MoNiTi target material and preparation method thereof
Through the mixing and multi -segment heating heating pressure, the problem of uneven grain and impurities in the preparation of Moniti target preparation is solved. The Moniti target with high density, uniform grains is made, and the coating quality is improved.
Patent Information
- Application Number
- CN202411486451.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-23
- Publication Date
- 2025-01-28
AI Technical Summary
In the prior art, when preparing MoNiTi targets, the grain sizes vary and impurities are easily introduced, which affects the quality of the target material and the progress of the coating process.
The ball grinding mixed with the ball grinding mixing the molybdenum powder, titanium pellets and nickel powder in the protective atmosphere, and then under the vacuum atmosphere of heating and the heat pressure treatment, which is dense and uniform Moniti target.
The MONITI targets made have the excellent characteristics of high density, uniform and small grain tissue, uniform texture, and not easy to crack, which improves the coating quality.
Smart Images
Figure CN119372606A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of semiconductor materials and relates to a target material preparation method, in particular to a MoNiTi target material and a preparation method thereof. Background Art
[0002] As people's living standards continue to improve, the requirements for displays in daily life are also getting higher and higher. The coating quality of the display screen is the most critical factor among the many factors that affect the quality of the display. Therefore, the production equipment and raw material quality of the coating need to be further improved.
[0003] MoNiTi target has a high melting point, excellent stability in high temperature environment, good physical and chemical properties, and has higher strength and excellent thermal expansion coefficient compared to other target materials, making it widely used in the fields of electronics, medical treatment, and display. The common process for preparing MoNiTi target in the prior art is the melting and casting method. The grain size of the prepared MoNiTi target is different, and impurities are easily introduced during the preparation process, which affects the quality of the target, is not conducive to the subsequent coating process, and affects the coating quality. Summary of the invention
[0004] In view of the defects and shortcomings of the prior art, in a first aspect, the present invention provides a method for preparing a MoNiTi target; in a second aspect, the present invention provides a MoNiTi target.
[0005] In a first aspect, the present invention provides a method for preparing a MoNiTi target, comprising the following steps: Step 1, mixing molybdenum powder, titanium powder and nickel powder by ball milling under a protective atmosphere to obtain a mixed powder; Step 2, putting the mixed powder into a mold, pre-pressing it, and then releasing the pressure to obtain a rough blank; Step 3, roasting the rough embryo in a vacuum atmosphere, the roasting stage includes a heating stage and a heating and heat preservation stage; In the heating stage, the temperature is raised to 500~600℃ and then enters the heating and insulation stage; The heating and heat preservation stage includes three stages: the first stage, heating to 600-800°C for roasting; the second stage, heating to 850-1000°C for roasting; the third stage, heating to 1050-1150°C for roasting to obtain an intermediate product; Step 4, hot pressing the intermediate product at 1050-1150° C., and keeping the temperature and pressure for a certain period of time, and then cooling and demolding with the furnace to obtain the MoNiTi target material.
[0006] Preferably, in the mixed powder, titanium powder accounts for 10-20 wt %; nickel powder accounts for 10-20 wt %; and the remainder is molybdenum powder and inevitable impurities.
[0007] Preferably, molybdenum powder, titanium powder and nickel powder are all high-purity powders; the D50 of molybdenum powder is 5-8 μm; the D50 of titanium powder is 30-45 μm; and the D50 of nickel powder is 8-10 μm.
[0008] Preferably, in step 1, the ball milling medium is zirconia ball, and the ball-to-material ratio is 1:1.5-2.5; the size of the ball milling medium is 10-20 mm.
[0009] Preferably, in step 1, the ball milling speed is 300-400 r / min; and the ball milling time is 16-28 h.
[0010] Preferably, in step 1, the protective gas providing the protective atmosphere is any one or both of argon and nitrogen.
[0011] Preferably, in step 2, the pressure increase rate during pre-pressing is 0.1-0.3 MPa / min; the pre-pressing pressure is 6-10 MPa; and the pressure holding time is 10-15 min.
[0012] Preferably, in step 3, the pressure of the vacuum atmosphere is less than 5 Pa.
[0013] Preferably, in step 3, the heating rate in the heating stage is 8-10° C. / min.
[0014] Preferably, in the heating and insulation stages of step 3, in the first stage, the temperature is increased to 600-800°C at a heating rate of 5-8°C / min; in the second stage, the temperature is increased to 850-1000°C at a heating rate of 5-6°C / min; in the third stage, the temperature is increased to 1050-1150°C at a heating rate of 3-5°C / min.
[0015] More preferably, in the heating and insulation stage, the calcination time of the three stages is 30 to 60 minutes.
[0016] Preferably, in step 4, a staged pressurization method is adopted during hot pressing, firstly pressurizing to 35-40 MPa at a rate of 0.25-0.35 MPa / min, and then maintaining the temperature and pressure at 35-40 MPa for 90-150 min.
[0017] In a second aspect, the present invention provides a MoNiTi target material prepared by the above preparation method.
[0018] Compared with the prior art, the present invention has the following obvious beneficial effects: The invention provides a method for preparing a MoTi target material. The prepared target material has the excellent characteristics of high density, uniform and fine grain structure, uniform texture and not easy to crack. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1This is a SEM image of the MoNiTi target prepared in Example 1 of the present invention. DETAILED DESCRIPTION
[0020] The present invention provides the following specific technical solutions.
[0021] In a first aspect, the present invention provides a method for preparing a MoNiTi target, comprising the following steps: Step 1, mixing molybdenum powder, titanium powder and nickel powder by ball milling under a protective atmosphere to obtain a mixed powder; Step 2, putting the mixed powder into a mold, pre-pressing it, and then releasing the pressure to obtain a rough blank; Step 3, roasting the rough embryo in a vacuum atmosphere, the roasting stage includes a heating stage and a heating and heat preservation stage; In the heating stage, the temperature is raised to 500~600℃ and then enters the heating and insulation stage; The heating and heat preservation stage includes three stages: the first stage, heating to 600-800°C for roasting; the second stage, heating to 850-1000°C for roasting; the third stage, heating to 1050-1150°C for roasting to obtain an intermediate product; Step 4, hot pressing the intermediate product at 1050-1150° C., and keeping the temperature and pressure for a certain period of time, and then cooling and demolding with the furnace to obtain the MoNiTi target material.
[0022] The inventors have found through research that titanium and nickel are doped into the target material, and titanium and nickel are dissolved in molybdenum to play a solid solution strengthening role, and nickel can improve the low-temperature plasticity of molybdenum and increase the recrystallization temperature of molybdenum. By adjusting the roasting process, the MoTi target material can be optimized to have the excellent characteristics of high density, high purity, fine grain structure, good conductivity, good sputtering performance, and not easy to crack.
[0023] Preferably, in the mixed powder, titanium powder accounts for 10-20 wt %; nickel powder accounts for 10-20 wt %; and the remainder is molybdenum powder and inevitable impurities.
[0024] Preferably, molybdenum powder, titanium powder and nickel powder are all high-purity powders; the D50 of molybdenum powder is 5-8 μm; the D50 of titanium powder is 30-45 μm; and the D50 of nickel powder is 8-10 μm.
[0025] Preferably, in step 1, the ball milling medium is zirconia ball, and the ball-to-material ratio is 1:1.5-2.5; the size of the ball milling medium is 10-20 mm.
[0026] Preferably, in step 3, the pressure of the vacuum atmosphere is less than 5 Pa.
[0027] Preferably, in the heating stage of step 3, the heating rate is 8-10°C / min.
[0028] Preferably, in the heating and insulation stages of step 3, in the first stage, the temperature is increased to 600-800°C at a heating rate of 5-8°C / min; in the second stage, the temperature is increased to 850-1000°C at a heating rate of 5-6°C / min; in the third stage, the temperature is increased to 1050-1150°C at a heating rate of 3-5°C / min.
[0029] The inventors have found through research that pre-burning the target material through staged heating in the first and second stages is conducive to a uniform temperature field, homogenizing the target material, and converting the impurity elements in the target material into waste gas for discharge; the third stage is conducive to the reaction of molybdenum, nickel and titanium elements in the target material, thereby producing a target material with uniform grains and low impurity content, thereby improving the quality of the target material.
[0030] Further preferably, the calcination time in the three heating and insulation stages of step 3 is 30 to 60 minutes.
[0031] Preferably, in step 4, a staged pressurization method is adopted during hot pressing, firstly pressurizing to 35-40 MPa at a rate of 0.25-0.35 MPa / min, and then maintaining the temperature and pressure at 35-40 MPa for 90-150 min.
[0032] By applying pressure in stages, on the one hand, the requirements for hot pressing equipment are reduced, and the practicality of the preparation method proposed by the present invention is improved; on the other hand, the target material is slowly pressed in the early stage of target sintering, so that the sintering neck can fully grow and combine, the densification rate is fast, and the pore volume and pore amount of the target material are reduced at the same time; in the heat preservation and pressure holding stage, it is beneficial to improve the density of the target material and refine the grain structure in the target material. The combination of the two stages of staged pressure application is beneficial to obtain a target material with high density and uniform and fine grain structure.
[0033] In a second aspect, the present invention provides a MoNiTi target material prepared by the above preparation method.
[0034] In order to make the technical problems, technical solutions and technical advantages to be solved by the present invention more clear, they will be described in detail below with reference to specific examples, but the protection scope of the present invention is not limited to the following specific embodiments.
[0035] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.
[0036] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.
[0037] Embodiment 1: A method for preparing a MoNiTi target comprises the following steps: Step 1, pour molybdenum powder, titanium powder and nickel powder into a ball mill and mix them by ball milling under argon atmosphere, wherein the molybdenum powder is 70wt%, the titanium powder is 15wt%, and the nickel powder is 15wt%; the ball-to-material ratio is 1:2, the size of the ball milling medium is 10mm, the ball milling speed is 350r / min, and the ball milling time is 22h to obtain a mixed powder.
[0038] Step 2: pre-press the mixed powder into a mold at a pressure increasing rate of 0.2 MPa / min to a pressure of 6 MPa, maintain the pressure for 10 minutes and then release it to obtain a rough blank.
[0039] Step 3, transfer the rough blank and the mold to the hot pressing furnace, maintain the vacuum pressure in the hot pressing furnace below 5Pa, enter the heating stage, the heating rate is 10℃ / min, the temperature is raised to 500℃, and then enter the heating and heat preservation stage. In the first stage, the heating rate is adjusted to 7℃ / min to 800℃, and the temperature is kept for 30min before entering the second stage, the heating rate is adjusted to 5℃ / min to 1000℃, and the temperature is kept for 30min before entering the third stage, the heating rate is adjusted to 3℃ / min to 1150℃, and the temperature is kept for 30min; Step 4, after the insulation is completed, the pressurization rate is adjusted to 0.35 MPa / min and the pressure is increased to 40 MPa; the temperature and pressure are maintained at 1150° C. for 120 minutes.
[0040] Step 5, after the heat preservation and pressure preservation are completed, the temperature is lowered to 200° C. with the furnace, and the mold is demolded to obtain the MoNiTi target.
[0041] Embodiment 2: A method for preparing a MoNiTi target comprises the following steps: Step 1, pour molybdenum powder, titanium powder and nickel powder into a ball mill and mix them under argon atmosphere, wherein the molybdenum powder is 80wt%, the titanium powder is 10wt%, and the nickel powder is 10wt%; the ball-to-material ratio is 1:1.5, the size of the ball milling medium is 10mm, the ball milling speed is 300r / min, and the ball milling time is 16h to obtain a mixed powder.
[0042] Step 2: pre-press the mixed powder into a mold at a pressure increasing rate of 0.1 MPa / min to a pressure of 8 MPa, maintain the pressure for 12 minutes and then release it to obtain a rough blank.
[0043] Step 3, transfer the rough blank and the mold to the hot pressing furnace, maintain the vacuum pressure in the hot pressing furnace below 5Pa, enter the heating stage, the heating rate is 8℃ / min, the temperature is raised to 550℃, and then the temperature is raised to the insulation stage. In the first stage, the heating rate is adjusted to 6℃ / min to 600℃, and the temperature is kept for 45min before entering the second stage, and the heating rate is adjusted to 5℃ / min to 900℃. After keeping warm for 45min, enter the third stage, adjust the heating rate to 4℃ / min to 1050℃, and keep warm for 45min; Step 4, after the insulation is completed, the pressurization rate is adjusted to 0.25 MPa / min and the pressure is increased to 35 MPa; the heat and pressure are maintained at 1150° C. for 60 minutes.
[0044] Step 5, after the heat preservation and pressure preservation are completed, the temperature is lowered to 200° C. with the furnace, and the mold is demolded to obtain the MoNiTi target.
[0045] Embodiment 3: A method for preparing a MoNiTi target comprises the following steps: Step 1, pour molybdenum powder, titanium powder and nickel powder into a ball mill and mix them under argon atmosphere, wherein the molybdenum powder is 60wt%, the titanium powder is 20wt%, and the nickel powder is 20wt%; the ball-to-material ratio is 1:2.5, the size of the ball milling medium is 10mm, the ball milling speed is 400r / min, and the ball milling time is 28h to obtain a mixed powder.
[0046] Step 2: Place the mixed powder into a mold for pre-compression at a rate of 0.3 MPa / min and increase the pressure to 8 MPa. Maintain the pressure for 15 minutes and then release it to obtain a rough blank.
[0047] Step 3, transfer the rough blank and the mold to the hot pressing furnace, maintain the vacuum pressure in the hot pressing furnace below 5Pa, enter the heating stage, the heating rate is 9℃ / min, the temperature is raised to 600℃, and then the temperature is raised to the heat preservation stage. In the first stage, the heating rate is adjusted to 8℃ / min to 700℃, and the temperature is kept for 30min before entering the second stage, and the heating rate is adjusted to 6℃ / min to 950℃. After keeping warm for 30min, enter the third stage, adjust the heating rate to 4℃ / min to 1100℃, and keep warm for 30min; Step 4: After the heat preservation is completed, the pressurization rate is adjusted to 0.3 MPa / min and the pressure is increased to 38 MPa; the heat and pressure are maintained at 1100° C. for 150 minutes.
[0048] Step 5: After the heat preservation and pressure preservation are completed, the temperature is lowered to 200°C with the furnace, and the mold is removed to obtain the MoNiTi target. Comparative Example 1: The difference from Example 1 is that in step 3, the rough blank and the mold are transferred to a hot pressing furnace, the vacuum pressure in the hot pressing furnace is maintained below 5 Pa, the temperature is increased to 1150° C. at a heating rate of 8° C. / min, and the temperature is kept for 30 minutes.
[0049] Comparative Example 2: The difference from Example 1 is that in step 3, the rough blank and the mold are transferred to the hot pressing furnace, the vacuum pressure in the hot pressing furnace is maintained below 5 Pa, and the heating stage is entered. The heating rate is 10°C / min and the temperature is increased to 500°C. Then the roasting stage is entered, and the heating rate is adjusted to 7°C / min to increase the temperature to 1150°C and keep warm for 30 minutes.
[0050] Comparative Example 3: The difference from Example 1 is that, in step 3, the rough blank and the mold are transferred to the hot pressing furnace, the vacuum pressure in the hot pressing furnace is maintained below 5 Pa, and the heating stage is entered. The heating rate is 10°C / min and the temperature is raised to 500°C before entering the roasting stage. The heating rate is adjusted to 7°C / min and the temperature is raised to 800°C. After keeping the temperature for 30 minutes, the second stage is entered, the heating rate is adjusted to 5°C / min and the temperature is raised to 1000°C. After keeping the temperature for 30 minutes, the third stage is entered, the heating rate is adjusted to 3°C / min and the temperature is raised to 1020°C, and the temperature is kept for 30 minutes.
[0051] Step 4, after the insulation is completed, the pressurization rate is adjusted to 0.35 MPa / min and the pressure is increased to 40 MPa; the heat and pressure are maintained at 1020° C. for 120 minutes.
[0052] Comparative Example 4: The difference from Example 1 is that, in step 3, the rough blank and the mold are transferred to the hot pressing furnace, the vacuum pressure in the hot pressing furnace is maintained below 5 Pa, and the heating stage is entered. The heating rate is 10°C / min and the temperature is raised to 500°C, and then the roasting stage is entered. The heating rate is adjusted to 7°C / min and the temperature is raised to 800°C. After keeping the temperature for 30 minutes, the second stage is entered, the heating rate is adjusted to 5°C / min and the temperature is raised to 1000°C. After keeping the temperature for 30 minutes, the third stage is entered, the heating rate is adjusted to 3°C / min and the temperature is raised to 1200°C, and the temperature is kept for 30 minutes.
[0053] Step 4, after the insulation is completed, the pressurization rate is adjusted to 0.35 MPa / min and the pressure is increased to 40 MPa; the heat and pressure are maintained at 1200° C. for 120 minutes.
[0054] The target materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to relative density tests, wherein the relative density was directly tested using the traditional Archimedean method.
[0055] It can be seen from Table 1 that the density of the target material prepared by the preparation method provided by the present invention is greater than 99%, and the purity is greater than 99.95%.
[0056] By comparing the target materials obtained in Example 1 and Comparative Example 1, it can be seen that the multi-stage heating process provided by the present invention can improve the density of the target material, and the obtained target material has no hole defects and finer grains, which is beneficial to improving the coating quality.
[0057] Comparing the target materials obtained in Example 1 and Comparative Example 2, it can be further proved that the multi-stage temperature increase process provided by the present invention can improve the density of the target material, and the obtained grains are also finer.
[0058] Comparing the target materials obtained in Example 1 with those obtained in Comparative Examples 3 and 4, it can be further proved that the target material obtained by the multi-stage heating process provided by the present invention has a higher density, no hole defects, and the obtained grains are also finer.
[0059] Comparing the targets prepared in Example 1 with those prepared in Comparative Examples 1 and 2, it can be proved that the final target material calcining temperature proposed in the present invention is beneficial to improving the density and morphology of the target material.
[0060] Figure 1 This is a SEM image of the target material prepared in Example 1 of the present invention. Figure 1 The grayish-white area is molybdenum grains, and the grayish-black area is titanium grains and nickel grains. Figure 1 It can be seen that the Mo phase, Ti phase and Ni phase of the MoTi alloy target blank are uniformly and densely distributed in the microscopic structure without hole defects, which proves that the preparation method provided by the present invention can produce a MoNiTi target material with high density, uniform and fine grain structure, uniform texture and not easy to crack.
[0061] The embodiments described above are only preferred specific implementation modes of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and concepts of the present invention within the technical scope of the present invention, which should be covered by the protection scope of the present invention.
Claims
1. A method for preparing a MoNiTi target, characterized in that: The steps include: Step 1, mixing molybdenum powder, titanium powder and nickel powder by ball milling under a protective atmosphere to obtain a mixed powder; Step 2, putting the mixed powder into a mold, pre-pressing it, and then releasing the pressure to obtain a rough blank; Step 3, roasting the rough embryo in a vacuum atmosphere, the roasting stage includes a heating stage and a heating and heat preservation stage; In the heating stage, the temperature is raised to 500~600℃ and then enters the heating and insulation stage; The heating and heat preservation stage includes three stages: the first stage, heating to 600-800°C for roasting; the second stage, heating to 850-1000°C for roasting; the third stage, heating to 1050-1150°C for roasting to obtain an intermediate product; Step 4, hot pressing the intermediate product at 1050-1150° C., and keeping the temperature and pressure for a certain period of time, and then cooling and demolding with the furnace to obtain the MoNiTi target material.
2. The method for preparing a MoNiTi target material according to claim 1, wherein: In the mixed powder, titanium powder accounts for 10-20wt%; nickel powder accounts for 10-20wt%; and the remainder is molybdenum powder and inevitable impurities.
3. The method for preparing a MoNiTi target material according to claim 1, wherein: In step 2, the pressure increase rate during pre-pressing is 0.1~0.3MPa / min; the pre-pressing pressure is 6~10MPa; and the pressure holding time is 10~15min.
4. The method for preparing a MoNiTi target material according to claim 1, wherein: In step 3, the heating rate in the heating stage is 8-10°C / min; in the heating and insulation stage, the calcination time of the three stages is 30-60min.
5. The method for preparing a MoNiTi target according to claim 1, characterized in that: In the heating and insulation stages of step 3, in the first stage, the temperature is increased to 600-800°C at a heating rate of 5-8°C / min; in the second stage, the temperature is increased to 850-1000°C at a heating rate of 5-6°C / min; in the third stage, the temperature is increased to 1050-1150°C at a heating rate of 3-5°C / min.
6. The method for preparing a MoNiTi target material according to claim 1, characterized in that: In step 4, a staged pressurization method is adopted during hot pressing, firstly pressurizing to 35-40 MPa at a rate of 0.25-0.35 MPa / min, and then maintaining the temperature and pressure at 35-40 MPa for 90-150 min.
7. The method for preparing a MoNiTi target according to claim 1, characterized in that: In step 1, molybdenum powder, titanium powder and nickel powder are all high-purity powders; the D50 of molybdenum powder is 5-8 μm; the D50 of titanium powder is 30-45 μm; and the D50 of nickel powder is 8-10 μm.
8. The method for preparing a MoNiTi target material according to claim 7, characterized in that: In step 1, the ball milling medium is zirconia ball, the ball-to-material ratio is 1:1.5-2.5; the size of the ball milling medium is 10-20 mm; the ball milling speed is 300-400 r / min; and the ball milling time is 16-28 h.
9. The method for preparing a MoNiTi target material according to claim 1, characterized in that: In step 1, the protective gas providing the protective atmosphere is any one or both of argon and nitrogen.
10. A MoNiTi target material, characterized in that: Prepared by the preparation method described in any one of claims 1 to 9.