CN112458537A - Growth method of millimeter-scale tungsten sulfide single crystal - Google Patents
Growth method of millimeter-scale tungsten sulfide single crystal Download PDFInfo
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- CN112458537A CN112458537A CN202011269161.2A CN202011269161A CN112458537A CN 112458537 A CN112458537 A CN 112458537A CN 202011269161 A CN202011269161 A CN 202011269161A CN 112458537 A CN112458537 A CN 112458537A
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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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
Abstract
The invention relates to a growth method of millimeter-scale tungsten sulfide single crystal, which adopts a semi-closed mode, introduces a very small amount of NaCl particles before the growth begins, and adopts the NaCl particles to form a W-containing compound at a relatively low temperature (about 800 ℃), so that WS can be effectively improved at the CVD growth temperature2And the supersaturation degree of the W source in the growth process further realizes the enlargement of the size of the single crystal. By adopting this method, WS can be converted into WS2Enlargement of the size of the single crystal to 1.5mm, WS obtained by conventional growth methods2Single crystals are typically only tens of microns in size. The supersaturation degree of the tungsten source in the nucleation process is obviously improved, so that the tungsten source supply on the surface of the substrate in the nucleation growth process is sufficient, the smooth growth is ensured, the domain size of the tungsten sulfide single crystal can be obviously increased, and the growth of the millimeter-magnitude tungsten sulfide single crystal is facilitated.
Description
Technical Field
The invention relates to a process for preparing tungsten sulfide single crystal by adopting a CVD method, in particular to a growth method of millimeter-scale tungsten sulfide single crystal.
Background
Two-dimensional WS2Is a typical representative of transition metal sulfides, is a typical two-dimensional layered material, a single layer of WS2The mobility of the direct band gap semiconductor material exceeds 1000cm2V.s, which is much higher than the mobility of silicon material with the same thickness; WS2The surface has no dangling bond, so that good stability can be maintained in a complex environment; WS2The base field effect transistor has ultra-low crystalline state power consumption, and the application of the base field effect transistor can remarkably reduce the system power consumption. Furthermore, WS2Has excellent optical performance and good mechanical flexibility. For this purpose, WS2Has potential application prospect in the fields of micro-electronics, flexible photoelectrons and the like.
WS has been obtained by researchers at present on wafer level using CVD2A single-layer continuous film is obtained by merging and growing single crystals which are spontaneously nucleated at different positions, and the spontaneously nucleated single crystals have different crystal orientations, so that a large number of grain boundaries exist in the continuous film, the grain boundaries are defect-enriched positions, the quality of the film is seriously reduced, and the WS is seriously reduced2The mobility of the material. Therefore, large domain size WS is achieved2Study of growth of Single Crystal is WS2The problem that must be solved in the research process. WS currently prepared by CVD2The domain size is only several tens of micrometers, and it is difficult to obtain WS having a large domain size2And (3) single crystal.
WS by current CVD method2Tungsten trioxide is mainly used as a W source in the process of single crystal growth, high-purity sulfur powder is used as a sulfur source, sulfur vapor heated under certain growth conditions reaches a tungsten trioxide source area along with the transportation of carrier gas, and reacts with tungsten trioxide to obtain degraded tungsten-containing oxide, and the degraded tungsten-containing oxideThe compound of W is deposited on the surface of the substrate, and with the continuous supply of sulfur vapor, the oxide of W is completely vulcanized, and WS is obtained2A film material. In WS2The main difficulty in the process of single crystal growth is that the supersaturation degree of the W source is too low in the nucleation and growth processes, and the required supersaturation degree of W cannot be obtained on the substrate surface due to the too low supersaturation degree of the W source, so that the size of a crystal domain is difficult to expand. The main reason for the over-low supersaturation of the W source is that the melting point of tungsten trioxide is as high as 1473 ℃, while the temperature of the conventional CVD growth system is 1200 ℃, so that the over-saturation of the W source in the growth process is difficult to meet the large domain size single crystal WS2The need for growth. Therefore, how to adopt effective measures to improve the supersaturation degree of the W source and realize the millimeter-scale WS2Stable growth of single crystals, is WS2The difficult problem to be solved urgently in the research process.
Disclosure of Invention
Aiming at solving the problem of growing WS by the existing CVD method2The invention provides a method for growing millimeter-scale tungsten sulfide single crystal, which not only increases WS2Single domain size and improved WS2Quality of the single crystal. The specific technical scheme is as follows: a growth method of millimeter-scale tungsten sulfide single crystal is characterized by comprising the following steps: the supersaturation degree of the W source is improved by adopting a halide auxiliary method in the growth process of the tungsten sulfide single crystal, thereby realizing WS2The method comprises the following steps of firstly, mixing 0.002-0.01 g of NaCl particles and tungsten trioxide powder by using an electronic balance, placing the mixture into a quartz boat, placing the growth surface of a sapphire substrate downwards on the surfaces of the NaCl particles and the tungsten trioxide powder in the quartz boat, and placing the quartz boat into a semi-closed quartz tube; secondly, putting the quartz tube into a CVD growth system; vacuumizing the CVD growth system, and introducing Ar gas for purging for 5 minutes when the pressure in the system is 0mbar, wherein the flow rate of the Ar gas is 500 sccm; thirdly, reducing the flow rate of Ar to 100sccm-150sccm, and keeping the pressure in the system at 10mbar-20 mbar; fourthly, heating the system to 900-1000 ℃, starting to heat the sulfur powder after the temperature of the system reaches the growth temperature, and controlling the heating temperature to 190 ℃ -250 ℃; fifthly, after the sulfur temperature reaches the set temperature, introducing sulfur steam into the system, and starting WS2Growing the single crystal for 20-50 min; and sixthly, cooling after growth is finished, and sampling for testing.
The invention has the advantages of realizing WS2The supersaturation degree of the W source is improved in the nucleation and growth processes, so that the enlargement of the size of the crystal domain is realized, and the application of the method can realize the WS in millimeter order2Controlled growth of single crystals.
Detailed Description
The present invention is further illustrated by the following examples.
Example (b): the growth method of millimeter-scale tungsten sulfide single crystal is completed according to the following steps,
firstly, mixing 0.002g of NaCl particles with 0.06g of high-purity tungsten trioxide powder, placing the mixture in a quartz boat, placing the sapphire substrate growth surface downwards on the surfaces of the NaCl particles and the tungsten trioxide powder in the quartz boat, and placing the quartz boat in a semi-closed quartz tube;
secondly, placing the growth device into a CVD growth system for furnace charging, carrying out vacuum-pumping treatment on the system, and introducing Ar gas for purging for 5 minutes when the pressure in the system is 0mbar, wherein the flow rate of the Ar gas is 500 sccm;
thirdly, reducing the flow rate of Ar to 100sccm, keeping the pressure in the system at 10mbar, and heating the system, wherein the temperature in a low-temperature area is 900 ℃ and the temperature in a high-temperature area is 920 ℃;
fourthly, heating the sulfur source after the temperature in the system reaches the set temperature, wherein the heating temperature is 190 ℃;
fifthly, introducing sulfur steam into the system and starting WS2Growing the single crystal for 30 min;
and sixthly, naturally cooling to room temperature after the growth is finished, and taking out a sample for testing.
By differential interference microscopy, WS2The single crystal size can reach 1.5 mm.
Preparation of millimeter-scale WS2Principle of single crystal by starting growthIntroducing a very small amount of NaCl particles which can form W-containing compounds at a relatively low temperature (about 800 ℃), and thus can effectively increase WS at CVD growth temperature2And the supersaturation degree of the W source in the growth process further realizes the enlargement of the size of the single crystal. By adopting this method, WS can be converted into WS2Enlargement of the size of the single crystal to 1.5mm, WS obtained by conventional growth methods2Single crystals are typically only tens of microns in size.
Claims (1)
1. A growth method of millimeter-scale tungsten sulfide single crystal is characterized by comprising the following steps: the supersaturation degree of the W source is improved by adopting a halide auxiliary method in the growth process of the tungsten sulfide single crystal, thereby realizing WS2The enlargement of the size of the crystal domain and the crystal growth process are completed according to the following steps,
firstly, mixing 0.002-0.01 g of NaCl particles and tungsten trioxide powder by using an electronic balance, placing the mixture into a quartz boat, placing the growth surface of a sapphire substrate downwards on the surfaces of the NaCl particles and the tungsten trioxide powder in the quartz boat, and placing the quartz boat into a semi-closed quartz tube;
secondly, putting the quartz tube into a CVD growth system; vacuumizing the CVD growth system, and introducing Ar gas for purging for 5 minutes when the pressure in the system is 0mbar, wherein the flow rate of the Ar gas is 500 sccm;
thirdly, reducing the flow rate of Ar to 100sccm-150sccm, and keeping the pressure in the system at 10mbar-20 mbar;
fourthly, heating the system to 900-1000 ℃, and starting heating the sulfur powder after the temperature of the system reaches the growth temperature, wherein the heating temperature is controlled at 190-250 ℃;
fifthly, after the sulfur temperature reaches the set temperature, introducing sulfur steam into the system, and starting WS2Growing the single crystal for 20-50 min;
and sixthly, cooling after growth is finished, and sampling for testing.
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| CN202011269161.2A CN112458537A (en) | 2020-11-13 | 2020-11-13 | Growth method of millimeter-scale tungsten sulfide single crystal |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106567055A (en) * | 2015-10-08 | 2017-04-19 | 中国科学院金属研究所 | A method of preparing large-area high-quality completely single-layered tungsten disulfide |
| CN110373718A (en) * | 2019-05-30 | 2019-10-25 | 杭州电子科技大学 | A kind of preparation method of two dimension tungsten disulfide film |
| US20190330735A1 (en) * | 2017-04-17 | 2019-10-31 | Massachusetts Institute Of Technology | Chemical Vapor Transport Growth of Two-Dimensional Transition-Metal Dichalcogenides |
| CN111304738A (en) * | 2020-03-16 | 2020-06-19 | 华中科技大学 | Method for growing multilayer tungsten diselenide single crystal by molten salt assisted chemical vapor deposition |
| CN111501097A (en) * | 2020-05-29 | 2020-08-07 | 中国电子科技集团公司第四十六研究所 | Large domain size WS2Method for growing single crystal |
-
2020
- 2020-11-13 CN CN202011269161.2A patent/CN112458537A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106567055A (en) * | 2015-10-08 | 2017-04-19 | 中国科学院金属研究所 | A method of preparing large-area high-quality completely single-layered tungsten disulfide |
| US20190330735A1 (en) * | 2017-04-17 | 2019-10-31 | Massachusetts Institute Of Technology | Chemical Vapor Transport Growth of Two-Dimensional Transition-Metal Dichalcogenides |
| CN110373718A (en) * | 2019-05-30 | 2019-10-25 | 杭州电子科技大学 | A kind of preparation method of two dimension tungsten disulfide film |
| CN111304738A (en) * | 2020-03-16 | 2020-06-19 | 华中科技大学 | Method for growing multilayer tungsten diselenide single crystal by molten salt assisted chemical vapor deposition |
| CN111501097A (en) * | 2020-05-29 | 2020-08-07 | 中国电子科技集团公司第四十六研究所 | Large domain size WS2Method for growing single crystal |
Non-Patent Citations (1)
| Title |
|---|
| 孙璐璐: "NaCl辅助制备单层MoS2/WS2及其晶界和电学性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 October 2018 (2018-10-15), pages 17 - 24 * |
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