CN112941473A - MoTiNi alloy target material and preparation method thereof - Google Patents
MoTiNi alloy target material and preparation method thereof Download PDFInfo
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- CN112941473A CN112941473A CN202110119591.4A CN202110119591A CN112941473A CN 112941473 A CN112941473 A CN 112941473A CN 202110119591 A CN202110119591 A CN 202110119591A CN 112941473 A CN112941473 A CN 112941473A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
Abstract
The invention provides a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target comprises, by atomic percentage, 60-70 at% of Mo, 30-40 at% of Ti and Ni; the Ti and the Ni exist in the form of TiNi solid solution; the atomic ratio of Ti to Ni is (2.75-6) to 1; the length of the MoTiNi alloy target is not less than 2 m. The preparation method comprises the following steps: prefabricating TiNi alloy powder; and mixing the obtained TiNi alloy powder and Mo powder, and then sequentially carrying out cold isostatic pressing, processing, splicing, degassing and hot isostatic pressing to obtain the large-size MoTiNi alloy target. According to the preparation method, the MoTiNi alloy target material with large size, high density and high purity is obtained by prefabricating TiNi alloy powder and optimizing the traditional process, and the preparation method has a good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of semiconductor manufacturing, and particularly relates to a MoTiNi alloy target and a preparation method thereof.
Background
With the enlargement of the size of the flat display panel and the pursuit of high efficiency of the flat display panel production, the requirements on the purity, the density, the grain size, the tissue uniformity and the size of the target material are higher and higher. The pure molybdenum target material is only 1/2 of chromium due to specific resistance and film stress, has good performance, and is mainly applied to film electrodes or film wiring materials of flat panel displays such as LCD, PDP and the like. However, because of the problems of corrosion resistance, compactness and the like of a film sputtered from a pure molybdenum target, many researchers add metals such as Ti, Ni and the like into molybdenum so as to improve the problems of corrosion resistance, compactness, heat resistance and the like of the target. However, since the Ni metal is a magnetic material, which affects normal sputtering, there is no method for removing the magnetism of the Ni metal, so that it is of great significance to develop a large-size, high-density, high-purity and non-magnetic MoTiNi alloy target material.
CN111304607A discloses a method for manufacturing a molybdenum-titanium alloy target, which comprises the following steps: selecting molybdenum powder and titanium powder, wherein the average particle size of the molybdenum powder is less than 20 micrometers, and the average particle size of the titanium powder is 10-300 micrometers; mixing molybdenum powder and titanium powder under the protection of inert gas; carrying out cold isostatic pressing on the mixed powder; performing pressure sintering on the formed molybdenum-titanium mixed powder to obtain a molybdenum-titanium pressing ingot; the pressure in the pressure sintering process is 75-300 MPa, the temperature is 650-1000 ℃, and the time is 2-12 hours; rolling the molybdenum-titanium pressed ingot to reach the required size; and carrying out heat treatment on the rolled molybdenum-titanium plate to form a recrystallization structure required by target sputtering, thus obtaining the target plate. The method only improves the performance of the target material by adding metal Ti, and has limited effect; the size of the target material is enlarged by rolling, so that the cost is high, and the method is not suitable for large-scale production.
CN104532201A discloses a method for preparing a molybdenum-titanium alloy sputtering target plate, which comprises the following steps: filling molybdenum powder and titanium powder into a three-dimensional mixer, and filling argon gas to fully mix the two kinds of powder in an argon gas atmosphere to obtain molybdenum-titanium alloy powder; putting the molybdenum-titanium alloy powder into a die for cold isostatic pressing to obtain a preformed blank; and (3) vacuumizing the preformed blank, sintering the preformed blank in a helium atmosphere to obtain a sintered blank, and finally machining the sintered blank to obtain the composite material. The method prepares the molybdenum-titanium alloy target material through common equipment, has limited size and is difficult to meet the requirements of modern production.
In summary, how to provide a large-size, high-density, high-purity and non-magnetic MoTiNi alloy target and a preparation method thereof become problems to be solved at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target is added with Ti and Ni, and the content of the Ti and Ni is controlled to effectively improve the corrosion resistance, the density and the heat resistance of the Mo target; the preparation method optimizes the traditional process flow to prepare the large-size, high-density, high-purity and non-magnetic MoTiNi alloy target material, meets the performance and size requirements of the target material for the LCD, and has good industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a large-size MoTiNi alloy target, which comprises, in atomic percentage, 60 to 70 at% of Mo, such as 60 at%, 62 at%, 64 at%, 66 at%, 68 at%, or 70 at%; ti and Ni are 30 to 40 at%, for example, 30 at%, 32 at%, 34 at%, 36 at%, 38 at% or 40 at%, and the selection of the above-mentioned contents is not limited to the values listed, and other values not listed in the respective numerical ranges are also applicable.
The Ti and Ni exist in the form of TiNi solid solution.
The atomic ratio of Ti to Ni is (2.75 to 6):1, for example, 2.75:1, 3:1, 3.5:1, 4:1, 5:1 or 6:1, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable.
The length of the MoTiNi alloy target is not less than 2m, such as 2m, 2.2m, 2.4m, 2.6m, 2.8m or 3m, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
According to the invention, the corrosion resistance, the density and the heat resistance of the Mo target are effectively improved by adding Ti and Ni and controlling the content of the Ti and the Ni; also, the problem that the target material shows magnetism due to the non-uniformity of the Ni powder in the Mo alloy is avoided by making Ti and Ni into a TiNi solid solution; meanwhile, the method breaks through the limitation of the existing equipment, prepares the MoTiNi alloy target material with the length not less than 2m, meets the performance and size requirements of the target material for the LCD, and has better industrial application prospect.
On the other hand, the invention provides a preparation method of the large-size MoTiNi alloy target, which comprises the following steps:
(1) mixing Ti powder and Ni powder, and then carrying out gas atomization to obtain TiNi alloy powder;
(2) mixing the TiNi alloy powder obtained in the step (1) with Mo powder, and then carrying out cold isostatic pressing to obtain cold isostatic blanks;
(3) processing the cold blank obtained in the step (2), and then sequentially splicing and degassing to obtain a degassed blank;
(4) and (4) carrying out hot isostatic pressing on the degassed blank obtained in the step (3) to obtain the large-size MoTiNi alloy target.
According to the preparation method, the TiNi alloy powder is prefabricated, so that the Ni powder is completely dissolved in the Ti structure to form a TiNi solid solution, and the inherent magnetism of Ni is eliminated; then fully mixing the powder with Mo powder to obtain uniform mixed powder of MoTiNi, carrying out cold isostatic pressing on the mixed powder to obtain a cold equal blank with the growth degree of not more than 1m, and finally sintering the cold equal blank in hot isostatic pressing equipment to form a MoTiNi alloy target material with the size length of more than 2m and uniform and nonmagnetic crystal grains; the preparation method is simple in process flow, and the prepared MoTiNi alloy target is high in density and purity and has a good industrial application prospect.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
In a preferred embodiment of the present invention, the atomic ratio of the Ti powder to the Ni powder in the step (1) is (2.75 to 6):1, for example, 2.75:1, 3:1, 3.5:1, 4:1, 5:1, or 6:1, but the present invention is not limited to the above-mentioned numerical values, and other numerical values not listed in the numerical value range are also applicable.
In the invention, the content of the TiNi alloy powder and the TiNi alloy powder needs to be controlled in the process of preparing the TiNi alloy powder. If the content of the Ni powder is too high, Ni cannot be completely dissolved in Ti, so that residual simple substance Ni exists, and the material has magnetism; if the content of the Ni powder is too low, the obtained MoTiNi sputtering target material has low corrosion resistance and cannot meet the use requirement.
Preferably, the TiNi alloy powder of step (1) is present in the form of a TiNi solid solution.
Preferably, the TiNi alloy powder of step (1) has a maximum particle size of not more than 100 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm, but is not limited to the recited values, and other values not recited in this range are also applicable.
In the present invention, the grain size of the TiNi alloy powder needs to be controlled. If the particle size is too large, the sintering cannot be compact, and more pores exist in the target material, so that the sputtering use is influenced;
as a preferable embodiment of the present invention, the particle size of the Mo powder in the step (2) is 5 to 8 μm, for example, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm or 8 μm, but the particle size is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the Mo powder and the TiNi alloy powder in step (2) are 60 to 70 at%, such as 60 at%, 62 at%, 64 at%, 66 at%, 68 at%, 70 at%, or the like, respectively, in atomic percentage; 30 to 40 at%, for example, 30 at%, 32 at%, 34 at%, 36 at%, 38 at% or 40 at%, and the selection of the above-mentioned content is not limited to the values listed, and other values not listed in the respective numerical ranges are also applicable.
Preferably, the mixing in the step (2) is performed by a V-shaped powder mixer.
Preferably, the mixing of step (2) is carried out under a protective atmosphere.
Preferably, the protective atmosphere comprises an inert gas and/or nitrogen.
Preferably, the mixing time in step (2) is 24-48 h, such as 24h, 28h, 32h, 36h, 40h, 44h or 48h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, Mo powder and TiNi alloy powder are mixed under protective atmosphere to prevent oxidation and introduce impurities to influence the performance of the final target material.
As a preferable technical scheme of the invention, the mixed powder is filled into a rubber sleeve after the mixing in the step (2).
Preferably, the cold isostatic pressing in step (2) has a pressure of 190 to 250MPa, such as 190MPa, 200MPa, 210MPa, 220MPa, 230MPa, 240MPa or 250MPa, but not limited to the values listed, and other values not listed within this range are equally applicable.
Preferably, the cold isostatic pressing in step (2) is performed for 5-15 min, such as 5min, 7min, 9min, 11min, 13min or 15min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferable technical solution of the present invention, the machining mode in the step (3) is milling.
Preferably, the cold blank processed in the step (3) is a cuboid.
Preferably, the width and height of the cuboid are independently not more than 600mm, for example 1mm, 5mm, 10mm, 50mm, 100mm, 150mm, 200mm, 300mm, 400mm, 500mm or 600mm, etc., but are not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the length of the rectangular parallelepiped is not more than 1m, for example 0.1m, 0.2m, 0.3m, 0.4m, 0.5m, 0.6m, 0.7m, 0.8m, 0.9m or 1m, but is not limited to the enumerated values, and other unrecited values within the numerical range are equally applicable.
In a preferred embodiment of the present invention, the length after splicing in step (3) is not less than 2m, for example, 2m, 2.2m, 2.3m, 2.4m, 2.5m, 2.6m, 2.7m, 2.8m, 2.9m or 3m, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the spliced cold blank in the step (3) is placed in a stainless steel sheath.
In the invention, the LCD target is mostly strip-shaped, and the processed cold equal blanks are spliced along the length direction, so that the length of the spliced target is not less than 2 m; meanwhile, the splicing can be carried out along the width or the height, and the width after the splicing is not required.
In the invention, the spliced cold equal blank is put into a stainless steel sheath, and the stainless steel sheath is welded well by argon arc welding; the stainless steel sheath is provided with a thin steel pipe which is communicated with the inside and the outside and is connected with the molecular pump for degassing operation.
Preferably, the degassing of step (3) is performed using a molecular pump.
Preferably, the degassing temperature in step (3) is 450 to 700 ℃, for example 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the absolute pressure in the degassed stainless steel jacket of step (3) is less than 3X 10-3Pa, e.g. 4X 10-4Pa、8×10-4Pa、10-4Pa、10-3Pa or 2X 10-3Pa, but is not limited to the recited values, and other values within the range are equally applicable.
In the present invention, the absolute pressure in the stainless steel jacket after degassing needs to be controlled. If the absolute pressure is too high, the degassing in the sheath is incomplete, air residue exists and the like, so that the material is oxidized in the sintering process, and the use is influenced.
In a preferred embodiment of the present invention, the hot isostatic pressing temperature in step (4) is 1100 to 1400 ℃, for example 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ or 1400 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable.
In the present invention, the temperature of hot isostatic pressing needs to be controlled. If the temperature is too high, the sheath material is easy to melt due to the failure of withstanding high temperature, great potential safety hazard is generated to equipment, and the machining performance of the target material is reduced due to overburning, so that the subsequent processing is difficult; if the temperature is too low, the target material cannot be compact, the internal pores of the material are large, and the diffusion layer at the splicing part is shallow, so that the splicing strength of the material is low, and the material is easy to break.
Preferably, the hot isostatic pressing in step (4) is performed at a pressure of 140 to 180MPa, such as 140MPa, 145MPa, 150MPa, 155MPa, 160MPa, 165MPa, 170MPa, 175MPa or 180MPa, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the hot isostatic pressing in step (4) is carried out for 4-6 hours, such as 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature of the furnace is reduced after the hot isostatic pressing in step (4).
Preferably, the temperature is reduced to room temperature.
And (3) as a preferable technical scheme of the invention, removing the stainless steel sheath after the hot isostatic pressing in the step (4).
Preferably, the stainless steel sheath is removed by milling.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing Ti powder and Ni powder according to the atomic ratio of (2.75-6) to 1, and performing gas atomization after mixing to obtain TiNi alloy powder with the maximum particle size not exceeding 100 mu m;
(2) mixing 30-40 at% TiNi alloy powder obtained in the step (1) and 60-70 at% Mo powder with the particle size of 5-8 mu m for 24-48 h under a protective atmosphere, then putting into a rubber sleeve, and then carrying out cold isostatic pressing for 5-15 min under the condition of 190-250 MPa to obtain a cold blank;
(3) machining the cold blank obtained in the step (2) into a blank with the width and the height of no more than 600mm and the length of no more than 1m independently by millingA cuboid, splicing the processed cold blanks into spliced blanks with the length not less than 2m, placing the spliced blanks into a stainless steel sheath, degassing at 450-700 ℃, wherein the absolute pressure in the stainless steel sheath after degassing is less than 3 multiplied by 10-3Pa, obtaining a degassed blank;
(4) and (4) carrying out hot isostatic pressing on the degassed blank obtained in the step (3) for 4-6 h at 1100-1400 ℃ and 140-180 MPa, then cooling to room temperature along with the furnace, and removing the stainless steel sheath to obtain the large-size MoTiNi alloy target.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the MoTiNi alloy target material, the corrosion resistance, the density and the heat resistance of the Mo target material are effectively improved by adding Ti and Ni; moreover, the purity and the density of the obtained MoTiNi alloy target are respectively over 99.95 percent and over 99.5 percent by further controlling the contents of Ti powder and Ni powder and the temperature of hot isostatic pressing;
(2) according to the preparation method, the inherent magnetism of Ni is eliminated by prefabricating TiNi alloy powder, and the large-size MoTiNi alloy target with the length of not less than 2m is prepared by the processes of cold isostatic pressing, splicing, hot isostatic pressing and the like, so that the limitation of the existing equipment is broken through, the use requirement of the LCD target is met, and the preparation method has a good industrial application prospect.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention provides a large-size MoTiNi alloy target material which comprises, by atomic percentage, 60-70 at% of Mo, 30-40 at% of Ti and Ni;
the Ti and the Ni exist in the form of TiNi solid solution;
the atomic ratio of Ti to Ni is (2.75-6) to 1;
the length of the MoTiNi alloy target is not less than 2 m.
The preparation method comprises the following steps:
(1) mixing Ti powder and Ni powder, and then carrying out gas atomization to obtain TiNi alloy powder;
(2) mixing the TiNi alloy powder obtained in the step (1) with Mo powder, and then carrying out cold isostatic pressing to obtain cold isostatic blanks;
(3) processing the cold blank obtained in the step (2), and then sequentially splicing and degassing to obtain a degassed blank;
(4) and (4) carrying out hot isostatic pressing on the degassed blank obtained in the step (3) to obtain the large-size MoTiNi alloy target.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target comprises 70 at% of Mo, 30 at% of Ti and Ni in terms of atomic percentage;
the Ti and the Ni exist in the form of TiNi solid solution;
the atomic ratio of Ti to Ni is 2.75: 1;
the length of the MoTiNi alloy target is 2 m.
The preparation method of the MoTiNi alloy target comprises the following steps:
(1) mixing Ti powder and Ni powder according to an atomic ratio of 2.75:1, and performing gas atomization after mixing to obtain TiNi alloy powder with the maximum particle size of 90 mu m;
(2) mixing the TiNi alloy powder with the grain size of 30at percent and Mo powder with the grain size of 5 mu m of 30at percent obtained in the step (1) for 24h under the argon atmosphere, then putting the mixture into a rubber sleeve, and then carrying out cold isostatic pressing for 15min under the condition of 190MPa to obtain a cold isostatic blank;
(3) processing the cold equal blanks obtained in the step (2) into cuboids with the width and the height of 200mm and the length of 1m by milling, splicing 2 processed cold equal blanks into spliced blanks with the length of 2m, placing the spliced blanks into a stainless steel sheath, degassing at 450 ℃, wherein the absolute pressure in the stainless steel sheath after degassing is 2 multiplied by 10-3Pa, obtaining a productGas blank;
(4) and (4) carrying out hot isostatic pressing on the degassed blank obtained in the step (3) for 5h at 1100 ℃ and 170MPa, then cooling to room temperature along with the furnace, and removing the stainless steel sheath to obtain the large-size MoTiNi alloy target.
Example 2:
the embodiment provides a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target comprises, by atomic percentage, 60 at% of Mo, 40 at% of Ti and 40 at% of Ni;
the Ti and the Ni exist in the form of TiNi solid solution;
the atomic ratio of Ti to Ni is 3: 1;
the length of the MoTiNi alloy target is 2.4 m.
The preparation method of the MoTiNi alloy target comprises the following steps:
(1) mixing Ti powder and Ni powder according to an atomic ratio of 3:1, and performing gas atomization after mixing to obtain TiNi alloy powder with the maximum particle size of 95 microns;
(2) mixing the TiNi alloy powder with the concentration of 40 at% obtained in the step (1) and Mo powder with the particle size of 8 mu m with the concentration of 60 at% in an argon atmosphere for 48h, then putting the mixture into a rubber sleeve, and then carrying out cold isostatic pressing for 5min under the condition of 250MPa to obtain a cold isostatic blank;
(3) processing the cold equal blanks obtained in the step (2) into cuboids with the width and the height of 600mm and the length of 0.8m by milling, splicing 6 processed cold equal blanks into spliced blanks with the length of 2.4m and the width of 1200mm, placing the spliced blanks into a stainless steel sheath, degassing at 700 ℃, and enabling the absolute pressure in the stainless steel sheath to be 10 after degassing-3Pa, obtaining a degassed blank;
(4) and (4) carrying out hot isostatic pressing on the degassed blank obtained in the step (3) for 4h at 1400 ℃ and 140MPa, then cooling to room temperature along with the furnace, and removing the stainless steel sheath to obtain the large-size MoTiNi alloy target.
Example 3:
the embodiment provides a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target comprises 65 at% of Mo, 35 at% of Ti and Ni in terms of atomic percentage;
the Ti and the Ni exist in the form of TiNi solid solution;
the atomic ratio of Ti to Ni is 6: 1;
the length of the MoTiNi alloy target is 2.1 m.
The preparation method of the MoTiNi alloy target comprises the following steps:
(1) mixing Ti powder and Ni powder according to an atomic ratio of 6:1, and performing gas atomization after mixing to obtain TiNi alloy powder with the maximum particle size of 85 microns;
(2) mixing the TiNi alloy powder with the grain size of 35at percent and Mo powder with the grain size of 8 mu m and the grain size of 35at percent obtained in the step (1) for 30h in a nitrogen atmosphere, then putting the mixture into a rubber sleeve, and then carrying out cold isostatic pressing for 8min under the condition of 210MPa to obtain a cold isostatic blank;
(3) processing the cold equal blanks obtained in the step (2) into cuboids with the width and the height of 400mm and the length of 0.7m by milling, splicing 3 processed cold equal blanks into spliced blanks with the length of 2.1m, placing the spliced blanks into a stainless steel sheath, degassing at 500 ℃, wherein the absolute pressure in the stainless steel sheath after degassing is 10-4Pa, obtaining a degassed blank;
(4) hot isostatic pressing the degassed blank obtained in the step (3) for 6h at 1200 ℃ and 180MPa, then cooling to room temperature along with the furnace, and removing the stainless steel sheath to obtain the large-size MoTiNi alloy target.
Example 4:
the embodiment provides a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target comprises, by atomic percent, Mo 63 at%, Ti and Ni 37 at%;
the Ti and the Ni exist in the form of TiNi solid solution;
the atomic ratio of Ti to Ni is 3.1:1
The length of the MoTiNi alloy target is 2.5 m.
The preparation method of the MoTiNi alloy target comprises the following steps:
(1) mixing Ti powder and Ni powder according to an atomic ratio of 3.1:1, and performing gas atomization after mixing to obtain TiNi alloy powder with the maximum particle size of 100 mu m;
(2) mixing the TiNi alloy powder with the grain size of 37at percent and Mo powder with the grain size of 7 mu m, wherein the TiNi alloy powder is obtained in the step (1), the mixture is put into a rubber sleeve after being mixed for 36 hours in a nitrogen atmosphere, and then the mixture is subjected to cold isostatic pressing for 10min under the condition of 230MPa to obtain a cold isostatic blank;
(3) processing the cold equal blanks obtained in the step (2) into cuboids with the width and the height of 100mm and the length of 0.85m by milling, splicing 5 processed cold equal blanks into spliced blanks with the length of 4.25m, placing the spliced blanks into a stainless steel sheath, degassing at the temperature of 600 ℃, wherein the absolute pressure in the stainless steel sheath after degassing is 8 multiplied by 10-4Pa, obtaining a degassed blank;
(4) hot isostatic pressing the degassed blank obtained in the step (3) for 5.5h at 1300 ℃ and 160MPa, then cooling to room temperature along with the furnace, and removing the stainless steel sheath to obtain the large-size MoTiNi alloy target.
Example 5:
the embodiment provides a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target refers to the MoTiNi alloy target in the embodiment 1.
The preparation process is as in example 1, except that: in the step (4), hot isostatic pressing is performed at 900 ℃ and 170 MPa.
Example 6:
the embodiment provides a large-size MoTiNi alloy target and a preparation method thereof, wherein the MoTiNi alloy target refers to the MoTiNi alloy target in the embodiment 2.
The preparation process is referred to the preparation process in example 2, with the only difference that: and (4) carrying out hot isostatic pressing under the conditions of 1600 ℃ and 140 MPa.
Comparative example 1:
the comparative example provides a MoTiNi alloy target and a preparation method thereof, and the MoTiNi alloy target refers to the MoTiNi alloy target in example 1.
The preparation process is as in example 1, except that: without carrying out the operation of step (1), 8 at% Ni powder, 22 at% Ti powder and 70 at% Mo powder having a particle size of 5 μm were directly mixed for 24 hours and charged into a rubber compound.
Comparative example 2:
the comparative example provides a large-size MoTiNi alloy target and a preparation method thereof, and the MoTiNi alloy target is different from the MoTiNi alloy target in example 3 only in that: the atomic ratio of Ti to Ni is 9: 1.
The preparation process is referred to the preparation process in example 3, with the only difference that: in the step (1), Ti powder and Ni powder are mixed in an atomic ratio of 9: 1.
Comparative example 3:
the comparative example provides a large-size MoTiNi alloy target and a preparation method thereof, and the MoTiNi alloy target is different from the MoTiNi alloy target in the embodiment 1 only in that: the atomic ratio of Ti to Ni is 1: 1.
The preparation process is as in example 1, except that: in the step (1), Ti powder and Ni powder are mixed in an atomic ratio of 1: 1.
The purity, the compactness and the magnetism of the MoTiNi alloy target materials obtained in the examples 1 to 6 and the comparative examples 1 to 3 are measured, and the measurement results are shown in Table 1.
The purity test method comprises the following steps: inductively coupled plasma mass spectrometry (ICP-Ms);
the density testing method comprises the following steps: archimedes drainage method;
the magnetic property test method comprises the following steps: and measuring the magnetic Permeability (PTF) of the material by using a magnetic permeability instrument so as to judge the magnetic strength of the material.
TABLE 1 purity, compactness and magnetic property measurement results of MoTiNi alloy targets obtained in examples 1-6 and comparative examples 1-3
| Purity/%) | Density/% | Magnetic Transmission Rate (PTF)/% | |
| Example 1 | 99.95 | 99.5 | 85 |
| Example 2 | 99.95 | 99.9 | 80 |
| Example 3 | 99.95 | 99.7 | 90 |
| Example 4 | 99.95 | 99.8 | 82 |
| Example 5 | 99.95 | 90.4 | 66 |
| Example 6 | 99.95 | 100 | 58 |
| Comparative example 1 | 99.80 | 99.3 | 68 |
| Comparative example 2 | 99.95 | 99.4 | 82 |
| Comparative example 3 | 99.95 | 99.3 | 63 |
In the examples 1 to 4, in the process of preparing the MoTiNi alloy target, the purity and the density of the obtained MoTiNi alloy target are both over 99.95% and over 99.5% by prefabricating the TiNi alloy powder and further controlling the contents of the Ti powder and the Ni powder and the temperature of hot isostatic pressing, and the problem that the target shows magnetism due to the nonuniformity of the Ni powder in the Mo alloy is avoided, generally, the higher the permeability requirement of the magnetic target is, the better the permeability is, the weaker the magnetism of the material is, and practical use experience proves that the target does not influence sputtering use when the permeability of the material is over 75%, so that the permeability of the MoTiNi alloy target prepared in the examples 1 to 4 is over 80%, and the material meets the use requirement; example 5 the hot isostatic pressing temperature is reduced during the preparation process, which results in the material not being able to be densified during the sintering process, so the density is lower, only 90.4%, and the material cannot meet the use requirements due to the larger porosity; example 6 raises the temperature of hot isostatic pressing during preparation, the density is increased to 100%, but Ni element is segregated in the alloy due to overhigh temperature, and the magnetic permeability is reduced.
Comparative example 1 Ti powder and Ni powder were not pre-prepared in the preparation process, so that other impurities were introduced in the powder mixing process, thereby causing a decrease in purity thereof, and the resulting alloy target had a low magnetic permeability due to the non-uniform distribution of Ni powder in Mo alloy.
Comparative example 2 reduces the content of Ni powder in the preparation process, and the obtained MoTiNi alloy target has high purity, density and magnetic permeability, but has low corrosion resistance and can not meet the use requirement; comparative example 3 increases the content of Ni powder during the preparation process, resulting in that Ni cannot be completely dissolved in Ti to form a saturated solid solution with residual Ni present.
It can be seen from the above examples and comparative examples that the corrosion resistance, the density and the heat resistance of the Mo target material are effectively improved by adding Ti and Ni and controlling the content and the hot isostatic pressing temperature of the Mo alloy target material, and the density is up to more than 99.5%; according to the preparation method, the inherent magnetism of Ni is eliminated by prefabricating TiNi alloy powder, and the large-size MoTiNi alloy target material with the length of not less than 2m is prepared by the processes of cold isostatic pressing, splicing, hot isostatic pressing and the like, so that the limitation of the existing equipment is broken through, the use requirement of the LCD target material is met, and the preparation method has a good industrial application prospect. Has better industrial application prospect.
The applicant states that the present invention is illustrated by the above examples to show the products and detailed methods of the present invention, but the present invention is not limited to the above products and detailed methods, i.e. it is not meant that the present invention must rely on the above products and detailed methods to be carried out. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents thereof, additions of additional operations, selection of specific ways, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The large-size MoTiNi alloy target is characterized by comprising 60-70 at% of Mo, 30-40 at% of Ti and Ni in terms of atomic percentage;
the Ti and the Ni exist in the form of TiNi solid solution;
the atomic ratio of Ti to Ni is (2.75-6) to 1;
the length of the MoTiNi alloy target is not less than 2 m.
2. The preparation method of the large-size MoTiNi alloy target material according to claim 1, wherein the preparation method comprises the following steps:
(1) mixing Ti powder and Ni powder, and then carrying out gas atomization to obtain TiNi alloy powder;
(2) mixing the TiNi alloy powder obtained in the step (1) with Mo powder, and then carrying out cold isostatic pressing to obtain cold isostatic blanks;
(3) processing the cold blank obtained in the step (2), and then sequentially splicing and degassing to obtain a degassed blank;
(4) and (4) carrying out hot isostatic pressing on the degassed blank obtained in the step (3) to obtain the large-size MoTiNi alloy target.
3. The method according to claim 2, wherein the atomic ratio of the Ti powder to the Ni powder in the step (1) is (2.75-6): 1;
preferably, the TiNi alloy powder of step (1) is present in the form of a TiNi solid solution;
preferably, the maximum particle size of the TiNi alloy powder of step (1) does not exceed 100 μm.
4. The production method according to claim 2 or 3, wherein the particle size of the Mo powder in the step (2) is 5 to 8 μm;
preferably, the Mo powder and the TiNi alloy powder in the step (2) are respectively 60 to 70 at% and 30 to 40 at% in atomic percentage;
preferably, the mixing in the step (2) is carried out by a V-shaped powder mixer;
preferably, the mixing of step (2) is carried out under a protective atmosphere;
preferably, the protective atmosphere comprises an inert gas and/or nitrogen;
preferably, the mixing time in the step (2) is 24-48 h.
5. The production method according to any one of claims 2 to 4, wherein the mixed powder is charged into a rubber boot after the mixing in step (2);
preferably, the pressure of the cold isostatic pressing in the step (2) is 190-250 MPa;
preferably, the time of the cold isostatic pressing in the step (2) is 5-15 min.
6. The production method according to any one of claims 2 to 5, wherein the processing in step (3) is milling;
preferably, the processed cold blank in the step (3) is a cuboid;
preferably, the width and height of the cuboid are independently no greater than 600 mm;
preferably, the length of the cuboid is not more than 1 m.
7. The production method according to any one of claims 2 to 6, wherein the length after the splicing in step (3) is not less than 2 m;
preferably, the cold blank after splicing in the step (3) is placed in a stainless steel sheath;
preferably, the degassing of step (3) is performed using a molecular pump;
preferably, the degassing temperature in the step (3) is 450-700 ℃;
preferably, the absolute pressure in the degassed stainless steel jacket of step (3) is less than 3X 10-3Pa。
8. The method of any one of claims 2 to 7, wherein the hot isostatic pressing in step (4) is performed at a temperature of 1100 to 1400 ℃;
preferably, the hot isostatic pressing pressure in the step (4) is 140-180 MPa;
preferably, the hot isostatic pressing time in the step (4) is 4-6 h;
preferably, the temperature of the furnace is reduced after the hot isostatic pressing in step (4);
preferably, the temperature is reduced to room temperature.
9. The production method according to claim 7 or 8, wherein the stainless steel capsule is removed after the hot isostatic pressing of step (4) is completed;
preferably, the stainless steel sheath is removed by milling.
10. The method of any one of claims 2 to 9, comprising the steps of:
(1) mixing Ti powder and Ni powder according to the atomic ratio of (2.75-6) to 1, and performing gas atomization after mixing to obtain TiNi alloy powder with the maximum particle size not exceeding 100 mu m;
(2) mixing 30-40 at% TiNi alloy powder obtained in the step (1) and 60-70 at% Mo powder with the particle size of 5-8 mu m for 24-48 h under a protective atmosphere, then putting into a rubber sleeve, and then carrying out cold isostatic pressing for 5-15 min under the condition of 190-250 MPa to obtain a cold blank;
(3) processing the cold equal blank obtained in the step (2) into a cuboid with the width and the height independently not more than 600mm and the length not more than 1m by milling, splicing the processed cold equal blank into a spliced blank with the length not less than 2m, placing the spliced blank into a stainless steel sheath, degassing at the temperature of 450-700 ℃, and enabling the absolute pressure in the stainless steel sheath to be less than 3 multiplied by 10 after degassing-3Pa, obtaining a degassed blank;
(4) and (4) carrying out hot isostatic pressing on the degassed blank obtained in the step (3) for 4-6 h at 1100-1400 ℃ and 140-180 MPa, then cooling to room temperature along with the furnace, and removing the stainless steel sheath to obtain the large-size MoTiNi alloy target.
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| CN114855131A (en) * | 2022-05-23 | 2022-08-05 | 安泰天龙(北京)钨钼科技有限公司 | Preparation method of molybdenum alloy target, molybdenum alloy target and application |
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| CN115261809A (en) * | 2022-07-25 | 2022-11-01 | 宁波江丰电子材料股份有限公司 | Preparation method of tubular target material |
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