CN112430093A - Preparation method of bismuth antimony tellurium alloy target - Google Patents
Preparation method of bismuth antimony tellurium alloy target Download PDFInfo
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- CN112430093A CN112430093A CN202011275607.2A CN202011275607A CN112430093A CN 112430093 A CN112430093 A CN 112430093A CN 202011275607 A CN202011275607 A CN 202011275607A CN 112430093 A CN112430093 A CN 112430093A
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- bismuth
- antimony
- tellurium alloy
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- 229910001215 Te alloy Inorganic materials 0.000 title claims abstract description 113
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 238000004857 zone melting Methods 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 25
- 238000003723 Smelting Methods 0.000 claims abstract description 24
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 20
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 19
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 238000007789 sealing Methods 0.000 claims abstract description 14
- 239000013077 target material Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 238000012216 screening Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000003754 machining Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 22
- 238000007731 hot pressing Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 2
- 230000008018 melting Effects 0.000 claims 2
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 229910016312 BiSb Inorganic materials 0.000 description 1
- 229910016339 Bi—Sb—Te Inorganic materials 0.000 description 1
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
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- C—CHEMISTRY; METALLURGY
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/653—Processes involving a melting step
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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
- C23C14/0623—Sulfides, selenides or tellurides
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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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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
Abstract
The invention discloses a preparation method of a bismuth antimony tellurium alloy target material, which comprises the following steps: weighing bismuth raw materials, antimony raw materials and tellurium raw materials according to the proportion required by the bismuth-antimony-tellurium alloy target material; putting a bismuth raw material, an antimony raw material and a tellurium raw material into a glass tube, vacuumizing, sealing the glass tube, and heating and smelting to obtain a bismuth-antimony-tellurium alloy melt; placing the bismuth-antimony-tellurium alloy melt in a crystal pulling furnace for zone melting to obtain a bismuth-antimony-tellurium alloy ingot; crushing and screening the bismuth antimony tellurium alloy ingot to obtain first bismuth antimony tellurium alloy powder; repeatedly grinding the bismuth antimony tellurium alloy powder in a ball mill to obtain second bismuth antimony tellurium alloy powder; placing the second bismuth antimony tellurium alloy powder in a graphite mold, and then placing the graphite mold into sintering equipment for sintering to obtain a bismuth antimony tellurium alloy target blank; and machining the bismuth-antimony-tellurium alloy target blank to obtain the bismuth-antimony-tellurium alloy target. The bismuth antimony tellurium alloy target material prepared by the invention has high purity, relative density of more than 99 percent and excellent performance, and can meet various application requirements.
Description
Technical Field
The invention relates to the technical field of preparation of high-performance targets, in particular to a preparation method of a bismuth antimony tellurium alloy target.
Background
With the increasing severity of the energy crisis, there is an urgent need to actively promote and advocate the use of clean renewable energy, and especially to pay attention to the combination of new technology development of renewable energy and industrial investment to reduce the utilization cost of renewable energy. The thermoelectric device can realize the interconversion between heat energy and electric energy, and is a green environment-friendly energy device with wide application range. The semiconductor generator and the refrigerator manufactured by the semiconductor temperature difference power generation module can generate power as long as temperature difference exists, can refrigerate when supplying power, have no noise and no pollution when working, have service life of more than ten years, and can be widely applied to important basic applications such as waste heat power generation, refrigerator refrigeration and the like. Therefore, the energy-saving device is a green energy device with wide application.
The performance of thermoelectric devices depends on their basic raw materials: a thermoelectric material. The performance of the thermoelectric material is mainly characterized by a dimensionless constant ZT, wherein ZT = S2X σ x T ÷ k, where S is the Seebeck (Seebeck) coefficient, σ is the electrical conductivity, T is the absolute temperature (i.e., the temperature at which the material is subjected, and the values of S, σ, and k are different under different temperature conditions), and k is the thermal conductivity. Bismuth antimony tellurium (Bi-Sb-Te) -based thermoelectric materials, such as Bi2Te3, Sb2Te3, and BiSb and other group V-VI semiconductor compounds, are one of the important materials currently applied to low-temperature thermoelectric devices, and are also one of the earliest and most mature thermoelectric materials in research, and have a large seebeck coefficient and a low thermal conductivity.
At present, the preparation of bismuth antimony tellurium thermoelectric films is reported at home and abroad, the bismuth antimony tellurium thermoelectric films are mainly prepared by methods such as chemical vapor deposition, electrochemical deposition, magnetron sputtering, electron beam evaporation, molecular epitaxy and the like, and as for the production of bismuth antimony tellurium alloy targets, the results of research on the aspect at home and abroad are not reported at present, so that the research on the preparation process of the bismuth antimony tellurium alloy targets is necessary, and the invention provides a preparation method of the bismuth antimony tellurium alloy targets aiming at the defects of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a bismuth antimony tellurium alloy target material.
In order to achieve the purpose, the invention adopts the following technical scheme.
The invention provides a preparation method of a bismuth antimony tellurium alloy target material, which comprises the following steps: weighing bismuth raw materials, antimony raw materials and tellurium raw materials according to the proportion required by the bismuth-antimony-tellurium alloy target material; placing the bismuth raw material, the antimony raw material and the tellurium raw material into a glass tube, vacuumizing, sealing the glass tube, and heating and smelting to obtain a bismuth-antimony-tellurium alloy melt; placing the bismuth antimony tellurium alloy melt in a crystal pulling furnace for zone melting to obtain a bismuth antimony tellurium alloy ingot; crushing and screening the bismuth antimony tellurium alloy ingot to obtain first bismuth antimony tellurium alloy powder; repeatedly grinding the bismuth antimony tellurium alloy powder in a ball mill to obtain second bismuth antimony tellurium alloy powder; placing the second bismuth antimony tellurium alloy powder in a graphite mold, and then placing the graphite mold into sintering equipment for sintering to obtain a bismuth antimony tellurium alloy target blank; and machining the bismuth-antimony-tellurium alloy target blank to obtain the bismuth-antimony-tellurium alloy target.
As a further improvement of the invention, the mixing mass ratio of the bismuth raw material, the antimony raw material and the tellurium raw material in the weighed ingredients is (1: 1.36: 3.05) to (1: 3.3: 6.1).
As a further improvement of the method, the smelting temperature in the step of sealed tube smelting is 680-710 ℃, and the smelting duration is 10-15 min.
As a further improvement of the invention, in the smelting process in the step of tube sealing smelting, swinging motion is applied to the glass tube, the swinging motion can swing at an angle of 45 degrees from side to side, and the swinging frequency is 10-15 times/min.
As a further improvement of the invention, the step zone melting process parameters are as follows: the zone-melting temperature is 710-750 ℃, the zone-melting times are 1-2 times, and the zone-melting speed is 15-35 mm/h.
As a further improvement of the invention, before crushing and pulverizing in the step, the head and tail impurity-enriched parts of the bismuth-antimony-tellurium alloy ingot are removed.
As a further improvement of the invention, the length of the head and the tail of the bismuth antimony tellurium alloy ingot is not more than 1/8-1/6 of the total length of the bismuth antimony tellurium alloy ingot.
As a further improvement of the invention, during the step of uniform ball milling, protective gas is filled in the ball mill.
As a further improvement of the invention, in the step of hot-pressing sintering, the sintering comprises the following specific steps: firstly, carrying out cold press molding, wherein the pressure is 10-20 MPa during cold pressing, releasing the pressure to 0MPa after the cold pressing is finished, then heating and boosting the pressure to 480-550 ℃ and 35-45 MPa, and continuously sintering for 2-4 h.
As a further improvement of the invention, the purities of the bismuth raw material, the antimony raw material and the tellurium raw material are more than or equal to 4N.
The invention provides a preparation method of a bismuth antimony tellurium alloy target, the prepared bismuth antimony tellurium alloy target has high purity and relative density of more than 99%, and a thin film thermoelectric material prepared by using the target can be bent, has excellent performance and can meet various application requirements.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a bismuth antimony tellurium alloy target material, which comprises the following steps:
weighing and proportioning: weighing a bismuth raw material, an antimony raw material and a tellurium raw material with the purity of more than or equal to 4N according to the required proportion of the bismuth-antimony-tellurium alloy target, wherein the mixing mass ratio of the bismuth raw material to the antimony raw material to the tellurium raw material is (1: 1.36: 3.05) to (1: 3.3: 6.1).
Tube sealing smelting: putting a bismuth raw material, an antimony raw material and a tellurium raw material into a glass tube, vacuumizing, sealing the glass tube, smelting at 680-710 ℃ for 10-15 min to obtain a bismuth-antimony-tellurium alloy melt, and applying swinging motion to the glass tube in the smelting process, wherein the swinging motion can be performed at a 45-degree left-right swinging angle, and the swinging frequency is 10-15 times/min.
Zone melting: the bismuth-antimony-tellurium alloy melt is placed in a crystal pulling furnace for zone melting to obtain a bismuth-antimony-tellurium alloy ingot, and the zone melting process parameters are as follows: the zone-melting temperature is 710-750 ℃, the zone-melting times are 1-2 times, and the zone-melting speed is 15-35 mm/h.
Crushing and pulverizing: removing the head and tail impurity enrichment parts of the bismuth antimony tellurium alloy ingot, wherein the length of the removed head and tail does not exceed 1/8-1/6 of the total length of the bismuth antimony tellurium alloy ingot, and crushing and screening to obtain first bismuth antimony tellurium alloy powder.
In the crushing process, the bismuth antimony tellurium alloy ingot is knocked, mechanical shears are adopted to cut the bismuth antimony tellurium alloy ingot while knocking, the bismuth antimony tellurium alloy ingot is cut into fine blocks, finally, first bismuth antimony tellurium alloy powder is obtained through screening, and an aviation screen of 60 meshes, 70 meshes or 100 meshes is adopted for screening.
Ball milling uniformly: and repeatedly grinding the bismuth-antimony-tellurium alloy powder in a ball mill to obtain second bismuth-antimony-tellurium alloy powder, uniformly ball-milling, filling protective gas into the ball mill, wherein the protective gas is argon or nitrogen, and the purpose of filling the protective gas is to prevent the bismuth-antimony-tellurium alloy powder from being oxidized to further deteriorate the thermoelectric property of the bismuth-antimony-tellurium alloy powder.
Hot-pressing and sintering: and placing the second bismuth antimony tellurium alloy powder in a graphite die, and then placing the graphite die into hot-pressing sintering equipment for sintering to obtain a bismuth antimony tellurium alloy target blank.
In the hot-pressing sintering process, the sintering specific steps are as follows: firstly, carrying out cold press molding, wherein the pressure is 10-20 MPa during cold pressing, releasing the pressure to 0MPa after the cold pressing is finished, then heating and boosting the pressure to 480-550 ℃ and 35-45 MPa, and continuously sintering for 2-4 h.
And (3) processing and forming: machining the bismuth-antimony-tellurium alloy target blank to obtain the bismuth-antimony-tellurium alloy target material with the theoretical chemical formula of BixSb2-xTe3Wherein x is more than or equal to 0.3 and less than or equal to 0.5.
For further understanding of the present invention, the method and effects of the present invention will be described in further detail with reference to specific examples. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1.
(1) Weighing and proportioning: weighing a bismuth raw material, an antimony raw material and a tellurium raw material according to the mixing mass ratio of 1:3.3: 6.1;
(2) tube sealing smelting: putting a bismuth raw material, an antimony raw material and a tellurium raw material into a glass tube, vacuumizing, sealing the glass tube, heating to 680 ℃, and smelting for 15min to obtain a bismuth-antimony-tellurium alloy melt, wherein in the smelting process, the glass tube is subjected to swinging motion, the swinging motion can be carried out at a left-right swinging angle of 45 degrees, and the swinging frequency is 10 times/min;
(3) zone melting: the bismuth-antimony-tellurium alloy melt is placed in a crystal pulling furnace to be subjected to zone melting at the zone melting temperature of 710 ℃, the zone melting frequency of 1 time and the zone melting rate of 15mm/h, and a bismuth-antimony-tellurium alloy ingot is obtained after zone melting;
(4) crushing and pulverizing: removing 1/8 head and tail of the total length of the bismuth-antimony-tellurium alloy ingot, and then crushing and screening to obtain first bismuth-antimony-tellurium alloy powder;
(5) ball milling uniformly: repeatedly grinding the bismuth antimony tellurium alloy powder in a ball mill to obtain second bismuth antimony tellurium alloy powder;
(6) hot-pressing and sintering: and placing the second bismuth antimony tellurium alloy powder in a graphite mold, then placing the graphite mold into sintering equipment, performing cold press molding, wherein the pressure is 10MPa during cold press, the pressure is released to 0MPa after the cold press is finished, then heating and boosting the pressure to 480 ℃ and 35MPa, continuously sintering for 4 hours, and obtaining the bismuth antimony tellurium alloy target blank after sintering.
(7) And (3) processing and forming: machining the bismuth-antimony-tellurium alloy target blank to obtain a target blank with a theoretical chemical formula of Bi0.3Sb1.7Te3Bismuth antimony tellurium alloy target material.
The obtained bismuth antimony tellurium alloy target is tested, and the component test result shows that Bi is 9.61wt.%, and Sb is 31.72wt.%, Te is 58.67 wt.%; all metal impurities are less than 5ppm except the inevitable oxygen content is 45ppm and the inevitable carbon content is less than 5ppm, and the test density of the sample is 6.78g/cm3The relative density reaches 99.5 percent.
Example 2.
(1) Weighing and proportioning: weighing a bismuth raw material, an antimony raw material and a tellurium raw material according to the mixing mass ratio of 1:1.75: 3.66;
(2) tube sealing smelting: putting a bismuth raw material, an antimony raw material and a tellurium raw material into a glass tube, vacuumizing, sealing the glass tube, heating to 700 ℃, smelting for 12min to obtain a bismuth-antimony-tellurium alloy melt, and applying swinging motion to the glass tube in the smelting process, wherein the swinging motion can be carried out at a left-right swinging angle of 45 degrees and a swinging frequency of 12 times/min;
(3) zone melting: the bismuth-antimony-tellurium alloy melt is placed in a crystal pulling furnace to be subjected to zone melting at the zone melting temperature of 720 ℃, the zone melting times of 2 times and the zone melting rate of 20mm/h, and a bismuth-antimony-tellurium alloy ingot is obtained after zone melting;
(4) crushing and pulverizing: removing 1/6 head and tail of the total length of the bismuth-antimony-tellurium alloy ingot, and then crushing and screening to obtain first bismuth-antimony-tellurium alloy powder;
(5) ball milling uniformly: repeatedly grinding the bismuth antimony tellurium alloy powder in a ball mill to obtain second bismuth antimony tellurium alloy powder;
(6) hot-pressing and sintering: and placing the second bismuth antimony tellurium alloy powder in a graphite mold, then placing the graphite mold into sintering equipment, performing cold press molding, wherein the pressure is 15MPa during cold press, the pressure is released to 0MPa after the cold press is finished, then heating and boosting the pressure to 500 ℃ and 40MPa, continuously sintering for 3h, and obtaining the bismuth antimony tellurium alloy target blank after sintering.
(7) And (3) processing and forming: machining the bismuth-antimony-tellurium alloy target blank to obtain a target blank with a theoretical chemical formula of Bi0.5Sb1.5Te3Bismuth antimony tellurium alloy target material.
The obtained bismuth-antimony-tellurium alloy target is tested, and the component test result shows that Bi is 15.60wt.%, Sb is 27.26wt.%, and Te is 57.14 wt.%; except for inevitable oxygen content45ppm, unavoidable carbon content of less than 5ppm, all metal impurities less than 5ppm, and a sample density of 6.75g/cm3The relative density reaches 99.3 percent.
Example 3.
(1) Weighing and proportioning: weighing a bismuth raw material, an antimony raw material and a tellurium raw material according to the mixing mass ratio of 1:2.33: 4.57;
(2) tube sealing smelting: putting a bismuth raw material, an antimony raw material and a tellurium raw material into a glass tube, vacuumizing, sealing the glass tube, heating to 710 ℃, smelting for 10min to obtain a bismuth-antimony-tellurium alloy melt, and applying swinging motion to the glass tube in the smelting process, wherein the swinging motion can be carried out at a left-right swinging angle of 45 degrees and a swinging frequency of 15 times/min;
(3) zone melting: the bismuth-antimony-tellurium alloy melt is placed in a crystal pulling furnace to be subjected to zone melting with the zone melting temperature of 750 ℃, the zone melting frequency of 2 times and the zone melting rate of 35mm/h, and a bismuth-antimony-tellurium alloy ingot is obtained after zone melting;
(3) crushing and pulverizing: removing 1/8-1/6 of the total length of the bismuth-antimony-tellurium alloy ingot, crushing and screening to obtain first bismuth-antimony-tellurium alloy powder;
(4) ball milling uniformly: repeatedly grinding the bismuth antimony tellurium alloy powder in a ball mill to obtain second bismuth antimony tellurium alloy powder;
(5) hot-pressing and sintering: and placing the second bismuth antimony tellurium alloy powder in a graphite mold, then placing the graphite mold into sintering equipment, performing cold press molding, wherein the pressure is 20MPa during cold press, the pressure is released to 0MPa after the cold press is finished, then heating and boosting the pressure to 550 ℃ and 45MPa, continuously sintering for 2h, and obtaining the bismuth antimony tellurium alloy target blank after sintering.
(6) And (3) processing and forming: machining the bismuth-antimony-tellurium alloy target blank to obtain a target blank with a theoretical chemical formula of Bi0.4Sb1.6Te3Bismuth antimony tellurium alloy target material.
The obtained bismuth-antimony-tellurium alloy target is tested, and the component test result shows that Bi is 12.64wt.%, Sb is 29.46wt.%, and Te is 57.89 wt.%; except that the inevitable oxygen content is 45ppm and the inevitable carbon content is less than 5ppm, soAll metal impurities are less than 5ppm, and the test density of a sample is 6.69g/cm3The relative density reaches 99.6 percent.
The invention provides a preparation method of a bismuth antimony tellurium alloy target, the prepared bismuth antimony tellurium alloy target has high purity and relative density of more than 99%, and a thin film thermoelectric material prepared by using the target can be bent, has excellent performance and can meet various application requirements.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (10)
1. The preparation method of the bismuth-antimony-tellurium alloy target material is characterized by comprising the following steps of:
s1, weighing and proportioning: weighing bismuth raw materials, antimony raw materials and tellurium raw materials according to the proportion required by the bismuth-antimony-tellurium alloy target material;
s2, sealing and smelting: placing the bismuth raw material, the antimony raw material and the tellurium raw material into a glass tube, vacuumizing, sealing the glass tube, and heating and smelting to obtain a bismuth-antimony-tellurium alloy melt;
s3, zone melting: placing the bismuth antimony tellurium alloy melt in a crystal pulling furnace for zone melting to obtain a bismuth antimony tellurium alloy ingot;
s4, crushing and pulverizing: crushing and screening the bismuth antimony tellurium alloy ingot to obtain first bismuth antimony tellurium alloy powder;
s5, ball milling uniformly: repeatedly grinding the bismuth antimony tellurium alloy powder in a ball mill to obtain second bismuth antimony tellurium alloy powder;
s6, hot-pressing and sintering: placing the second bismuth antimony tellurium alloy powder in a graphite mold, and then placing the graphite mold into sintering equipment for sintering to obtain a bismuth antimony tellurium alloy target blank;
s7, processing and forming: and machining the bismuth-antimony-tellurium alloy target blank to obtain the bismuth-antimony-tellurium alloy target.
2. The method according to claim 1, wherein the mixing mass ratio of the bismuth raw material, the antimony raw material and the tellurium raw material in the weighed ingredients is (1: 1.36: 3.05) to (1: 3.3: 6.1).
3. The method as claimed in claim 1, wherein the temperature of the smelting in the step of sealed tube smelting is 680-710 ℃, and the smelting duration is 10-15 min.
4. The method according to claim 1, wherein during the step of melting in the tube sealing melting, a swinging motion is applied to the glass tube, the swinging motion can swing at an angle of 45 degrees from side to side, and the swinging frequency is 10-15 times/min.
5. The method of claim 4, wherein the step zone melting process parameters are: the zone-melting temperature is 710-750 ℃, the zone-melting times are 1-2 times, and the zone-melting speed is 15-35 mm/h.
6. The method of claim 1, wherein the bismuth antimony tellurium alloy ingot is subjected to removal of a head and tail impurity-enriched portion before being crushed to prepare powder.
7. The method of claim 6, wherein the length of the head and the tail of the bismuth antimony tellurium alloy ingot is not more than 1/8-1/6 of the total length of the bismuth antimony tellurium alloy ingot.
8. The method of claim 1, wherein during the step of ball milling, a protective gas is filled in the ball mill.
9. The method according to claim 1, wherein in the step of hot-pressing sintering, the sintering comprises the following specific steps: firstly, carrying out cold press molding, wherein the pressure is 10-20 MPa during cold pressing, releasing the pressure to 0MPa after the cold pressing is finished, then heating and boosting the pressure to 480-550 ℃ and 35-45 MPa, and continuously sintering for 2-4 h.
10. The method of claim 1, wherein the bismuth, antimony and tellurium raw materials have a purity of 4N or more.
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