deteriorate the performance of the thin film transistor. Therefore, it is necessary to provide a laminated wiring film between Al / Cu and Si.

[0004] Mo and molybdenum alloys such as Mo-Nb and Mo-Ti have excellent corrosion resistance, heat resistance, and adhesion to substrates, and can be used to prepare laminated wiring films. However, after the laminated wiring film is formed on the substrate during the preparation process, it may be left in the air for a long period of time. In addition, when attaching a signal cable to a display panel, it may be necessary to heat it in the air, and in semiconductor thin films using oxides, it is necessary to heat them in an oxygen-containing environment to improve and stabilize their performance. Therefore, there is a strong need to improve the oxidation resistance of laminated wiring films. In addition, resin films used in portable, lightweight, and flexible display panels have moisture permeability compared to glass substrates, and laminated wiring films are required to have high moisture resistance. However, materials such as pure Mo and Mo-Ti do not have sufficient moisture resistance or oxidation resistance, and oxidation may occur, resulting in a problem of a significant increase in the resistance value of Al and Cu.

[0005] The patent "CN2012102930608" discloses a molybdenum alloy target material for laminated wiring films, which is obtained by adding a certain amount of Ni and Ti to molybdenum in order to improve the moisture resistance and oxidation resistance of pure molybdenum plating film, and is useful for the stable preparation and reliability of electronic components.

[0006] Patent "CN2014100909230" discloses a molybdenum alloy target material for electronic components, which can improve oxidation resistance by adding Ni and moisture resistance by adding W element.

[0007] Patent "CN2017114460697" discloses molybdenum alloy target material components containing elements such as Ni, Nb, Ti, etc., which can effectively improve the moisture resistance and oxidation resistance of pure molybdenum and maintain low film resistance. Summary of the Invention [Problem to be solved by the invention]

[0008] In the above patent, a certain amount of elements such as Ni, Ti, or W is added to the molybdenum substrate to improve both the moisture resistance and oxidation resistance of the molybdenum target material sputtering film and maintain a low resistance value. However, the target is mainly prepared by hot isostatic pressing (HIP), and as the length of the target material increases, the HIP forming dimensions are greatly restricted by the dimensions of the HIP equipment, making it impossible to mass-produce high-performance molybdenum alloy target material. In addition, the formability of the molybdenum alloy target material is poor, so it is impossible to prepare tubular target material products of different lengths by deformation methods such as extrusion and forging. [Means for solving the problem]

[0009] In view of the above problems, the present application aims to provide a method for preparing a molybdenum alloy tube target material, and a molybdenum alloy tube target material and its application.

[0010] The molybdenum alloy tube target material provided by the present application can improve the ductility and toughness of the target material and the deformation processing ability of the target material after adding rhenium element. The molybdenum alloy tube target material can be refined in grain size through extrusion in the subsequent preparation process. In addition, considering that the price of rhenium is relatively high, the present application can effectively play a role in improving the performance and processing ability of the target material by adding a small amount of rhenium and blending it with other components.

[0011] In order to achieve the above object, the present application adopts the following technical proposal. A first aspect of the present application provides a method for preparing a molybdenum alloy tube target material, comprising the steps of: Powder mixing: The raw materials are weighed according to the mass fraction of each element in the molybdenum alloy tube target material, and then uniformly mixed to obtain molybdenum alloy powder. Here, the molybdenum alloy tube target material contains, in mass%, Ni: 10 to 30% (e.g., 12%, 15%, 20%, 25%), Ti: 5 to 25% (e.g., 6%, 8%, 10%, 15%, 20%), Re: 0.5 to 5% (e.g., 0.7%, 0.9%, 1.2%, 1.5%, 2%, 2.5%, 3%, 4%), M: 0 to 15% (e.g., 1%, 3%, 5%, 8%, 10%, 13%), where M is at least one of Cr, Zr, Ta, and Nb, the M is used in place of a portion of Ti, and the remainder is Mo and unavoidable impurities, and the mass% content of Mo in the molybdenum alloy tube target material is 50% or more (e.g., 52%, 60%, 70%). Cold isostatic pressing: The mixed powder is placed in a mold and cold isostatic pressing is performed to obtain a first blank. Hot isostatic pressing: The first blank is hot isostatically pressed to obtain a second blank. Extrusion molding: The second blank is extruded to obtain a third blank. Annealing treatment: The third blank is annealed.

[0012] The Ni component of the molybdenum alloy tube target material of the present invention can increase the oxidation resistance of the film layer formed from the target material of the present invention, and the Ti component can increase the moisture resistance of the film layer. The addition of appropriate amounts of both elements not only ensures the oxidation resistance and moisture resistance of the film layer, but also ensures low resistance of the wiring film and does not affect the etching speed of the etching agent.

[0013] A small amount of Re element is added to the molybdenum alloy tube target material of the present invention. The addition of a certain proportion of Re element acts in conjunction with a certain proportion of other elements in the molybdenum alloy, allowing Re to exert the "rhenium effect" in this molybdenum alloy, improving the room temperature plasticity of the molybdenum alloy, lowering the plastic-brittle transition temperature, and refining the crystal grains. The addition of Re element to this molybdenum alloy tube target material can improve the deformation performance of the target material, and cracks do not occur even during large deformation processing. Since the target material structure crystal grains are small, the target material crystal grain steps obtained with the preferred molybdenum alloy group distribution ratio are particularly small, the crystal grains are uniform, the thickness of the film layer prepared by the target material of the present invention is more uniform, and the sputtering rate is faster. If the amount of Re element used exceeds 5%, the cost increases, while if the amount of Re element added is excessive, Re can form an alloy phase with other elements, which affects the subsequent plating effect. If the amount of Re element used is less than 0.5%, the effect of effectively refining the crystal grains and improving the plasticity of the target material cannot be obtained.

[0014] The M element in the present application has the effect of enhancing the moisture resistance of the plating film of the target material, and can partially replace Ti, which also has moisture resistance, and this element can also improve the oxidation resistance of the plating film of the target material, etc. However, from the viewpoint of the interaction of various components of the target material, it is preferable that the M element can replace only a part of Ti.

[0015] In some embodiments, the method for preparing the molybdenum alloy tube target material further comprises the steps of: Shaping: The first blank after the cold isostatic pressing is shaped. Cladding: Prior to the hot isostatic pressing, the shaped first blank is placed in a sheath, which is evacuated and vacuum sealed. Removal of sheath: After the hot isostatic pressing, the sheath of the second blank is removed by machining. Machining: The third blank is machined prior to the annealing treatment.

[0016] In some embodiments, the molybdenum alloy tube target material contains, in mass%, Ni: 10-30% (e.g., 12%, 14%, 18%, 20%, 25%), Ti: 5-25% (e.g., 6%, 8%, 10%, 13%, 16%, 19%, 23%), Re: 1-5% (e.g., 1.2%, 1.5%, 2%, 3%, 4%), M: 0-5% (e.g., 0.5%, 1%, 2%, 3%, 4%), and the remainder is Mo and unavoidable impurities, and the mass% content of Mo in the molybdenum alloy tube target material is 60% or more (e.g., 61%, 65%, 70%, 80%). In this preferred range of components, the performance of the molybdenum alloy tube target material is more excellent.

[0017] In some embodiments, in the powder mixing step, the raw materials include molybdenum powder having a purity of 3N5 or more and a FSSS (Fisher Sub-sieve Size) range, preferably 2.5 to 4 μm, nickel powder having a purity of 3N or more and a FSSS range, preferably 2 to 3 μm, a titanium source which is titanium powder or titanium hydride, the purity of the titanium powder being 3N or more and the FSSS range of the titanium powder being preferably 2 to 4 μm, the purity of the titanium hydride being 2N or more and the FSSS range of the titanium hydride being preferably 2 to 4 μm, and rhenium powder having a purity of 4N or more and a FSSS range of preferably 2 to 4 μm.

[0018] In some embodiments, the titanium element in the molybdenum alloy tube target material is added in the form of molybdenum titanium alloy powder, and the molybdenum titanium alloy powder is obtained by mixing a part of the molybdenum powder in the raw material with titanium hydride powder and then reducing the mixture.

[0019] Preferably, the molybdenum:titanium mass ratio of the molybdenum-titanium alloy powder is 90:10 to 70:30 (eg, 85:15, 80:20, 75:25).

[0020] Preferably, during the preparation of the molybdenum titanium alloy powder, the reduction treatment is carried out in a hydrogen atmosphere, the temperature of the reduction treatment is 500-900°C (for example, 600°C, 700°C, 800°C), and the time of the reduction treatment is 2-8h (3h, 4h, 5h, 6h).

[0021] In the above hydrogen gas reduction process, the gas flow rate varies depending on the size of the reduction furnace, and the pressure only needs to be a slight positive pressure. Titanium hydride was selected as the titanium source in order to make the prepared molybdenum titanium alloy powder more uniform and consistent. Although titanium powder can be directly used as the supply source and mixed, it is better to use the reduction process after mixing titanium hydride and molybdenum powder to ensure powder uniformity.

[0022] In some embodiments, the powder mixing is performed in a ball mill, the BPR (Ball-to-Power Ratio) is 1:1 to 2:1, the ball mill is evacuated to a negative pressure and then filled with argon gas, preferably the argon gas pressure in the ball mill is atmospheric pressure, the mixing time is 10 h to 16 h (e.g., 12 h, 14 h), and the rotation speed is 50 to 300 r / min.

[0023] In some embodiments, the cold isostatic pressing has a pressing pressure of 150 to 200 MPa (e.g., 170 MPa, 190 MPa) and a pressure retention time of 5 to 20 minutes (e.g., 8 minutes, 10 minutes, 15 minutes, 18 minutes). Preferably, the mold is a stainless steel tubular mold.

[0024] The cold isostatic pressing process of the present invention can make the relative density of the first blank 55 to 65%.

[0025] In some embodiments, the hot isostatic pressing temperature is 900°C to 980°C (e.g., 920°C, 940°C, 960°C), the pressure is 100 to 170 MPa (e.g., 120 MPa, 140 MPa, 160 MPa), and the pressure holding time is 2 to 5 hours (e.g., 3 hours, 4 hours).

[0026] The present hot isostatic pressing process can provide a 100% relative density for the second blank formed from several molybdenum alloy components. If the relative density of the blank cannot reach 100% through the hot isostatic pressing process alone, a high-temperature sintering process can be added between the hot isostatic pressing process and the cold isostatic pressing process to improve the sintering effect of the alloy components and further increase the relative density of the blank.

[0027] In some embodiments, the extrusion is low-temperature extrusion, the start temperature of the extrusion is 1100 to 1400°C (e.g., 1150°C, 1200°C, 1300°C), and the end temperature of the extrusion is 900 to 1100°C (e.g., 950°C, 1000°C, 1050°C). Before each pass of extrusion, the second blank is placed in a muffle furnace and heated in an air or argon gas atmosphere, the heat retention temperature is 1100 to 1400°C, the heat retention time is 30 to 120 minutes (e.g., 40 minutes, 60 minutes, 80 minutes, 100 minutes), and the extrusion of each pass is started after the blank is taken out of the furnace.

[0028] Specifically, in the temperature-reducing extrusion, the heating and keeping temperature before the extrusion in the subsequent pass is lower than the heating and keeping temperature before the extrusion in the previous pass.

[0029] Preferably, the pre-extrusion heating and holding temperature of the subsequent pass is reduced by more than 0 and up to 100° C. (e.g., 10° C., 20° C., 40° C., 50° C., 60° C., 80° C.) based on the pre-extrusion heating and holding temperature of the previous pass.

[0030] Preferably, the extrusion deformation rate of each pass of the extrusion is 15 to 25% (eg, 17%, 19%, 21%, 23%), and the total deformation amount of the extrusion molding is 40 to 80% (eg, 50%, 60%, 70%).

[0031] When the extrusion start temperature is controlled in the range of 1100-1400°C, the extrusion effect is good. If the extrusion start temperature is too high, nickel will melt and oxidation will be serious. If the extrusion start temperature is low, the blank is easy to crack during extrusion. The extrusion end temperature can be controlled at 900-1100°C (for example, 1050°C, 1100°C, 1150°C) to ensure the forming performance and avoid cracks.

[0032] By controlling the extrusion deformation rate of each pass at 15-25%, the deformation performance of the material can be fully utilized. If the deformation rate is too large, the blank will crack during the extrusion deformation. At the same time, the temperature drop of the pass can be controlled within 100 ° C to maintain the good strength and plasticity of the material and avoid cracks.

[0033] In some embodiments, the annealing treatment is performed in an argon gas atmosphere, the annealing temperature is 1000 to 1300°C (e.g., 1050°C, 1100°C, 1150°C, 1200°C, 1250°C), and the annealing temperature retention time is 60 to 120 minutes (e.g., 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes).

[0034] By controlling the annealing temperature within this range, the anisotropy of the target material after extrusion can be eliminated, and a molybdenum alloy tube target material with a uniform structure and fine crystal grains can be obtained. If the annealing temperature is lower than 1000°C, the target material will have a non-uniform structure, and if the annealing temperature is higher than 1300°C, the crystal grains will become abnormally large and mixed crystals will occur, both of which will affect the effectiveness of the subsequent sputter plating film of the target material.

[0035] In some embodiments, after the annealing treatment, a uniformly fine crystalline target material having a crystal grain size of ≦100 μm (eg, 60 μm, 70 μm, 80 μm, 90 μm) and a crystal grain size of class 4 to 5 can be obtained.

[0036] The molybdenum alloy tube target material prepared in the present application has small crystal grains, and the sputtering rate is faster than that of a target material with coarse crystal grains. In addition, the difference in crystal grain size of the target material is small (uniform distribution), and the thickness distribution of the thin film deposited by target sputtering is more uniform. The quality of the thin film obtained by sputtering with the molybdenum alloy tube target material prepared in the present application is greatly improved.

[0037] A second aspect of the present application provides a molybdenum alloy tube target material prepared using the above method.

[0038] In some embodiments, the grain size of the molybdenum alloy tube target material is 100 μm or less (eg, 60 μm, 70 μm, 80 μm, 90 μm), and the grain size is grade 4-5.

[0039] The third aspect of the present application provides an application of the molybdenum alloy tube target material, which is deposited by sputtering on a main conductive layer of a laminated wiring film for electronic components to form a metal coating layer, and the electronic components are flat display, thin-film solar energy, or semiconductor device, etc. Effect of the Invention

[0040] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) After adding rhenium element, the ductility and toughness of the target material can be increased, and the deformation processing ability of the target material can be improved. 2) The grain size of the molybdenum alloy tube target material can be refined by extrusion molding in the subsequent preparation process, and a uniform fine crystal target material with a grain size of ≦100 μm and a grain size of 4 to 5 can be obtained. 3) The present invention can effectively improve the performance and processing ability of the target material by adding a small amount of rhenium in cooperation with other components. 4) The crystal grains of the molybdenum alloy tube target material prepared in this application are small, and the sputtering rate is faster than that of a target material with coarse crystal grains. In addition, the difference in crystal grain size of the target material is small (uniform distribution), and the thickness distribution of the thin film deposited by target sputtering is more uniform. The quality of the thin film obtained by sputtering with the molybdenum alloy tube target material prepared in this application is greatly improved. [Brief description of the drawings]

[0041] [Figure 1] FIG. 2 is a schematic diagram of the microscopic structure of a molybdenum alloy tube target material prepared in an embodiment of the present application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] The following examples will further describe the contents of the present application, and the scope of protection of the present application includes, but is not limited to, the following examples. If no specific conditions are specified in the examples, they can be carried out according to the conditions commonly used in the art or the conditions suggested by the manufacturer. If the chemicals or equipment used do not specify the manufacturer, they are all ordinary products available on the market.

[0043] The "rhenium effect" that the Re element exerts in molybdenum improves the room temperature plasticity of the material, lowers the plastic-brittle transition temperature, and refines the crystal grains. By adding the Re element to the molybdenum alloy tube target material, the deformation performance of the target material can be improved, that is, a large-sized plate-shaped target material can be prepared by deformation methods such as extrusion, and a target material with uniform microcrystals can be obtained by annealing.

[0044] The present invention will now be described in detail with reference to specific examples. Unless otherwise specified, all powder particle sizes in the following examples are FSSS and ratios are mass ratios. The standard for the grain size level (classification) test in the examples of this application is "GB / T6394 Metal Average Grain Size Measurement Method." The yield in the following examples is the number of acceptable tube blanks obtained after extrusion deformation / the number of hot-rolled blanks subjected to extrusion deformation*100%.

[0045] Example 1 The method for preparing a molybdenum alloy tube target according to the present embodiment includes the following steps: 140 kg of raw materials are prepared according to the mass ratio of each element of the target material Mo:Ni:Ti:Re=60:20:18:2, using pure Mo powder with a purity of 3N5 and a particle size of 3.5 μm, Ni powder with a purity of 3N and a particle size of 3.2 μm, TiH2 powder with a purity of 3N and a particle size of 3.4 μm, and rhenium powder with a purity of 4N and a particle size of 4 μm. Here, titanium is added by adding all of the titanium hydride powder to a part of the raw molybdenum powder, and then reducing it in a hydrogen atmosphere at 800 ° C for 4 hours to obtain a molybdenum titanium alloy powder after reduction (the mass ratio of the molybdenum element to the titanium element in the molybdenum titanium alloy powder is 1:1), and then adding the molybdenum titanium alloy powder to the remaining powder to be mixed; The powder obtained in step 1 is placed in a ball mill can, the BPR is set to 1:1, the can is evacuated to negative pressure, and argon gas is filled to atmospheric pressure, the mixing time is set to 13 h, and the rotation speed is set to 200 r / min. Step 3: Put the mixed powder obtained in step 2 into a stainless steel tubular mold and perform cold isostatic pressing (CIP) molding at a pressing pressure of 200 MPa and a holding time of 10 minutes. Step 4 of shaping the CIP tubular blank obtained in step 3 to make the geometric dimensions of the blank regular and complete; In step 4, the blank is placed in a sheath, evacuated to 10-1 Pa, and then sealed after 5 hours of evacuation. Step 6: hot isostatic pressing (HIP) the sheath of step 5, with the temperature and pressure held at 920°C, 120MPa, and 4h; Step 7 is to remove the sheath from step 6 by machining, to ensure that the outer peripheral surface of the tube target is flat and free of protrusions, and that the tube blank has an outer diameter of 180 mm and an inner diameter of 140 mm; Step 8: The tube blank obtained in step 7 is placed in a muffle furnace and heated in an air atmosphere, the extrusion start temperature is 1350°C, the warming time is 90 minutes, the extrusion deformation rate of each pass is 15-25%, the warming temperature before extrusion of each pass is 50°C lower than the previous pass, the warming time before extrusion of each pass is 90 minutes, the extrusion deformation end temperature is around 980°C, and the tube blank dimensions are an outer diameter of 120 mm and an inner diameter of 100 mm. Step 9: machining the inner and outer surfaces of the tube blank obtained in step 8 to obtain a tube blank having an outer diameter of 115 mm and an inner diameter of 105 mm; Step 10 includes annealing the tube blank obtained in step 9 under an Ar gas atmosphere at an annealing temperature of 1100°C and a heat retention time of 90 minutes to obtain a uniform microcrystalline tube material with a grain size of 66 μm to 92 μm and a grain size of class 4, which can be specifically seen in FIG. 1. The tube target material obtained by the preparation method of this example was free of cracks, and the yield was 100%.

[0046] Example 2 The method for preparing a molybdenum alloy tube target according to the present embodiment includes the following steps: 200 kg of raw materials are prepared according to the mass ratio of each element of the target material Mo:Ni:Ti:Re=73:15:10:2, using pure Mo powder with a purity of 3N5 and a grain size of 3.8 μm, Ni powder with a purity of 3N and a grain size of 2.4 μm, TiH2 powder with a purity of 3N and a grain size of 3.0 μm, and rhenium powder with a purity of 4N and a grain size of 3.5 μm; and titanium is added by adding all of the titanium hydride powder to a part of the raw molybdenum powder, and then reducing it in a hydrogen atmosphere at 750 ° C for 4 hours to obtain a molybdenum titanium alloy powder after reduction (the mass ratio of the molybdenum element to the titanium element in the molybdenum titanium alloy powder is 2:1), and adding the molybdenum titanium alloy powder to the remaining powder to be mixed; The powder obtained in step 1 is placed in a ball mill can, the BPR is set to 1:2, the can is evacuated to negative pressure, and argon gas is filled to atmospheric pressure, the mixing time is set to 15 h, and the rotation speed is set to 200 r / min. Step 3: The mixed powder obtained in step 2 is placed in a stainless steel tubular mold and subjected to cold isostatic pressing at a press pressure of 200 MPa and a holding time of 8 minutes. Step 4 of shaping the CIP tubular blank obtained in step 3 to make the geometric dimensions of the blank regular and complete; In step 5, the blank after shaping in step 4 is placed in a sheath, evacuated to 10-2 Pa, and then sealed after 4 hours of evacuation. Step 6: hot isostatically pressing (HIP) the sheath of step 5, with the heat retention temperature set to 940°C, the pressure set to 150MPa, and the heat retention and pressure retention time set to 3h; Step 7 is to remove the sheath from step 6 by machining, to ensure that the outer peripheral surface of the tube target is flat and free of protrusions, and that the tube blank has an outer diameter of 200 mm and an inner diameter of 120 mm; Step 8: the tube blank obtained in step 7 is placed in a muffle furnace and heated in an air atmosphere, the extrusion start temperature is 1300°C, the warming time is 90 minutes, the extrusion deformation rate of each pass is 15-25%, the warming temperature before extrusion of each pass is 50°C lower than the previous pass, the warming time before extrusion of each pass is 90 minutes, the extrusion deformation end temperature is around 1050°C, and the tube blank dimensions are an outer diameter of 150 mm and an inner diameter of 130 mm; Step 9: machining the inner and outer surfaces of the tube blank obtained in step 8 to obtain a tube blank having an outer diameter of 145 mm and an inner diameter of 135 mm; The method includes a step 10 of annealing the tube blank obtained in the step 9 under an Ar gas atmosphere at an annealing temperature of 1250°C for a heat retention time of 90 minutes to obtain a uniform fine crystal tube material having a crystal grain size of 60 μm to 85 μm and a crystal grain size of class 5. The molybdenum alloy tubular target material obtained by the preparation method of this example was free of cracks, and the yield was 100%.

[0047] Example 3 The molybdenum alloy tube target and preparation method according to the present embodiment include, in particular, the preparation method includes the following steps: 70 kg of raw materials are prepared according to the mass ratio of each element of the target material Mo:Ni:Ti:Re=70:15:10:5, using pure Mo powder with a purity of 3N5 and a particle size of 3.2 μm, Ni powder with a purity of 3N and a particle size of 3.5 μm, TiH2 powder with a purity of 3N and a particle size of 3.5 μm, and rhenium powder with a purity of 4N and a particle size of 3.5 μm. Here, titanium is added by adding titanium hydride powder with a mass ratio of 40% to a part of the raw molybdenum powder, and then reducing it in a hydrogen atmosphere at 800 ° C for 3 hours to obtain a molybdenum titanium alloy powder after reduction, and adding the molybdenum titanium alloy powder to the remaining powder to be mixed; The powder obtained in step 1 is placed in a ball mill can, the BPR is set to 1:1, the can is evacuated to negative pressure, and argon gas is filled to atmospheric pressure, the mixing time is set to 16 h, and the rotation speed is set to 200 r / min. Step 3: The mixed powder obtained in step 2 is placed in a stainless steel tubular mold and subjected to cold isostatic pressing at a pressing pressure of 150 MPa and a holding time of 15 minutes. Step 4 of shaping the CIP tubular blank obtained in step 3 to make the geometric dimensions of the blank regular and complete; In step 5, the blank after shaping in step 4 is placed in a sheath, evacuated to 10-1 Pa, and then sealed after maintaining the evacuation for 6 hours. Step 6: hot isostatically pressing (HIP) the sheath of step 5, with a heat retention temperature of 920°C, a pressure of 170MPa, and a heat retention and pressure retention time of 3h; Step 7 is to remove the sheath from step 6 by machining, to ensure that the outer peripheral surface of the tube target is flat and free of protrusions, and that the tube blank has an outer diameter of 240 mm and an inner diameter of 100 mm; Step 8: the tube blank obtained in step 7 is placed in a muffle furnace and heated in an air atmosphere, the extrusion start temperature is 1350°C, the warming time is 120 minutes, the extrusion deformation rate of each pass is 15-25%, the warming temperature before extrusion of each pass is 50°C lower than the previous pass, the warming time before extrusion of each pass is 90 minutes, the extrusion deformation end temperature is around 1080°C, and the tube blank dimensions are an outer diameter of 160 mm and an inner diameter of 130 mm; Step 9: machining the inner and outer surfaces of the tube blank obtained in step 8 to obtain a tube blank having an outer diameter of 155 mm and an inner diameter of 135 mm; The method includes a step 10 of annealing the tube blank obtained in the step 9 under an Ar gas atmosphere at an annealing temperature of 1250°C for a heat retention time of 60 minutes to obtain a uniform fine crystal tube material having a crystal grain size of 55 μm to 80 μm and a crystal grain size of class 5. The tubular target material obtained in this example was free of cracks, and the yield was 100%.

[0048] Example 4 The molybdenum alloy tube target and preparation method according to the present embodiment include, in particular, the preparation method includes the following steps: 150 kg of raw materials are prepared according to the mass ratio of each element of the target material Mo:Ni:Ti:Re=74:15:10:1, using pure Mo powder with a purity of 3N5 and a grain size of 3.8 μm, Ni powder with a purity of 3N and a grain size of 3.5 μm, TiH2 powder with a purity of 3N and a grain size of 3.2 μm, and rhenium powder with a purity of 4N and a grain size of 2.8 μm; where, titanium is added by adding all of the titanium hydride powder to a part of the raw molybdenum powder, and then reducing it in a hydrogen atmosphere at 800 ° C for 4 hours to obtain a molybdenum titanium alloy powder after reduction (the mass ratio of the molybdenum element to the titanium element in the molybdenum titanium alloy powder is 2:1), and adding the molybdenum titanium alloy powder to the remaining powder to be mixed; The powder obtained in step 1 is placed in a ball mill can, the BPR is set to 1:2, the can is evacuated to negative pressure, and argon gas is filled to atmospheric pressure, the mixing time is set to 16 h, and the rotation speed is set to 200 r / min. Step 3: The mixed powder obtained in step 2 is placed in a stainless steel tubular mold and subjected to cold isostatic pressing at a press pressure of 200 MPa and a holding time of 10 minutes. Step 4 of shaping the CIP tubular blank obtained in step 3 to make the geometric dimensions of the blank regular and complete; In step 5, the blank after shaping in step 4 is placed in a sheath, evacuated to 10-2 Pa, and then sealed after maintaining the evacuation for 4 hours. Step 6: hot isostatically pressing (HIP) the sheath of step 5, with the temperature at 930°C, the pressure at 150MPa, and the time for holding the temperature and pressure at 4h; Step 7 is to remove the sheath from step 6 by machining, to ensure that the outer peripheral surface of the tube target is flat, has no protrusions, and has a tube blank outer diameter of 220 mm and an inner diameter of 100 mm; Step 8: the tube blank obtained in step 7 is placed in a muffle furnace and heated in an air atmosphere, the extrusion start temperature is 1350°C, the warming time is 90 minutes, the extrusion deformation rate of each pass is 15-25%, the warming temperature before extrusion of each pass is 50°C lower than the previous pass, the warming time before extrusion of each pass is 90 minutes, the extrusion deformation end temperature is around 1080°C, and the tube blank dimensions are an outer diameter of 165 mm and an inner diameter of 135 mm; Step 9: machining the inner and outer surfaces of the tube blank obtained in step 8 to obtain a tube blank having an outer diameter of 160 mm and an inner diameter of 140 mm; The method includes a step 10 of annealing the tube blank obtained in the step 9 under an Ar gas atmosphere at an annealing temperature of 1200°C for a heat retention time of 100 minutes to obtain a uniform fine crystal tube material having a crystal grain size of 70 μm to 100 μm and a crystal grain size of class 4. The tubular target material obtained in this example was free of cracks, and the yield was 100%.

[0049] Example 5 Step 1, pure Mo powder with a purity of 3N5 and a grain size of 3.8 μm, Ni powder with a purity of 3N and a grain size of 2.4 μm, TiH2 powder with a purity of 3N and a grain size of 3.4 μm, rhenium powder with a purity of 4N and a grain size of 4 μm, and chromium powder with a grain size of 3.5 μm, which is a raw material of Cr, are prepared in accordance with the mass ratio of each element of the target material Mo:Ni:Ti:Re:Cr=60:20:16:2:2, where titanium is added by adding all of the titanium hydride powder to a part of the raw material molybdenum powder, and then reducing it in a hydrogen atmosphere at 800 ° C for 4 hours to obtain a molybdenum titanium alloy powder after reduction (the mass ratio of molybdenum element to titanium element in the molybdenum titanium alloy powder is 1:1), and adding the molybdenum titanium alloy powder to the remaining powder to be mixed. The next steps are the same as in Example 1. The crystal grain size of the obtained target material is 55 μm to 85 μm, and the crystal grain size is class 5. The tubular target material obtained in this example was free of cracks, and the yield was 100%.

[0050] Comparative Example 1 Except for the parameters of the extrusion molding process being different from those of Example 1, the rest of the preparation method is the same as that of Example 1. The pass deformation amount in the extrusion molding process of this comparative example was 30%. During the first pass of extrusion, surface cracks occurred on the blank, and during the second pass of extrusion, the blank split. The molybdenum alloy tube target material prepared in Comparative Example 1 has many cracks, and the cracked areas need to be removed by machining, which affects the utilization rate of the material.

[0051] Comparative Example 2 The preparation method was the same as in Example 1, except that rhenium element was not added. The molybdenum alloy tube target material prepared in Comparative Example 2 was difficult to deform, and serious cracks occurred during the first pass of extrusion, making it impossible to carry out the deformation treatment.

[0052] Comparative Example 3 In this comparative example, 140 kg of raw materials were prepared in accordance with the mass ratio of each element of the target material Mo:Ni:Ti:Re=69:15:10:6, and the remainder was the same as in Example 3. The molybdenum alloy tube target material prepared in Comparative Example 3 was significantly expensive, and the rhenium content was too high, which made deformation more difficult and caused cracks on the blank surface during the deformation process. At the same time, when the Re content is high, Re can form alloy phases with other elements, which will affect the subsequent plating effect. Some crystal grains exceed 100 μm in size, and the crystal grain uniformity is poor. The tubular target material of this comparative example had cracks, and the yield was 50%.

[0053] Comparative Example 4 The same as in Example 1, except for the extrusion start temperature of 1500°C. In Comparative Example 4, the extrusion start temperature was too high, so that the nickel in the blank melted locally, the surface was oxidized seriously, the thermoplasticity of the blank was deteriorated, and the blank cracked during extrusion.

[0054] Comparative Example 5 Similar to Example 1, the only difference between the extrusion process of this comparative example was that the heating and keeping temperature of each pass was reduced by 120° C. based on the heating and keeping temperature of the previous pass. The crystal grain size of the tubular target material obtained in this comparative example was 90 μm to 160 μm, and the crystal grain uniformity was poor. The tubular target material obtained in this example had cracks, and the yield was less than 50%.

[0055] Comparative Example 6 This is similar to Example 1, except that the annealing temperature was 1350°C. The molybdenum alloy tube target material prepared in Comparative Example 6 has large crystal grains, 120 μm to 200 μm, with crystal grain sizes of grades 1 to 3, with mixed crystals appearing and large crystal grains being present locally.

[0056] The present application has been described in detail above. Those skilled in the art can carry out the present application in a wide range under equivalent parameters, ratios and conditions without departing from the spirit and scope of the present application and without unnecessary experimentation. It should be understood that the present application provides specific embodiments, but the present application can be further improved. In short, according to the principles of the present application, the present application is intended to include any modification, use, or improvement to the present application, including modifications made using conventional techniques known in the art, beyond the scope disclosed in the present application. Some basic features can be applied according to the claims attached below.

Claims

1. A method for preparing a molybdenum alloy tube target material, comprising the steps of: A molybdenum alloy tube target material containing, in mass%, Ni: 10-30%, Ti: 5-25%, Re: 0.5-5%, M: 0-15%, where M is at least one of Cr, Zr, Ta, and Nb, said M being used in place of a part of Ti, the remainder being Mo and unavoidable impurities, and the mass% content of Mo in said molybdenum alloy tube target material being 50% or more, said molybdenum alloy tube target material comprising: a powder mixing process for weighing and uniformly mixing raw materials based on the mass fraction of each element in said molybdenum alloy tube target material to obtain a molybdenum alloy powder; a cold isostatic pressing step of placing the mixed powder in a mold and performing cold isostatic pressing to obtain a first blank; a hot isostatic pressing step of hot isostatically pressing the first blank to obtain a second blank; an extrusion molding step of extruding the second blank to obtain a third blank; Annealing the third blank; The extrusion molding is a temperature-reducing extrusion, the start temperature of the extrusion molding is 1100 to 1400°C, and the end temperature of the extrusion molding is 900 to 1100°C; Before each extrusion pass, the second blank is placed in a muffle furnace and heated in an air or argon gas atmosphere, the heat retention temperature is 1100 to 1400°C, the heat retention time is 30 to 120 minutes, and the extrusion passes are started after the blank is taken out of the furnace. Specifically, the temperature-reducing extrusion is such that the heating and keeping temperature before the extrusion of a subsequent pass is successively lower than the heating and keeping temperature before the extrusion of a previous pass, The heating and keeping temperature before extrusion of the subsequent pass is reduced by more than 0 to 100° C. based on the heating and keeping temperature of the previous pass, The extrusion deformation rate of each pass of the extrusion is 15 to 25%, and the total deformation amount of the extrusion molding is 40 to 80%, The annealing treatment is carried out in an argon gas atmosphere, the annealing temperature is 1000 to 1300°C, and the annealing temperature retention time is 60 to 120 minutes.

2. A method for preparing a molybdenum alloy tube target material comprising the steps of:

2. Shaping the first blank after the cold isostatic pressing; a cladding step in which the first blank after the shaping is placed in a sheath and evacuated to vacuum seal it before the hot isostatic pressing; removing the sheath of the second blank by machining after the hot isostatic pressing; and machining the third blank before the annealing treatment. The method for preparing a molybdenum alloy tube target material according to claim 1 .

3. The molybdenum alloy tube target material contains, in mass%, Ni: 10-30%, Ti: 5-25%, Re: 1-5%, and M: 0-5%, where M is at least one of Cr, Zr, Ta, and Nb, M is used in place of a portion of Ti, and the remainder is Mo and unavoidable impurities, and the mass% content of Mo in the molybdenum alloy tube target material is 60% or more. The method for preparing a molybdenum alloy tube target material according to claim 2 .

4. In the powder mixing step, the raw materials include molybdenum powder having a purity of 3N5 or more and an FSSS range of 2.5 to 4 μm, nickel powder having a purity of 3N or more and an FSSS range of 2 to 3 μm, a titanium source which is titanium powder or titanium hydride, the purity of the titanium powder being 3N or more and the FSSS range of the titanium powder being 2 to 4 μm, the purity of the titanium hydride being 2N or more and the FSSS range of the titanium hydride being 2 to 4 μm, and rhenium powder having a purity of 4N or more and an FSSS range of 2 to 4 μm. The method for preparing a molybdenum alloy tube target material according to claim 1 .

5. The titanium element in the molybdenum alloy tube target material is added in the form of molybdenum titanium alloy powder, and the molybdenum titanium alloy powder is obtained by mixing a part of the molybdenum powder in the raw material with titanium hydride powder and then reducing the mixture. The method for preparing a molybdenum alloy tube target material according to claim 4 .

6. The molybdenum-titanium mass ratio of the molybdenum-titanium alloy powder is 90:10 to 70:30; During the preparation of the molybdenum titanium alloy powder, the reduction treatment is carried out in a hydrogen atmosphere, the temperature of the reduction treatment is 500-900°C, and the time of the reduction treatment is 2-8h. The method for preparing a molybdenum alloy tube target material according to claim 5 .

7. The powder mixing is carried out in a ball mill, the BPR is 1:1 to 2:1, the ball mill is evacuated to a negative pressure and then filled with argon gas, the argon gas pressure in the ball mill is atmospheric pressure, the mixing time is 10h to 16h, and the rotation speed is 50 to 300r / min. In the cold isostatic pressing, the press pressure of the cold isostatic pressing is 150 to 200 MPa, and the pressure retention time is 5 to 20 minutes. The hot isostatic pressing temperature is 900°C to 980°C, the pressure is 100 to 170 MPa, and the pressure holding time is 2 to 5 hours.

7. A method for preparing a molybdenum alloy tube target material according to claim 1.

8. A molybdenum alloy tube target material prepared by the method of any one of claims 1 to 7.

9. The grain size of the molybdenum alloy tube target material is 100 μm or less, and the grain size is 4-5 grade; 9. The molybdenum alloy tube target material according to claim 8.

10. A molybdenum alloy tube target material is sputtered onto a main conductive layer of a laminated wiring film for electronic components to form a metal coating layer, and the electronic components are flat display, solar energy thin film or semiconductor device.

10. Application of the molybdenum alloy tube target material according to claim 8 or 9.

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