CN113937210A - Preparation of SnSe/SnSe by selenization2Method for compounding thermoelectric film - Google Patents
Preparation of SnSe/SnSe by selenization2Method for compounding thermoelectric film Download PDFInfo
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- CN113937210A CN113937210A CN202111186758.5A CN202111186758A CN113937210A CN 113937210 A CN113937210 A CN 113937210A CN 202111186758 A CN202111186758 A CN 202111186758A CN 113937210 A CN113937210 A CN 113937210A
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- 238000013329 compounding Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000010453 quartz Substances 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011669 selenium Substances 0.000 claims abstract description 29
- 238000005516 engineering process Methods 0.000 claims abstract description 28
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 7
- 238000010030 laminating Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 239000013077 target material Substances 0.000 claims description 12
- 229910001134 stannide Inorganic materials 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009461 vacuum packaging Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 16
- 239000010408 film Substances 0.000 description 49
- 239000000463 material Substances 0.000 description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- MFIWAIVSOUGHLI-UHFFFAOYSA-N selenium;tin Chemical compound [Sn]=[Se] MFIWAIVSOUGHLI-UHFFFAOYSA-N 0.000 description 4
- 229910002665 PbTe Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
The invention provides a method for preparing SnSe/SnSe by selenylation2A method of laminating a thermoelectric film comprising the steps of: (a) preparing the SnSe thermoelectric film by using a pulsed laser deposition technology; (b) repeatedly carrying out ultrasonic cleaning on the quartz tube by using water and alcohol, and then putting the quartz tube into a constant-temperature drying box for drying; (c) packaging the SnSe thermoelectric film and the selenium particles in the quartz tube by using a vacuum tube sealing technology; (d) putting the quartz tube into an annealing furnace, heating to 350 ℃ within 10-60min, keeping the temperature for 10-120min to selenize the SnSe film in the quartz tube, and finally naturally cooling to room temperatureWarming to obtain SnSe/SnSe2And compounding the thermoelectric film. The composite film has excellent thermoelectric performance and wide application prospect in the field of thermoelectric micro-nano devices.
Description
Technical Field
The invention relates to the technical field of thermoelectric film preparation, in particular to a method for preparing SnSe/SnSe by selenization2A method for laminating a thermoelectric film.
Background
The thermoelectric material is a functional material which can realize the interconversion of thermal energy and electric energy. The thermoelectric power generation and refrigeration device made of the material has the advantages of small volume, light weight, no noise, no pollution, high reliability, no mechanical transmission part and the like, and has wide application prospect. With the rapid development of world economy, the demand of human beings on energy is increasing day by day, and at present, about 80% of energy in the world is still derived from traditional energy (coal, petroleum and natural gas), but the utilization rate of the traditional energy is low, about more than half of the energy is wasted in the form of heat energy, and meanwhile, the problem of environmental pollution caused by the combustion of the traditional energy is more and more serious, and the thermoelectric material is concerned about recovering part of waste heat energy and improving the utilization rate of the energy.
The performance of thermoelectric materials is typically measured by a dimensionless thermoelectric figure of merit, zT, which is defined as zT ═ S (S)2σ/κ) T. Where S is the Seebeck coefficient of the material, σ is the electrical conductivity of the material, and κ is the thermal conductivity of the material (mainly including the carrier thermal conductivity κ)cAnd lattice thermal conductivity κL) And T is the absolute temperature. For a long time, the research on thermoelectric materials has mainly focused on compound semiconductors and alloy materials composed of heavy metal elements, such as the conventional thermoelectric material Bi in commercial use2Te3PbTe, SiGe alloys, etc., but these materials contain many toxic and rare elements, which greatly limits the practical application and popularization of thermoelectric materials. In 2014, Zhao et al reported that a simple binary compound SnSe monocrystal block has excellent thermoelectric performance on Nature for the first time and is the thermoelectric material with the best performance reported at present. The material does not contain toxic elements, is low in raw material price, and is expected to become one of candidate materials for replacing PbTe base materials in commercial use.
Compared with a three-dimensional block sample, the two-dimensional film material is more compatible with a modern semiconductor process, and has the advantage that the block material is not replaceable in the aspect of thermoelectric micro-nano device application. Therefore, the research on the two-dimensional film SnSe material with excellent thermoelectric properties such as conductivity, power factor and the like has important practical significance.
Disclosure of Invention
The invention aims to provide a method for preparing SnSe/SnSe by selenizing2The method for compounding the thermoelectric film aims to solve the problems of non-ideal thermoelectric performance and high preparation difficulty of the existing material.
The technical scheme of the invention is as follows: SnSe/SnSe prepared by selenization2A method of laminating a thermoelectric film comprising the steps of:
(a) preparing the SnSe thermoelectric film by using a pulsed laser deposition technology;
(b) repeatedly carrying out ultrasonic cleaning on the quartz tube by using water and alcohol, and then putting the quartz tube into a constant-temperature drying box for drying;
(c) packaging the SnSe thermoelectric film and the selenium particles in the quartz tube by using a vacuum tube sealing technology;
(d) putting the quartz tube into an annealing furnace, heating to 350 ℃ within 10-60min, keeping the temperature for 10-120min to selenize the SnSe film in the quartz tube, and finally naturally cooling to room temperature to obtain the SnSe/SnSe2And compounding the thermoelectric film.
In the step (a), the preparation of the SnSe thermoelectric film by using the pulsed laser deposition technology comprises the following steps:
(a-1) uniformly mixing tin powder and selenium powder according to the atomic molar ratio Sn: Se being 1:1.15-1.25, then carrying out vacuum packaging in a quartz tube, then putting the quartz tube into a muffle furnace to be smelted into ingots and ground into powder, and then sintering by using a discharge plasma sintering technology to obtain a selenium stannide polycrystalline target material;
and (a-2) placing the selenium stannide polycrystalline target and the ultrasonically cleaned single crystal substrate into a PLD (programmable logic device) cavity, and preparing the SnSe thermoelectric film by using a pulsed laser deposition technology.
In the step (a), the substrate is a MgO (001) single crystal substrate, and during deposition, the laser frequency is 3-5Hz, and the laser density is 1.2-3.0J/cm2The argon pressure is 0.05-0.2Pa, the substrate temperature is 330-370 ℃, and the distance between the substrate and the target material is 4-6 cm.
In the step (b), the water is deionized water, and the alcohol purity is more than or equal to 95 percent.
In the step (b), the drying temperature is 70-120 ℃, and the time is more than or equal to 30 min.
In the step (c), the diameter of the quartz tube is 8-12mm, the volume of the packaged quartz tube is 4-10 mL, and the pressure intensity in the quartz tube is 4 multiplied by 10-5Pa-4×10-3Pa。
In the step (c), the purity of the selenium particles is 99.9% -99.999%, and the dosage of the selenium particles is 40-100 mg.
SnSe/SnSe prepared by the invention2The composite thermoelectric film has excellent thermoelectric performance, and the preparation method is simple and convenient, is easy to popularize, and has wide application prospect in the aspect of thermoelectric micro-nano devices.
Drawings
FIG. 1 is SnSe/SnSe prepared on MgO (001) single crystal substrate2XRD pattern of the composite thermoelectric film.
FIG. 2 is SnSe/SnSe prepared on MgO (001) single crystal substrate2The horizontal coordinate of the Seebeck spectrum of the composite thermoelectric film is temperature, and the vertical coordinate of the spectrum is the Seebeck coefficient.
FIG. 3 is SnSe/SnSe prepared on MgO (001) single crystal substrate2The electrical resistivity of the composite thermoelectric film is mapped, wherein the abscissa of the map is temperature, and the ordinate is electrical resistivity.
FIG. 4 is SnSe/SnSe prepared on MgO (001) single crystal substrate2The abscissa of the conductivity graph is temperature, and the ordinate is conductivity.
FIG. 5 is SnSe/SnSe prepared on MgO (001) single crystal substrate2The abscissa of the power factor map of the composite thermoelectric film is temperature, and the ordinate is power factor.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
Example 1: preparation of SnSe/SnSe2And compounding the thermoelectric film.
(1) Preparing the SnSe thermoelectric film by using a pulsed laser deposition technology;
and (1) packaging high-purity tin powder and high-purity selenium powder which are weighed according to the atomic molar ratio Sn to Se of 1 to 1.2 in a quartz tube by using a vacuum tube sealing technology, then putting the quartz tube into a muffle furnace to be melted into ingots and ground into powder, and finally sintering by using a discharge plasma sintering technology to obtain the selenium-enriched stannide selenium polycrystalline target material.
<2>Placing a target material and a single crystal substrate subjected to ultrasonic cleaning into a PLD (programmable logic device) cavity, and growing a tin selenide thermoelectric film on a MgO (001) single crystal substrate by a pulsed laser deposition technology under the conditions that the laser frequency is 5Hz and the laser density is 1.5J/cm2The back pressure is 2 x 10-4Pa, argon pressure of 0.1Pa, substrate temperature of 350 ℃, and substrate and target distance of 5 cm.
(2) The quartz tube was ultrasonically cleaned with deionized water and 98% alcohol 5 times each.
(3) And (3) putting the cleaned quartz tube into a constant-temperature drying box, and drying for 20 hours at the drying temperature of 70 ℃.
(4) The SnSe thermoelectric film and 70mg of selenium particles (purity 99.99%) are packed together in a quartz tube with a diameter of 10mm and a pressure of 8 x 10 inside the quartz tube-4Pa, the volume of the sealed quartz tube is 7 mL.
(5) And (3) putting the packaged quartz tube into an annealing furnace, raising the temperature from room temperature to 275 ℃ after 15min, keeping the temperature for 20min, and finally naturally cooling to room temperature. Namely obtaining SnSe/SnSe2And compounding the thermoelectric film.
SnSe/SnSe prepared by the implementation2The composite thermoelectric film is tested and analyzed by XRD, the analysis result is shown in figure 1, and the film prepared by the invention is SnSe/SnSe as can be seen from figure 12And compounding the thermoelectric film.
SnSe/SnSe prepared by the implementation2The composite thermoelectric film is subjected to a Seebeck coefficient test, the test result is shown in figure 2, and the SnSe/SnSe prepared by the invention can be known from figure 22The composite thermoelectric film showed a Seebeck coefficient of about 360 μ V/K at 600K.
SnSe/SnSe prepared by the implementation2The composite thermoelectric film is subjected to resistivity measurementThe test results are shown in FIGS. 3 and 4, and from FIGS. 3 and 4, the SnSe/SnSe prepared by the present invention can be seen2The composite thermoelectric film exhibited a resistivity of about 220 μ Ω. m and an electrical conductivity of about 4553S/m at 600K.
SnSe/SnSe prepared by the implementation2The composite thermoelectric film calculates the power factor according to the resistivity test and the Seebeck coefficient test, the result is shown in figure 5, and the SnSe/SnSe prepared by the invention can be known from figure 52The composite thermoelectric film shows a power factor of about 5.9 muW/cm K at 600K2。
Example 2: preparation of SnSe/SnSe2And compounding the thermoelectric film.
(1) Preparing the SnSe thermoelectric film by using a pulsed laser deposition technology;
and (1) packaging high-purity tin powder and high-purity selenium powder which are weighed according to the atomic molar ratio Sn to Se of 1 to 1.15 in a quartz tube by using a vacuum tube sealing technology, then putting the quartz tube into a muffle furnace to be melted into ingots and ground into powder, and finally sintering by using a discharge plasma sintering technology to obtain the selenium-enriched stannide selenium polycrystalline target material.
<2>Placing a target material and a single crystal substrate subjected to ultrasonic cleaning into a PLD (programmable logic device) cavity, and growing a tin selenide thermoelectric film on a MgO (001) single crystal substrate by a pulsed laser deposition technology under the conditions that the laser frequency is 5Hz and the laser density is 1.5J/cm2The back pressure is 1 × 10-4Pa, argon pressure of 0.1Pa, substrate temperature of 330 ℃ and substrate-target distance of 5 cm.
(2) The quartz tube was ultrasonically cleaned with deionized water and 98% alcohol 7 times each.
(3) And (3) putting the cleaned quartz tube into a constant-temperature drying box, wherein the drying temperature is 90 ℃, and drying for 15 hours.
(4) The SnSe thermoelectric film and 100mg selenium particles (purity 99.9%) were packed together in a 15mm diameter quartz tube at a pressure of 3X 10-4Pa, the volume of the sealed quartz tube is 10 mL.
(5) And (3) putting the packaged quartz tube into an annealing furnace, raising the temperature to 300 ℃ from room temperature for 20min, keeping the temperature for 10min, and finally naturally cooling to room temperature. To obtainTo SnSe/SnSe2And compounding the thermoelectric film. The preparation method is SnSe/SnSe2The PF of the composite thermoelectric film is about 4 mu W/cm.K at 600K2。
Example 3: preparation of SnSe/SnSe2And compounding the thermoelectric film.
(1) Preparing the SnSe thermoelectric film by using a pulsed laser deposition technology;
and (1) packaging high-purity tin powder and high-purity selenium powder which are weighed according to the atomic molar ratio Sn to Se of 1 to 1.17 in a quartz tube by using a vacuum tube sealing technology, then putting the quartz tube into a muffle furnace to be melted into ingots and ground into powder, and finally sintering by using a discharge plasma sintering technology to obtain the selenium-enriched stannide selenium polycrystalline target material.
<2>Placing a target material and a single crystal substrate subjected to ultrasonic cleaning into a PLD (programmable logic device) cavity, and growing a tin selenide thermoelectric film on a MgO (001) single crystal substrate by a pulsed laser deposition technology under the conditions that the laser frequency is 5Hz and the laser density is 1.6J/cm2The back pressure is 4 x 10-4Pa, argon pressure of 0.1Pa, substrate temperature of 360 ℃, and substrate-target distance of 5.5 cm.
(2) The quartz tube was ultrasonically cleaned with deionized water and 98% alcohol 6 times each.
(3) And (3) putting the cleaned quartz tube into a constant-temperature drying box, wherein the drying temperature is 80 ℃, and drying for 17 hours.
(4) SnSe thermoelectric thin film and 80mg selenium particles (purity 99.99%) are packaged together with 12mm diameter
In the quartz tube of (1), the pressure in the quartz tube is 7X 10-4Pa, the volume of the sealed quartz tube is 8 mL.
(5) And (3) putting the packaged quartz tube into an annealing furnace, raising the temperature to 250 ℃ from the room temperature for 10min, keeping the temperature for 20min, and finally naturally cooling to the room temperature. Namely obtaining SnSe/SnSe2And compounding the thermoelectric film. The preparation method is SnSe/SnSe2The PF of the composite thermoelectric film is about 3.17 muW/cm.K at 600K2。
Example 4: preparation of SnSe/SnSe2And compounding the thermoelectric film.
(1) Preparing the SnSe thermoelectric film by using a pulsed laser deposition technology;
and (1) packaging high-purity tin powder and high-purity selenium powder which are weighed according to the atomic molar ratio Sn to Se of 1 to 1.22 in a quartz tube by using a vacuum tube sealing technology, then putting the quartz tube into a muffle furnace to be melted into ingots and ground into powder, and finally sintering by using a discharge plasma sintering technology to obtain the selenium-enriched stannide selenium polycrystalline target material.
<2>Placing a target material and a single crystal substrate subjected to ultrasonic cleaning into a PLD (programmable logic device) cavity, and growing a tin selenide thermoelectric film on a MgO (001) single crystal substrate by a pulsed laser deposition technology under the conditions that the laser frequency is 5Hz and the laser density is 1.4J/cm2The back pressure is 3 x 10-4Pa, argon pressure of 0.1Pa, substrate temperature of 360 ℃, and substrate-target distance of 4.5 cm.
(2) The quartz tube was ultrasonically cleaned with deionized water and 98% alcohol 7 times each.
(3) And (3) putting the cleaned quartz tube into a constant-temperature drying box, and drying for 12 hours at the drying temperature of 70 ℃.
(4) The SnSe thermoelectric film and 60mg selenium particles (purity 99.99%) are packed together in a quartz tube with a diameter of 8mm and a pressure of 3X 10 inside the quartz tube-3Pa, the volume of the sealed quartz tube is 6 mL.
(5) And (3) putting the packaged quartz tube into an annealing furnace, raising the temperature from room temperature to 275 ℃ after 15min, keeping the temperature for 60min, and finally naturally cooling to room temperature. Namely obtaining SnSe/SnSe2And compounding the thermoelectric film. The preparation method is SnSe/SnSe2The PF of the composite thermoelectric film is about 4.55 mu W/cm K at 600K2。
Claims (7)
1. SnSe/SnSe prepared by selenization2A method of laminating a thermoelectric film, comprising the steps of:
(a) preparing the SnSe thermoelectric film by using a pulsed laser deposition technology;
(b) repeatedly carrying out ultrasonic cleaning on the quartz tube by using water and alcohol, and then putting the quartz tube into a constant-temperature drying box for drying;
(c) packaging the SnSe thermoelectric film and the selenium particles in the quartz tube by using a vacuum tube sealing technology;
(d) putting the quartz tube into an annealing furnace, heating to 350 ℃ within 10-60min, keeping the temperature for 10-120min to selenize the SnSe film in the quartz tube, and finally naturally cooling to room temperature to obtain the SnSe/SnSe2And compounding the thermoelectric film.
2. The selenization preparation of SnSe/SnSe of claim 12The method for preparing the SnSe thermoelectric film by using the pulsed laser deposition technology in the step (a) is characterized by comprising the following steps of:
(a-1) uniformly mixing tin powder and selenium powder according to the atomic molar ratio Sn: Se =1:1.15-1.25, then carrying out vacuum packaging in a quartz tube, then putting the quartz tube into a muffle furnace to be smelted into ingots and ground into powder, and then sintering by using a discharge plasma sintering technology to obtain the selenium stannide polycrystalline target material;
and (a-2) placing the selenium stannide polycrystalline target and the ultrasonically cleaned single crystal substrate into a PLD (programmable logic device) cavity, and preparing the SnSe thermoelectric film by using a pulsed laser deposition technology.
3. The selenization preparation of SnSe/SnSe of claim 22The method for compounding the thermoelectric film is characterized in that in the step (a), the substrate is an MgO (001) single crystal substrate, and during deposition, the laser frequency is 3-5Hz, and the laser density is 1.2-3.0J/cm2The argon pressure is 0.05-0.2Pa, the substrate temperature is 330-370 ℃, and the distance between the substrate and the target material is 4-6 cm.
4. The selenization preparation of SnSe/SnSe of claim 12The method for compounding the thermoelectric film is characterized in that in the step (b), water is deionized water, and the purity of alcohol is more than or equal to 95%.
5. The selenization preparation of SnSe/SnSe of claim 12The method for compounding the thermoelectric film is characterized in that in the step (b), the drying temperature is 70-120 ℃, and the time is more than or equal to 30 min.
6. The selenization preparation of SnSe/SnSe of claim 12The method for compounding the thermoelectric film is characterized in that in the step (c), the diameter of the quartz tube is 8-12mm, the volume of the packaged quartz tube is 4-10 mL, and the pressure in the quartz tube is 4 multiplied by 10- 5Pa-4×10-3Pa。
7. The selenization preparation of SnSe/SnSe of claim 12The method for compounding the thermoelectric film is characterized in that in the step (c), the purity of the selenium particles is 99.9% -99.999%, and the dosage of the selenium particles is 40-100 mg.
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| CN114686986A (en) * | 2022-04-02 | 2022-07-01 | 齐齐哈尔大学 | SnSe2Method for producing single crystal |
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