CN110344120B - SnSe2Base single crystal material and method for producing same - Google Patents
SnSe2Base single crystal material and method for producing same Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000001816 cooling Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 230000005496 eutectics Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 239000006184 cosolvent Substances 0.000 abstract description 3
- 239000010453 quartz Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004857 zone melting Methods 0.000 description 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L Cadmium iodide Inorganic materials [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
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- 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
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- 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
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/06—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using as solvent a component of the crystal composition
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Abstract
The invention relates to SnSe2The stoichiometric ratio of Sn and Se of the two components of the base single crystal material deviates from 1: 2, chemical composition of SnSe2+xWherein x is 0.1 to 0.4. The invention uses Se as cosolvent, can inhibit eutectic reaction from generating SnSe impurities during liquid phase cooling, thereby obtaining pure phase SnSe2+xSingle crystal material having a large number of intrinsic defects, i.e. Se interstitial atoms and SeSnInversion defect, which can be used to study SnSe2Intrinsic properties of the base single crystal material; meanwhile, the crystal growth period is short, the instrument cost is low, and the success rate is high.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to SnSe2A base single crystal material and a method for producing the same.
Background
SnSe2The material is a nontoxic semiconductor material with cheap raw materials, has good photoelectric property, energy storage property and thermoelectric conversion property, has certain flexibility, and has wide application prospect in the fields of photoelectric detectors, lithium battery anodes, flexible all-solid-state supercapacitors and thermoelectric conversion, so that the material has wide application prospect in recent years about SnSe2Semiconductor materials are increasingly studied, but in phase diagrams, when a high-temperature solution is condensed at a liquidus line, a liquid-phase eutectic reaction occurs at 638 ℃ to generate SnSe2And SnSe, so that SnSe is produced2Single crystals are a great challenge.
SnSe2Is a hexagonal layered structure, and the crystal structure thereof belongs to CdI2Type, space group is P-3m1, SnSe2The atomic layers are bonded by Van der Waals bonds, the atomic layers are bonded by covalent bonds, and the layered structure ensures that SnSe is bonded2Has strong orientation, intrinsic low thermal conductivity between layers, and SnSe calculation2Energy band structure of (1) shows, SnSe2The lowest value of conduction band is located in L-M direction, and the highest value of valence bandIn the K-direction, SnSe2Has a degeneracy of 6 and a high effective mass of state density, so that in theory SnSe is present in the above-mentioned respective fields2Has good application prospect. SnSe2+xCompare SnSe2Containing an excess of Se, thus altering SnSe2The energy band structure has a large number of defects, which is beneficial to improving the comprehensive performance.
Currently prepared SnSe2Mainly adopts a solvent method, a chemical vapor deposition method, a mechanical alloy method and a zone melting method, but adopts the solvent method to prepare SnSe2The preparation process has high requirements on instruments and equipment, and the chemical vapor deposition method is used for preparing SnSe2The reaction time is too long, and the mechanical alloying method is used for preparing SnSe2Containing a large amount of mixed phases, and preparing SnSe by a zone melting method2Prepared is not a single crystal.
Disclosure of Invention
The invention aims to solve the problems of the prior art and provides SnSe2A base single crystal material and a method for producing the same. The SnSe2The base material is pure-phase monocrystal, and Se is simultaneously used as SnSe2+xThe source and cosolvent of medium Se can inhibit eutectic reaction to generate SnSe impurities during liquid phase cooling, thereby obtaining pure phase SnSe2A base single crystal material.
The technical scheme adopted by the invention for solving the problems is as follows:
SnSe2Based on a single crystal material having a chemical composition of SnSe2+xWherein x is 0.1 to 0.4.
SnSe as described above2A base single crystal material having a density of 5.41g/cm or more3(theoretical Density 5.95 g/cm)3) Preferably 5.42g/cm3～5.48g/cm3。
The above SnSe2The preparation method of the base single crystal material mainly comprises the following steps:
1) preparing materials: according to the mass ratio of Sn to Se as 1: (2+ y) weighing Sn and Se as reaction raw materials, wherein y is 1.0-5.0;
2) putting the reaction raw materials in the step 1) into a quartz tube, vacuumizing and sealing, and putting the sealed quartz tube into a muffle furnace;
3) heating the muffle furnace with the quartz tube in the step 2) to SnSe2Keeping the temperature for a period of time above the melting point to melt and fully mix the raw materials, then slowly cooling and crossing SnSe2Melting point, and then rapidly cooling to a temperature above Se melting point;
4) putting the quartz tube in the muffle furnace in the step 3) above the Se melting point, and centrifuging to separate Se and SnSe2Separating the base single crystal material;
5) cooling the centrifuged quartz tube obtained in the step 4) to room temperature, and then breaking the quartz tube to obtain SnSe2+x(x is 0.1 to 0.4) a single crystal material.
According to the scheme, the preferable value range of y in the step 1) is 2.0-4.0.
According to the scheme, the vacuum degree of the vacuumized sealed quartz tube in the step 2) is not more than 10-1Pa。
According to the scheme, when the temperature of the muffle furnace in the step 3) is raised, the temperature is raised to 700-800 ℃ within 2-6 hours.
According to the scheme, the muffle furnace in the step 3) is subjected to heat preservation for 6-12 hours at 700-800 ℃.
According to the scheme, in the muffle furnace cooling process in the step 3), the first cooling is carried out for 50-200 hours and then the temperature is cooled to 550-600 ℃; and cooling the mixture to 350-500 ℃ within 2-6 h for the second time.
According to the scheme, the step 3) is specifically as follows: heating the muffle furnace with the quartz tube in the step 2) for 2-6 hours to 700-800 ℃, preserving heat for 6-12 hours, then slowly cooling to 550-600 ℃ for 75-200 hours, and then rapidly cooling to 350-500 ℃ from 2-6 hours. Preferably, the temperature rise rate is within the range of 100-400 ℃/h; the slow cooling rate is within the range of 1.5-2.5 ℃/h, and the fast cooling rate is within the range of 25-50 ℃/h.
According to the scheme, the step 4) is specifically as follows: enabling the quartz tube in the muffle furnace in the step 3) to be at 350-500 ℃, and enabling Se and SnSe to be separated by a centrifuge2The base single crystal material is separated. Further, the separation conditions were: separating Se solvent and SnSe at 20-150 s, 2000-4000 r/min2A base single crystal.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a single crystal SnSe2The base material is pure phase single crystal. In the present invention, a part of Se is SnSe2+xThe source of medium Se and the other part of Se used as cosolvent can inhibit the eutectic reaction generated during liquid phase cooling to generate SnSe impurities, thereby obtaining pure phase SnSe2The growth period of the crystal is short, the cost of the instrument is low, and the success rate is high.
2. The invention provides a single crystal SnSe2A base material having a plurality of intrinsic defects. SnSe prepared in the invention2+xA single crystal (x is 0.1 to 0.4) having a large number of Se interstitial atoms and SeSnInversion defect, which can be used to study SnSe2Intrinsic properties of the base single crystal material.
Drawings
FIG. 1 is SnSe prepared in example 12.27XRD pattern of single crystal material;
FIG. 2 is SnSe prepared in example 12.27BSE spectra of single crystal materials;
FIG. 3 is SnSe prepared in example 22.24XRD pattern of single crystal material
FIG. 4 is SnSe prepared in example 22.24BSE spectra of single crystal materials;
FIG. 5 is SnSe prepared in example 32.18XRD pattern of single crystal material
FIG. 6 is SnSe prepared in example 32.18BSE spectra of single crystal materials.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the present invention is not limited to the following examples.
Example 1
SnSe2The preparation method of the base single crystal material comprises the following steps:
1) preparing materials: according to the mass ratio of Sn to Se as 1: (2+ y) weighing Sn and Se as reaction raw materials, wherein y is 3.0, the mass purity of Sn is better than 99.99 percent, and the mass purity of Se is better than 99.99 percent;
2) sealing the quartz tube: putting the reaction raw materials in the step 1) into a quartz tube, and carrying out vacuum pumping and sealing treatment, wherein the vacuum degree is less than 10-3Pa, placing the sealed quartz tube in a muffle furnace;
3) growing a single crystal: heating the muffle furnace with the quartz tube in the step 2) for 2h to 700 ℃ (the heating rate is 325-350 ℃/h), preserving heat for 10h to fully mix the raw materials, slowly cooling to 600 ℃ (the cooling rate is 2 ℃/h) for 50h, and then cooling to 400 ℃ (the cooling rate is 50 ℃/h) for 4 h;
4) separating the Se solvent and the SnSe by a centrifuge at the temperature of 400 ℃ and at the speed of 2000r/min for 30s2Cooling the base single crystal to room temperature, breaking the quartz tube, taking out the sample, and obtaining the SnSe with the composition through an EPMA test2.27Single crystal with a density of 5.48g/cm3。
SnSe obtained in the example2.27XRD pattern of single crystal material is shown in figure 1, SnSe2.27Is a single phase; the BSE spectrum is shown in figure 2, from which the SnSe can be seen2.27The single crystal material has no impurity and the elements are distributed uniformly.
Example 2
SnSe2The preparation method of the base single crystal material comprises the following steps:
1) preparing materials: according to the mass ratio of Sn to Se as 1: (2+ y) weighing Sn and Se as reaction raw materials, wherein y is 3.5, the mass purity of Sn is better than 99.99 percent, and the mass purity of Se is better than 99.99 percent;
2) sealing the quartz tube: putting the reaction raw materials in the step 1) into a quartz tube, and carrying out vacuum pumping and sealing treatment, wherein the vacuum degree is less than 10-2Pa, placing the sealed quartz tube in a muffle furnace;
3) growing a single crystal: heating the muffle furnace with the quartz tube in the step 2) for 2h to 750 ℃ (the heating rate is 350-370 ℃/h), preserving heat for 8h to fully mix the raw materials, then slowly cooling to 550 ℃ (the cooling rate is 2 ℃/h) for 100h, and then cooling to 500 ℃ (the cooling rate is 25 ℃/h) for 2 h;
4) using a centrifuge for 20s at 500 ℃ for the quartz tube obtained in the step 3),2500r/min separation of Se solvent and SnSe2Cooling the base single crystal to room temperature, breaking the quartz tube, taking out the sample, and obtaining the SnSe with the composition through an EPMA test2.24Single crystal with a density of 5.45g/cm3。
SnSe obtained in the example2.24XRD pattern of single crystal material is shown in figure 3, SnSe2.24Is a single phase; the BSE spectrum is shown in figure 4, from which the SnSe can be seen2.24The single crystal material has no impurity and the elements are distributed uniformly.
Example 3
SnSe2The preparation method of the base single crystal material comprises the following steps:
1) preparing materials: according to the mass ratio of Sn to Se as 1: (2+ y) weighing Sn and Se as reaction raw materials, wherein y is 4.0, the mass purity of Sn is better than 99.99 percent, and the mass purity of Se is better than 99.99 percent;
2) sealing the quartz tube: putting the reaction raw materials in the step 1) into a quartz tube, and carrying out vacuum pumping and sealing treatment, wherein the vacuum degree is less than 10-2Pa, placing the sealed quartz tube in a muffle furnace;
3) growing a single crystal: heating the muffle furnace with the quartz tube in the step 2) for 6 hours to 800 ℃ (the heating rate is 100-150 ℃/h), preserving heat for 12 hours to fully mix the raw materials, then slowly cooling the raw materials to 500 ℃ (the cooling rate is 2 ℃/h) for 150 hours, and then cooling the raw materials to 350 ℃ (the cooling rate is 25 ℃/h) for 6 hours;
4) separating Se solvent and SnSe by using a centrifuge at the temperature of 350 ℃ and at the speed of 4000r/min for the quartz tube obtained in the step 3)2Cooling the base single crystal to room temperature, breaking the quartz tube, taking out the sample, and obtaining the SnSe with the composition through an EPMA test2.18Single crystal with a density of 5.42g/cm3。
SnSe obtained in the example2.18The XRD pattern of the single crystal material is shown in figure 5, SnSe2.18Is a single phase; the BSE spectrum is shown in FIG. 6, from which SnSe can be seen2.18The single crystal material has no impurity and the elements are distributed uniformly.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (8)
1. SnSe2The preparation method of the base single crystal material is characterized by mainly comprising the following steps:
1) preparing materials: according to the mass ratio of Sn to Se as 1: (2+ y) weighing Sn and Se as reaction raw materials, wherein y is 1.0-5.0;
2) carrying out vacuum pumping and sealing treatment on the reaction raw material in the step 1);
3) heating the reaction raw material obtained in the step 2) after the vacuum-pumping sealing treatment to SnSe2Melting point is higher, the temperature is kept for a period of time to ensure that the reaction raw materials are melted and fully mixed, and then the temperature is reduced and the temperature is over SnSe2Melting point, and then cooling to a temperature above Se melting point;
4) separating Se and SnSe when the product obtained in the step 3) is above the Se melting point2A base single crystal material; wherein, SnSe2The chemical composition of the base single crystal material is SnSe2+xAnd x is 0.1 to 0.4.
2. The SnSe of claim 12The preparation method of the base single crystal material is characterized in that the value range of y in the step 1) is 2.0-4.0.
3. The SnSe of claim 12The preparation method of the base single crystal material is characterized in that the temperature rise process in the step 3) is as follows: the temperature is raised to 700-800 ℃ within 2-6 h.
4. The SnSe of claim 12The preparation method of the base single crystal material is characterized in that the heat preservation conditions in the step 3) are as follows: keeping the temperature at 700-800 ℃ for 6-12 h.
5. The SnSe of claim 12The preparation method of the base single crystal material is characterized in that the first temperature reduction condition in the step 3) is as follows: cooling to 550-600 ℃ within 50-200 h; the second temperature reduction condition is that: cooling to 350-500 ℃ within 2-6 h.
6. The SnSe of claim 12The preparation method of the base single crystal material is characterized in that the step 3) is specifically as follows: heating the reaction raw material subjected to the vacuum-pumping sealing treatment in the step 2) to 700-800 ℃ within 2-6 h, preserving the heat for 6-12 h, then cooling to 550-600 ℃ within 75-200 h, and then cooling to 350-500 ℃ within 2-6 h.
7. The SnSe of claim 12The preparation method of the base single crystal material is characterized in that the step 4) is specifically as follows: separating Se and SnSe from the product obtained in the step 3) at 350-500 ℃ by using a centrifugal machine2A base single crystal material.
8. The SnSe of claim 72A method for producing a base single crystal material, characterized in that the separation conditions are: se and SnSe are separated at the speed of 2000-4000 r/min within 20-150 s2A base single crystal material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060889A (en) * | 2011-10-19 | 2013-04-24 | 中国科学院大连化学物理研究所 | Solution phase method for synthesizing tin selenide monocrystal nanowire |
| CN104831362A (en) * | 2015-06-08 | 2015-08-12 | 广东工业大学 | Method for preparing tin selenide single-crystal nano-belt |
| CN107400917A (en) * | 2017-07-26 | 2017-11-28 | 武汉理工大学 | A kind of SnSe2Crystalline compounds and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060889A (en) * | 2011-10-19 | 2013-04-24 | 中国科学院大连化学物理研究所 | Solution phase method for synthesizing tin selenide monocrystal nanowire |
| CN104831362A (en) * | 2015-06-08 | 2015-08-12 | 广东工业大学 | Method for preparing tin selenide single-crystal nano-belt |
| CN107400917A (en) * | 2017-07-26 | 2017-11-28 | 武汉理工大学 | A kind of SnSe2Crystalline compounds and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Growth of large size single crystals of SnSe2 using a direct transport method;M.K. Agarwal等;《Journal of Crystal Growth》;19911231;第110卷;553-558 * |
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