CN102897841A - Preparation method of tungsten disulfide micron structure - Google Patents
Preparation method of tungsten disulfide micron structure Download PDFInfo
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- CN102897841A CN102897841A CN2012103711792A CN201210371179A CN102897841A CN 102897841 A CN102897841 A CN 102897841A CN 2012103711792 A CN2012103711792 A CN 2012103711792A CN 201210371179 A CN201210371179 A CN 201210371179A CN 102897841 A CN102897841 A CN 102897841A
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- thiocarbamide
- tungsten
- tungsten disulfide
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Abstract
The invention belongs to the manufacturing field of semiconductor micron materials and particularly relates to a preparation method of a tungsten disulfide micron structure. The preparation method is characterized in that the chemical vapor deposition (CVD) method is adopted, thiourea and tungsten hexachloride (WC16) are taken as reaction sources, and the structure is obtained in a vacuum state at 750-950 DEG C. According to the preparation method, the thiourea and WC16 are placed in a constant temperature area and a low temperature area respectively, the reaction temperature of the WC16 is maintained at 750-950 DEG C, the temperature difference between the WC16 and the thiourea is maintained at 50-150 DEG C, the saturated vapor pressure is reached simultaneously at a specific temperature by using the temperature difference, and steam is generated for reaction. The preparation method has the advantages of being simple and easy to implement, environment-friendly, non-toxic and even in product size; particularly the non-toxic thiourea is used as the S source, the production cost and toxicity of S sources such as H2S are reduced, and the preparation method is economical and environment-friendly.
Description
Technical field
The invention belongs to semi-conductor micron material and make class, a kind of preparation method of tungsten disulfide micrometer structure specifically, especially a kind of preparation method of tungsten disulfide micron tube.
Background technology
The fanciful structures of inorganic fullerene nano material, excellent properties and many potential application make its extensive concern that has caused whole world scientist and research interest.Tungsten disulfide (WS
2) be lamellar structure compound generally, have the structure that is similar to graphite, be WS
2Layer is stacking along C axle (perpendicular to sulfurized layer), WS
2The strong covalent bonds of metal W atom and S atom in the layer, and WS
2By weak Van der Waals force combination between the layer, in addition, WS
2Itself has important application potential quality as a kind of semi-conductor aspect energy band engineering.More there is recently scientist to propose available WS
2The unimolecular layer material make semiconducter device, or be used for making the electronic chip less, that efficiency is higher, in nanoelectronic apparatus field of future generation, will more have superiority than traditional silicon materials or soccerballene.Therefore, WS
2Nanostructure is once discovery, just becomes research focus because of its unique microtexture, physicals with in the potential application of various fields.On the preparation method, WS
2The preparation of nanostructure mainly comprises the hydro-thermal reaction method, chemical vapor deposition (CVD) method, sonic oscillation method, microwave irradiation, WO
3Method of reducing etc., wherein method relatively more commonly used is hydrothermal method and CVD method, has prepared WS such as (JACS) such as Y.D.Li by hydrothermal method
2Nanotube, but the method preparation cycle is long; (Material Lett.) such as Jifen Wu prepared WS by hydrothermal method
2Hollow ball, but it uses reaction source expensive; (Chem.Mater.) such as Yan Qiu Zhu prepared WS by the CVD method
2Nano wire, but its temperature of reaction that adopts is high, and in reaction process with H
2S has severe toxicity, reacts seriously polluted, the W such as Maja Remskar as the S source
5O
14Nanowires is presoma, at H
2/ H
2Vulcanize in the mixed gas of S/Ar and obtain with the nano-particle modified WS of soccerballene shape
2Nanotube, but in reaction process, adopt H
2/ H
2The mixed gas of S/Ar is as S source and carrier gas, H
2Explosive, H
2S has severe toxicity.
Summary of the invention
For the problem of above existence, the purpose of this invention is to provide a kind of preparation method of tungsten disulfide micrometer structure of simple, size uniform.
The present invention adopts following technical scheme:
A kind of preparation method of tungsten disulfide micrometer structure is characterized in that: adopt the chemical vapor deposition (CVD) method, with thiocarbamide and tungsten hexachloride (WCl
6) be reaction source, under 750-950 ℃ of vacuum state the reaction and obtain.
The present invention with the tubular annealing stove as reactive system, in the reaction source, thiocarbamide and WCl
6Mol ratio remain on 6:1-12:1; With thiocarbamide and WCl
6Place respectively flat-temperature zone and the cold zone of tubular annealing stove, and vacuumize the air in the vent pipe; Be filled with purity and be the high-purity argon gas more than 99.99%, inflation is bled repeatedly, and intrasystem air is thoroughly discharged; To be evacuated to the system sealing of vacuum, be warming up to 750-950 ℃ in 40-80 minute, insulation is 60-120 minute under this temperature, and in the whole reaction process, system is in vacuum state always; React complete after, make system naturally be cooled to room temperature, take out sample.
The present invention passes through thiocarbamide and WCl
6Be placed on respectively flat-temperature zone and the cold zone of reactive system, make WCl
6Temperature of reaction remains on 750-950 ℃, WCl
6Remain on 50-150 ℃ with the temperature difference of thiocarbamide, utilize the temperature difference of the two to make its vapour pressure that under specified temp, reaches capacity simultaneously, produce steam, react.Not only have simple, environment-protecting asepsis, also have the characteristics of product size uniform, particularly with nontoxic thiocarbamide as the S source, not only reduced production cost but also reduced H
2The toxicity in the S sources such as S is the preparation method of a kind of not only economical and practical but also environmental protection.
Embodiment
Describe in detail below in conjunction with embodiment:
Embodiment 1
With thiocarbamide and WCl
6Be reaction raw materials, as reactive system, prepare WS with the tubular annealing stove
2Micron tube.
At first take by weighing a certain amount of thiocarbamide and WCl
6, make thiocarbamide and WCl
6Mol ratio be 9:1.Then be placed in the reactive system, reactive system is vacuumized, when being evacuated to the 10Pa left and right sides, be filled with purity in the system and be high-purity argon gas to 1 normal atmosphere more than 99.99%, and then be evacuated to 10Pa, so repeatedly, circulation is bled and is inflated three times, until air is got rid of substantially fully in the system, reactive system is sealed.Then system was warming up to 800 ℃ in 50 minutes, growth is 60 minutes under this temperature, then stopped heating.System is in vacuum state always in the whole reaction process.After system is cooled to room temperature naturally, take out sample, carry out structure and morphology characterization, after reaction finishes, collect product and products therefrom is carried out structure and purity sign, comprise X-ray diffraction (XRD) θ-2 θ scanning, field emission scanning electron microscope (FESEM) observation, selected area electron diffraction (SAED) analysis etc.Wherein the XRD structural analysis shows, products therefrom is hexagonal WS
2, do not have WO
3Occur Deng relevant secondary phase, FESEM result shows, products therefrom is the micron tube of hollow, and the diameter of pipe is at 150-300nm, and wall thickness is about 50-70nm, length of tube is 3-7um, SAED the analysis showed that, single pipe only contains W, two kinds of elements of S, its ratio of components is near 1:2, and further specifying products therefrom is highly purified WS
2
Embodiment 2
With thiocarbamide and WCl
6Be reaction raw materials, as reactive system, prepare WS with the tubular annealing stove
2Micron tube.
At first take by weighing a certain amount of thiocarbamide and WCl
6, make thiocarbamide and WCl
6Mol ratio be 7:1.Then be placed in the reactive system, reactive system is vacuumized, when being evacuated to the 10Pa left and right sides, be filled with purity in the system and be high-purity argon gas to 1 normal atmosphere more than 99.99%, and then be evacuated to 10Pa, so repeatedly, circulation is bled and is inflated three times, until air is got rid of substantially fully in the system, reactive system is sealed.Then system was warming up to 850 ℃ in 60 minutes, growth is 60 minutes under this temperature, then stopped heating.System is in vacuum state always in the whole reaction process.After system is cooled to room temperature naturally, take out sample, carry out structure and morphology characterization, after reaction finishes, collect product and products therefrom is carried out structure and purity sign, comprise X-ray diffraction (XRD) θ-2 θ scanning, field emission scanning electron microscope (FESEM) observation, selected area electron diffraction (SAED) analysis etc.Wherein the XRD structural analysis shows, products therefrom is hexagonal WS
2, do not have WO
3Occur Deng relevant secondary phase, FESEM result shows, products therefrom is the micron tube of hollow, and the diameter of pipe is at 180-300nm, and wall thickness is about 50-70nm, length of tube is 4-7.5um, SAED the analysis showed that, single pipe only contains W, two kinds of elements of S, its ratio of components is near 1:2, and further specifying products therefrom is highly purified WS
2
Embodiment 3
With thiocarbamide and WCl
6Be reaction raw materials, as reactive system, prepare WS with the tubular annealing stove
2Micron tube.
At first take by weighing a certain amount of thiocarbamide and WCl
6, make thiocarbamide and WCl
6Mol ratio be 6:1.Then be placed in the reactive system, reactive system is vacuumized, when being evacuated to the 10Pa left and right sides, be filled with purity in the system and be high-purity argon gas to 1 normal atmosphere more than 99.99%, and then be evacuated to 10Pa, so repeatedly, circulation is bled and is inflated three times, until air is got rid of substantially fully in the system, reactive system is sealed.Then system was warming up to 850 ℃ in 60 minutes, growth is 80 minutes under this temperature, then stopped heating.System is in vacuum state always in the whole reaction process.After system is cooled to room temperature naturally, take out sample, carry out structure and morphology characterization, after reaction finishes, collect product and products therefrom is carried out structure and purity sign, comprise X-ray diffraction (XRD) θ-2 θ scanning, field emission scanning electron microscope (FESEM) observation, selected area electron diffraction (SAED) analysis etc.Wherein the XRD structural analysis shows, products therefrom is hexagonal WS
2, do not have WO
3Occur Deng relevant secondary phase, FESEM result shows, products therefrom is the micron tube of hollow, and the diameter of pipe is at 180-320nm, wall thickness is about 50-70nm, length of tube is 4-8.5um, and SAED the analysis showed that, single pipe only contains W, two kinds of elements of S, but ratio of components illustrates that S is not enough in the products therefrom, the more excessive a little WS that is conducive to obtain stoichiometric ratio of S in reaction source near 1.2:1.8
2Micron tube.
Claims (5)
1. the preparation method of a tungsten disulfide micrometer structure is characterized in that: adopt chemical gaseous phase depositing process, and take thiocarbamide and tungsten hexachloride as reaction source, reaction under 750-950 ℃ of vacuum state and obtaining.
2. the preparation method of tungsten disulfide micrometer structure according to claim 1, it is characterized in that: the mol ratio of thiocarbamide and tungsten hexachloride is controlled between the 6:1-12:1 in the reaction source.
3. the preparation method of tungsten disulfide micrometer structure according to claim 1, it is characterized in that: the reaction times is 60-120 minute.
4. the preparation method of tungsten disulfide micrometer structure according to claim 1, it is characterized in that: as reactive system, tungsten hexachloride and thiocarbamide place respectively flat-temperature zone and the cold zone of tubular annealing stove with the tubular annealing stove.
5. the method for preparing the tungsten disulfide micrometer structure according to claim 1 is characterized in that:
A) take thiocarbamide and tungsten hexachloride as reaction source, make the mol ratio of thiocarbamide and tungsten hexachloride remain on 6:1-12:1, as reactive system, take by weighing flat-temperature zone and cold zone that a certain amount of tungsten hexachloride and thiocarbamide place respectively the tubular annealing stove with the tubular annealing stove;
B) after reaction source is inserted tube furnace, vacuumize the air in the vent pipe;
C) being filled with purity is high-purity argon gas more than 99.99%, again reactive system is found time after reaching normal pressure;
D) inflation is bled three times repeatedly, and purpose is for intrasystem air is thoroughly discharged;
E) will be evacuated to the system sealing of vacuum, and be warming up to 750-950 ℃ in 40-80 minute, insulation is 60-120 minute under this temperature, and in the whole reaction process, system is in vacuum state always;
F) reaction complete after, make system naturally be cooled to room temperature, take out sample, carry out structure and morphology characterization.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641173A (en) * | 2013-11-04 | 2014-03-19 | 江苏大学 | Preparation method of graphite alkene like tungsten disulfide nanometer sheet |
| CN104310485A (en) * | 2014-10-20 | 2015-01-28 | 安徽工业大学 | Tungsten disulfide nano powder material with aluminum sulfide shell, and preparation method of tungsten disulfide nano powder material |
| CN104561937A (en) * | 2015-01-05 | 2015-04-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing WS2 film having solid lubrication function by means of atomic layer deposition |
| CN104993141A (en) * | 2015-06-08 | 2015-10-21 | 陕西科技大学 | Preparation method for one-dimensional WS2 nanotube negative electrode material for sodium-ion battery |
| CN105197998A (en) * | 2015-09-14 | 2015-12-30 | 天津大学 | One-step method for preparing high-quality tungsten disulfide nanosheet through chemical vapor deposition |
| CN105668636A (en) * | 2016-04-06 | 2016-06-15 | 江苏理工学院 | Vanadium-doped tungsten disulfide nanosheet material and preparation method thereof |
| CN107416905A (en) * | 2017-06-22 | 2017-12-01 | 河南大学 | A kind of preparation method of oil-soluble tungsten disulfide nano slices |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641173A (en) * | 2013-11-04 | 2014-03-19 | 江苏大学 | Preparation method of graphite alkene like tungsten disulfide nanometer sheet |
| CN103641173B (en) * | 2013-11-04 | 2016-03-02 | 江苏大学 | The preparation method of one kind Graphene tungsten disulfide nano slices |
| CN104310485A (en) * | 2014-10-20 | 2015-01-28 | 安徽工业大学 | Tungsten disulfide nano powder material with aluminum sulfide shell, and preparation method of tungsten disulfide nano powder material |
| CN104310485B (en) * | 2014-10-20 | 2015-12-09 | 安徽工业大学 | A kind of Wolfram disulfide nano powdered material with aluminium sulfide shell and preparation method thereof |
| CN104561937A (en) * | 2015-01-05 | 2015-04-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing WS2 film having solid lubrication function by means of atomic layer deposition |
| CN104993141A (en) * | 2015-06-08 | 2015-10-21 | 陕西科技大学 | Preparation method for one-dimensional WS2 nanotube negative electrode material for sodium-ion battery |
| CN105197998A (en) * | 2015-09-14 | 2015-12-30 | 天津大学 | One-step method for preparing high-quality tungsten disulfide nanosheet through chemical vapor deposition |
| CN105668636A (en) * | 2016-04-06 | 2016-06-15 | 江苏理工学院 | Vanadium-doped tungsten disulfide nanosheet material and preparation method thereof |
| CN107416905A (en) * | 2017-06-22 | 2017-12-01 | 河南大学 | A kind of preparation method of oil-soluble tungsten disulfide nano slices |
| WO2018233371A1 (en) * | 2017-06-22 | 2018-12-27 | 河南大学 | Method for preparing oil-soluble tungsten disulfide nanosheet |
| CN107416905B (en) * | 2017-06-22 | 2019-03-08 | 河南大学 | A kind of preparation method of oil-soluble tungsten disulfide nano slices |
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Application publication date: 20130130 |