CN104828772A - Method for growing graphene in silicon micro-channel plate - Google Patents
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- CN104828772A CN104828772A CN201510232694.6A CN201510232694A CN104828772A CN 104828772 A CN104828772 A CN 104828772A CN 201510232694 A CN201510232694 A CN 201510232694A CN 104828772 A CN104828772 A CN 104828772A
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 4
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- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 4
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Abstract
The invention discloses a method for growing graphene in a silicon micro-channel plate. The method comprises the following steps: (1) pretreatment: soaking the silicon micro-channel plate into corrosive liquid; (2) electroless nickel plating: putting the pretreated silicon micro-channel plate into an electroless nickel plating solution to perform chemical plating of porous nickel; (3) hydrothermal polyol carburization: soaking the nickel-plated silicon micro-channel plate into a surfactant once again, and putting the soaked nickel-plated silicon micro-channel plate into a hydrothermal reaction kettle filled with polyol and a sodium salt catalyst; and (4) annealing: annealing the silicon micro-channel plate containing nickel carbide in a tubular furnace. Compared with the prior art, the method has the advantages that the problem of failure in plugging graphene into a silicon micro-channel with an electrophoretic technique is solved; and meanwhile, the defects of complex graphene growing process and high cost in a chemical vapor deposition method are overcome. A plurality of layers of graphene can be grown on the surface and in holes of the nickel-plated silicon micro-channel plate with a high depth-width ratio. The method has the characteristics of environmental friendliness, easiness, feasibility, low cost and the like.
Description
Technical Field
The invention belongs to the technical field of micro electro mechanical systems, and particularly relates to a method for growing graphene in a silicon microchannel plate.
Background
Graphene was obtained by two scientists, Andre geom and konnstatin Novoselov, manchester university, uk, in 2004 by means of mechanical stripping with adhesive tape, two people in 2010 thus enjoyed the nobel prize for physics. The graphene is a two-dimensional crystal formed by carbon atoms, the single-layer thickness of the graphene is 0.335nm, the thickness of the graphene is 1/200, the thickness of 1 mm of graphite has 150 ten thousand layers of graphene, and the specific surface area of the graphene reaches 26002600m2(ii) in terms of/g. Graphene has excellent conductivityThe performance, the extra-large specific surface area, the strength which is dozens of times higher than that of steel and good light transmission performance have wide application prospect in the fields of electronic devices, touch screens, biological medicines, sensors, supercapacitors, lithium ion batteries and the like.
Porous Silicon (PS) is a material formed by anodic dissolution of silicon in an HF solution. The formation of porous silicon was first reported when the electrochemical polishing of silicon was studied in the 50's of the 20 th century. According to the classification standard of the International Union of applied chemistry (International Union of Pure and applied chemistry IUPAC) for porous silicon, porous silicon can be classified into three types according to the size (width or diameter) of the pores: those larger than 50nm are called macro pores (macroporouss), those between 2 and 50nm are called meso pores (mesoporous), and those smaller than 2nm are called micropores. The microchannel structure of the present invention generally has pore sizes on the micrometer (um) scale and is therefore also referred to as macroporous silicon. The microchannel plate was developed by this group of subjects, with 5 micron times 5 micron pore size, 250 micron pore depth, and proprietary intellectual property. The microchannel plate has the characteristics of large specific surface area, light weight and thin weight, and the preparation process is compatible with an Integrated Circuit (IC) process. The method has good application prospect in the fields of photomultipliers, high-energy particle detection, heat conduction devices, three-dimensional lithium ion batteries, supercapacitors, three-dimensional sensors and the like.
The composite electrode is synthesized by graphene and a silicon microchannel plate, and the electrode is subjected to an annealing process by utilizing the characteristics of good conductivity, large specific surface area of the silicon microchannel plate, regular structure, compatibility of a preparation process and an IC (integrated circuit) process, light weight and the like to form an MLG (Multi-layer graphene)/Ni/Si-MCP electrode, and the electrode has a good application prospect in field emission sensors and super-capacitor cathode materials.
The preparation method of the graphene is more, and comprises mechanical stripping, silicon carbide surface epitaxial growth, metal surface growth, oxidation reduction, graphite acoustic wave treatment, a carbon nanotube cutting method and the like. The methods mostly use a redox method and a metal surface growth method, and the graphene prepared by the redox method has high yield and is suitable for large-scale production, but the graphene prepared by the method has many defects and can only be applied to energy storage devices such as super capacitors, lithium ion batteries and the like. The graphene prepared by the metal surface growth method has fewer layers and high purity, and can be applied to occasions with higher requirements, such as electronic devices and the like, but all CVD equipment for preparing graphene by the method is expensive, has higher process difficulty, and is not easy to industrialize. At present, according to literature reports, a scientific household electrophoresis method is adopted to prepare graphene on the surface and in pores of a porous silicon. In 2013, graphene is prepared by redox method in an article published in surface science by king et al, and then the graphene is plugged into porous silicon by electrophoresis method and applied to electrolytic water with good effect, and the depth of the porous silicon used in the report is 20 microns. The method is a technical problem on how to manufacture the graphene in the silicon micro-channel with the depth of 250 microns and the aspect ratio of 50. If achievable, the structure will have unlimited use in devices such as field emission sensors, lithium ion batteries and supercapacitors.
Disclosure of Invention
The invention aims to provide a method for growing graphene in a silicon microchannel plate, so as to solve the problems in the prior art.
The purpose of the invention is realized by the following technical scheme.
A method for growing graphene in a silicon microchannel plate comprises the following steps:
(1) pretreatment: soaking the silicon microchannel plate in an etching solution mainly containing hydrofluoric acid to remove silicon dioxide naturally growing on the surface, and activating the silicon microchannel plate by using a surfactant;
(2) electroless nickel plating: putting the pretreated silicon microchannel plate into an electroless nickel plating solution at a certain temperature to carry out chemical plating on porous nickel;
(3) carburizing of hydrothermal polyol: soaking the nickel-silicon plated microchannel plate with the surfactant again, putting the nickel-silicon plated microchannel plate into a hydrothermal reaction kettle filled with the polyalcohol and sodium salt catalyst, and forming nickel carbide after a certain temperature and time;
(4) annealing: and annealing the silicon microchannel plate containing the nickel carbide in a tubular furnace to separate out carbon in the nickel carbide to form multilayer graphene, wherein the multilayer graphene is coated on the inner wall and the upper surface of the nickel-plated silicon microchannel.
Wherein,
in the step (1), the size of the silicon microchannel plate is 3 multiplied by 3 to 9 multiplied by 9 microns2The depth is controllable from 100 to 300 microns.
The corrosive liquid is HF and C2H5OH and H2O, wherein the volume ratio of the mixture is HF: c2H5OH：H2And (3) soaking for 3-5 minutes to remove the silicon dioxide naturally grown on the surface of the silicon microchannel when the O is 100:125: 10.
In the step (1), the surfactant is Triton-X100, and the volume ratio of the surfactant to water is Triton-X100: h2O-1/500-1/1000; soaking for 20-60 seconds. Silicon dioxide is removed by corroding the silicon microchannel, and a surfactant is soaked, so that the wettability of the silicon microchannel plate is improved.
In the step (2), the electroless nickel plating solution is also called electroless nickel plating, and comprises nickel chloride, ammonium chloride and sodium hypophosphite in a mass ratio of 5:5.1:1.2, the temperature is 70-90 ℃, the pH value is 8-10, and the time is 20-60 minutes.
In the step (3), the polyhydric alcohol is one of xylitol and triethylene glycol, and the sodium salt of the catalyst is one of sodium sulfate, sodium carbonate, sodium acetate and sodium acetate, so that the formation of nickel carbide is promoted. The temperature range is 250 ℃ and 260 ℃, the time is 1-24 hours, and the volume ratio of the polyhydric alcohol to the catalyst is as follows: 20:1-40:1. By utilizing the characteristic that carbon has high solid solubility in nickel, carbon is dissolved in nickel in a hexagonal atomic structure to form nickel carbide.
In the step (3), the inner container of the hydrothermal reaction kettle is made of PPL material and can resist the temperature of 300 ℃.
In the step (4), the annealing temperature range is 500-800 ℃, and the time is 15-60 min. The carbon in the nickel carbide is separated from the nickel carbide by annealing and exists as hexagonal carbon atoms.
In the present invention, the polyhydric alcohol refers to an alcohol having three or more hydroxyl groups in the molecule. In the step (3), nickel carbide is formed at the temperature of 250-260 ℃ by utilizing the characteristic that the carbonization temperature of the polyol is close to the temperature of forming the nickel carbide in the nickel by the carbon, and in the step (4), the nickel carbide is decomposed to separate out the carbon and the nickel by utilizing the characteristic that the nickel carbide is unstable when the temperature is higher than 480 ℃. The precipitated carbon exists in the form of hexagonal carbon atoms (graphite phase carbon), the annealing temperature is raised again, and the graphite is stripped, so that the multilayer graphene is obtained.
According to the method for growing the graphene in the silicon microchannel plate by the hydrothermal polyol carburization method, electroless nickel plating (chemical nickel plating) is a very critical step on the surface and in holes of the silicon microchannel plate, nickel-plated particles cannot be too large, the particles are large, the activity of porous nickel is reduced, the hydrothermal carburization process is carried out slowly, and a universal meter is used for measuring the resistance of the surface of the nickel-plated microchannel plate to be 4-10 ohms optimally. Because the substrate is a silicon microchannel plate, the catalyst selected by the hydrothermal carburization cannot corrode silicon, namely the pH value of the catalyst cannot be more than 7, and only partial sodium salts (sodium sulfate, sodium carbonate, sodium acetate and the like) can be selected. The carbon content in nickel in the nickel plated micro-channel increases with the increase of the carburizing time, and the carburizing amount reaches a peak value at the temperature after 6 hours, and reaches about 5 percent (relative to nickel). The nickel carbide with the temperature of more than 480 ℃ is unstable, the annealing temperature is 15min-60min, argon is used as protective gas, carbon is separated out in the form of graphite phase carbon, and the graphite phase carbon is stripped along with the increase of the temperature to form multilayer graphene. The annealing temperature is crucial to maintaining the integrity of the structure, and nickel is easy to agglomerate when the temperature is over 800 ℃, so the annealing temperature is lower than 800 ℃. The invention innovatively provides a method for preparing multilayer graphene in the surface and the surface of a nickel-plated microchannel plate, which is characterized in that polyhydric alcohol is carbonized by a hydrothermal method and permeates into the surface and the holes of the nickel-plated microchannel plate (hydrothermal carburization), and the multilayer graphene is prepared in the holes and the surface of the nickel-plated microchannel plate with the depth-to-width ratio of 50 after annealing.
Compared with the prior art, the method overcomes the difficulty that the electrophoresis technology is utilized to plug graphene (with the transverse size of tens of microns) into a silicon microchannel (with the size of 5 multiplied by 250, the unit is micron, and the depth-to-width ratio is 50) which cannot be realized; meanwhile, the defects of complex process and high cost of graphene growth by using a Chemical Vapor Deposition (CVD) method are avoided. The method has the characteristics of environmental friendliness, simplicity, feasibility, low cost and the like.
Drawings
FIG. 1 is an SEM image of a p-type silicon microchannel used in the present invention. Wherein, FIG. 1(a) is a surface structure SEM image, and FIG. 1(b) is a cross-sectional structure SEM image.
Fig. 2 is a flow chart of the present invention for growing graphene in silicon micro-channels.
FIG. 3 is an SEM image of a silicon microchannel after electroless nickel plating according to the present invention; in which, fig. 3(a) is a surface structure SEM image, and fig. 3(b) is a cross-sectional structure SEM image.
FIG. 4 is an SEM image of a nickel-silicon plated microchannel plate for hydrothermal carburization according to the present invention; fig. 4(a) is a surface structure SEM image, and fig. 4(b) is a cross-sectional structure SEM image.
FIG. 5 is an EDX energy spectrum of a nickel-silicon micro-channel plate for hydrothermal carburizing in the method of the invention. Wherein, FIG. 5(a) is an EDX spectrum position diagram of a sample section after carburization, and FIG. 5(b) is an EDX spectrum of a position (a).
Figure 6 is an XRD pattern of a nickel-carburized microchannel plate obtained by the process of the present invention.
FIG. 7 is a Raman spectrum and SEM image after annealing for the method of the present invention. Fig. 7(a) is a raman spectrum of silicon microchannel-grown graphene, and fig. 7(b) is a cross-sectional SEM image of silicon microchannel-grown graphene.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
As shown in fig. 2, the growth of graphene in a silicon microchannel plate according to the present invention is divided into four steps.
1. Pretreatment:
(1) a silicon microchannel plate prepared from (100) crystal orientation p-type silicon is selected, the size is 5 multiplied by 250, the unit is micrometer, and the depth-to-width ratio is 50.
(2) The etching solution is HF: C2H5 OH: and (3) soaking for 3-5 minutes at the volume ratio of 100:125:10 of H2O to remove the silicon dioxide naturally grown on the surface of the silicon microchannel.
(3) Soaking in surfactant at a concentration of Triton-X100: H2O is 1/500-1/1000 volume ratio, and soaking for 20-60 seconds. Improve the wettability of the wall and the surface of the silicon micro-channel hole and expel the air in the silicon micro-channel hole.
2. Electroless nickel plating:
carrying out chemical nickel plating on the pretreated silicon microchannel plate in a chemical nickel plating solution; wherein the electroless nickel plating solution comprises nickel chloride, ammonium chloride and sodium hypophosphite in a mass ratio of 5:5.1:1.2, 100ml of solution is prepared, and ammonia water is used for adjusting the pH value to 8-10, the temperature to 70-90 ℃ and the time to 20-60 minutes. Electroless nickel plating (chemical nickel plating) on the surface and in holes of the silicon microchannel plate is a very critical step, nickel-plated particles cannot be too large, the particles are large, the activity of porous nickel is reduced, the hydrothermal carburization process is carried out slowly, and a universal meter is used for measuring the resistance of the surface of the nickel-plated microchannel plate to 4-10 ohms optimally.
3. And (3) hydrothermal carburization:
the hydrothermal polyol is carburized to the surface of the nickel-plated microchannel and the inner wall of the hole, and a catalyst is dissolved in the polyol (xylitol, triethylene glycol and the like) to promote the formation of nickel carbide. And putting the polyol mixed solution into a PPL material lining, wherein the liquid level is not more than 4/5, and putting into a stainless steel reaction kettle. Putting the mixture into a vacuum box at the temperature range of 250 ℃ and 260 ℃ for 1-24 hours, wherein the mass ratio of polyhydric alcohol: catalyst 20:1-40:1 (volume ratio). Because the substrate is a silicon microchannel plate, the catalyst selected by the hydrothermal carburization cannot corrode silicon, namely the pH value of the catalyst cannot be more than 7, and only partial sodium salts (sodium sulfate, sodium carbonate, sodium acetate and the like) can be selected. The carbon content in nickel in the nickel plated micro-channel increases with the increase of the carburizing time, and the carburizing amount reaches a peak value at the temperature after 6 hours, and reaches about 5 percent (relative to nickel).
4. Annealing:
and (2) at the high temperature of more than 250 ℃, the carbonized polyol permeates into the surface of the nickel-plated microchannel plate to form nickel carbide with a hexagonal structure, the nickel carbide is unstable, the annealing temperature is more than 480 ℃, the time is 15min-60min, argon is used as protective gas, carbon is separated out in the form of graphite phase carbon, and the graphite phase carbon is stripped along with the increase of the temperature to form multilayer graphene. The annealing temperature is crucial to maintaining the integrity of the structure, and nickel is easy to agglomerate when the temperature is over 800 ℃, so the annealing temperature is lower than 800 ℃. With the increase of the annealing temperature, the higher the graphite exfoliation degree is, the fewer the number of graphene layers is.
Example 1
A method for growing graphene in a microchannel plate comprises the following steps:
1. selecting a silicon microchannel plate prepared from (100) crystal orientation p-type silicon, wherein the aperture size is 5 multiplied by 250, the unit is micrometer, the depth-to-width ratio is 50, the area is 1 multiplied by 1, and the unit is centimeter, and the silicon microchannel plate is shown in figure 1;
2. taking 50ml of corrosive liquid as HF: C2H5 OH: soaking the silicon microchannel plate for 3 minutes at the volume ratio of H2O-100: 125:10, and removing silicon dioxide naturally growing on the surface of the silicon microchannel;
3. soaking the silicon microchannel plate with the silicon dioxide removed in a surfactant, wherein the concentration of the silicon microchannel plate is Triton-X100: H2O volume ratio 1/500, soak 60 seconds. The wettability of the wall and the surface of the silicon micro-channel hole is improved, and air in the silicon micro-channel hole is expelled; preparing chemical nickel plating solution of NiCl2:NH4Cl:NaH2PO4Preparing 100ml of solution (mass ratio) 5:5.1:1.2, adjusting the pH value to 8 by using ammonia water, adjusting the temperature to 90 ℃, putting the soaked silicon microchannel into plating solution, and chemically plating nickel for 30 minutes, wherein as shown in figure 3, a multimeter is used for measuring the resistance of 10 ohms on the surface of the nickel plating microchannel plate to be optimal; as can be seen from FIG. 3, the silicon microchannel plate maintains the original shape after nickel plating, and nickel is uniformly coated on the surface and inside of the silicon microchannel in the form of nanoparticles.
4. After soaking the nickel-plated silicon microchannel plate in Triton-X for 1001 minutes, the plate was put into 50ml of a polyol (xylitol) mixed solution in which a catalyst was dissolved, wherein the ratio of polyol to catalyst was 20:1 (by volume), and the catalyst was 1M sodium salt (sodium carbonate). And putting the polyol mixed solution into a lining of 25ml of PPL material, wherein the liquid level is not more than 4/5, putting the mixture into a stainless steel reaction kettle, screwing the stainless steel reaction kettle, putting the stainless steel reaction kettle into a vacuum box, setting the hydrothermal temperature to be 260 ℃ and the hydrothermal reaction time to be 6 hours. As shown in fig. 4-6, it can be seen from fig. 4(a) and 4(b) that after low temperature hydrothermal polyol carburization, the structure of the silicon microchannel is not changed, and the nano nickel particles on the sidewall and surface are not dropped off, and the original nano structure is maintained. As can be seen in fig. 5(a), hydrothermal polyol carburization can occur inside the silicon microchannels, and in fig. 5(b) it can be seen that the peak for carbon is present, indicating that the carburization process forms nickel carbide inside the microchannels. As can be seen from FIG. 6, the nickel-coated silicon micro-channels can form a standard peak of nickel carbide (JCPDS 77-0194) after being subjected to hydrothermal carburization. And the nickel carbide peak is more complete and stronger along with the prolonging of time.
Taking out the nickel plated microchannel plate after carburization, soaking in alcohol and deionized water for 5 minutes respectively, drying at 60 ℃, putting into a tube furnace, introducing argon for 40 minutes, heating to 700 ℃, heating at a heating rate of 10 ℃/minute, taking argon as a protective gas, keeping the temperature for 30 minutes, and then naturally cooling. As shown in fig. 7, it can be seen from fig. 7 that the annealed multilayer graphene-coated nickel-plated silicon microchannel plate has D, G and 2D peaks specific to graphene, which indicate that graphene successfully grows in the microchannel, and as seen from fig. 7(a), the morphology of the silicon microchannel-grown graphene is wrinkled and conforms to the morphology of graphene.
Example 2
1. A method for growing graphene in a microchannel plate comprises the following steps: selecting a silicon microchannel plate prepared from (100) crystal orientation p-type silicon, wherein the aperture size is 5 multiplied by 250, the unit is micrometer, the depth-to-width ratio is 50, and the area is 1cm multiplied by 1cm, as shown in figure 1;
2. taking 50ml of corrosive liquid as HF: c2H5OH: soaking the silicon microchannel plate for 4 minutes at the volume ratio of H2O-100: 125:10, and removing silicon dioxide naturally growing on the surface of the silicon microchannel;
3. soaking the silicon microchannel plate with the silicon dioxide removed in a surfactant, wherein the concentration of the silicon microchannel plate is Triton-X100: h2And O is 1/1000 volume ratio, and soaking is carried out for 30 seconds. The wettability of the wall and the surface of the silicon micro-channel hole is improved, and air in the silicon micro-channel hole is expelled;
4. preparing chemical nickel plating solution of NiCl2:NH4Cl:NaH2PO4Preparing 100ml of solution (mass ratio) 5:5.1:1.2, adjusting the pH value to 9 by using ammonia water, adjusting the temperature to 80 ℃, putting the soaked silicon microchannel into plating solution, and chemically plating nickel for 40 minutes, wherein as shown in figure 3, a universal meter is used for measuring the resistance of 8 ohms on the surface of the nickel plating microchannel plate to be optimal;
5. after soaking the nickel-plated silicon microchannel plate in Triton-X10030 seconds, the plate was put into 50ml of a polyol (triethylene glycol) mixed solution in which a catalyst was dissolved, wherein the ratio of polyol to catalyst was 30:1 (by volume), and the catalyst was 1M sodium salt (sodium acetate). And putting the polyol mixed solution into a lining of 25ml of PPL material, wherein the liquid level is not more than 4/5, putting the mixture into a stainless steel reaction kettle, screwing the stainless steel reaction kettle, putting the stainless steel reaction kettle into a vacuum box, setting the hydrothermal temperature to be 250 ℃ and the hydrothermal reaction time to be 12 hours. As shown in fig. 4-6.
6. Taking out the nickel plated microchannel plate after carburization, soaking in alcohol and deionized water for 5 minutes respectively, drying at 65 ℃, putting into a tube furnace, introducing argon for 50 minutes, heating to 800 ℃, heating at a heating rate of 10 ℃/minute, taking argon as a protective gas, keeping the temperature for 40 minutes, and then naturally cooling. The annealed multilayer graphene-coated nickel-silicon-plated microchannel plate is shown in fig. 7.
The method utilizes the high solid solubility of carbon in nickel and forms hexagonal carbon atoms after annealing to form multilayer graphene, successfully prepares the multilayer graphene into the silicon microchannel plate, and overcomes the difficulty that the electrophoresis technology is utilized to plug graphene (with the transverse size of dozens of microns) into a silicon microchannel (with the size of 5 multiplied by 250, the unit of micron and the depth-to-width ratio of 50) which cannot be realized; meanwhile, the defects of complex process and high cost of the CVD method for growing the graphene are avoided. Cleaning the silicon microchannel plate by using hydrofluoric acid corrosive liquid, and removing silicon dioxide naturally grown on the silicon microchannel plate; soaking an active agent to drive away air in the holes of the silicon microchannel plate; electroless nickel plating; soaking an activating agent, and carburizing the hydrothermal polyol to form nickel carbide; and (4) annealing at high temperature to form the nickel-silicon plated microchannel plate coated by the multilayer graphene. According to the invention, by using a hydrothermal polyol method, carbon carbonized by the polyol is dissolved on the nickel surface of the nickel-silicon-plated microchannel in a solid form to form nickel carbide, and multi-layer graphene coated nickel is formed after annealing. The method is low in cost and environment-friendly, and can be used for preparing the multilayer graphene on the surface and the hole wall of the nickel-plated micro-channel.
Claims (9)
1. A method for growing graphene in a silicon microchannel plate is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment: soaking the silicon microchannel plate in an etching solution mainly containing hydrofluoric acid to remove silicon dioxide naturally growing on the surface, and activating the silicon microchannel plate by using a surfactant;
(2) electroless nickel plating: putting the pretreated silicon microchannel plate into an electroless nickel plating solution at a certain temperature to carry out chemical plating on porous nickel;
(3) carburizing of hydrothermal polyol: soaking the nickel-silicon plated microchannel plate with the surfactant again, putting the nickel-silicon plated microchannel plate into a hydrothermal reaction kettle filled with the polyalcohol and sodium salt catalyst, and forming nickel carbide after a certain temperature and time;
(4) annealing: and annealing the silicon microchannel plate containing the nickel carbide in a tubular furnace to separate out carbon in the nickel carbide to form multilayer graphene, wherein the multilayer graphene is coated on the inner wall and the upper surface of the nickel-plated silicon microchannel.
2. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: in the step (1), the size of the silicon microchannel plate is 3 multiplied by 3 to 9 multiplied by 9 microns2The depth is controllable from 100 to 300 microns.
3. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: the corrosive liquid is HF and C2H5OH and H2O, wherein the volume ratio of the mixture is HF: c2H5OH：H2Soaking for 3-5 minutes when the ratio of O to O is 100:125: 10.
4. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: in the step (1), the surfactant is Triton-X100, and the volume ratio of the surfactant to water is Triton-X100: h2O-1/500-1/1000; soaking for 20-60 seconds.
5. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: in the step (2), the electroless nickel plating solution is nickel chloride, ammonium chloride and sodium hypophosphite with the mass ratio of 5:5.1:1.2, the temperature is 70-90 ℃, the pH value is 8-10, and the time is 20-60 minutes.
6. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: in the step (3), the polyhydric alcohol is one of xylitol and triethylene glycol, and the sodium salt of the catalyst is one of sodium sulfate, sodium carbonate, sodium acetate and sodium acetate.
7. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: in the step (3), the temperature range is 250-260 ℃, the time is 1-24 hours, and the volume ratio of the polyhydric alcohol to the catalyst is as follows: 20:1-40:1.
8. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: in the step (3), the inner container of the hydrothermal reaction kettle is made of PPL material and can resist the temperature of 300 ℃.
9. The method of claim 1, wherein the graphene is grown in a silicon microchannel plate, and the method comprises the following steps: in the step (4), the annealing temperature range is 500-800 ℃, and the time is 15-60 min.
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