CN114378294A - High-purity tantalum plate and preparation method thereof - Google Patents
High-purity tantalum plate and preparation method thereof Download PDFInfo
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- CN114378294A CN114378294A CN202111635883.XA CN202111635883A CN114378294A CN 114378294 A CN114378294 A CN 114378294A CN 202111635883 A CN202111635883 A CN 202111635883A CN 114378294 A CN114378294 A CN 114378294A
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 238000005096 rolling process Methods 0.000 claims abstract description 29
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 238000011049 filling Methods 0.000 claims abstract description 20
- 238000010894 electron beam technology Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000007731 hot pressing Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000003723 Smelting Methods 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 210000001161 mammalian embryo Anatomy 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 239000013077 target material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/24—Obtaining niobium or tantalum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/228—Remelting metals with heating by wave energy or particle radiation by particle radiation, e.g. electron beams
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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
- 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
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- 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
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention discloses a high-purity tantalum plate and a preparation method thereof, which relate to the field of metal metallurgy manufacturing and comprise electron beam melting, ball milling, hydraulic classification, drying, tantalum powder spheroidization, die filling, heating and pressurizing, blank forming and plate rolling, wherein the purity of the manufactured high-purity tantalum plate is more than 99.95 percent, and the average grain size is 20-26 mu m.
Description
Technical Field
The invention relates to the field of metal metallurgy manufacturing, in particular to a high-purity tantalum plate and a preparation method thereof.
Background
The tantalum has the advantages of high melting point, good conductivity, high thermal stability, stable chemical property, good room temperature toughness and the like, and is widely applied to the fields of electronics, electrics, energy chemical industry, aerospace and the like. In recent years, tantalum and tantalum-based films become key materials for preparing diffusion barrier layers between copper wires and silicon substrates in integrated circuits, copper can be prevented from diffusing into the silicon substrates to form copper-silicon alloys, and therefore the service life of equipment is greatly prolonged. Magnetron sputtering is a main method for preparing tantalum films, and a tantalum target material for sputtering is a key consumable material in the process. Therefore, the preparation of the tantalum target with excellent performance is crucial to the manufacture of modern integrated circuits.
Magnetron sputtering coating has many advantages such as high homogeneity, strong controllability, etc. and gradually becomes one of the most critical processes in the production process of integrated circuits and semiconductor chips. The quality of the sputtering target determines the coating effect of magnetron sputtering and the performance of a semiconductor device, so that the sputtering target becomes an indispensable key material in the semiconductor field, particularly in the chip manufacturing industry. The quality of the film formed by sputtering the target material, such as the thickness and uniformity of the film, can significantly affect the performance of products in the semiconductor industry, and the thickness and uniformity of the film almost completely depend on the structure of the target material, such as the refinement degree and uniformity of crystal grains. Therefore, in order to improve the quality of the tantalum target material, it is very important to improve the grain size and grain orientation when preparing the tantalum target material.
The existing preparation process of the high-purity tantalum plate mainly adopts an electron beam melting process to prepare a tantalum cast ingot, and carries out later-stage shaping processing and heat treatment processes on the cast ingot, so that the structure of the cast ingot is regulated, controlled and relatively ideal grain size is obtained, and then machining is carried out to finally finish a finished product, however, the cold deformation resistance of tantalum is large, the work hardening rate is high, and cracks are easy to generate when large plastic deformation occurs; and the high-temperature oxidation resistance of tantalum is poor, so the temperature deformation and thermal deformation process is complex, the cost is high, and fine and uniform crystal grains are difficult to form.
Disclosure of Invention
In order to solve the technical problems, the technical scheme solves the problems that the existing preparation process of the high-purity tantalum plate proposed in the background technology mainly adopts an electron beam melting process to prepare a tantalum cast ingot, and the cast ingot is subjected to later-stage shaping processing and heat treatment processes, so that the structure of the cast ingot is regulated and controlled to obtain relatively ideal grain size, and then the cast ingot is machined to finally finish a finished product, however, the cold deformation resistance of tantalum is larger, the processing hardening rate is higher, and cracks are easy to generate when large plastic deformation occurs; and the high-temperature oxidation resistance of the tantalum is poor, so that the temperature deformation and thermal deformation process is complex, the cost is high, and fine and uniform crystal grains are difficult to form.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a preparation method of a high-purity tantalum plate comprises the following steps:
electron beam melting: weighing pure tantalum strips, placing the pure tantalum strips in a smelting furnace for first electron beam smelting, and smelting to obtain cast ingots with the diameter of 220 mm;
ball milling: the method comprises the following steps of (1) crushing tantalum ingots by using a crusher, then putting the crushed tantalum ingots into a ball mill, and carrying out ball milling, wherein the diameter of ball-milled tantalum balls is 8mm, and the ball-material ratio is 6: 1, rotating speed of 60r/min, ball milling time of 90min, sieving with a 80-mesh sieve after the tantalum powder is taken out of a ball mill, and continuously ball milling the coarse tantalum powder on the sieve until all the tantalum powder can pass through the 80-mesh sieve to obtain tantalum powder;
hydraulic classification: placing the tantalum powder into a hydraulic classifier to perform hydraulic classification, and dividing the tantalum powder into horn-shaped tantalum powder with three granularity grades of 6-8 mu m, 3 +/-1 mu m and 1 +/-0.5 mu m according to the Fisher's particle size control;
drying: drying the horn-shaped tantalum powder with three grades of granularity in vacuum at the temperature of 75 ℃;
spheroidizing tantalum powder: respectively carrying out heating treatment on the tantalum powder with the three-stage granularity grade by using high-frequency thermal plasma to melt corners of corner-shaped tantalum powder particles so as to obtain spherical tantalum powder with the three-stage granularity grade;
die filling: uniformly mixing the spherical tantalum powder with the three grades of particle sizes in proportion, then filling the mixture into a die, and compacting by vibration;
heating and pressurizing: placing a die filled with tantalum powder in a hot pressing furnace, evacuating the hot pressing furnace, filling argon for 2 times, then filling argon, heating to 1700-2000 ℃, simultaneously pressing to 15-30 MPa, and keeping the temperature and pressure for 60-80 min, wherein when the temperature in the hot pressing furnace is 0-1200 ℃, the heating speed is 8 ℃/min, when the temperature in the hot pressing furnace is 1200-1600 ℃, the heating speed is 4 ℃/min, and when the temperature in the hot pressing furnace is 1600-2000 ℃, the heating speed is 2 ℃/min;
embryo forming: after the temperature in the hot pressing furnace is reduced to room temperature, the pressure is removed, and the high-purity tantalum billet is taken out after vacuum breaking;
rolling into a plate: and rolling the high-purity tantalum billet into a high-purity tantalum plate by adopting an asynchronous rolling method.
Preferably, the parameters of the primary electron beam melting are as follows: the vacuum degree of the smelting furnace is 4x10-3Pa, the voltage is 18KV-20KV, the current is 4A-6A, the feeding speed is 16kg/h-18kg/h, and the cooling time is 2h-5 h.
Preferably, the crusher lining, the ball mill lining and the ball-milled tantalum balls are all made of high-purity tantalum with the purity of more than 99.95%.
Preferably, the percentage content of the spherical tantalum powder with three grades of particle sizes in the step of die filling is as follows: 30-60% of tantalum powder with the Fischer particle size of 6-8 mu m, 10-30% of tantalum powder with the Fischer particle size of 3 +/-1 mu m and 30-60% of tantalum powder with the Fischer particle size of 1 +/-0.5 mu m.
Preferably, the rotation speed ratio of the two rollers for asynchronous rolling is K (K is more than 1.05 and less than or equal to 1.2), the asynchronous rolling is carried out for 8 times in total, and the tantalum plate is placed in an environment with the temperature of 1100 ℃ for heat preservation for 25min before the asynchronous rolling step of each time.
Further provides a high-purity tantalum plate, which is characterized in that: the purity of the high-purity tantalum plate is more than 99.95%, and the average grain size is 20-26 mu m.
Compared with the prior art, the invention has the advantages that:
1) according to the invention, the pure tantalum strip is subjected to electron beam melting before processing, and refined, so that the chemical purity of the pure tantalum strip reaches 4N (99.99%), subsequent acid washing or other purification processes are not required, the process flow is shortened, the method is economic and environment-friendly, the pollution source is reduced, and the high purity of the tantalum is ensured;
2) according to the invention, the high-purity tantalum blank is obtained by hot pressing after mixing three different grain sizes of 6-8 μm of Fisher grain size, 3 +/-1 μm of Fisher grain size and 1 +/-0.5 μm of Fisher grain size, and compared with a processing mode of directly performing shaping processing on an ingot, the grain size of the high-purity tantalum blank under the tantalum powder mixing hot pressing is smaller, so that the high-purity tantalum blank can be made into the required tantalum plate size under a lower rolling pass, thereby reducing the situation that the tantalum blank is easy to generate a belt-shaped inherent structure under multiple plastic deformation, causing the grain layering of a tantalum plate tissue, and improving the grain uniformity of the high-purity tantalum plate;
3) the method adopts the heating treatment of the high-frequency thermal plasma to prepare the horn-shaped tantalum powder into the spherical tantalum powder, compared with the horn-shaped tantalum powder, the grain size distribution of the spherical tantalum powder is centralized and controllable, the grain size of a subsequent mixed blank can be ensured to be more uniform, and the grain uniformity of the prepared tantalum plate is further improved;
4) the high-purity tantalum plate provided by the invention has the advantages of uniform grain size, average grain size of 20-26 mu m, low plasma impedance and capability of effectively improving the film coating effect of magnetron sputtering and the performance of a semiconductor device.
Drawings
FIGS. 1 to 3 are metallographic photographs of the high purity tantalum plates prepared in examples 1 to 3, respectively;
FIGS. 4 to 6 are graphs showing the analysis of the spectral data of the high purity tantalum plates prepared in examples 4 to 6, respectively.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
Weighing pure tantalum strips, placing the pure tantalum strips into a smelting furnace for electron beam smelting to obtain ingots with the diameter of 220mm, wherein the parameters of the electron beam smelting are as follows: the vacuum degree of the smelting furnace is 4x10-3Pa, voltage of 18KV, current of 4A-, feeding speed of 16kg/h, and cooling time of 4 h;
the method comprises the following steps of (1) crushing tantalum ingots by using a crusher, then putting the crushed tantalum ingots into a ball mill, and carrying out ball milling, wherein the diameter of ball-milled tantalum balls is 8mm, and the ball-material ratio is 6: 1, rotating speed is 60r/min, ball milling time is 90min, after the tantalum powder is taken out of a ball mill, sieving the tantalum powder by a sieve with 80 meshes, and continuously ball milling the coarse tantalum powder on the sieve until all the tantalum powder can pass through the sieve with 80 meshes to obtain the tantalum powder, wherein the crusher lining, the ball mill lining and the ball milling tantalum ball are all made of high-purity tantalum with purity of more than 99.95 percent;
placing the tantalum powder into a hydraulic classifier to perform hydraulic classification, and dividing the tantalum powder into horn-shaped tantalum powder with three granularity grades of 6-8 mu m, 3 +/-1 mu m and 1 +/-0.5 mu m according to the Fisher's particle size control;
drying the horn-shaped tantalum powder with three grades of granularity in vacuum at the temperature of 75 ℃;
respectively carrying out heating treatment on the tantalum powder with the three-stage granularity grade by using high-frequency thermal plasma to melt corners of corner-shaped tantalum powder particles so as to obtain spherical tantalum powder with the three-stage granularity grade;
uniformly mixing three-stage granularity grade spherical tantalum powder according to the percentage content of 60 percent of tantalum powder with the Fischer particle size of 6-8 mu m, 10 percent of tantalum powder with the Fischer particle size of 3 +/-1 mu m and 30 percent of tantalum powder with the Fischer particle size of 1 +/-0.5 mu m, then filling the mixture into a mould, and compacting the mixture by vibration;
placing a die filled with tantalum powder in a hot pressing furnace, evacuating the hot pressing furnace, filling argon for replacement for 2 times, then filling argon, heating to 1700 ℃, simultaneously pressing to 15Mpa, and keeping the temperature and pressure for 60min, wherein when the temperature in the hot pressing furnace is 0-1200 ℃, the heating speed is 8 ℃/min, when the temperature in the hot pressing furnace is 1200-1600 ℃, the heating speed is 4 ℃/min, and when the temperature in the hot pressing furnace is 1600-1700 ℃, the heating speed is 2 ℃/min;
after the temperature in the hot pressing furnace is reduced to room temperature, the pressure is removed, and the high-purity tantalum billet is taken out after vacuum breaking;
and rolling the high-purity tantalum billet into a high-purity tantalum plate by adopting an asynchronous rolling method, wherein the rotation speed ratio of two rollers for asynchronous rolling is 1.05, 4 passes of asynchronous rolling are performed in total, and the tantalum plate is placed in an environment at 1100 ℃ for heat preservation for 25min before the asynchronous rolling step of each pass.
The resulting high purity tantalum plate was designated as example 1.
Example 2
Weighing pure tantalum strips, placing the pure tantalum strips into a smelting furnace for electron beam smelting to obtain ingots with the diameter of 220mm, wherein the parameters of the electron beam smelting are as follows: the vacuum degree of the smelting furnace is 4x10-3Pa, voltage of 20KV, current of 6A, feeding speed of 18kg/h and cooling time of 5 h;
the method comprises the following steps of (1) crushing tantalum ingots by using a crusher, then putting the crushed tantalum ingots into a ball mill, and carrying out ball milling, wherein the diameter of ball-milled tantalum balls is 8mm, and the ball-material ratio is 6: 1, rotating speed is 60r/min, ball milling time is 90min, after the tantalum powder is taken out of a ball mill, sieving the tantalum powder by a sieve with 80 meshes, and continuously ball milling the coarse tantalum powder on the sieve until all the tantalum powder can pass through the sieve with 80 meshes to obtain the tantalum powder, wherein the crusher lining, the ball mill lining and the ball milling tantalum ball are all made of high-purity tantalum with purity of more than 99.95 percent;
placing the tantalum powder into a hydraulic classifier to perform hydraulic classification, and dividing the tantalum powder into horn-shaped tantalum powder with three granularity grades of 6-8 mu m, 3 +/-1 mu m and 1 +/-0.5 mu m according to the Fisher's particle size control;
drying the horn-shaped tantalum powder with three grades of granularity in vacuum at the temperature of 75 ℃;
respectively carrying out heating treatment on the tantalum powder with the three-stage granularity grade by using high-frequency thermal plasma to melt corners of corner-shaped tantalum powder particles so as to obtain spherical tantalum powder with the three-stage granularity grade;
uniformly mixing three-stage granularity grade spherical tantalum powder according to the percentage content of 30 percent of tantalum powder with the Fischer particle size of 6-8 mu m, 30 percent of tantalum powder with the Fischer particle size of 3 +/-1 mu m and 40 percent of tantalum powder with the Fischer particle size of 1 +/-0.5 mu m, then filling the mixture into a mould, and compacting the mixture by vibration;
placing a die filled with tantalum powder in a hot pressing furnace, evacuating the hot pressing furnace, filling argon for 2 times, then filling argon, heating to 2000 ℃, simultaneously pressing to 30Mpa, and keeping the temperature and pressure for 80min, wherein when the temperature in the hot pressing furnace is 0-1200 ℃, the heating speed is 8 ℃/min, when the temperature in the hot pressing furnace is 1200-1600 ℃, the heating speed is 4 ℃/min, and when the temperature in the hot pressing furnace is 1600-2000 ℃, the heating speed is 2 ℃/min;
after the temperature in the hot pressing furnace is reduced to room temperature, the pressure is removed, and the high-purity tantalum billet is taken out after vacuum breaking;
and rolling the high-purity tantalum billet into a high-purity tantalum plate by adopting an asynchronous rolling method, wherein the rotation speed ratio of two rollers for asynchronous rolling is 1.2, 4 passes of asynchronous rolling are performed in total, and the tantalum plate is placed in an environment at 1100 ℃ for heat preservation for 25min before the asynchronous rolling step of each pass.
The resulting high purity tantalum plate was designated as example 2.
Example 3
Weighing pure tantalum strips, placing the pure tantalum strips into a smelting furnace for electron beam smelting to obtain ingots with the diameter of 220mm, wherein the parameters of the electron beam smelting are as follows: the vacuum degree of the smelting furnace is 4x10-3Pa, voltage of 20KV, current of 6A, feeding speed of 18kg/h and cooling time of 5 h;
the method comprises the following steps of (1) crushing tantalum ingots by using a crusher, then putting the crushed tantalum ingots into a ball mill, and carrying out ball milling, wherein the diameter of ball-milled tantalum balls is 8mm, and the ball-material ratio is 6: 1, rotating speed is 60r/min, ball milling time is 90min, after the tantalum powder is taken out of a ball mill, sieving the tantalum powder by a sieve with 80 meshes, and continuously ball milling the coarse tantalum powder on the sieve until all the tantalum powder can pass through the sieve with 80 meshes to obtain the tantalum powder, wherein the crusher lining, the ball mill lining and the ball milling tantalum ball are all made of high-purity tantalum with purity of more than 99.95 percent;
placing the tantalum powder into a hydraulic classifier to perform hydraulic classification, and dividing the tantalum powder into horn-shaped tantalum powder with three granularity grades of 6-8 mu m, 3 +/-1 mu m and 1 +/-0.5 mu m according to the Fisher's particle size control;
drying the horn-shaped tantalum powder with three grades of granularity in vacuum at the temperature of 75 ℃;
respectively carrying out heating treatment on the tantalum powder with the three-stage granularity grade by using high-frequency thermal plasma to melt corners of corner-shaped tantalum powder particles so as to obtain spherical tantalum powder with the three-stage granularity grade;
uniformly mixing 30% of three-stage granularity grade spherical tantalum powder, 10% of Fischer-Tropsch tantalum powder and 60% of Fischer-Tropsch tantalum powder, wherein the Fischer-Tropsch tantalum powder is 6-8 mu m in percentage content, the Fischer-Tropsch tantalum powder is 3 +/-1 mu m in percentage content, and the Fischer-Tropsch tantalum powder is 1 +/-0.5 mu m in percentage content, then filling the mixture into a mold, and compacting the mixture by vibration;
placing the die filled with the tantalum powder in a hot pressing furnace, firstly evacuating the hot pressing furnace, filling argon for 2 times, then filling argon, then heating to 1850 ℃, simultaneously pressing to 22Mpa, and keeping the temperature and pressure for 80min, wherein when the temperature in the hot pressing furnace is 0-1200 ℃, the heating speed is 8 ℃/min, when the temperature in the hot pressing furnace is 1200-1600 ℃, the heating speed is 4 ℃/min, and when the temperature in the hot pressing furnace is 1600-1850 ℃, the heating speed is 2 ℃/min;
after the temperature in the hot pressing furnace is reduced to room temperature, the pressure is removed, and the high-purity tantalum billet is taken out after vacuum breaking;
and rolling the high-purity tantalum billet into a high-purity tantalum plate by adopting an asynchronous rolling method, wherein the rotation speed ratio of two rollers for asynchronous rolling is 1.1, 4 passes of asynchronous rolling are performed in total, and the tantalum plate is placed in an environment at 1100 ℃ for heat preservation for 25min before the asynchronous rolling step of each pass.
The resulting high purity tantalum plate was designated as example 3.
The grain structure of the high purity tantalum plate prepared by the present invention is uniform when the grain structure of the high purity tantalum plate is observed under a microscope in examples 1 to 3, as shown in FIGS. 1 to 3.
The average grain sizes of examples 1 to 3 were counted according to the method for determining the average grain size of metals (GB/T6394-2017), and the results are shown in the following table:
| sample(s) | Grain size (μm) |
| Example 1 | 26 |
| Example 2 | 24 |
| Example 3 | 23 |
As can be seen from the above table, the grain size of the high-purity tantalum plate prepared by the method can reach 20-26 μm, compared with the prior art, the grain size is greatly reduced, the plasma impedance can be effectively reduced, and the film coating effect of magnetron sputtering and the performance of a semiconductor device are improved.
The results of the energy spectrum data analysis of examples 1 to 3 are shown in FIGS. 4 to 6, and it can be seen from the energy spectrum data graphs that the peaks of examples 1 to 3 containing only tantalum element do not contain other impurities and the purity of examples 1 to 3 can be up to (99.95%).
In conclusion, the method has the advantages that the purity of the prepared high-purity tantalum plate can reach (99.95%), the average grain size is 20-26 mu m, the grains are uniformly distributed, the plasma impedance can be effectively reduced, and the coating effect of magnetron sputtering and the performance of a semiconductor device are improved.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. The preparation method of the high-purity tantalum plate is characterized by comprising the following steps:
electron beam melting: weighing pure tantalum strips, placing the pure tantalum strips in a smelting furnace for first electron beam smelting, and smelting to obtain cast ingots with the diameter of 220 mm;
ball milling: the method comprises the following steps of (1) crushing tantalum ingots by using a crusher, then putting the crushed tantalum ingots into a ball mill, and carrying out ball milling, wherein the diameter of ball-milled tantalum balls is 8mm, and the ball-material ratio is 6: 1, rotating speed of 60r/min, ball milling time of 90min, sieving with a 80-mesh sieve after the tantalum powder is taken out of a ball mill, and continuously ball milling the coarse tantalum powder on the sieve until all the tantalum powder can pass through the 80-mesh sieve to obtain tantalum powder;
hydraulic classification: placing the tantalum powder into a hydraulic classifier to perform hydraulic classification, and dividing the tantalum powder into horn-shaped tantalum powder with three granularity grades of 6-8 mu m, 3 +/-1 mu m and 1 +/-0.5 mu m according to the Fisher's particle size control;
drying: drying the horn-shaped tantalum powder with three grades of granularity in vacuum at the temperature of 75 ℃;
spheroidizing tantalum powder: respectively carrying out heating treatment on the tantalum powder with the three-stage granularity grade by using high-frequency thermal plasma to melt corners of corner-shaped tantalum powder particles so as to obtain spherical tantalum powder with the three-stage granularity grade;
die filling: uniformly mixing the spherical tantalum powder with the three grades of particle sizes in proportion, then filling the mixture into a die, and compacting by vibration;
heating and pressurizing: placing a die filled with tantalum powder in a hot pressing furnace, evacuating the hot pressing furnace, filling argon for 2 times, then filling argon, heating to 1700-2000 ℃, simultaneously pressing to 15-30 MPa, and keeping the temperature and pressure for 60-80 min, wherein when the temperature in the hot pressing furnace is 0-1200 ℃, the heating speed is 8 ℃/min, when the temperature in the hot pressing furnace is 1200-1600 ℃, the heating speed is 4 ℃/min, and when the temperature in the hot pressing furnace is 1600-2000 ℃, the heating speed is 2 ℃/min;
embryo forming: after the temperature in the hot pressing furnace is reduced to room temperature, the pressure is removed, and the high-purity tantalum billet is taken out after vacuum breaking;
rolling into a plate: and rolling the high-purity tantalum billet into a high-purity tantalum plate by adopting an asynchronous rolling method.
2. The method of claim 1, wherein the parameters of the electron beam melting are as follows: the vacuum degree of the smelting furnace is 4x10-3Pa, voltage of 18KV-20KV, current of 4A-6A, feeding speed of 16kg/h-18kg/h, and cooling time of 4h-5 h.
3. The method of claim 1, wherein the crusher liner, the ball mill liner and the ball mill tantalum balls are made of high purity tantalum with a purity of greater than 99.95%.
4. The method for preparing a high-purity tantalum plate according to claim 1, wherein the percentage content of the spherical tantalum powder with three grades of particle sizes in the step of die filling is as follows: 30-60% of tantalum powder with the Fischer particle size of 6-8 mu m, 10-30% of tantalum powder with the Fischer particle size of 3 +/-1 mu m and 30-60% of tantalum powder with the Fischer particle size of 1 +/-0.5 mu m.
5. The method for preparing the high-purity tantalum plate according to claim 1, wherein the rotation speed ratio of the two rollers for asynchronous rolling is K (1.05 < K & lt 1.2), the asynchronous rolling is carried out for 4 times, and the tantalum plate is kept at 1100 ℃ for 25min before the asynchronous rolling step of each time.
6. The high purity tantalum plate prepared by the method of any one of claims 1 to 5, wherein: the purity of the high-purity tantalum plate is more than 99.95%, and the average grain size is 20-26 mu m.
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