CN115692132A - Graphene-based composite material and preparation method and application thereof - Google Patents
Graphene-based composite material and preparation method and application thereof Download PDFInfo
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 51
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 41
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Abstract
The invention is suitable for the technical field of graphene materials, and provides a preparation method of a graphene-based composite material, which comprises the following steps: providing a silicon nanopore pillar array; depositing a catalyst nickel nanocrystal on the silicon nanopore column array; the method comprises the steps of taking a silicon nanopore column array deposited with nickel nanocrystals as a substrate, taking methane as a carbon source, taking a mixed gas of argon and hydrogen as a carrier gas, and obtaining the graphene-based composite material by a chemical vapor deposition method, wherein graphene grows parallel to the substrate in the composite material. According to the invention, the catalyst nano-grade metallic nickel is deposited on the silicon nano-pore column array, the graphene nanosheet parallel to the substrate is grown, the problem of unstable structure of the vertical substrate is solved, compared with the structure of the graphene vertical substrate, the emission stability is greatly enhanced in the electron emission process, meanwhile, the transverse nano-scale of the graphene has a higher perimeter area ratio, the number of edge emission points is more, and the field emission density of the material is ensured.
Description
Technical Field
The invention belongs to the technical field of graphene materials, and particularly relates to a graphene-based composite material and a preparation method and application thereof.
Background
Carbon nanotubes are considered to be a preferred material for cold cathode fabrication because of their stable electron emission, low turn-on field strength and large forward emission current density, however, the wide application of carbon nanotube cold cathode materials still suffers from some inherent problems, for example, the tubular structure of carbon nanotubes limits electron emission to a top position, thus exhibiting non-uniform emission for a layered carbon nanotube film, and furthermore, electrostatic shielding between carbon nanotubes is not negligible, thus the development of other carbon cathode materials is highly scientific and necessary.
As a most promising cold cathode material to replace carbon nanotubes, graphene has received increasing attention in recent years. Compared with the carbon nanotube, the graphene has higher aspect ratio (transverse dimension to thickness ratio), unique electrical property, high transparency, inherent flexible structure and good mechanical property, and is more suitable for being used as a flexible cold cathode material than the carbon nanotube.
In order to fully utilize the high electron emission characteristics of the graphene edge defect points, in the prior art, a structure in which graphene is perpendicular to a substrate is adopted to maximally utilize graphene field emission edge points (feses) to obtain high-intensity electron emission, for example, few-layer graphene is prepared by a microwave plasma enhanced chemical vapor deposition method and is arranged perpendicular to the substrate; the graphene film is screen printed perpendicular to the substrate or a blade-like electron emitter is built. However, in combination with the reference, the emission current of these vertically placed graphene is less stable at slightly higher voltages, and after multiple cyclic pressurization, the emission current density of the material gradually decreases: taking a typical case of graphene grown vertically on a substrate prepared by Alexander Malesevic group as an example (Malesevic a, keys R, vanhulsel a, et al, field emission from vertical aligned fed-layer graphene [ J ]. J Appl Phys, 2008, 104: 084301-084301-084305), after five cycles, not only the emission current density is significantly attenuated, but also the Field enhancement factor has a large floating range of 3000 to 5000.
Therefore, how to improve the stability of electron emission while maintaining high emission current density is a key problem to be solved in the development process of the graphene-based cold cathode material.
Disclosure of Invention
An embodiment of the present invention provides a preparation method of a graphene-based composite material, which aims to solve the problems in the background art.
The embodiment of the invention is realized in such a way that the preparation method of the graphene-based composite material comprises the following steps:
providing a silicon nanopore pillar array;
depositing a catalyst nickel nanocrystal on the silicon nanopore column array;
the method comprises the steps of taking a silicon nanopore column array deposited with nickel nanocrystals as a substrate, taking methane as a carbon source, taking a mixed gas of argon and hydrogen as a carrier gas, and obtaining a graphene-based composite material through a chemical vapor deposition method, wherein graphene in the composite material grows parallel to the substrate.
Preferably, the silicon nanopore column array is prepared by a chemical hydrothermal corrosion method.
Preferably, the preparation method of the silicon nanopore column array by adopting a chemical hydrothermal corrosion method comprises the following steps:
removing organic pollutants on the surface of the silicon wafer by using acetone, and then cleaning;
mixing Fe (NO) 3 ) 3 Corrosive liquid formed by HF aqueous solution is put into a high furnace with a polytetrafluoroethylene liningAnd (3) clamping the silicon wafer in a polytetrafluoroethylene fixing support in a pressure kettle, then putting the pressure kettle into the pressure kettle, then putting the pressure kettle into a heating furnace for heating, and then preserving heat and cooling to obtain the silicon nano-porous column array.
Preferably, the silicon wafer is heavily doped P-type monocrystalline silicon, and the doping concentration is 10 17 ~10 19 cm -3 。
Preferably, the step of depositing the catalyst nickel nanocrystals on the silicon nanopore pillar array employs a chemical water bath deposition method.
Preferably, the chemical water bath deposition method specifically comprises the following steps:
preparing a mixed solution containing ammonium fluoride and nickel acetate;
and putting the silicon nano-pore column array into the mixed solution for reaction, and cleaning after the reaction is finished to obtain the silicon nano-pore column array deposited with the nickel nano-crystals.
Preferably, the molar ratio of the ammonium fluoride to the nickel acetate is 30 to 80:1.
preferably, the step of obtaining the graphene-based composite material by the chemical vapor deposition method specifically includes:
putting the silicon nano-pore column array deposited with the nickel nano-crystals into a magnetic boat, pushing the magnetic boat into a clean quartz tube, fixing two ends of the quartz tube by using flanges, and exhausting air in the quartz tube;
and introducing mixed gas of argon and hydrogen into the quartz tube, raising the furnace temperature to a specified temperature, introducing methane into the mixed gas, pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed gas of argon and hydrogen in the process to obtain the graphene-based composite material.
Another object of the embodiments of the present invention is to provide a graphene-based composite material prepared by the above preparation method of a graphene-based composite material.
Another object of an embodiment of the present invention is to provide an application of the graphene-based composite material in preparation of a field emission device.
The embodiment of the invention provides a preparation method of a graphene-based composite material, which is provided aiming at the problem that the practical application is limited due to the unstable field emission performance in a vertical substrate graphene structure, the nano-scale metallic nickel catalyst is deposited on a silicon nano-pore column array to grow a graphene nanosheet parallel to a substrate, and the problem of unstable structure of the vertical substrate is overcome due to the structure of the graphene parallel substrate.
Drawings
Fig. 1 is a schematic structural diagram of a graphene-silicon composite material prepared in embodiment 1 of the present invention (where GNS represents a graphene nanosheet, and fess represents a graphene field emission edge point);
fig. 2 is a scanning electron microscope photograph of the graphene-silicon composite material prepared in example 1 of the present invention;
fig. 3 is an X-ray diffraction spectrum of the graphene-silicon composite material prepared in example 1 of the present invention;
FIG. 4 is a graph illustrating the field emission performance and stability of the graphene-silicon composite material prepared in example 1 (wherein a represents a J-E curve measured by a sample at four voltage periods, and b represents a F-N curve corresponding to the sample at four measurement cycles).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A graphene-based composite material is a graphene-silicon composite material, and a preparation method thereof comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon wafer is prepared by a chemical hydrothermal etching method, wherein the Si wafer is monocrystalline p-type heavy doping, and the doping concentration is 10 17 ~10 19 cm -3 ，<111>Orientation; before corrosion, soaking in acetone to remove organic pollutants on the surface, loading into a sample rack, cleaning by adopting a standard CRA process, and using Fe (NO) as corrosive liquid 3 ) 3 And the mixture is placed into an autoclave with a polytetrafluoroethylene lining, a Si sheet is clamped in a polytetrafluoroethylene fixing support and placed into the autoclave, the autoclave is placed into a heating furnace, the temperature is raised to 120 to 140 ℃, the temperature is kept for 22 to 30min, and then the autoclave is placed into a ventilation place for cooling;
s2: depositing Ni nanocrystalline catalyst by Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing a mixed solution containing ammonium fluoride and nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 5-20min, and washing with deionized water for later use, wherein the molar ratio of the ammonium fluoride to the nickel acetate is (30-80): 1;
s3: preparing a graphene-Si composite (graphene-silicon composite):
the preparation method comprises the steps of firstly washing a quartz tube with a mixed solution of water and ethanol, airing, putting a Si nano-pore column array deposited with a Ni nano-crystalline catalyst into a magnetic boat, then pushing the magnetic boat into the quartz tube, fixing two ends of the quartz tube with flanges, pumping the quartz tube to 0.1 Pa by using a vacuum pump, introducing argon until the pressure in the tube reaches atmospheric pressure, pumping the tube to vacuum by using the vacuum pump, repeating the steps for three times to discharge air in the tube, continuously introducing a mixed gas of argon and hydrogen, raising the furnace temperature to 800-1000 ℃ at a speed of 10 ℃/min, keeping the temperature for 18-20 min, and then adding CH into the mixed gas 4 Introduction of CH 4 And then pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed protective gas of argon and hydrogen for 8-10 min in the process to finally prepare the graphene-Si composite material.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example 1
A preparation method of the graphene-based composite material comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon-based solar cell is prepared by a chemical hydrothermal corrosion method, wherein the resistivity of a Si sheet is 0.015 omega-cm, the Si sheet is single-crystal p-type heavily doped, and the doping concentration is 10 18 cm -3 ，<111>Orientation; before corrosion, soaking in acetone to remove organic pollutants on the surface, loading into a sample rack, and cleaning by adopting a standard CRA process, wherein the corrosion solution is 0.04 mol/l Fe (NO) 3 ) 3 And 13 mol/l HF aqueous solution, placing into a high-pressure autoclave with a polytetrafluoroethylene lining, clamping a Si sheet in a polytetrafluoroethylene fixing bracket, placing into the high-pressure autoclave, placing the high-pressure autoclave into a heating furnace, heating to 140 ℃, preserving heat for 25min, and then placing into a ventilation position for cooling;
s2: depositing Ni nanocrystalline catalyst by using Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing 20ml of mixed solution containing 4 mol/L ammonium fluoride and 0.05 mol/L nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 15min, and washing with deionized water for later use;
s3: preparing a graphene-Si composite material:
the preparation method comprises washing quartz tube with mixed solution of water and ethanol, air drying, placing Si nano-porous column array deposited with Ni nano-crystalline catalyst into magnetic boat, pushing quartz tube, fixing two ends of quartz tube with flanges, vacuum pumping to 0.1 Pa, introducing 200 sccm argon gas until the pressure in the tube reaches atmospheric pressure, vacuum pumping to vacuum, repeating the steps for three times to exhaust air in the tube, continuously introducing mixed gas of 200 sccm argon gas and 65 sccm hydrogen gas, heating the furnace temperature to 1000 deg.C at 10 deg.C/min, maintaining for 20min, adding 10 sccm CH into the mixed gas 4 Introduction of CH 4 And then pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed protective gas of argon and hydrogen for 10 min in the process to finally obtain the graphene-Si composite material.
And (3) performance testing:
(1) The structure diagram of the graphene-Si composite material is shown in FIG. 1;
(2) Scanning the graphene-Si composite material by an electron microscope, and obtaining a result shown in FIG. 2;
(3) The results are shown in FIG. 3 by X-ray diffraction of graphene-Si composite material;
(3) Carrying out a field emission performance test on the graphene-Si composite material:
the carrier concentration of the graphene-Si composite material is 5.45' 10 measured by a Hall instrument and a four-probe method 24 cm -3 And plane resistivity of 2.52' 10 -8 Ω·cm；
At room temperature, using a diode structure model, at about 2X 10 -4 Pa pressure in a vacuum chamber, using Indium Tin Oxide (ITO) coated glass (ρ = 8 × 10) -4 Ω · cm) as an anode, a graphene-Si composite material as a cathode, the anode and the cathode being separated by a mica insulating sheet having a thickness of 375 μm, and current-voltage data were recorded by a digital multimeter (Sourcemeter-2400, keithley), and as a result, 53.9 μ a/cm at an electric field of 4.2V/μm was obtained, with a typical open field strength of 2.85V/μm as shown in fig. 4 2 The current intensity is not obviously changed after 4 cycles, and the F-N curve is not greatly changed;
in conclusion, the composite system prepared by the embodiment of the invention is measured on a Hall instrument by a four-probe method, and has high carrier concentration of 5.45' 10 24 cm -3 And a low sheet resistivity of 2.52' 10 -8 Omega cm, which is two orders of magnitude lower than the resistivity of most metals, provides enough conduction electrons for the graphene emitting electrons, and ensures stable and continuous emission current;
compared with the structure of the graphene vertical substrate, the graphene-Si-based material prepared by the embodiment of the invention has the advantages that the field emission stability is greatly improved, and the emission area of the graphene/Si-NPA is considered to be 1 cm 2 In graphene-based field emission cathode materials, having relatively strong field emission properties, e.g., nitrogen passivated vertically aligned few-layer graphene, emission surface, according to the disclosure in the prior artProduct of 0.2 cm 2 While the on-field reaches 4.6V/μm (10.0 μ A/cm) 2 ) Whereas field electrons also emitted from the edge of a graphene film with a size of 1.0 x 1.0 cm require a turn-on field strength of 50V/μm and are tested in a Hall instrument by the four-probe method, the conduction current at the turn-on voltage is only 10 -4 μA/cm 2 It is obvious that, under the condition of the same field intensity, the current density of the composite material is not as strong as that of the composite material prepared by the embodiment of the invention, the emission surface is smaller than that of the composite material prepared by the embodiment of the invention, and the composite material with the same emission area is not as strong as that of the open field of the composite material prepared by the embodiment of the invention.
Example 2
A preparation method of the graphene-based composite material comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon-based solar cell is prepared by a chemical hydrothermal etching method, wherein a Si sheet is monocrystalline p-type heavily doped with a doping concentration of 10 17 cm -3 ，<111>Orientation; before corrosion, soaking in acetone to remove organic pollutants on the surface, loading into a sample rack, cleaning by adopting a standard CRA process, and using Fe (NO) as corrosive liquid 3 ) 3 And HF water solution, placing into a high-pressure autoclave with a polytetrafluoroethylene lining, clamping a Si sheet in a polytetrafluoroethylene fixing support, placing into the high-pressure autoclave, placing the high-pressure autoclave into a heating furnace, heating to 120 ℃, preserving heat for 30min, and then placing into a ventilation position for cooling;
s2: depositing Ni nanocrystalline catalyst by using Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing a mixed solution containing ammonium fluoride and nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 15min, and cleaning with deionized water for later use, wherein the molar ratio of ammonium fluoride to nickel acetate is 30:1;
s3: preparing a graphene-Si composite material:
the preparation method comprises washing quartz tube with mixed solution of water and ethanol, air drying, and depositing Ni nanocrystallinePutting the Si nano-pore column array of the catalyst into a magnetic boat, pushing a quartz tube, fixing two ends of the quartz tube by flanges, pumping the quartz tube to 0.1 Pa by a vacuum pump, introducing 200 sccm argon until the pressure in the tube reaches atmospheric pressure, pumping the quartz tube to vacuum by the vacuum pump, repeating the process for three times to exhaust the air in the tube, continuously introducing a mixed gas of 200 sccm argon and 65 sccm hydrogen, raising the furnace temperature to 800 ℃ at the speed of 10 ℃/min, keeping the temperature for 20min, and adding 10 sccm CH into the mixed gas 4 Introduction of CH 4 And pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed protective gas of argon and hydrogen for 10 min in the process to finally obtain the graphene-Si composite material.
Example 3
A preparation method of the graphene-based composite material comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon-based solar cell is prepared by a chemical hydrothermal etching method, wherein a Si sheet is monocrystalline p-type heavily doped with a doping concentration of 10 17 cm -3 ，<111>Orientation; before corrosion, soaking in acetone to remove organic pollutants on the surface, loading into a sample rack, cleaning by adopting a standard CRA process, and using Fe (NO) as corrosive liquid 3 ) 3 And the high-pressure autoclave is placed in a high-pressure autoclave with a polytetrafluoroethylene lining, a Si sheet is clamped in a polytetrafluoroethylene fixing support and placed in the high-pressure autoclave, the high-pressure autoclave is placed in a heating furnace, the temperature is raised to 130 ℃, the temperature is kept for 25min, and then the high-pressure autoclave is placed in a ventilation position for cooling;
s2: depositing Ni nanocrystalline catalyst by using Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing a mixed solution containing ammonium fluoride and nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 15min, and cleaning with deionized water for later use, wherein the molar ratio of ammonium fluoride to nickel acetate is 40:1;
s3: preparing a graphene-Si composite material:
the preparation method comprises cleaning quartz tube with mixed solution of water and ethanol, air drying, placing Si nanopore column array with Ni nanocrystalline catalyst deposited in magnetic boat, pushing into quartz tube, and placing the quartz tubeFixing two ends with flange, pumping to 0.1 Pa with vacuum pump, introducing argon gas until the pressure in the tube reaches atmospheric pressure, pumping to vacuum with vacuum pump, repeating the steps for three times to remove air in the tube, continuously introducing mixed gas of argon gas and hydrogen gas, heating the furnace temperature to 850 deg.C at a speed of 10 deg.C/min, maintaining for 18min, adding CH into the mixed gas 4 Introduction of CH 4 And then pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed protective gas of argon and hydrogen for 8min in the process to finally obtain the graphene-Si composite material.
Example 4
A preparation method of the graphene-based composite material comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon wafer is prepared by a chemical hydrothermal etching method, wherein the Si wafer is monocrystalline p-type heavy doping, and the doping concentration is 10 18 cm -3 ，<111>Orientation; soaking in acetone to remove organic contaminants on the surface before etching, loading into sample rack, cleaning by standard CRA process, and etching with Fe (NO) as etching solution 3 ) 3 And the water solution, the mixture is put into a high-pressure autoclave with a polytetrafluoroethylene lining, a Si sheet is clamped in a polytetrafluoroethylene fixed support and put into the high-pressure autoclave, the high-pressure autoclave is put into a heating furnace, the temperature is raised to 140 ℃, the temperature is kept for 30min, and then the high-pressure autoclave is put into a ventilation place for cooling;
s2: depositing Ni nanocrystalline catalyst by using Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing a mixed solution containing ammonium fluoride and nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 20min, and cleaning with deionized water for later use, wherein the molar ratio of ammonium fluoride to nickel acetate is 50:1;
s3: preparing a graphene-Si composite material:
the preparation method comprises cleaning quartz tube with mixed solution of water and ethanol, air drying, placing Si nanopore column array with Ni nanocrystalline catalyst deposited in magnetic boat, pushing into quartz tube, fixing two ends of the quartz tube with flanges, pumping to 0.1 Pa with vacuum pump, introducing argon until the pressure in the tube reaches atmospheric pressure, and pumping to vacuum pump with vacuum pumpRepeating the above steps for three times to remove air in the tube, continuously introducing mixed gas of argon and hydrogen, heating the furnace temperature to 900 deg.C at a speed of 10 deg.C/min, maintaining for 18min, and adding CH into the mixed gas 4 Introduction of CH 4 And then pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed protective gas of argon and hydrogen for 10 min in the process to finally obtain the graphene-Si composite material.
Example 5
A preparation method of the graphene-based composite material comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon-based solar cell is prepared by a chemical hydrothermal etching method, wherein a Si sheet is monocrystalline p-type heavily doped with a doping concentration of 10 19 cm -3 ，<111>Orientation; soaking in acetone to remove organic contaminants on the surface before etching, loading into sample rack, cleaning by standard CRA process, and etching with Fe (NO) as etching solution 3 ) 3 And the water solution, the mixture is put into an autoclave with a polytetrafluoroethylene lining, a Si sheet is clamped in a polytetrafluoroethylene fixed support and put into the autoclave, the autoclave is put into a heating furnace, the temperature is raised to 120 ℃, the temperature is kept for 30min, and then the autoclave is put into a ventilation place for cooling;
s2: depositing Ni nanocrystalline catalyst by Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing a mixed solution containing ammonium fluoride and nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 18min, and cleaning with deionized water for later use, wherein the molar ratio of ammonium fluoride to nickel acetate is 60:1;
s3: preparing a graphene-Si composite material:
the preparation method comprises cleaning quartz tube with mixed solution of water and ethanol, air drying, placing Si nanopore column array with Ni nanocrystalline catalyst in magnetic boat, pushing into quartz tube, fixing two ends of the quartz tube with flanges, pumping to 0.1 Pa with vacuum pump, introducing argon until the pressure in the tube reaches atmospheric pressure, pumping to vacuum with vacuum pump, repeating the above steps for three times to discharge air in the tube, continuously introducing mixed gas of argon and hydrogen, and heating at 10 deg.C/min in furnace temperatureThe temperature is increased to 950 ℃, and CH is added into the mixed gas after the temperature is maintained for 20min 4 Introduction of CH 4 And pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed protective gas of argon and hydrogen for 10 min in the process to finally obtain the graphene-Si composite material.
Example 6
A graphene-based composite material, wherein the preparation method comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon wafer is prepared by a chemical hydrothermal etching method, wherein the Si wafer is monocrystalline p-type heavy doping, and the doping concentration is 10 19 cm -3 ，<111>Orientation; before corrosion, soaking in acetone to remove organic pollutants on the surface, loading into a sample rack, cleaning by adopting a standard CRA process, and using Fe (NO) as corrosive liquid 3 ) 3 And the high-pressure autoclave is placed in a high-pressure autoclave with a polytetrafluoroethylene lining, a Si sheet is clamped in a polytetrafluoroethylene fixing support and placed in the high-pressure autoclave, the high-pressure autoclave is placed in a heating furnace, the temperature is raised to 140 ℃, the temperature is kept for 28 min, and then the high-pressure autoclave is placed in a ventilation position for cooling;
s2: depositing Ni nanocrystalline catalyst by Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing a mixed solution containing ammonium fluoride and nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 20min, and cleaning with deionized water for later use, wherein the molar ratio of ammonium fluoride to nickel acetate is 70:1;
s3: preparing a graphene-Si composite material:
the preparation method comprises cleaning quartz tube with mixed solution of water and ethanol, air drying, placing Si nanopore column array with Ni nanocrystalline catalyst in magnetic boat, pushing into quartz tube, fixing two ends of the quartz tube with flanges, pumping to 0.1 Pa with vacuum pump, introducing argon until the pressure in the tube reaches atmospheric pressure, pumping to vacuum with vacuum pump, repeating the steps for three times to discharge air in the tube, continuously introducing mixed gas of argon and hydrogen, raising furnace temperature to 1000 deg.C at 10 deg.C/min, maintaining for 20min, adding CH in the mixed gas 4 Introduction of CH 4 After that, the air conditioner is started to work,pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed protective gas of argon and hydrogen for 10 min in the process to finally obtain the graphene-Si composite material.
Example 7
A preparation method of the graphene-based composite material comprises the following steps:
s1: preparing a Si nanopore column array:
the silicon wafer is prepared by a chemical hydrothermal etching method, wherein the Si wafer is monocrystalline p-type heavy doping, and the doping concentration is 10 19 cm -3 ，<111>Orientation; soaking in acetone to remove organic contaminants on the surface before etching, loading into sample rack, cleaning by standard CRA process, and etching with Fe (NO) as etching solution 3 ) 3 And the water solution, the mixture is put into an autoclave with a polytetrafluoroethylene lining, a Si sheet is clamped in a polytetrafluoroethylene fixed support and put into the autoclave, the autoclave is put into a heating furnace, the temperature is raised to 120 ℃, the temperature is kept for 22 min, and then the autoclave is put into a ventilation place for cooling;
s2: depositing Ni nanocrystalline catalyst by using Si nanopore column array:
preparing Ni nanocrystalline by adopting a chemical water bath deposition method, firstly, preparing a mixed solution containing ammonium fluoride and nickel acetate, putting a Si nanopore column array into the mixed solution, reacting for 5min, and cleaning with deionized water for later use, wherein the molar ratio of ammonium fluoride to nickel acetate is 80:1;
s3: preparing a graphene-Si composite material:
the preparation method comprises cleaning quartz tube with mixed solution of water and ethanol, air drying, placing Si nanopore column array with Ni nanocrystalline catalyst in magnetic boat, pushing into quartz tube, fixing two ends of the quartz tube with flanges, pumping to 0.1 Pa with vacuum pump, introducing argon until the pressure in the tube reaches atmospheric pressure, pumping to vacuum with vacuum pump, repeating the steps for three times to discharge air in the tube, continuously introducing mixed gas of argon and hydrogen, raising furnace temperature to 800 deg.C at 10 deg.C/min, maintaining for 18min, adding CH in the mixed gas 4 Introduction of CH 4 Then, the quartz tube is pushed out of the heating area to a room temperature area for cooling, and argon and hydrogen mixed protective gas is continuously introduced in the processAnd 8min, finally preparing the graphene-Si composite material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the graphene-based composite material is characterized by comprising the following steps of:
providing a silicon nanopore pillar array;
depositing a catalyst nickel nanocrystal on the silicon nanopore column array;
the method comprises the steps of taking a silicon nanopore column array deposited with nickel nanocrystals as a substrate, taking methane as a carbon source, taking a mixed gas of argon and hydrogen as a carrier gas, and obtaining a graphene-based composite material through a chemical vapor deposition method, wherein graphene in the composite material grows parallel to the substrate.
2. The method for preparing the graphene-based composite material according to claim 1, wherein the silicon nano-porous pillar array is prepared by a chemical hydrothermal corrosion method.
3. The method for preparing the graphene-based composite material according to claim 2, wherein the silicon nano-porous pillar array is prepared by a chemical hydrothermal etching method, and the method comprises the following steps:
removing organic pollutants on the surface of the silicon wafer by using acetone, and then cleaning;
mixing Fe (NO) 3 ) 3 And putting the corrosive liquid formed by the HF aqueous solution into an autoclave provided with a polytetrafluoroethylene lining, clamping a silicon wafer into a polytetrafluoroethylene fixing support, putting the silicon wafer into the autoclave, putting the autoclave into a heating furnace, heating, preserving heat and cooling to obtain the silicon nano-porous column array.
4. The method for preparing the graphene-based composite material according to claim 3, wherein the silicon wafer is heavily doped P-typeSingle crystal silicon, the doping concentration is 10 17 ~10 19 cm -3 。
5. The method of claim 1, wherein the step of depositing the nickel nanocrystals as the catalyst on the array of silicon nanopores is performed by chemical water bath deposition.
6. The method for preparing the graphene-based composite material according to claim 5, wherein the chemical water bath deposition method specifically comprises the following steps:
preparing a mixed solution containing ammonium fluoride and nickel acetate;
and putting the silicon nano-pore column array into the mixed solution for reaction, and cleaning after the reaction is finished to obtain the silicon nano-pore column array deposited with the nickel nano-crystals.
7. The preparation method of the graphene-based composite material according to claim 6, wherein the molar ratio of the ammonium fluoride to the nickel acetate is 30 to 80:1.
8. the method for preparing the graphene-based composite material according to claim 1, wherein the step of obtaining the graphene-based composite material by a chemical vapor deposition method specifically comprises:
putting the silicon nano-pore column array deposited with the nickel nano-crystals into a magnetic boat, pushing the magnetic boat into a clean quartz tube, fixing two ends of the quartz tube by using flanges, and exhausting air in the quartz tube;
and introducing mixed gas of argon and hydrogen into the quartz tube, raising the furnace temperature to a specified temperature, introducing methane into the mixed gas, pushing the quartz tube out of the heating area to a room temperature area for cooling, and continuously introducing the mixed gas of argon and hydrogen in the process to obtain the graphene-based composite material.
9. The graphene-based composite material prepared by the preparation method of the graphene-based composite material according to any one of claims 1 to 8.
10. Use of the graphene-based composite material according to claim 9 in the preparation of a field emission device.
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