CN111041449A - Preparation method of tungsten disulfide with specific morphology - Google Patents

Preparation method of tungsten disulfide with specific morphology Download PDF

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CN111041449A
CN111041449A CN201911385340.XA CN201911385340A CN111041449A CN 111041449 A CN111041449 A CN 111041449A CN 201911385340 A CN201911385340 A CN 201911385340A CN 111041449 A CN111041449 A CN 111041449A
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quartz
substrate
tungsten disulfide
quartz tube
tube
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CN111041449B (en
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董孟孟
吕燕飞
赵士超
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Shenzhen Dragon Totem Technology Achievement Transformation Co ltd
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Hangzhou Dianzi University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber

Abstract

The invention discloses a preparation method of tungsten disulfide with a specific morphology, which takes argon and hydrogen as carrier gases and metal palladium as a catalyst to synthesize tungsten disulfide with a triangular frame structure by a CVD method at high temperature. Compared with the triangular and hexagonal solid continuous film synthesized by the existing CVD method, the proportion of the edge atoms in the tungsten disulfide film obtained by the method in the total atomic number is increased, and the catalytic activity of the tungsten disulfide when used as a catalyst material is improved.

Description

Preparation method of tungsten disulfide with specific morphology
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of tungsten disulfide with a hollow triangular frame structure.
Background
The two-dimensional tungsten disulfide can be synthesized by a Chemical Vapor Deposition (CVD) method, wherein precursors are subjected to chemical reaction at high temperature, and then a tungsten sulfide monomolecular layer or polymolecular layer thick film material is deposited and grown on the surface of a substrate. The tungsten disulfide synthesized by the method is a film formed by the interconnection of single crystal domains or a plurality of crystal domains which are dispersed on the surface of a substrate and are separated from each other and have a triangular or hexagonal shape, and the crystal domains or the film is a continuous and non-hollow plane.
Sulfur reacts with most metals except gold at high temperature to form metal sulfides, so that a metal catalyst is hardly used in the sulfide preparation process. The growth of tungsten disulfide usually uses a mixed gas of argon and hydrogen as a carrier gas, and the mechanism of the influence of hydrogen on the synthesis of tungsten disulfide needs to be further researched.
Tungsten disulfide (WS)2) The forbidden bandwidth changes with the thickness of the material, the forbidden bandwidth of the monomolecular layer is about 2.0eV, the forbidden bandwidth of the bulk material is about 1.3eV, and the forbidden bandwidth of the tungsten disulfide is in the visible light energy range, so that the material can be used as a photoconductive detector and a photocatalytic material. When used as a catalyst material, the sites that are active catalytically are primarily the edge portions of the tungsten disulfide material. In order to improve the catalytic performance, it is necessary to reduce the size of the material or to introduce defects.
Disclosure of Invention
The invention provides a method for synthesizing tungsten disulfide with a triangular frame structure by using argon and hydrogen as carrier gases and metal palladium as a catalyst through a CVD (chemical vapor deposition) method at high temperature. Compared with the triangular and hexagonal solid continuous film synthesized by the existing CVD method, the proportion of the edge atoms in the tungsten disulfide film obtained by the method in the total atomic number is increased, and the catalytic activity of the tungsten disulfide when used as a catalyst material is improved. In addition, the product is taken as a template, and other materials are continuously deposited and grown, so that the method can be used for synthesizing electronic devices with special structures.
The preparation method of the tungsten disulfide with the specific morphology comprises the following specific steps:
step (1) taking WS21-5 g of solid powder is put into a quartz boat, and then WS is filled in the quartz boat2The quartz boat of solid powder was placed in a quartz tube (1 inch diameter) in a tube-type electric furnace. The quartz boat is placed in the middle of the quartz tube.
Step (2), cleaning a substrate (with the size of 2.5-3.5 cm multiplied by 1.5-2.0 cm) by deionized water, drying by blowing nitrogen, and drying by blowing 0.05-0.2mol/l of palladium chloride (PdCl)2) Hydrochloric acid solution, spraying onto the substrate surface, and addingHeating the mixture on a hot plate to 80-100 ℃ to ensure that PdCl is added2Spray droplet drying. Then, placing the substrate in a quartz tube, wherein the position is 20-25 cm away from the quartz boat in the downstream direction of the carrier gas flow;
and (3) starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas (5% H) into the quartz tube2) The carrier gas flow is 20-50 sccm. The vacuum degree in the tube is 100-600 Pa.
And (4) heating the quartz tube to 900-1000 ℃, wherein the heating rate is 20-30 ℃/min. And (3) keeping the temperature after the temperature is increased to 900-1000 ℃, wherein the heat preservation time is 30-300 min.
And (5) stopping heating the quartz tube, rapidly cooling the quartz tube to room temperature at a cooling rate of 10-100 ℃/min, then taking out the substrate, and obtaining the tungsten sulfide with the frame structure on the substrate.
The quartz tube in the step (1) is a quartz tube or a corundum tube, and the quartz boat is a quartz boat or a corundum boat.
And (3) the substrate in the step (2) is a silicon wafer or sapphire with an oxide layer growing on the surface.
Has the advantages that: according to the invention, metal palladium and hydrogen are applied to a chemical vapor deposition method to prepare tungsten disulfide, the product is in a triangular frame structure, the proportion of edge atoms in the tungsten disulfide film in the total atomic number is increased, and the catalytic activity of tungsten disulfide when used as a catalyst material is improved. The formation of the tungsten disulfide film with the triangular frame structure is related to metal palladium and hydrogen. Unlike gold as a catalyst, the synthesis of tungsten disulfide with a framework structure cannot be achieved by using gold as a catalyst.
Drawings
FIG. 1 is a scanning electron microscope photograph of a tungsten disulfide thin film single crystal domain with a triangular frame structure;
FIG. 2 is an optical microscope photograph of a tungsten disulfide thin film single crystal domain with a triangular frame structure;
fig. 3 is an optical microscope photograph of multiple domains of a tungsten disulfide thin film with a triangular frame structure.
Detailed Description
Example 1:
step (ii) of(1) Get WS21g of solid powder, put into a quartz boat, and then put into a chamber containing WS2The quartz boat of solid powder was placed in a quartz tube (1 inch diameter) in a tube-type electric furnace. The quartz boat is placed in the middle of the quartz tube.
Step (2), the size of the substrate is 2.5cm multiplied by 1.5cm, the substrate is cleaned by deionized water and is dried by nitrogen, and 0.05mol/l of palladium chloride (PdCl) is dried2) Spraying hydrochloric acid solution on the surface of the silicon wafer substrate, and heating to 80 ℃ by a heating plate to ensure that PdCl is added2Spray droplet drying. The substrate, which is sapphire with an oxide layer grown on the surface, was then placed in a quartz tube downstream of the carrier gas.
And (3) starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas (5% H) into the quartz tube2) The flow rate of the carrier gas was 20 sccm. The vacuum degree in the tube is 100 Pa.
And (4) heating the quartz tube to 900 ℃, wherein the heating rate is 20 ℃/min. And (3) keeping the temperature after the temperature is increased to 900 ℃, wherein the heat preservation time is 30 min.
Step (5), stopping heating the quartz tube, rapidly cooling the quartz tube to room temperature at a cooling rate of 10 ℃/min, then taking out the substrate, and obtaining tungsten sulfide with a frame structure on the substrate, as shown in fig. 1, 2 and 3;
example 2:
step (1) taking WS25g of solid powder, put into a corundum boat, and then filled with WS2The corundum boat of solid powder was placed in a quartz tube (1 inch diameter) in a tube electric furnace. The corundum boat is placed in the middle of the quartz tube.
Step (2), cleaning a substrate (with the size of 2.5cm multiplied by 2.0cm by deionized water, drying by nitrogen, and drying by blowing 0.2mol/l of palladium chloride (PdCl)2) Spraying hydrochloric acid solution on the surface of the silicon wafer substrate, and heating to 100 ℃ by a heating plate to ensure that PdCl is added2Spray droplet drying. The substrate was then placed in a quartz tube downstream of the carrier gas.
And (3) starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas (5% H) into the quartz tube2) The flow rate of the carrier gas was 50 sccm. The vacuum degree in the tube is 600 Pa.
And (4) heating the quartz tube to 1000 ℃, wherein the heating rate is 30 ℃/min. And (3) keeping the temperature after the temperature is raised to 1000 ℃, wherein the heat preservation time is 300 min.
And (5) stopping heating the quartz tube, rapidly cooling the quartz tube to room temperature at a cooling rate of 100 ℃/min, then taking out the substrate, and obtaining the tungsten sulfide with the frame structure on the substrate.
Example 3:
step (1) taking WS23g of solid powder, put into a quartz boat, and then put into a chamber containing WS2The quartz boat of solid powder was placed in a quartz tube (1 inch diameter) in a tube-type electric furnace. The quartz boat is placed in the middle of the quartz tube.
Step (2), the size of the substrate is 3.5cm multiplied by 2.0cm, the substrate is cleaned by deionized water and is dried by nitrogen, and 0.1mol/l of palladium chloride (PdCl) is dried2) Spraying hydrochloric acid solution on the surface of the silicon wafer substrate, and heating to 95 ℃ through a heating plate to ensure that PdCl2Spray droplet drying. The substrate, which is a silicon wafer with an oxide layer grown on the surface, was then placed in a quartz tube downstream of the carrier gas.
And (3) starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas (5% H) into the quartz tube2) The flow rate of the carrier gas was 30 sccm. The vacuum degree in the tube is 450 Pa.
And (4) heating the quartz tube to 950 ℃ at a heating rate of 25 ℃/min. And keeping the temperature for 100min after the temperature is raised to 950 ℃.
And (5) stopping heating the quartz tube, rapidly cooling the quartz tube to room temperature at a cooling rate of 50 ℃/min, then taking out the substrate, and obtaining the tungsten sulfide with the frame structure on the substrate.

Claims (5)

1. A preparation method of tungsten disulfide with a specific morphology is characterized by comprising the following steps:
step (1) taking WS21-5 g of solid powder is put into a quartz boat, and then WS is filled in the quartz boat2Putting the quartz boat of the solid powder into a quartz tube in the tube type electric furnace; the quartz boat is placed in the middle of the quartz tube;
step (ii) of(2) Cleaning a substrate with deionized water, drying with nitrogen, spraying a palladium chloride hydrochloric acid solution with the concentration of 0.05-0.2mol/l onto the surface of the substrate, and heating to 80-100 ℃ through a heating plate to ensure that PdCl is subjected to PdCl2Spray droplet drying; then, placing the substrate in a quartz tube, wherein the position is 20-25 cm away from the quartz boat in the downstream direction of the carrier gas flow;
and (3) starting a mechanical pump to pump vacuum, and simultaneously inputting carrier gas argon-hydrogen mixed gas into the quartz tube, wherein H is2The volume content of the catalyst is 5%, and the flow rate of carrier gas is 20-50 sccm; the vacuum degree in the tube is 100-600 Pa;
step (4), heating the quartz tube to 900-1000 ℃, wherein the heating rate is 20-30 ℃/min; keeping the temperature after the temperature is increased to 900-1000 ℃, wherein the heat preservation time is 30-300 min;
and (5) stopping heating the quartz tube, rapidly cooling the quartz tube to room temperature at a cooling rate of 10-100 ℃/min, then taking out the substrate, and obtaining the tungsten sulfide with the frame structure on the substrate.
2. The method for preparing tungsten disulfide with a specific morphology as claimed in claim 1, wherein: the quartz tube in the step (1) is a quartz tube or a corundum tube, and the quartz boat is a quartz boat or a corundum boat.
3. The method for preparing tungsten disulfide with a specific morphology as claimed in claim 1, wherein: and (3) the substrate in the step (2) is a silicon wafer or sapphire with an oxide layer growing on the surface.
4. The method for preparing tungsten disulfide with a specific morphology as claimed in claim 1, wherein: the diameter of the quartz tube is 1 inch.
5. The method for preparing tungsten disulfide with a specific morphology as claimed in claim 1, wherein: the size of the substrate is 2.5-3.5 cm multiplied by 1.5-2.0 cm.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1060141A1 (en) * 1998-03-03 2000-12-20 PPG Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
US20080170984A1 (en) * 2005-04-07 2008-07-17 Reshef Tenne Process And Apparatus For Producing Inorganic Fullerene-Like Nanoparticles
CN103480856A (en) * 2013-09-09 2014-01-01 南京邮电大学 Method for preparing nanocomposite by using two-dimensional transition metal chalcogenide nanosheets and metal
CN104445419A (en) * 2014-12-02 2015-03-25 湖南省华京粉体材料有限公司 Method for preparing tungsten disulfide composite material for carbon brush
CN106711225A (en) * 2016-11-17 2017-05-24 北京交通大学 Sulfide field effect transistor and production method thereof
CN107146815A (en) * 2017-03-21 2017-09-08 广东工业大学 A kind of Schottky gate field-effect transistor and preparation method and application
CN107557754A (en) * 2017-07-21 2018-01-09 杭州电子科技大学 A kind of preparation method of tungsten disulfide film
CN107849642A (en) * 2015-06-01 2018-03-27 耶达研究及发展有限公司 Metal alloy composite
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

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1060141A1 (en) * 1998-03-03 2000-12-20 PPG Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
JP2004156197A (en) * 1998-03-03 2004-06-03 Ppg Ind Ohio Inc Impregnated glass fiber strand and products including the same
US20080170984A1 (en) * 2005-04-07 2008-07-17 Reshef Tenne Process And Apparatus For Producing Inorganic Fullerene-Like Nanoparticles
CN103480856A (en) * 2013-09-09 2014-01-01 南京邮电大学 Method for preparing nanocomposite by using two-dimensional transition metal chalcogenide nanosheets and metal
CN104445419A (en) * 2014-12-02 2015-03-25 湖南省华京粉体材料有限公司 Method for preparing tungsten disulfide composite material for carbon brush
CN107849642A (en) * 2015-06-01 2018-03-27 耶达研究及发展有限公司 Metal alloy composite
CN106711225A (en) * 2016-11-17 2017-05-24 北京交通大学 Sulfide field effect transistor and production method thereof
CN107146815A (en) * 2017-03-21 2017-09-08 广东工业大学 A kind of Schottky gate field-effect transistor and preparation method and application
CN107557754A (en) * 2017-07-21 2018-01-09 杭州电子科技大学 A kind of preparation method of tungsten disulfide film
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

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