CN113697812B - Preparation method of silicon carbide nanotube based on high-frequency electromagnetic field excitation - Google Patents
Preparation method of silicon carbide nanotube based on high-frequency electromagnetic field excitation Download PDFInfo
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- CN113697812B CN113697812B CN202111157300.7A CN202111157300A CN113697812B CN 113697812 B CN113697812 B CN 113697812B CN 202111157300 A CN202111157300 A CN 202111157300A CN 113697812 B CN113697812 B CN 113697812B
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Abstract
The invention relates to the technical field of nano material preparation, and discloses a preparation method of a silicon carbide nanotube based on high-frequency electromagnetic field excitation, which comprises the steps of introducing a gaseous carbon source, loading a radio frequency or microwave high-frequency electromagnetic field on the gaseous carbon source, and enabling an excited annular high-voltage electric field to cause electron avalanche to form a carbon plasma active group; the carbon plasma active groups react with silicon vapor to generate silicon carbide clusters, and the silicon carbide clusters self-assemble into the silicon carbide nanotubes at the nucleation sites. The method has the advantages of simple process equipment, high product purity, strong controllability and the like.
Description
Technical Field
The invention relates to the technical field of nano material preparation, and particularly provides a preparation method of a silicon carbide nanotube based on high-frequency electromagnetic field excitation.
Background
Silicon carbide has many advantages of good high temperature stability, wide band gap, high breakdown voltage, thermal conductivity, high electron mobility and the like, and is an important material for developing next-generation microelectronic and optoelectronic technologies. The one-dimensional silicon carbide nano material shows more excellent performances due to the quantum size effect, and structures such as nano particles, nano wires, nano belts, nano tubes and the like are widely researched. The nanotube with a hollow structure has a higher specific surface area, can be used as a catalyst carrier or a lithium battery electrode, and has important research value.
The preparation of the silicon carbide nanotube mainly comprises two methods of solvothermal and template sacrifice. A solvothermal method, for example, CN110156020A discloses a process for preparing silicon carbide nanotubes, which comprises adding an additive, a carbon source and a silicon source into polyhydric alcohol in a certain order, and reacting at a high temperature to obtain the silicon carbide nanotubes. A sacrificial template method, CN109110763A discloses a silicon carbide nanotube and a preparation method thereof, wherein the carbon nanotube is used as a template and a carbon source and reacts with silicon vapor to obtain the silicon carbide nanotube; CN100515942C discloses a method for preparing a silicon carbide nanotube with a high specific surface, which uses porous alumina as a template and polysiloxane as a raw material to prepare the silicon carbide nanotube. In addition, the preparation of silicon carbide nanotubes by electrochemical (CN 105714322B) and vapor deposition (CN 100424011C) methods has been reported.
Disclosure of Invention
The purpose of the invention is: by utilizing the advantages of high reaction activity and strong controllability of the plasma, the novel method for preparing the silicon carbide nanotube, which has simple and safe process, high yield and good product uniformity, is provided. Overcomes the defects of serious pollution, fussy flow, poor controllability and the like of the traditional method.
The technical scheme of the invention is as follows:
the preparation method of the silicon carbide nanotube based on high-frequency electromagnetic field excitation comprises the following steps:
step 1, placing silicon materials and metals with catalytic activity in a heating furnace, wherein the heating furnace is in a protective atmosphere, the protective gas forming the protective atmosphere is argon or a mixed gas of argon and hydrogen, and the heating furnace gradually raises the temperature to a set temperature; enabling the metal with catalytic activity to form metal steam at a heating temperature, and enabling the metal steam to form metal clusters on the surface of the silicon material; the metal cluster is used as a nucleation point for the growth of the silicon carbide nanotube; silicon vapor is simultaneously formed during the heating process; the silicon material is physically isolated from the catalytically active metal;
step 2, introducing a gaseous carbon source, loading a radio frequency or microwave high-frequency electromagnetic field to the gaseous carbon source, and enabling an excited annular high-voltage electric field to cause electron avalanche to form carbon plasma active groups;
the carbon plasma active groups react with silicon vapor to generate silicon carbide clusters, and the silicon carbide clusters self-assemble into the silicon carbide nanotubes at the nucleation sites.
Further, the parameters of the radio frequency or microwave high-frequency electromagnetic field are as follows: the power is 200W-500W.
Further, the air pressure in the hot furnace in the step 2 is 10 Pa-400 Pa.
Further, the ionization degree of the plasma in the step 2 is 1-1.5%.
Further, the metal with catalytic activity is copper, iron or nickel. Preferably, an isolation layer is arranged between the silicon chip and the metal with catalytic activity, and the isolation layer is made of aluminum oxide, quartz or mica.
Further, the silicon material is a silicon wafer.
Further, the set temperature is 700-1070 ℃.
Further, the gaseous carbon source is an organic gas or a gas carrying an organic substance. Preferably the gaseous carbon source is methane, acetylene, argon through organic solution hydrogen mixture.
Furthermore, the rate of gradual temperature rise of the heating furnace is 5 ℃/min to 20 ℃/min.
Further, the heat preservation time is 10min to 30min after the set temperature is reached in the step 1.
Further, after the gaseous carbon source is introduced in the step 2, the reaction time is 10min to 60min.
Further, in step 1, the concentration of the metal vapor is 10 3 /cm 3 ～10 7 /cm 3 . Preferably, the metal vapor concentration is obtained by mass spectrometer detection.
The invention has the advantages that: in the non-plasma process, the carbon source gas reacts with the silicon wafer completely under the action of high temperature, the reaction temperature is higher than 1000 ℃, the carbon source gas is ionized by plasma in the invention to form carbon plasma groups with high chemical activity, and the silicon carbide nanotube can be prepared at 700 ℃. The process has the advantages that the preparation temperature set by the non-plasma process is higher than the reaction temperature of the carbon source and the silicon wafer, and the carbon source gas is ionized in the plasma process, so the set preparation temperature only needs to consider the growth of the silicon carbide nanotube, and the size and the tube diameter of the nanotube are more controllable at the set temperature.
Drawings
FIG. 1 is a scanning electron microscope image of the average diameter of the SiC nanotubes produced by the present invention;
FIG. 2 is a scanning electron micrograph of monomeric silicon carbide nanotubes.
Detailed Description
The present invention is described in further detail below.
Embodiment 1 provides a method for preparing a silicon carbide nanotube based on excitation of a high-frequency electromagnetic field, comprising the steps of:
step 1, placing a silicon chip and a copper sheet in a heating furnace, physically isolating the silicon chip and the copper sheet by using a quartz sheet, introducing argon as a protective gas, and heating the heating furnace to 700 ℃ at a speed of 20 ℃/min; at this temperature, the concentration of copper vapor was 10 3 /cm 3 The copper steam forms copper clusters on the surface of the silicon wafer, and the copper clusters are used as nucleation points for the growth of the silicon carbide nanotubes; preserving the heat for 10min;
step 2, introducing methane, wherein the air pressure in the hot furnace is 10Pa; loading a radio frequency electromagnetic field with the power of 500W; the excited annular high-voltage electric field causes electron avalanche to form carbon plasma active groups, and the ionization degree is 1.5%; the reaction time of the carbon plasma group and the silicon vapor is 30min; the length of the silicon carbide nanotube prepared under the condition is 16 microns, the outer diameter of the nanotube is 500nm, and the thickness of the tube wall is 90nm.
Embodiment 2 provides a method for preparing a silicon carbide nanotube based on excitation of a high-frequency electromagnetic field, comprising the steps of:
step 1, placing a silicon wafer and a nickel sheet in a hot furnace, physically isolating the silicon wafer and the nickel sheet by using an aluminum oxide sheet, introducing argon-hydrogen mixed gas as protective gas, and heating the hot furnace to 900 ℃ at the speed of 5 ℃/min; at this temperature, the concentration of nickel vapor was 10 5 /cm 3 The nickel steam forms nickel clusters on the surface of the silicon wafer, and the nickel clusters are used as nucleation points for the growth of the silicon carbide nanotubes; preserving the heat for 20min;
step 2, introducing acetylene, wherein the air pressure in the hot furnace is 150Pa; loading a microwave electromagnetic field with the power of 300W; the excited annular high-voltage electric field causes electron avalanche to form carbon plasma active groups, and the ionization degree is 1.2%; the reaction time of the carbon plasma group and the silicon vapor is 10min; the length of the silicon carbide nanotube prepared under the condition is 10 microns, the outer diameter of the nanotube is 300nm, and the thickness of the tube wall is 50nm.
Embodiment 3 provides a method for preparing a silicon carbide nanotube based on excitation of a high-frequency electromagnetic field, comprising the steps of:
step 1, placing a silicon wafer and an iron sheet in a hot furnace, physically isolating the silicon wafer and the iron sheet by using a mica sheet, introducing argon as a protective gas, and heating the hot furnace to 1050 ℃ at a speed of 10 ℃/min; at this temperature, the concentration of iron vapor was 10 7 /cm 3 The iron vapor forms nickel clusters on the surface of the silicon wafer, and the iron clusters are used as nucleation points for the growth of the silicon carbide nanotubes; preserving the heat for 30min;
step 2, introducing argon carrying ethanol steam, wherein the air pressure in the heating furnace is 400Pa; loading a microwave electromagnetic field with the power of 200W; the excited annular high-voltage electric field causes electron avalanche to form carbon plasma active groups, and the ionization degree is 1%; the reaction time of the carbon plasma group and the silicon vapor is 60min; the length of the silicon carbide nanotube prepared under the condition is 13 mu m, the outer diameter of the nanotube is 400nm, and the thickness of the tube wall is 70nm.
Claims (13)
1. The preparation method of the silicon carbide nanotube based on high-frequency electromagnetic field excitation is characterized by comprising the following steps:
step 1, placing silicon materials and metals with catalytic activity in a heating furnace, wherein the heating furnace is in a protective atmosphere, the protective gas forming the protective atmosphere is argon or a mixed gas of argon and hydrogen, and the heating furnace gradually raises the temperature to a set temperature; enabling the metal with catalytic activity to form metal steam at a heating temperature, and enabling the metal steam to form metal clusters on the surface of the silicon material; the metal cluster is used as a nucleation point for the growth of the silicon carbide nanotube; silicon vapor is simultaneously formed during the heating process; the silicon material is physically isolated from the catalytically active metal;
step 2, introducing a gaseous carbon source, loading a radio frequency or microwave high-frequency electromagnetic field on the gaseous carbon source, and enabling an excited annular high-voltage electric field to cause electron avalanche to form carbon plasma active groups;
the carbon plasma active groups react with silicon vapor to generate silicon carbide clusters, and the silicon carbide clusters can be self-assembled into the silicon carbide nanotubes on the nucleation points.
2. The method for preparing silicon carbide nanotubes excited by a high-frequency electromagnetic field according to claim 1, wherein the method comprises the following steps: the parameters of the radio frequency or microwave high-frequency electromagnetic field are as follows: the power is 200W-500W.
3. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: and 2, the air pressure in the hot furnace in the step 2 is 10-400 Pa.
4. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: in the step 2, the ionization degree of the plasma is 1-1.5%.
5. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: the metal with catalytic activity is copper, iron or nickel.
6. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: the silicon material is a silicon wafer.
7. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 6, wherein: an isolation layer is arranged between the silicon chip and the metal with catalytic activity, and the isolation layer is made of aluminum oxide, quartz or mica.
8. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: the set temperature is 700-1070 ℃.
9. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: the gaseous carbon source is organic gas or gas carrying organic matters.
10. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 9, wherein: the gaseous carbon source is methane, acetylene, argon passing through the organic solution, and a mixed gas of argon and hydrogen passing through the organic solution.
11. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: the heating rate of the heating furnace is 5 ℃/min-20 ℃/min.
12. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: and (3) keeping the temperature for 10-30 min after the set temperature is reached in the step (1).
13. The method for preparing silicon carbide nanotubes excited based on high-frequency electromagnetic field according to claim 1, wherein: and (3) after the gaseous carbon source is introduced in the step (2), the reaction time is 10-60 min.
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| JP3742877B2 (en) * | 2002-03-22 | 2006-02-08 | 独立行政法人産業技術総合研究所 | Method for producing SiC single crystal thin film |
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