CN117385473A - Preparation method of quaternary copper-based diamond-like semiconductor crystal - Google Patents
Preparation method of quaternary copper-based diamond-like semiconductor crystal Download PDFInfo
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- CN117385473A CN117385473A CN202311709975.7A CN202311709975A CN117385473A CN 117385473 A CN117385473 A CN 117385473A CN 202311709975 A CN202311709975 A CN 202311709975A CN 117385473 A CN117385473 A CN 117385473A
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- 239000013078 crystal Substances 0.000 title claims abstract description 87
- 239000010949 copper Substances 0.000 title claims abstract description 79
- 239000004065 semiconductor Substances 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010453 quartz Substances 0.000 claims abstract description 116
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 116
- 238000002844 melting Methods 0.000 claims abstract description 46
- 230000008018 melting Effects 0.000 claims abstract description 46
- 238000000137 annealing Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000010432 diamond Substances 0.000 abstract description 3
- 229910003460 diamond Inorganic materials 0.000 abstract description 3
- 239000000155 melt Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000629 Rh alloy Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- -1 carbon structure compound Chemical class 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
Abstract
The invention relates to the field of semiconductors, and provides a preparation method of a quaternary copper-based diamond-like semiconductor crystal, aiming at the problems of limited size and performance of the compound with a quaternary diamond structure in the prior art, wherein the preparation method comprises the steps that 1 high-purity simple substances are subjected to melting reaction to obtain diamond-like Cu 2 XYZ 4 A crystal raw material; 2, placing the crystal raw material into a quartz crucible, and vacuumizing and sealing; 3, putting the quartz crucible into a vertical growth furnace, and sequentially passing through a high-temperature melting zone, a medium-temperature growth zone and a low-temperature annealing zone to obtain a product; the temperature of the high-temperature melting zone is 950-1200 ℃, the temperature of the medium-temperature growth zone is 750-950 ℃, and the temperature of the low-temperature annealing zone is 450-750 ℃; the temperature gradient of the medium temperature growth area is 10-30 ℃/cm, and the moving speed of the quartz crucible in the medium temperature growth area is 0.2-3mm/h. The invention can obtain a large sizeThe quaternary copper-based diamond-like semiconductor crystal with excellent size and performance has simple process.
Description
Technical Field
The invention relates to the field of semiconductors, in particular to a preparation method of a quaternary copper-based diamond-like semiconductor crystal.
Background
The development of thermoelectric materials with high thermoelectric figure of merit has great practical application implications for solving the thermal problems of electronic devices and integrated circuits. Thermoelectric materials which are well-developed and have excellent thermoelectric properties are semiconductor alloy materials (such as Bi 2 Te 3 PbTe, skutterudite-based, etc.), although these materials have high thermoelectric figure of merit, they have various problems such as easy oxidation, easy decomposition, high cost, small element reserves, toxicity to human bodies, etc., which limit the large-scale application of these materials. Compared with the diamond-like carbon structure compound, the diamond-like carbon structure compound has the characteristics of rich content of constituent elements, no toxicity, high-efficiency charge transport performance, proper band gap width, high absorption coefficient and the like, and is considered to be a novel thermoelectric material system with application prospect.
Diamond-like structured compounds have evolved from diamond structures with distorted tetrahedral structures, and were studied in the early days only in the optoelectronic field, due to limitations in manufacturing process and test conditions, until 2009, quaternary diamond-like structured compound Cu 2 ZnSnSe 4 And Cu 2 CdSnSe 4 After the thermoelectric performance of diamond-like structured compounds was reported, diamond-like structured compounds have been attracting attention in the thermoelectric field as a class of wide bandgap semiconductor thermoelectric materials.
Cu 2 XYZ 4 (x= Zn, cd, mn, fe, co, y=sn, ge, z=s, se, te) is a quaternary diamond structure compound having a tetragonal crystal structure of a stannous mine structure, and the space group is I-42m. The crystal structure can be regarded as being formed by stacking lattices of two sphalerite structures along the C-axis direction. However, the crystal sample is currently mainly obtained by spark plasma sintering (e.g., song, Q. F, qia, P, hao, F, zhao, K, zhang, T; ren, D, shi, X, chen, L. QuaternaryPseudocubic Cu) 2 TMSnSe 4 (TM=Mn,Fe, Co) Chalcopyrite Thermoelectric Materials [J]AdvancedElectronic Materials 2016, 2 (12) has limited dimensions and the inability to obtain studies on the anisotropic thermal and electrical transport properties of the crystal integrity has limited the research, development and use of such materials by growth techniques. There is a need for an ideal solution.
Disclosure of Invention
The invention provides a preparation method of a quaternary copper-based diamond-like semiconductor crystal, which aims to solve the problems of limited size and performance of the existing preparation of a quaternary diamond-like structure compound, and adopts a melt growth method to obtain the large-size quaternary copper-based diamond-like semiconductor crystal. Melting and spontaneous nucleation of the diamond-like carbon raw material in a high-temperature region, completing the growth of crystals in a medium-temperature region until the completion of melt crystallization, completing the annealing of the crystals in a low-temperature region, and adjusting the temperatures and the temperature change rates of different temperature regions to obtain the quaternary copper-based diamond-like carbon semiconductor crystal with excellent thermoelectric performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a quaternary copper-based diamond-like semiconductor crystal comprises the following steps:
1) The high-purity simple substance is subjected to melting reaction to obtain diamond-like Cu 2 XYZ 4 Crystal raw materials (x= Zn, cd, mn, fe, co, y=sn, ge, z=s, se, te);
2) Cu is added with 2 XYZ 4 Putting the crystal raw materials into a quartz crucible, sequentially vacuumizing the quartz crucible, filling inert gas into the quartz crucible, and sealing the quartz crucible;
3) Putting a quartz crucible into a vertical growth furnace, sequentially passing the quartz crucible through a high-temperature melting zone, a medium-temperature growth zone and a low-temperature annealing zone along the vertical direction, and finally cooling to room temperature to obtain a quaternary copper-based diamond-like semiconductor crystal; the temperature of the high-temperature melting zone is 950-1200 ℃, the temperature of the medium-temperature growth zone is 750-950 ℃, and the temperature of the low-temperature annealing zone is 450-750 ℃; the temperature gradient of the medium temperature growth area is 10-30 ℃/cm, and the moving speed of the quartz crucible in the medium temperature growth area is 0.2-3mm/h.
Preferably, the melting reaction of step 1) is carried out in a vertical melting furnace or a swinging furnace, wherein the temperature of the swinging furnace is 950-1200 ℃, the heating rate is 4-10 ℃/min, the swinging time is 0.5-3 h, and the swinging rate is 10-30 r/min.
The diamond-like material may be single crystal or polycrystalline.
Preferably, step 2) Cu 2 XYZ 4 Is 50-200 and g.
Preferably, step 2) is evacuated to 10 -3 Pa, the inert gas is argon, and a gas flame, an acetylene flame or a hydrogen flame is adopted for sealing. As a further preference, the vacuum is applied to 10 -3 Pa, argon is flushed in, and then the vacuum is pumped again to 10 -3 Pa, the cycle is thus 3 times. The diamond-like carbon raw material is filled into a crucible, and is sealed after vacuumizing, so that Se is prevented from volatilizing in the growth process, and the accuracy of the stoichiometric ratio of the crystal is improved.
Preferably, the bottom of the quartz crucible is conical, and the taper is 17-54 degrees; and/or; the diameter of the quartz crucible is 10-80 mm, and the length is 10-40 cm. The melt spontaneously generates a plurality of crystal nuclei at the bottom of the quartz crucible, and the conical bottom can effectively reduce the generation of the crystal nuclei, so that the growth of crystals along a certain crystal nucleus direction is facilitated.
Preferably, the quartz crucible is a double-layered quartz crucible.
Preferably, a lifting device in the vertical direction is arranged in the vertical growth furnace, a support base is placed on the lifting device, the support base is made of high-heat-conductivity heat-resistant steel, the quartz crucible is placed on the support base, and the bottom of the quartz crucible is in contact with the support base. The quartz crucible is supported by the heat-resistant steel base, so that the crystallization latent heat can be effectively conducted, the solid-liquid interface is optimized, and the complete crystal can be obtained.
Preferably, the vertical growth furnace is a vertical melting furnace, the furnace body is built by high-temperature-resistant mullite, 3 temperature areas in the growth furnace are separated by heat insulation boards, and the heat insulation boards are made of high-temperature-resistant alumina materials.
Preferably, thermocouples are arranged at the bottom of the quartz crucible and inside the vertical growth furnace and are respectively used for monitoring the real-time temperature of the bottom of the quartz crucible and setting the temperature of the furnace body. The thermocouple is preferably a platinum rhodium thermocouple.
Preferably, the time of the quartz crucible in the step 3) in the high-temperature melting zone is 8-20 h, so that melt melting and solid-liquid interface stability are ensured; the time in the low temperature annealing zone is 10-20 h.
Preferably, the temperature rising rate of the high-temperature melting zone in the step 3) is 1-2.5 ℃/min.
The melt growth method may or may not use a seed crystal. Preferably, no seed crystal is used, the process is simple, and the operation is convenient.
The melt growth method can adopt a pulling method or a descending method. Preferably, a descent method is employed.
Preferably, the diameter of the obtained quaternary copper-based diamond-like semiconductor crystal is 10-80 mm, the length is 10-100 mm, and the thermoelectric figure of merit zT is 0.2-0.8. Further preferably, the crystals have a diameter of 35-70 a mm a.
Therefore, the invention has the beneficial effects that: (1) The diamond-like carbon raw material melts and spontaneously nucleates in a high-temperature area, the growth of crystals is completed in a medium-temperature area until the crystallization of the melt is completed, the annealing of the crystals is completed in a low-temperature area, and the temperature of different temperature areas is regulated, so that the quaternary copper-based diamond-like carbon semiconductor crystals with excellent performance can be obtained. (2) The invention adopts a melt growth method, can grow large-size crystals, and has the advantages of simple device and easy operation.
Drawings
FIG. 1 is a schematic view of the structure of a quartz crucible in a vertical growth furnace; in the figure: 1. the heating element, 2, the heat insulating board, 3, the furnace body, 4, the quartz crucible, 5, the melt, 6, the crystal, 7, the support base, 8, elevating gear.
FIG. 2 is a Cu film obtained in example 1 2 CoSnSe 4 X-ray diffraction pattern of pyroelectric crystal.
FIG. 3 is Cu obtained in example 1 2 CoSnSe 4 The thermal conductivity of thermoelectric crystals in different directions is plotted against temperature.
Detailed Description
The technical scheme of the invention is further described through specific embodiments.
In the present invention, unless otherwise specified, the materials and equipment used are commercially available or are commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
General examples
A preparation method of a quaternary copper-based diamond-like semiconductor crystal comprises the following steps:
1) The high-purity simple substance is subjected to melting reaction to obtain diamond-like Cu 2 XYZ 4 Crystal raw materials (x= Zn, cd, mn, fe, co, y=sn, ge, z=s, se, te);
2) 50-200/g of Cu 2 XYZ 4 Putting the crystal raw material into a quartz crucible, vacuumizing to 10 -3 Pa, argon is injected, and then the vacuum is pumped to 10 -3 Pa, circulating for 3 times, and sealing by adopting gas flame, acetylene flame or hydrogen flame;
3) And putting the quartz crucible into a vertical growth furnace, sequentially passing through a high-temperature melting region, a medium-temperature growth region and a low-temperature annealing region along the vertical direction from top to bottom, and finally cooling to room temperature to obtain the quaternary copper-based diamond-like semiconductor crystal. The temperature of the high-temperature melting zone is 950-1200 ℃, the heating rate is 1-2.5 ℃/min, and the residence time of the quartz crucible is 8-20 h; the temperature of the medium temperature growth area is 750-950 ℃ and the temperature gradient is 10-30 ℃/cm; the temperature of the low-temperature annealing zone is 450-750 ℃, and the residence time of the quartz crucible is 10-20 h. The moving speed of the quartz crucible in the vertical growth furnace is 0.2-3mm/h. The diameter of the obtained quaternary copper-based diamond-like semiconductor crystal is 10-80 mm, the length is 10-100 mm, and the thermoelectric figure of merit zT is 0.2-0.8.
As shown in FIG. 1, the quartz crucible 4 is a double-layer quartz crucible, the bottom of the quartz crucible is conical, the taper is 17-54 degrees, the melt 5 is placed in the quartz crucible 4, and the crystal 6 preferentially grows at the bottom of the cone; the diameter of the quartz crucible is 10-80 mm, and the length is 10-40 cm. The vertical growth furnace is internally provided with a lifting device 8 in the vertical direction, a support base 7 is placed on the lifting device 8, the support base 7 is made of heat-resistant steel with high heat conductivity, the quartz crucible 4 is placed on the support base 7, and the bottom of the quartz crucible 4 is in contact with the support base 7. The vertical growth furnace is a vertical melting furnace, the furnace body 3 is built by high-temperature-resistant mullite through heating of the heating body 1, 3 temperature areas in the growth furnace are separated by the heat insulation plate 2, and the heat insulation plate 2 is made of high-temperature-resistant alumina material.
Preferably, thermocouples are arranged at the bottom of the quartz crucible and inside the vertical growth furnace and are respectively used for monitoring the real-time temperature of the bottom of the quartz crucible and setting the temperature of the furnace body. The thermocouple is preferably a platinum rhodium thermocouple.
Example 1
Quaternary copper base diamond-like semiconductor crystal Cu 2 CoSnSe 4 The preparation method of (2) comprises the following steps:
1) Mixing high-purity Cu particles, co particles, sn particles and Se particles according to the molar ratio of 2:1:1:4, placing into a quartz crucible for vacuum sealing, then placing into a swinging furnace, heating to 1000 ℃, preserving heat for 1 h to enable raw materials to be completely melted, swinging for 1 h at a swinging speed of 15 r/min to enable the raw materials to be fully mixed and react completely, and obtaining diamond-like Cu 2 CoSnSe 4 Polycrystalline raw material.
2) 50 to g Cu 2 CoSnSe 4 Placing the polycrystalline raw material into a quartz crucible, and vacuumizing to 10 -3 Pa, argon is injected, and then the vacuum is pumped to 10 -3 Pa, circulating for 3 times, and finally sealing by adopting oxyhydrogen flame. The quartz crucible is a double-layer quartz crucible with the diameter of 17 mm, the length of 35 cm, the bottom of the quartz crucible is conical, and the taper is 44 degrees.
3) And putting the quartz crucible into a vertical growth furnace, sequentially passing through a high-temperature melting region, a medium-temperature growth region and a low-temperature annealing region along the vertical direction from top to bottom, and finally cooling to room temperature to obtain the quaternary copper-based diamond-like semiconductor crystal. The bottom of the quartz crucible and the inside of the vertical growth furnace are provided with platinum-rhodium alloy thermocouples which are respectively used for monitoring the real-time temperature of the bottom of the quartz crucible and setting the temperature of the furnace body. The temperature of the high-temperature melting zone is 1000 ℃, the heating rate is 2 ℃/min, the residence time of the quartz crucible is 8 h, and the melt melting and the solid-liquid interface stability are ensured; starting a lifting device to move the quartz crucible downwards to a medium temperature growth area of the vertical growth furnace, wherein the descending speed is 1 mm/h, and the temperature of the medium temperature growth area is equal to that of the quartz crucibleThe temperature is 800 ℃, the temperature gradient is 15 ℃/cm, cu 2 CoSnSe 4 Starting crystal growth in the medium-temperature growth area until the complete crystallization of the melt; the lifting device moves the quartz crucible downwards to a low-temperature annealing area of the vertical growth furnace, the temperature of the low-temperature annealing area is 550 ℃, and the residence time of the quartz crucible is 10 h.
The prepared quaternary copper-based diamond-like semiconductor crystal is cylindrical in main body, one end of the quaternary copper-based diamond-like semiconductor crystal is conical, the diameter of the quaternary copper-based diamond-like semiconductor crystal is 17 mm, and the length of the quaternary copper-based diamond-like semiconductor crystal is 25 mm. The X-ray diffraction pattern of the crystal is shown in fig. 2, and the XRD pattern indicates that the grown crystal is a single phase. FIG. 3 shows the thermal conductivity of the crystals in different directions as a function of temperature, in accordance with the references (Song, Q. F, qia, P, hao, F, zhao, K, zhang, T; ren, D, shi, X, chen, L. QuaternaryPseudocubic Cu) 2 TMSnSe 4 (TM=Mn,Fe, Co) Chalcopyrite Thermoelectric Materials [J]AdvancedElectronic Materials 2016, 2 (12) in comparison with the Cu prepared according to the invention 2 CoSnSe 4 The crystals have different values of thermal conductivity in different directions.
Example 2
Quaternary copper base diamond-like semiconductor crystal Cu 2 FeSnSe 4 The preparation method of (2) comprises the following steps:
1) Mixing high-purity Cu particles, fe particles, sn particles and Se particles according to a molar ratio of 2:1:1:4, placing the mixture into a quartz crucible for vacuum sealing, and then placing the quartz crucible into a melting furnace for melting reaction to obtain diamond-like Cu 2 FeSnSe 4 Polycrystalline raw material.
2) Cu of 150 g 2 FeSnSe 4 Placing the polycrystalline raw material into a quartz crucible, and vacuumizing to 10 -3 Pa, argon is injected, and then the vacuum is pumped to 10 -3 Pa, circulating for 3 times, and sealing by using gas flame. The quartz crucible is a double-layer quartz crucible with the diameter of 15 mm, the length of 35 cm, the bottom of the quartz crucible is conical, and the taper is 40 degrees.
3) And putting the quartz crucible into a vertical growth furnace, sequentially passing through a high-temperature melting region, a medium-temperature growth region and a low-temperature annealing region along the vertical direction from top to bottom, and finally cooling to room temperature to obtain the quaternary copper-based diamond-like semiconductor crystal. Quartz crucible bottomAnd a platinum-rhodium alloy thermocouple is arranged in the vertical growth furnace and is respectively used for monitoring the real-time temperature of the bottom of the quartz crucible and setting the temperature of the furnace body. The temperature of the high-temperature melting zone is 1050 ℃, the heating rate is 2 ℃/min, the residence time of the quartz crucible is 12 h, and the melt melting and the solid-liquid interface stability are ensured; starting a lifting device to move the quartz crucible downwards to a medium temperature growth area of a vertical growth furnace, wherein the descending speed is 1.2 mm/h, the temperature of the medium temperature growth area is 850 ℃, the temperature gradient is 18 ℃/cm, and Cu is contained 2 FeSnSe 4 Starting crystal growth in the medium-temperature growth area until the complete crystallization of the melt; the lifting device moves the quartz crucible downwards to a low-temperature annealing area of the vertical growth furnace, the temperature of the low-temperature annealing area is 600 ℃, and the residence time of the quartz crucible is 15 h. The diameter of the obtained quaternary copper-based diamond-like semiconductor crystal is 15 mm, and the length is 60 mm.
Example 3
Quaternary copper base diamond-like semiconductor crystal Cu 2 MnSnSe 4 The preparation method of (2) comprises the following steps:
1) Mixing high-purity Cu particles, mn particles, sn particles and Se particles according to the molar ratio of 2:1:1:4, placing into a quartz crucible for vacuum sealing, then placing into a swinging furnace, heating to 1150 ℃, preserving heat for 1 h to enable raw materials to be completely melted, swinging for 2 h at a swinging speed of 15 r/min to enable the raw materials to be fully mixed and react completely, and obtaining diamond-like Cu 2 MnSnSe 4 Polycrystalline raw material.
2) Cu of 120 g 2 MnSnSe 4 Placing the polycrystalline raw material into a quartz crucible, and vacuumizing to 10 -3 Pa, argon is injected, and then the vacuum is pumped to 10 -3 Pa, circulating for 3 times, and sealing by acetylene flame. The quartz crucible is a double-layer quartz crucible with the diameter of 12 mm, the length of 20 cm, the bottom of the quartz crucible is conical, and the taper is 32 degrees.
3) And putting the quartz crucible into a vertical growth furnace, sequentially passing through a high-temperature melting region, a medium-temperature growth region and a low-temperature annealing region along the vertical direction from top to bottom, and finally cooling to room temperature to obtain the quaternary copper-based diamond-like semiconductor crystal. Platinum-rhodium alloy thermocouples are arranged at the bottom of the quartz crucible and inside the vertical growth furnace and are respectively used for monitoring stonesReal-time temperature of the bottom of the crucible and set furnace temperature. The temperature of the high-temperature melting zone is 1100 ℃, the heating rate is 2.5 ℃/min, the residence time of the quartz crucible is 12 h, and the melt melting and the solid-liquid interface stability are ensured; starting a lifting device to move the quartz crucible downwards to a medium temperature growth area of a vertical growth furnace, wherein the descending speed is 1.2 mm/h, the temperature of the medium temperature growth area is 750 ℃, the temperature gradient is 18 ℃/cm, and Cu is contained 2 MnSnSe 4 Starting crystal growth in the medium-temperature growth area until the complete crystallization of the melt; the lifting device moves the quartz crucible downwards to a low-temperature annealing area of the vertical growth furnace, the temperature of the low-temperature annealing area is 500 ℃, and the residence time of the quartz crucible is 20 h. The diameter of the obtained quaternary copper-based diamond-like semiconductor crystal is 12 mm, and the length is 43 mm.
Example 4
Quaternary copper base diamond-like semiconductor crystal Cu 2 MnGeTe 4 The preparation method of (2) comprises the following steps:
1) Mixing high-purity Cu particles, mn particles, ge particles and Te particles according to a molar ratio of 2:1:1:4, placing the mixture into a quartz crucible for vacuum sealing, and then placing the quartz crucible into a melting furnace for melting reaction to obtain diamond-like Cu 2 MnGeTe 4 Polycrystalline raw material.
2) Cu of 80 g 2 MnGeTe 4 Placing the polycrystalline raw material into a quartz crucible, and vacuumizing to 10 -3 Pa, argon is injected, and then the vacuum is pumped to 10 -3 Pa, circulating for 3 times, and finally sealing by adopting oxyhydrogen flame. The quartz crucible is a double-layer quartz crucible with the diameter of 25 mm, the length of 35 cm, the bottom of the quartz crucible is conical, and the taper is 44 degrees.
3) And putting the quartz crucible into a vertical growth furnace, sequentially passing through a high-temperature melting region, a medium-temperature growth region and a low-temperature annealing region along the vertical direction from top to bottom, and finally cooling to room temperature to obtain the quaternary copper-based diamond-like semiconductor crystal. The bottom of the quartz crucible and the inside of the vertical growth furnace are provided with platinum-rhodium alloy thermocouples which are respectively used for monitoring the real-time temperature of the bottom of the quartz crucible and setting the temperature of the furnace body. The temperature of the high-temperature melting zone is 1080 ℃, the heating rate is 1 ℃/min, the residence time of the quartz crucible is 20 h, and the melt melting and the melting of the melt are ensuredThe solid-liquid interface is stable; starting a lifting device to move the quartz crucible downwards to a medium temperature growth area of a vertical growth furnace, wherein the descending speed is 1.2 mm/h, the temperature of the medium temperature growth area is 780 ℃, the temperature gradient is 25 ℃/cm, and Cu is contained 2 MnGeTe 4 Starting crystal growth in the medium-temperature growth area until the complete crystallization of the melt; the lifting device moves the quartz crucible downwards to a low-temperature annealing area of the vertical growth furnace, the temperature of the low-temperature annealing area is 600 ℃, and the residence time of the quartz crucible is 15 h. The diameter of the obtained quaternary copper-based diamond-like semiconductor crystal is 25 mm, and the length is 35 mm.
Example 5
Quaternary copper base diamond-like semiconductor crystal Cu 2 CdGeS 4 The preparation method of (2) comprises the following steps:
1) Mixing high-purity Cu particles, cd particles, ge particles and S particles according to a molar ratio of 2:1:1:4, placing the mixture into a quartz crucible for vacuum sealing, and then placing the quartz crucible into a melting furnace for melting reaction to obtain diamond-like Cu 2 CdGeS 4 Polycrystalline raw material.
2) Will be 180 g Cu 2 CdGeS 4 Placing the polycrystalline raw material into a quartz crucible, and vacuumizing to 10 -3 Pa, argon is injected, and then the vacuum is pumped to 10 -3 Pa, circulating for 3 times, and finally sealing by adopting oxyhydrogen flame. The quartz crucible is a double-layer quartz crucible with the diameter of 40 mm, the length of 40 cm, the bottom of the quartz crucible is conical, and the taper is 50 degrees.
3) And putting the quartz crucible into a vertical growth furnace, sequentially passing through a high-temperature melting region, a medium-temperature growth region and a low-temperature annealing region along the vertical direction from top to bottom, and finally cooling to room temperature to obtain the quaternary copper-based diamond-like semiconductor crystal. The bottom of the quartz crucible and the inside of the vertical growth furnace are provided with platinum-rhodium alloy thermocouples which are respectively used for monitoring the real-time temperature of the bottom of the quartz crucible and setting the temperature of the furnace body. The temperature of the high-temperature melting zone is 1100 ℃, the heating rate is 2 ℃/min, the residence time of the quartz crucible is 20 h, and the melt melting and the solid-liquid interface stability are ensured; starting a lifting device to move the quartz crucible downwards to a medium temperature growth area of a vertical growth furnace, wherein the descending speed is 2 mm/h, the temperature of the medium temperature growth area is 900 ℃, the temperature gradient is 20 ℃/cm, and the temperature gradient is Cu 2 CdGeS 4 Starting crystal growth in the medium-temperature growth area until the complete crystallization of the melt; the lifting device moves the quartz crucible downwards to a low-temperature annealing area of the vertical growth furnace, the temperature of the low-temperature annealing area is 680 ℃, and the residence time of the quartz crucible is 15 h. The diameter of the obtained quaternary copper-based diamond-like semiconductor crystal is 40 mm, and the length is 25 mm.
Comparative example 1
The difference from example 1 is that the quartz crucible used in step 2) is a single-layer crucible.
As a result, the grown crystal fails to grow during the growth stage due to the breakage of the crucible and the outflow of the melt.
Comparative example 2
The difference from example 4 is that the temperature of the high temperature growth zone in step 3) is 900 ℃.
Results Cu taken out after growth was completed 2 MnGeTe 4 The sample, consistent with the appearance of the initially placed sample, showed that the sample did not melt in the high temperature zone, resulting in failure of crystal growth.
Comparative example 3
The difference from example 5 is that the quartz crucible used in step 2) has a round bottom at the bottom.
After the end of the growth, cu is taken out 2 CdGeS 4 The sample at the bottom is in fine particles, because the melt at the bottom of the crucible is preferentially supercooled, so that a large number of crystal nuclei are generated, and the crystal nuclei are too many to mutually influence, so that the crystal nuclei cannot grow up, and therefore the crystal nuclei are in fine particles.
Comparative example 4
The difference from example 2 is that the temperature in the warm growth zone in step 2) is 970 ℃.
The temperature of the intermediate temperature region is too high, so that the raw material is still in a melt state in the intermediate temperature growth region, and the temperature gradient is too large and the growth speed is increased in the process of moving to the low temperature annealing region, so that stress and dislocation density increase in the crystal are generated.
Comparative example 5
The difference from example 2 is that the temperature gradient in the warm growth zone in step 2) is 5℃C/cm.
Because the temperature gradient of the medium-temperature growth area is smaller, components of the solid-liquid interface deviate to cause supercooling of components, so that the solution growth interface is unstable, and crystal defects such as twin crystals, polycrystal and the like are generated.
As can be seen from the comparative examples, the quaternary copper-based diamond-like semiconductor crystal prepared by the method has more complex crystallization influencing factors because of 4 metal elements, has high requirement on crystallization parameters, and can obtain crystals with excellent structure and performance within a preferable range.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the quaternary copper-based diamond-like semiconductor crystal is characterized by comprising the following steps of:
1) The high-purity simple substance is subjected to melting reaction to obtain diamond-like Cu 2 XYZ 4 Crystal raw materials (x= Zn, cd, mn, fe, co, y=sn, ge, z=s, se, te);
2) Cu is added with 2 XYZ 4 Putting the crystal raw materials into a quartz crucible, sequentially vacuumizing the quartz crucible, filling inert gas into the quartz crucible, and sealing the quartz crucible;
3) Putting a quartz crucible into a vertical growth furnace, and sequentially passing through a high-temperature melting zone, a medium-temperature growth zone and a low-temperature annealing zone along the vertical direction of the quartz crucible to obtain a quaternary copper-based diamond-like semiconductor crystal; the temperature of the high-temperature melting zone is 950-1200 ℃, the temperature of the medium-temperature growth zone is 750-950 ℃, and the temperature of the low-temperature annealing zone is 450-750 ℃; the temperature gradient of the medium temperature growth area is 10-30 ℃/cm, and the moving speed of the quartz crucible in the medium temperature growth area is 0.2-3mm/h.
2. The method according to claim 1, wherein the melting reaction of step 1) is performed in a vertical melting furnace or a rocking furnace having a temperature of 950 to 1200 ℃, a heating rate of 4 to 10 ℃/min, a rocking time of 0.5 to 3 h, and a rocking rate of 10 to 30 r/min.
3. The method of claim 1, wherein step 2) Cu 2 XYZ 4 Is 50-200 and g.
4. A method according to claim 1 or 3, wherein step 2) is vacuum-pumped to 10 -3 Pa, the inert gas is argon, and a gas flame, an acetylene flame or a hydrogen flame is adopted for sealing.
5. The preparation method according to claim 1, wherein the bottom of the quartz crucible is conical, and the taper is 17-54 degrees; the diameter of the quartz crucible is 10-80 mm, and the length is 10-40 cm.
6. The method of manufacturing according to claim 1, wherein the quartz crucible is a double-layered quartz crucible.
7. The method according to claim 1, 5 or 6, wherein a vertical lifting device is provided in the vertical growth furnace, a support base is placed on the lifting device, the support base is made of high-heat-conductivity heat-resistant steel, the quartz crucible is placed on the support base, and the bottom of the quartz crucible is in contact with the support base.
8. The method of claim 1, wherein the quartz crucible of step 3) has a time of 8 to 20 h in the high temperature melting zone and a time of 10 to 20 h in the low temperature annealing zone.
9. The method of claim 1 or 8, wherein the high temperature melting zone of step 3) has a heating rate of 1-2.5 ℃/min.
10. The method of manufacturing according to claim 1, wherein the quaternary copper-based diamond-like semiconductor crystal is manufactured to have a diameter of 10-80 mm and a length of 10-100 mm.
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