WO2021212469A1 - 一种超快生长石墨烯的方法 - Google Patents

一种超快生长石墨烯的方法 Download PDF

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WO2021212469A1
WO2021212469A1 PCT/CN2020/086682 CN2020086682W WO2021212469A1 WO 2021212469 A1 WO2021212469 A1 WO 2021212469A1 CN 2020086682 W CN2020086682 W CN 2020086682W WO 2021212469 A1 WO2021212469 A1 WO 2021212469A1
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graphene
substrate
quenching
current
metal
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PCT/CN2020/086682
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English (en)
French (fr)
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徐建勋
赵宇亮
梁建波
葛逸飞
王鲁峰
杨宜
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国家纳米科学中心
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Priority to CN202080005008.0A priority Critical patent/CN113840801A/zh
Priority to PCT/CN2020/086682 priority patent/WO2021212469A1/zh
Publication of WO2021212469A1 publication Critical patent/WO2021212469A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation

Definitions

  • the invention belongs to the field of material surface functionalization, and specifically relates to a method for ultra-fast growth of graphene in a large area on the surface of a metal, non-metal plane and a needle tip substrate.
  • Graphene is a two-dimensional network material composed of a single layer of carbon atoms stacked in a honeycomb-like configuration. It has excellent optical, electrical, thermal, mechanical and other physical properties, as well as unique chemical properties. It can be used in many applications. Functional composite materials, organic optoelectronic materials, hydrogen storage materials, supercapacitors, and microelectronic devices. Graphene has attracted wide attention from researchers in recent years. The controllable preparation of high-quality large-area graphene is a prerequisite for its application. Expanding the preparation methods of graphene to meet the needs of different applications is the primary problem that needs to be solved in this field.
  • the main methods for preparing graphene include mechanical exfoliation, oxidation-reduction, epitaxial growth, and chemical vapor deposition.
  • the chemical vapor deposition (CVD) method generally uses a special gas carbon source, grows on a metal substrate (Ni or Cu) in a suitable atmosphere, and controls the temperature gradient, gas flow rate and other conditions to obtain High-quality graphene.
  • the functionalization of graphene on the surface of the target material mainly includes the graphene transfer method and the CVD direct growth method.
  • CVD growth of graphene usually uses single crystal Cu, Ni, or an alloy substrate of both, the synthesized graphene is transferred to the target material, which easily causes defects and contaminants in the graphene during the transfer process, and the graphene and the target material are different The interface contact between them is uncontrollable; in addition, the CVD method is limited by the furnace body and cannot obtain larger graphene, and it also has the disadvantages of long high-temperature growth time and high energy consumption.
  • the first is the transfer method, which uses graphene slurry on the glass surface. It is prepared by a liquid coating method, or is prepared on a metal substrate by the CVD method and then transferred to the glass surface. The other is to directly grow graphene on the glass surface by the CVD method.
  • the first transfer method has a small size of graphene, many defects, and pollution problems during the transfer process. Therefore, the prepared graphene glass has poor performance.
  • the graphene glass prepared by the second CVD method has good performance, but the size of the inner diameter of the tube furnace limits the size of the graphene glass, and it is impossible to prepare a larger size graphene glass.
  • the CVD direct growth method is not suitable for growing graphene on the surface of materials that cannot withstand high temperatures for a long time (such as polymer materials, nano-needle tips, etc.).
  • Graphene flexible polymer materials have special electrical and mechanical properties, and have unique application prospects in fields such as flexible displays and smart sensors.
  • the base material cannot withstand high temperatures for a long time, graphene functionalization of flexible materials is currently mainly prepared by physical coating methods.
  • Dua and Ruoff et al. used a chemical method to reduce graphene oxide flakes (rGO) on a polyethylene terephthalate (PET) film to make an rGO solution made by inkjet printing to produce an atmosphere sensor for detecting H 2 and other atmospheres.
  • the graphene functionalized AFM tip was fabricated by growing graphene on copper foil and transferring it to a commercial atomic force microscope (AFM) probe tip, which showed higher conductivity and service life; but graphite The transfer process of ene is uncontrollable, and the force between the transferred graphene and the AFM probe body is small and the adhesion is not tight.
  • Martin-Olmos et al. used semiconductor processing technology to form a pyramidal groove array on the surface of a silicon wafer and plated a layer of copper on the surface, and then used the CVD method to grow a continuous pattern on the copper coating (including the pyramidal grooves).
  • Graphene layer and further spin-coated the base material SU-8 on the graphene layer to obtain a graphene-functionalized AFM probe.
  • the tip of the pyramidal groove is passivated due to high temperature for a long time, resulting in the size of the final AFM probe tip being larger than 1um, and the resulting AFM probe has a reduced spatial resolution.
  • the physical adsorption method is uncontrollable and cannot guarantee good contact between the needle tip surface and the graphene layer, and the CVD method causes damage to the nanometer size of the probe tip due to the long-term high temperature environment required for growth.
  • the current methods for realizing the functionalization of graphene on the material surface mainly include the transfer method and the CVD direct growth method.
  • the transfer method is easy to cause defects and contaminants in the graphene during the transfer process, and the interface contact between the graphene and the target substrate is uncontrollable; while the CVD direct growth method requires high substrate temperature resistance, long time, high energy consumption, and product The size limitation hinders the mass production and application expansion of graphene functionalized products.
  • Xiong et al. reported a method of using micro-nano laser direct writing equipment to generate graphene patterns on the surface of insulating substrate materials such as glass or Si sheets.
  • the laser spot is focused on the surface of the substrate to heat the irradiated area on the surface of the substrate to reach the growth temperature and conditions of graphene, which avoids the long-term high temperature of the substrate surface and realizes the rapid growth of graphene.
  • the laser spot size used in this method is very small (about 800 nanometers), which can only achieve graphene growth in a small area (micron level), but cannot achieve macroscopic substrate surface. The rapid growth of large-area graphene.
  • the present invention provides a new type of ultra-fast graphene growth method, which uses pulse current, induced current or concentrated microwave energy to act on the carbonized substrate material, and generates a large amount of heat in situ through the current on the substrate surface. Realize the instantaneous quenching of the material and generate a large range of continuous single-layer or multi-layer graphene on the surface of the material ( Figure 1).
  • the ultra-fast growth method provided by the present invention is not limited by the size of the vacuum tube furnace, and realizes the growth of graphene on a large-size substrate material, and has a wide range of materials (type, size) and environment (vacuum, inert atmosphere or atmosphere). Fast and low energy consumption.
  • the purpose of the present invention is to propose a preparation method for realizing large-area ultra-fast graphene functionalization on the surface of different materials.
  • the present invention provides a method for ultra-fast growth of graphene.
  • the method includes the following steps:
  • the quenching treatment specifically includes increasing the temperature of the base material to 500-2000°C and then cooling it immediately; the heating time of the quenching treatment is 1 us ⁇ 10s.
  • the cooling is not particularly limited, and the substrate material is naturally cooled immediately after the heating is completed.
  • step 1) before the carbonization treatment, the base material is cleaned to remove surface impurities.
  • the base material in step 1) includes some common metal, non-metal plane and needle tip materials, preferably, the metal material is Fe, Ni, W, etc., and the non-metal base is preferably glass, silicon, nitride Silicon, polymer materials, etc.
  • the base material is silicon wafer, glass wafer, iron foil, Ni tip, commercial AFM probe, and the like.
  • the carbonization treatment of the surface of the base material in step 1) is completed by one or more of the following methods: a carbon powder slurry coating method, a high temperature carbonization method, and a vacuum evaporation method.
  • the carbon powder slurry coating method includes the following steps: adding carbon powder to the Cyrene solvent to obtain a carbon powder slurry, and coating the carbon powder slurry on the surface of the substrate so that the carbon powder slurry is The surface of the substrate is uniformly formed into a film, and then the substrate after the surface is formed into a film is subjected to heating treatment to completely volatilize the solvent to obtain a continuous carbon film; preferably, the thickness of the continuous carbon film is 1-100um.
  • the high-temperature carbonization method includes the following steps: drip PMMA glacial acetic acid solution on the substrate, homogenize the glue to obtain a PMMA film, and heat the substrate with the PMMA film on the surface to 350-400°C to obtain a surface carbonization treatment
  • the substrate preferably, the thickness of the PMMA film is 10nm-100 ⁇ m.
  • the vacuum evaporation method includes the following steps: fixing the substrate in a vacuum chamber, and then heating the carbon rod with current or bombarding the target with high-energy ions to coat the surface of the substrate with a carbon film or a metal/carbon composite film;
  • the thickness of the carbon film or the metal/carbon composite film is 1 nm to 1 um.
  • the quenching treatment in step 2) is performed in a vacuum, an inert atmosphere or an atmospheric environment.
  • step 2) the quenching treatment is completed by a pulse current quenching method, an induction current quenching method or a concentrated microwave energy quenching method.
  • the pulse current quenching method includes the following steps: placing the carbonized substrate in a vacuum chamber, and applying a pulse current at both ends of the conductive substrate in a vacuum or inert atmosphere, so that the substrate quickly reaches a red hot state. Natural cooling.
  • the pulse width of the pulse current ranges from 1 us to 10 s, and the current magnitude ranges from 1 to 50A.
  • the induction current quenching method includes integral induction heating and movement induction heating.
  • the overall induction current quenching method includes the following steps: placing the carbonized substrate in a quartz tube, placing the quartz tube in a copper induction coil, and starting the electric current in a vacuum or inert atmosphere.
  • Magnetic induction is used to excite eddy currents in the conductive layer on the surface of the substrate to generate self-heating to a red hot state. After the heating is completed, the sample cools naturally.
  • the output power of the electromagnetic induction power supply is 0.1 kW-10 kW, and the heating time is 0.1-10 s.
  • the mobile induction current quenching method includes the following steps: placing the carbonized substrate on a two-dimensional electric translation table, setting an electromagnetic induction copper ring 5-10 mm above the substrate, and starting the electric
  • the translation table and the electromagnetic induction copper ring enable the electric translation table to drive the substrate to move, and the local area of the substrate under the electromagnetic induction copper ring is heated to a red hot state; then the substrate is heated The area is moved out of the sensing range of the copper ring to cool it down.
  • the convergent microwave energy quenching includes the following steps: by converging microwave energy on the carbonized substrate, causing the substrate to generate an instantaneous high temperature to a red hot state, and then cooling it naturally.
  • the method for ultra-fast graphene growth includes the following specific steps:
  • pulse current, induced current or concentrated microwave energy is used to act on the whole or partial area of the above-mentioned carbonized material, so that the temperature of the substrate rises instantaneously to a high temperature of 500-2000 °C and cools rapidly, thereby Realize the functionalization of graphene on the surface of the material.
  • the heating time range of this single quenching process is 1 us-10s.
  • the carbon powder slurry coating method includes the following steps: adding carbon powder to Cyrene solvent (dihydrovinyl glucone), and then using an ultrasonic cleaner and a probe to ultrasonically treat for 1 hour and For 30 minutes (33% duty cycle), a black viscous solution was obtained. Add the prepared carbon powder slurry dropwise to the surface of the substrate, and use a homogenizer or a film wiper to process until the carbon powder slurry forms a uniform film on the surface of the substrate. The spin-coated substrate is placed on a heating plate at 80° C. for 24 hours, until the solvent is completely volatilized to obtain a continuous carbon film with a certain thickness, preferably 1-100 um in thickness.
  • Cyrene solvent dihydrovinyl glucone
  • the high-temperature carbonization method includes the following steps: configuring PMMA (polymethyl methacrylate) glacial acetic acid solution, placing the clean substrate on the turntable of the homogenizer, and adding dropwise
  • PMMA solution is homogenized to obtain a uniform PMMA film with a certain thickness.
  • the substrate with the PMMA film on the surface is heated in a vacuum tube furnace, and the temperature is maintained at 350-400°C for 2 hours to obtain a substrate with a surface carbonization treatment, and the thickness is preferably 10 nm-100 ⁇ m.
  • the vacuum evaporation method includes the following steps: fixing a clean substrate on a sample table in a vacuum chamber, and then covering the chamber to vacuum;
  • the carbon rod is heated by electric current (DC evaporation equipment) or the target material is bombarded with high-energy ions (magnetron sputtering equipment), and a certain thickness of carbon film or metal/carbon (such as Ni/C) composite film is plated on the surface of the substrate, the thickness is preferred It is 1nm ⁇ 1um.
  • the preferred solution for quenching using pulsed current is as follows:
  • the pulse current is passed through the conductive metal/carbon composite layer on the substrate or the surface of the substrate, and the substrate quickly reaches a red hot state and then cools naturally.
  • the pulse width of the above-mentioned pulse current ranges from 1us to 10s, and the current magnitude ranges from 1 to 50A.
  • the current passes through the conductive substrate or the surface coating to generate a large amount of Joule heat, so that the substrate or its surface quickly reaches a red hot state.
  • the magnitude and duration of the current flow are closely related to the resistivity and size specifications of the base material.
  • the resistivity of the metal material used is large, the thickness and width are small and the length is large, the current passing through is correspondingly small, and the duration is correspondingly short; when the resistivity of the metal material used is small, the thickness and width are relatively large.
  • the length is smaller, the current passed is correspondingly larger, and the duration is correspondingly longer.
  • the quenching is accomplished by induction current quenching, and the induction current quenching method is divided into integral induction heating and mobile induction heating.
  • a metal substrate with a carbon layer on the surface or a non-metal substrate with a metal/carbon composite layer on the surface is placed in a quartz tube; the quartz tube is placed in electromagnetic induction In the copper induction coil of the power supply device (DDCGP-06-III), the quartz tube is evacuated or replaced with an inert atmosphere (as shown in Figure 3).
  • the quartz tube is evacuated or replaced with an inert atmosphere (as shown in Figure 3).
  • the electromagnetic induction power supply is activated, and the eddy current is excited in the surface layer of the metal substrate or the surface conductive layer of the non-metal substrate to generate self-heating Phenomenon, the sample is quickly heated to a red hot state, and the sample cools naturally after the heating is completed.
  • the output power and heating time of the electromagnetic induction power supply are related to the working frequency, substrate material and size of the power supply.
  • the metal substrate with a carbon layer on the surface is sandwiched between two clean and flat glass, and the glass is clamped at the four corners; or two non-metal substrates of the same size are clamped.
  • a piece of graphite sheet with a thickness of 1mm is clamped to form a sandwich structure, and the four corners of the base are clamped.
  • the speed range is 10-40mm/s
  • the output power range of the electromagnetic induction power supply is 0.5-6kW.
  • the preferred solution for quenching using convergent microwave energy is as follows:
  • FIG. 5 The schematic diagram of the device used in this solution is shown in Figure 5, which includes a high-voltage power supply, a magnetron (Samsung OM74P, 1000W, 2450MHz), a circulator, a load, and a stainless steel vacuum waveguide cavity (BJ22 type).
  • the microwave generated by the magnetron enters the waveguide cavity through the circulator, and then stabilizes in a standing wave state.
  • the maximum electric field intensity appears at the 1/4 wavelength of the center line of the wide surface of the waveguide cavity, forming a microwave energy hot spot.
  • the waveguide cavity is evacuated or replaced with an inert atmosphere, and the wave number generated by the magnetron is controlled by a programmable high-voltage pulse power supply to accurately control the microwave output time.
  • the concentrated microwave energy loss occurs accurately on the metal sample or its surface coating
  • the microwave energy is converted into a large amount of heat energy, causing the sample surface to generate an instantaneous high temperature to reach a red hot state, and then it is naturally cooled.
  • the heating time range of the single quenching is 0.001 to 10 seconds.
  • the guide wire is made of metal, such as Ni, W, Fe, stainless steel wire, etc., with a diameter of 0.2-5 mm. Among them, different positions of the guide wire can be welded with clips or other holders adapted to the shape of the sample to fix the sample.
  • the length of the microwave output time is related to the wire size, substrate material and size.
  • the pulse current, the eddy current excited by electromagnetic induction and the concentrated microwave energy directly act on the metal substrate or the coating on the surface of the substrate, and a large amount of heat is generated in situ to increase the temperature of the substrate surface at a large rate of temperature rise.
  • a large amount of heat is generated in situ to increase the temperature of the substrate surface at a large rate of temperature rise.
  • the heating time in the entire single quenching process time is 1us-10s.
  • the carbon layer on the surface of the substrate penetrates into the metal substrate or the metal coating on the surface of the substrate under high temperature conditions, and then the substrate rapidly cools down, and the infiltrated carbon precipitates on the surface of the substrate to form graphene.
  • an electric furnace or induction current is usually used to heat the sample stage (such as a tungsten boat, etc.), and then heat energy is transferred to the sample to achieve the purpose of heating the sample.
  • the sample heating and cooling process is relatively long (Piner R, Li H, Kong X, et al. ACS Nano, 2013, 7(9): 7495).
  • microwaves are continuously reflected in the multi-mode cavity upstream of the CVD tube furnace to form a uniform microwave field to crack the carbon source precursor, which has no direct effect on the growth substrate of graphene, and the substrate is still heated by an electric furnace. Then the substrate is raised and maintained at a high temperature suitable for graphene growth by means of heat conduction (Li XS, Cai W., An J. et al. Science, 2009, 324(5932): 1312).
  • the ultrafast graphene method proposed in the present invention uses pulse current, eddy current excited by electromagnetic induction and microwave alternating electromagnetic field to directly heat the substrate, and completes the growth of graphene on the surface of the substrate in a very short time.
  • the method of the present invention ensures that a large area of graphene is generated on the surface of the substrate while avoiding high temperature causing damage to the substrate such as melting and oxidation, expanding the types of graphene functionalized substrate materials, and the size of the substrate is not limited by the size of the tube furnace , Can be used for rapid graphene functionalization of large-size substrate materials; at the same time, it can effectively speed up production and reduce energy consumption and costs.
  • Figure 1 is a schematic diagram of the ultrafast graphene growth method of the present invention.
  • a large amount of heat is generated by the electromagnetic energy on the surface of the substrate material, which realizes the rapid quenching of the substrate surface and generates a wide range of continuous graphene on the surface of the material.
  • Figure 2a is a schematic diagram of the device used to fix the substrate during the instantaneous high temperature quenching process of the sample with pulse current;
  • Figure 2b is the single pulse recorded by the oscilloscope when the current is set to heat the sample;
  • Figure 2c, Figure 2d, and Figure 2e are A series of photos showing the red heat on the surface of the silicon wafer treated by instantaneous high temperature quenching;
  • the left arrow is a series of photos showing the temperature of the surface of the silicon wafer treated by instantaneous high temperature quenching.
  • Figure 3 is a schematic diagram of an induction heating device.
  • a is the schematic diagram of the vacuum equipment
  • b is the schematic diagram of the induction coil and the quartz tube
  • c is the schematic diagram of the overall experimental device (without cooling water and temperature measuring device).
  • Figure 4 is a schematic diagram of a mobile induction heating device for glass substrates, where a is a schematic diagram of a part of the experimental device for mobile induction heating; b is a schematic diagram of an induction coil and a quartz glass device.
  • FIG. 5 is a schematic diagram of a microwave ultra-fast quenching system device.
  • the device consists of a programmable high-voltage pulse power supply, a magnetron (an electric vacuum device that generates microwave energy), a coaxial line (a microwave transmission line composed of coaxial cylindrical conductors), and an excitation cavity ( Receive microwave energy and propagate to the circulator), three-port circulator (only allow the microwave to extend the excitation cavity ⁇ waveguide ⁇ load unidirectional transmission to protect the magnetron), waveguide (concentrate the microwave in the space for sample quenching) Comprised of chamber), load (consumption of excess microwave energy), pump set (a combination pump set of mechanical pump and molecular pump to provide a vacuum environment for the waveguide), the waveguide is designed with an observation window and an inlet for use with an adapter.
  • a magnetron an electric vacuum device that generates microwave energy
  • a coaxial line a microwave transmission line composed of coaxial cylindrical conductors
  • an excitation cavity Receive microwave energy and propagate to the
  • Figure 6a is a photo of the sample stage with the Si substrate fixed in the vacuum chamber during the instantaneous high temperature quenching treatment with pulse current;
  • Figure 6b is a series of Raman corresponding to the growth of graphene at different positions (8 points dispersed) on the silicon wafer after quenching Atlas;
  • Figure 6c is a photo of the sample table with the glass substrate fixed in the vacuum chamber when the pulse current is used for instantaneous high-temperature quenching treatment;
  • Figure 6d is a series of graphene corresponding to different positions (13 points dispersed) grown on the silicon wafer after quenching Raman Atlas.
  • Figure 7a is a photo of the sample stage with the flexible substrate PDMS fixed in the vacuum chamber when the pulse current is used for instantaneous high-temperature quenching;
  • Figure 7b is a series of Raman corresponding to the growth of graphene at different positions (dispersed at 4 points) on the PDMS after quenching Atlas.
  • Fig. 8 is the image of the vacuum induction heating experiment of the metal iron substrate, where a and c are the Raman spectra of the carbon-plated iron substrate before and after quenching; b is the photo of the iron substrate instantaneously red hot under the action of electromagnetic induction; d is the iron substrate after quenching AFM image of surface graphene.
  • Figure 9 is a photo of a carbon-coated glass substrate and its Raman spectrum after vacuum induction hardening.
  • Figure 10 is a glass substrate moving induction heating experiment image, where a is a schematic diagram of the moving path of the electric translation stage in the moving induction heating experiment; b is the state of local red heat during the glass substrate moving induction heating process; c is the glass substrate after moving induction heating Raman spectrum of surface graphene.
  • Figure 11 is a photograph of a carbon-coated iron substrate and its Raman spectrum after motion induction heating.
  • Figure 12a is a transmission electron microscope image of a nickel needle, the tip size is less than 50nm;
  • Figure 12b is a sample fixing method of the nickel needle, the gold-plated metal lead wire welded with a gold-plated stainless steel tube (inner diameter 0.26mm) is fixed on the adapter, and the nickel needle is inserted into the stainless steel Fixed in the tube;
  • Figure 12c is the red hot photo of the nickel needle at the moment of microwave quenching;
  • Figure 12d is the transmission electron microscope photo of the graphene-coated nickel needle prepared by the microwave instantaneous high temperature quenching treatment. The tip size of the needle is still maintained at about 100nm;
  • 12e is a nickel needle tip after quenching measured Raman spectrum, the spectra appeared located 1350cm -1, 1580cm -1 and 2700cm graphene characteristic peak around 1, where D is located in the vicinity of 1350 cm -1 peak from graphene defect located near 1600cm -1 to G sharp peak indicates a higher degree of crystallinity, the lower the peak near 2700cm -1 2D relative peak intensity G, the peak half width of more than 50cm -1, multilayered graphene Features are consistent.
  • Figure 13a is a scanning electron microscope photo of a typical graphene-modified AFM probe prepared by the microwave instantaneous high temperature quenching method, the tip of the needle is clean and kept sharp;
  • Figure 13b is a transmission electron microscope corresponding to the graphene-modified AFM probe In the photo, there are about 7 or 8 layers of continuous multilayer graphene along the contour of the needle tip at the red line. The tip size is only about 30nm. The graphene and the tip surface form a good interface contact;
  • Figure 13c is the AFM probe at the moment of microwave high temperature quenching Red heat photo;
  • Figure 13d is the Raman spectrum corresponding to the graphene-modified AFM probe. The characteristic D peak, G peak, and 2D peak of graphene confirm the presence of graphene.
  • FIG 14 is a characteristic D band microwave quench instant photography and the red-hot silicon wafer samples after quenching measured Raman spectra, respectively, it appears near 1580cm graphene 1350cm -1, -1 and 2700cm -1, G, and 2D peak , The relative intensities of the Raman signal peaks measured at different positions on the silicon wafer are different, indicating that the silicon wafer is covered by a mixture of single-layer and multi-layer graphene.
  • the silicon wafer cut into 10 ⁇ 10mm is ultrasonically treated with a large amount of alcohol, acetone, and water, then rinsed with a large amount of water, and dried with nitrogen.
  • the silicon wafer is subjected to magnetron sputtering to form a 5nm carbon layer (magnetron sputtering carbon target purity: 99.99%) and a 30nm nickel layer (magnetron sputtering nickel target purity: 99.999%) on the surface successively.
  • a 30nm nickel carbide layer is formed on the surface by magnetron sputtering (magnetron sputtering nickel carbide target purity: 99.99%).
  • the Cu electrode is connected to an external power source through a vacuum electrode flange.
  • the substrate Si wafer instantly reaches a red hot state (as shown in Figure 2c, d, and e). After the sample is cooled, the Si wafer is taken out.
  • Fig. 6a is a physical photo of the Si substrate fixed in the vacuum chamber.
  • Figure 6b is excited under 514nm laser Raman spectra of graphene; found therefrom, is located near the peak of 1580cm G-1 and 2675cm 2D located peaks shift to higher wave number -1 , I 2D /I G ⁇ 1 and the peak at 2D has obvious peak separation, which can prove that the number of graphene layers generated is double-layered, and the D peak is lower, which proves that the graphene has fewer defects; based on existing microscopic observations Conditions, double-layer continuous graphene is formed in most areas of the surface of the Si sheet, with a coverage rate of 75% to 100%.
  • the glass sheet cut into 10 ⁇ 10mm is ultrasonically treated with a large amount of alcohol, acetone, and water, then rinsed with a large amount of water, and dried with nitrogen.
  • the glass substrate is subjected to magnetron sputtering to form a 5nm carbon layer (magnetron sputtering carbon target purity: 99.99%) and a 30nm nickel layer (magnetron sputtering nickel target purity: 99.999%) on the surface successively.
  • a 30nm nickel carbide layer is formed on the surface by magnetron sputtering (magnetron sputtering nickel carbide target purity: 99.99%).
  • the above clean PDMS sheet was adsorbed on a 10 ⁇ 10mm glass slide.
  • the glass substrate is subjected to magnetron sputtering to form a 5nm carbon layer (magnetron sputtering carbon target purity: 99.99%) and a 30nm nickel layer (magnetron sputtering nickel target purity: 99.999%) on the surface successively.
  • a 30nm nickel carbide layer is formed on the surface by magnetron sputtering (magnetron sputtering nickel carbide target purity: 99.99%).
  • the above quenched PDMS substrate was subjected to Raman characterization.
  • the Raman spectrum of Fig. 7b found that under the excitation of 514nm laser, the G peak located near 1582cm -1 shifted to high wavenumber and the peak at D had obvious peak separation, which can prove The number of graphene layers produced is multi-layered and has many defects; among them, based on the existing microscopic observation conditions, multi-layer graphene is produced in most areas of the surface of the PDMS substrate, with a coverage rate of 75% to 100%.
  • a Pt sheet was selected as the cathode to be connected to the negative electrode of the DC power supply, and the iron foil to be polished was used as the anode to be connected to the positive electrode of the DC power supply, and the two electrodes were put into the electrolyte for electrochemical polishing.
  • Fig. 8a is the Raman spectrum before induction heating showing the characteristic peaks of the Raman image of graphite powder
  • Fig. 8c is the Raman spectrum showing the characteristic peaks of graphene after the reaction.
  • the 2D peak intensity and the G peak intensity before and after the reaction can be seen by comparison.
  • the ratio of I 2D /I G increases, and the 2D peak position shifts to the left without peak splitting. It can be explained that the substance has changed before and after the reaction, and the graphite powder has changed from graphite to low-layer graphene. It is proved that graphene is formed on the surface of the iron substrate after electromagnetic induction heating.
  • the quartz tube Place the quartz coated with carbon film on the bottom of the quartz tube, and the quartz tube is connected to the vacuum system.
  • the vacuum gauge shows below 1x10 -4 pa, turn on the water-cooled circulation machine first, and then turn on the electromagnetic induction heating power supply.
  • the heating power is set to 1kW, and the heating time is set to 3.2s. After setting, press the switch. After 3.2s, the switch will automatically disconnect and stop heating.
  • remove the iron foil remove the iron foil.
  • the iron foil was ultrasonically cleaned 3 times in alcohol, 30 minutes each time, to remove the graphite powder remaining on the surface.
  • Figure 9 is the Raman image of the surface of the quartz glass substrate after vacuum induction heating. It can be seen that the peak positions of the D, G, and 2D peaks are the same as the Raman characteristic peaks of standard graphene, which proves that graphene is indeed generated. It can be seen that the graphene D peak is lower, which proves that graphene has fewer defects. I 2D /I G ⁇ 1 proves that graphene is double-layer graphene.
  • a 100x100mm quartz glass in a 5L super-large beaker and ultrasonically clean it with acetone alcohol for 30 minutes to remove oil stains on the surface.
  • the piranha solution is used to carboxylate the quartz glass to enhance the adsorption force on the surface of the quartz glass.
  • the schematic diagram of the route is shown in Figure 10a.
  • the running speed of the electric translation stage is set to 20mm/s.
  • Set the induction heating power to 3.3kW, press the switch of the induction heating device to heat, and turn on the operation switch of the electric translation table at the same time, and stop heating after the operation of the electric translation table ends.
  • Figure 10a The moving path set by the electric translation stage in the glass substrate induction moving heating experiment. It moves back and forth several times in the "s" shape, so that all the carbon film parts are heated by the induction coil; 10b is the heating picture during induction moving heating, and the graphite sheet appears The red hot state is measured to be about 1500°C; 10c is the Raman image of graphene on the surface of the glass substrate. It can be seen that its characteristic peaks are consistent with graphene, which proves that graphene is formed, and the D peak in the spectrum is low, which proves Graphene has fewer defects.
  • the intensity ratio of the 2D peak to the G peak I 2D /I G is slightly less than 1, which proves that the number of graphene layers is 2-3 layers. Compared with graphene produced by vacuum induction heating of a glass substrate, defects are increased, and the number of graphene layers is increased.
  • a Pt sheet was selected as the cathode to be connected to the negative electrode of the DC power supply, and the iron foil to be polished was used as the anode to be connected to the positive electrode of the DC power supply, and the two electrodes were put into the electrolyte for electrochemical polishing.
  • the schematic diagram of the route is shown in Figure 10a.
  • the running speed of the electric translation stage is set to 30mm/s.
  • Set the induction heating power to 2.0kW, press the switch of the induction heating device to heat, and turn on the operation switch of the electric translation table at the same time.
  • stop heating After the operation of the electric translation table is finished, stop heating.
  • the quartz glass After the quartz glass is cooled, it is ultrasonically cleaned 3 times in alcohol, 30 minutes each time, to remove the residual graphite powder on the surface.
  • Figure 11 is the Raman spectrum of the surface of the iron substrate after induction moving and heating, and its peaks are consistent with the characteristic peaks of the standard graphene Raman spectrum, which proves that graphene is produced. And the graphene D peak is low, which proves that graphene has defects but fewer defects. From the intensity ratio of the 2D peak to the G peak, I 2D / IG is slightly less than 1, it can be proved that the number of graphene layers is 2-3 layers. Compared with the graphene produced by vacuum induction heating of an iron substrate, the defects are increased, but the number of graphene layers is the same.
  • nickel needles ( Figure 12a).
  • the nickel needle was immersed in 1-butyl-3-methylimidazole acetate ionic liquid, and heated at 200°C for 35 minutes to carbonize the surface of the nickel needle.
  • Figure 12 shows the corresponding transmission electron microscope photo and the corresponding Raman spectrum of the nickel tip after quenching.
  • the electron microscope photos showed that the tip of the nickel needle melted into a spherical shape after quenching under this condition, but the surface was flat and smooth, with a size of about 60nm; the Raman test results confirmed the existence of the graphene structure.
  • a high-purity carbon target (99.99%) and a high-purity nickel target (99.999%) were magnetron sputtered on the front of the AFM probe (Sunano, NSG10) with a 5nm thick carbon film and a 25nm thick nickel film.
  • the magnetron is controlled by the programmable high-voltage power supply to generate microwaves with a duration of 0.17 seconds, and the AFM probe fixed at the clip instantly reaches a red hot state. After the sample is cooled, take it out to obtain a graphene-modified AFM probe.
  • Figure 13 shows the corresponding scanning and transmission electron micrographs of the graphene functionalized AFM probe and the corresponding Raman spectrum after quenching.
  • Scanning electron microscopy photos show that the tip of the probe is covered by a wrinkled film, and the tip of the tip is very clean;
  • the high-resolution transmission image shows that the tip of the tip is wrapped by continuous multilayer graphene, the tip size is only about 30nm, graphene and The tip surface forms a good interface contact.
  • the Raman test results of the tip area of the needle also confirmed the existence of the graphene structure.
  • a high-purity carbon target (99.99%) and a high-purity nickel target (99.999%) were used to magnetron sputter a 5nm thick carbon film and a 25nm thick nickel film on the surface of an 8x8mm silicon wafer.
  • the above-mentioned silicon wafer plated with carbon-nickel coating is fixed on the guide wire with a clip, and then the guide wire is fixed on the waveguide adapter, and the adapter is installed in the vacuum waveguide cavity.
  • the magnetron is controlled by the programmable high-voltage power supply to generate microwaves with a duration of 0.3 seconds, and the silicon wafers fixed at the clamps instantly reach a red hot state. Take out the sample after cooling down.
  • Figure 14 shows the instantaneous red heat of the silicon wafer during microwave ultrafast processing and the Raman spectrum after quenching.
  • the Raman test results corresponding to different positions of the silicon wafer confirmed the mixed presence of single-layer and multi-layer graphene structures on the silicon wafer.
  • the present invention provides a method for large-area ultra-fast growth of graphene on the surface of metal, non-metal plane and needle tip substrate.
  • the metal substrate is preferably Fe, Ni, W, etc.
  • the non-metal substrate is preferably glass, silicon, silicon nitride. , Polymer materials, etc.
  • the present invention uses pulse current, induced current or concentrated microwave energy to act on the carbonized substrate material, and generates a large amount of heat in situ through the current on the substrate surface, so as to realize the instant quenching of the material and generate a large amount on the surface of the material.
  • the present invention provides an ultra-fast synthesis method for realizing graphene functionalization on the surface of different materials, and can grow graphene with good interface contact on the surface of materials that cannot withstand high temperature for a long time (such as flexible polymer materials, needle tips); the present invention
  • the provided method is not limited by the size of the vacuum tube furnace, and realizes the growth of graphene on a large-size substrate material.
  • the graphene growth method provided by the present invention has the characteristics of wide adaptation range of materials (type, size) and environment (vacuum, inert atmosphere or atmosphere), fast speed, low energy consumption and the like.

Abstract

本发明提供一类在金属、非金属平面以及针尖基底表面大面积超快生长石墨烯的方法，所述金属基底优选为Fe、Ni、W等，非金属基底优选为玻璃、硅、氮化硅、高分子材料等。本发明针对不同材料的性质，利用脉冲电流、感应电流或汇聚微波能等作用于碳化后的基底材料，通过基底表面的电流原位产生大量的热，实现材料的瞬间淬火进而在材料表面生成大范围的连续单层或多层石墨烯。本发明所述方法，可在不耐受长时间高温的材料表面生长界面接触良好的石墨烯；本发明提供的方法可不受真空管式炉的尺寸限制，实现大尺寸基底材料上的石墨烯生长。本发明提供的石墨烯生长方法具有材料和环境适应范围广、快速、能耗低等特点。

Description

一种超快生长石墨烯的方法 技术领域
本发明属于材料表面功能化领域，具体涉及一类在金属、非金属平面及针尖基底表面大面积范围内超快生长石墨烯的方法。
背景技术
石墨烯是一种由单层碳原子以类蜂巢构型平面堆积而成的二维网状材料，具有优异的光学、电学、热学、力学等物理性质，以及独特的化学性能，可应用于多功能复合材料、有机光电子材料、储氢材料、超级电容器以及微电子器件等领域。石墨烯近年来引起研究人员的广泛关注。高质量大面积石墨烯的可控制备是其应用的先决条件，拓展石墨烯的制备方法以满足不同领域应用的需求是该领域研究需要解决的首要问题。目前石墨烯制备的主要方法包括机械剥离法、氧化还原法、外延生长法和化学气相沉积法等。其中化学气相沉积(Chemical vapor deposition，CVD)法，一般使用特殊的气体碳源，在合适的气氛环境于金属基底(Ni或Cu)上生长，通过控制温度梯度，气体流速等条件，以获得具有高品质的石墨烯。
目前在目标材料表面实现石墨烯功能化主要包含石墨烯转移法和CVD直接生长法。由于CVD生长石墨烯通常使用单晶Cu、Ni或两者的合金基底，合成的石墨烯再转移至目标材料，在转移过程中容易引起石墨烯的缺陷和污染物，且石墨烯和标的物之间的界面接触不可控；另外，CVD法受炉体限制无法得到更大尺寸石墨烯，同时存在高温生长时间长、能耗高的缺点。
玻璃基底生长石墨烯是当今的石墨烯生长领域研究的热点之一。玻璃作为一种透明的非晶氧化物，制备成本低，现已广泛应用于日常生活中，并具有与石墨烯相同的透明的特点，并在导电性、导热性以及液体的浸润性方面互补。因此将二者结合在一起形成石墨烯玻璃，即可以保持二者的透明性，又拥有优良的导电、导热性及高疏水性，有望成为代替普通玻璃的新材料。要想实现将石墨烯玻璃完全替代普通玻璃，首先需解决其大规模的制作问题，现在实验室制备石墨烯玻璃主要由两种方法，第一种为转移法，使用石墨烯浆料在玻璃表面使用液相涂膜的方式制备，或使用CVD法在金属基底上制备后转移到玻璃表面，另一种是使用CVD法直接在玻 璃表面生长石墨烯。如前所述，第一种转移方法石墨烯尺寸小，缺陷多，转移过程中也会带来污染等问题，因此制备出的石墨烯玻璃性能差。第二种CVD方法制备出的石墨烯玻璃性能好，但是管式炉内径的大小限制了石墨烯玻璃的尺寸，无法制备更大尺寸的石墨烯玻璃。
另外，CVD直接生长法也不适合用于在无法长时间耐受高温的材料(例如高分子材料、纳米针尖尖端等)表面生长石墨烯。石墨烯柔性高分子材料具有特殊的电学和机械性能，在柔性显示屏和智能传感器等领域具有独到的应用前景。然而由于基底材料不能长时间耐受高温，柔性材料的石墨烯功能化目前主要通过物理涂布法制备。Dua和Ruoff等人在聚对苯二甲酸乙二酯(PET)薄膜上用化学法还原氧化石墨烯薄片(rGO)制成的rGO溶液通过喷墨打印制成检测H 2等气氛传感器。但是rGO溶液喷涂石墨烯片内缺陷较多，片间接触电阻较大，限制在传感器中的应用。Bae等人通过用CVD法在金属基底上生成的高质量石墨烯湿法转移至PET制成G/PEF显示屏，但是转移过程中通常会引起石墨烯的破损以及带来一些不可避免的有机杂质。另一方面，石墨烯功能化纳米针尖具有增强的电学和机械性能，在扫描探针成像、纳米电学测量和传感器等领域有突出的应用前景。目前，关于石墨烯修饰纳米针尖的研究可分为石墨烯转移法和直接CVD生长法。Duan等人报道了通过在铜箔上生长石墨烯并将其转移到商用原子力显微镜(AFM)探针尖端来制造石墨烯功能化AFM尖端，表现出了更高的导电率和使用寿命；但石墨烯的转移过程不可控，转移后的石墨烯与AFM探针本体间的作用力较小附着不紧密。Martin-Olmos等人采用半导体加工工艺在硅片表面形成金字塔形凹槽阵列并在其表面镀上一层铜后，用CVD法在铜涂层上(包括金字塔形凹槽内)生长出连续的石墨烯层；并进一步将基体材料SU-8旋涂在石墨烯层上以获得石墨烯功能化的AFM探针。但是在CVD生长过程中，金字塔形凹槽的尖端由于长时间高温发生钝化，导致最终的AFM探针尖端的尺寸大于1um，得到的AFM探针空间分辨率下降。总而言之，物理吸附的方法不可控且无法保证针尖表面与石墨烯层的良好接触，而CVD法由于生长所需要的长时间高温环境，导致探针尖端纳米尺寸受损。
综上所述，目前在材料表面实现石墨烯功能化的方法主要包括转移法和CVD直接生长法。转移法在转移过程中容易引起石墨烯的缺陷和污染 物，且石墨烯和目标基底之间的界面接触不可控；而CVD直接生长法对基底耐温性能要求高、时间长能耗高、产品尺寸受限制，阻碍了石墨烯功能化产品的大量生产和应用拓展。除去上述方法，Xiong等人报道了一种利用微纳米激光直写设备在玻璃或Si片等绝缘基底材料表面生成石墨烯图案的方法。在该方法中，激光光斑聚焦于基底表面以加热基底表面的照射区域达到石墨烯的生长温度和条件，避免了基底表面的长时间高温的同时实现了石墨烯的快速生长。然而，除去复杂的设备所带来的限制外，该方法所使用的激光光斑尺寸很小(约800纳米)，只能实现小范围内(微米级别)的石墨烯生长，而无法实现宏观基底表面的大面积石墨烯的快速生长。针对以上问题，本发明提供了一类新型的超快石墨烯生长方法，采用脉冲电流、感应电流或汇聚微波能等作用于碳化后的基底材料，通过基底表面的电流原位产生大量的热，实现材料的瞬间淬火进而在材料表面生成大范围的连续单层或多层石墨烯(如图1)。本发明提供的超快生长方法可不受真空管式炉的尺寸限制，实现大尺寸基底材料上的石墨烯生长，同时具有材料(种类、尺寸)和环境(真空、惰性气氛或大气)适应范围广、快速、能耗低等特点。
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发明内容
针对目前制备石墨烯功能化材料方法时间过长、能耗高、无法大面积生长的缺点，本发明的目的是提出一类在不同材料表面实现大面积超快石墨烯功能化的制备方法。
为实现上述目的，本发明提供了一种超快生长石墨烯的方法，所述方法包括如下步骤：
1)将基底材料进行碳化处理，以在表面形成碳层或金属化碳层；
2)将碳化处理后的所述基底材料进行淬火处理；所述淬火处理具体为将所述基底材料的温度升高到500-2000℃，然后立即冷却；所述淬火处理的升温时间为1us～10s。
其中，本发明通过控制升温时间使基底达到合适石墨烯生长的高温，对冷却不作特别限定，所述基底材料升温完成后即立即自然冷却。
优选地，在步骤1)中，在所述碳化处理前，将所述基底材料清洁以去除表面杂质。
其中，步骤1)中的所述基底材料包括一些常见的金属、非金属平面和针尖材料，优选地，所述金属材料为Fe、Ni、W等，非金属基底优选为玻璃、硅、氮化硅、高分子材料等。
在本发明的一个具体实施方案中，所述基底材料为硅片、玻璃片、铁箔、Ni针尖、商用AFM探针等。
其中，步骤1)中的所述基底材料表面的碳化处理通过以下方法中的一种或几种来完成：碳粉浆料涂布法、高温碳化法和真空蒸镀法。
优选地，所述碳粉浆料涂布法包括如下步骤：在Cyrene溶剂中加入碳粉得碳粉浆料，将碳粉浆料涂覆到所述基底表面，使所述碳粉浆料在所述基底表面均匀成膜，然后将表面成膜后的基底进行加热处理，使溶剂完 全挥发，得连续碳膜；优选地，所述连续碳膜的厚度为1～100um。
优选地，所述高温碳化法包括如下步骤：在所述基底上滴加PMMA冰醋酸溶液，匀胶得到PMMA薄膜，将表面有PMMA薄膜的所述基底加热至350-400℃，得表面碳化处理的基底；优选地，所述PMMA薄膜的厚度为10nm～100μm。
优选地，所述真空蒸镀法包括如下步骤：将基底固定在真空腔体内，然后通电流加热碳棒或利用高能离子轰击靶材，以在基底表面镀上碳膜或金属/碳复合膜；优选地，所述碳膜或金属/碳复合膜的厚度为1nm～1um。
其中，步骤2)中的所述淬火处理在真空、惰性气氛或大气环境中进行。
其中，在步骤2)中，所述淬火处理通过脉冲电流淬火法、感应电流淬火法或汇聚微波能淬火法完成。
优选地，所述脉冲电流淬火法包括如下步骤：将碳化处理后的基底置于真空腔体内，在真空或惰性气氛环境下，在导电基底两端施加脉冲电流，使基底迅速达到红热状态后自然冷却。优选地，所述脉冲电流脉宽范围为1us～10s，电流大小范围为1～50A。
优选地，所述感应电流淬火法分包括整体感应加热和移动感应加热法。
优选地，所述整体感应电流淬火法包括如下步骤：将碳化处理后的所述基底置于石英管中，将所述石英管置于铜感应线圈内，在真空或惰性气氛环境下，启动电磁感应，以在基底的表面导电层内激发出涡流产生自加热至红热状态，加热完成后样品自然冷却。优选地，所述电磁感应电源输出功率为0.1kW-10kW，所述加热时间为0.1-10s。
优选地，所述移动感应电流淬火法包括如下步骤：将碳化处理后的所述基底置于二维电动平移台上，设置电磁感应铜圈位于所述基底上方5～10mm处，启动所述电动平移台以及所述电磁感应铜圈，使所述电动平移台带动所述基底移动，并使所述电磁感应铜圈下方的所述基底局部区域被加热至红热状态；然后将所述基底加热区域移出铜圈感应范围以使其冷却。
优选地，所述汇聚微波能淬火包括如下步骤：通过微波能量汇聚于碳化处理后的所述基底上，使所述基底产生瞬时高温达到红热状态，随后自 然冷却。
在本发明的一个具体实施方案中，所述超快生长石墨烯的方法包括如下具体步骤：
1)将清洁的基底材料进行碳化处理，在表面形成碳层或金属化碳层；
2)在真空、惰性气氛或大气环境中，利用脉冲电流、感应电流或汇聚微波能作用于上述碳化后材料的整体或局部区域，使基底温度瞬时上升至500～2000℃高温并迅速冷却，从而实现在材料表面的石墨烯功能化。该单次淬火过程的升温时间范围为1us～10s。
在本发明的一个优选实施方案中，所述碳粉浆料涂布法包括如下步骤：在Cyrene溶剂(二氢乙烯基葡萄糖酮)中加入碳粉，先后用超声清洗机和探头超声处理1h和30min(占空比33％)，得到黑色粘稠状溶液。将制备好的碳粉浆料滴加到基底表面，使用匀胶机或刮膜器处理，直至碳粉浆料在基底表面均匀成膜。将旋涂处理后的基底放在80℃的加热板上处理24h，至溶剂完全挥发，得到一定厚度的连续碳膜，厚度优选为1～100um。
在本发明的另一个优选实施方案中，所述高温碳化法包括如下步骤：配置PMMA(聚甲基丙稀酸甲酯)冰醋酸溶液，将洁净的基底置于匀胶机转台上，滴加PMMA溶液，匀胶得到一定厚度的均匀PMMA薄膜。将表面有PMMA薄膜的基底放入真空管式炉中加热，350-400℃保温2h，得到表面碳化处理的基底，厚度优选为10nm～100μm。
在本发明的另一个优选实施方案中，所述真空蒸镀法包括如下步骤：将洁净的基底固定在真空腔体内的样品台上，盖上腔体抽真空；待真空度达到要求后，通电流加热碳棒(直流蒸镀设备)或利用高能离子轰击靶材(磁控溅射设备)，在基底表面镀上一定厚度的碳膜或金属/碳(如Ni/C)复合膜，厚度优选为1nm～1um。
在本发明的一个优选实施方案中，利用脉冲电流淬火的优选方案如下：
将表面有碳层的金属基底或表面有金属/碳复合层的非金属基底置于真空腔体内，抽真空或将腔体置换为惰性气氛环境，在基底两端施加一个电压脉冲(如图2a)，让脉冲电流通过基底或基底表面的导电金属/碳复合层，基底迅速达到红热状态后自然冷却。上述脉冲电流脉宽范围为 1us～10s，电流大小范围为1～50A。该电流通过导电基底或表面镀层产生大量焦耳热而使基底或其表面迅速达到红热状态。所通电流的大小和持续时间与所述基底材料的电阻率和尺寸规格密切相关。当所用金属材质的电阻率较大，厚度、宽度较小而长度较大时，所通电流即相应较小，持续时间相应较短；当所用金属材质电阻率较小，厚度、宽度较大而长度较小时，所通电流即相应较大，持续时间相应较长。
在本发明的另一个优选实施方案中，所述淬火利用感应电流淬火来完成，所述感应电流淬火法分为整体感应加热和移动感应加热法。
在本发明的又一个优选实施方案中，若采用整体感应法，将表面有碳层的金属基底或表面有金属/碳复合层的非金属基底放入在石英管中；石英管置于电磁感应电源设备(东达DDCGP-06-III)的铜感应线圈内，石英管抽真空或置换为惰性气氛环境(如图3所示)。设置电磁感应电源输出功率与加热时间，功率范围为0.1kW-6kW，加热时间设置为0.1-10s，启动电磁感应电源，在金属基底表层或非金属基底的表面导电层内激发出涡流产生自加热现象，样品迅速被加热至红热状态，加热完成后样品自然冷却。电磁感应电源输出功率和加热时间与电源的工作频率、基底材质及尺寸有关。
在本发明的又一个优选实施方案中，若采用移动感应法，将表面有碳层的金属基底夹在两片洁净平整的玻璃中间，玻璃四角夹紧；或将两片大小一致的非金属基底夹住一块大小相当厚度为1mm的石墨片形成三明治结构，基底四角夹紧。将上述样品放在二维电动平移台样品座上，电磁感应铜圈位于样品上方5～10mm处(如图4所示)，整体装置位于大气中。使用电动平移台控制软件，设置电动平移台的运行路径及运行速率，速率范围为10-40mm/s，、电磁感应电源的输出功率范围为0.5-6kW。启动电磁感应电源后，开启电动平移台带动样品沿设定路径移动，在优化条件下，电磁感应铜圈下方的样品区域被迅速加热至红热状态；当该样品区域移出铜圈感应范围后即可迅速冷却。
在本发明的又一个优选实施方案中，利用汇聚微波能淬火的优选方案如下：
该方案中所使用的装置示意图如图5所示，包含高压电源、磁控管(三星OM74P，1000W，2450MHz)、环行器、负载及不锈钢制真空波导腔(BJ22 型)组成。磁控管产生的微波通过环行器进入波导腔后稳定为驻波状态，在波导腔宽面中心线上1/4波长处出现电场强度最大点，形成微波能量热点。在电场强度最大点处***金属引丝，将汇聚的微波能量馈入引丝。将表面有碳层或金属/碳复合层的基底固定在金属引丝上。波导腔抽真空或置换为惰性气氛环境，用程控高压脉冲电源控制磁控管产生波数来精准控制微波输出时间，在本发明的条件下，汇聚微波能量损耗精准地发生在金属样品或其表面镀层处，微波能转化为大量热能，使样品表面产生瞬时高温达到红热状态，随后自然冷却。上述单次淬火的升温时间范围为0.001～10秒。所述引丝为材质为金属，如Ni、W、Fe、不锈钢丝等，直径为0.2-5mm。其中，引丝的不同位置可焊接夹片或其他适配样品形状的固定器以固定样品。微波输出时间的长短与引丝尺寸、基底材质和尺寸等相关。
本发明所提供的超快石墨烯生长方法的有益效果如下。
在本发明所述方法和条件下，脉冲电流、电磁感应所激发的涡流和汇聚微波能量直接作用于金属基底或基底表面的镀层，原位产生大量的热将基底表面以一个很大的升温速率(可大于1000℃/s)迅速加热至高温(500～2000℃)，随后快速自然冷却，整个单次淬火过程时间中的升温时间为1us～10s。在此超快淬火过程中，基底表面的碳层在高温条件下渗入金属基底或基底表面的金属镀层，随后基底迅速降温，渗入的碳在基底表面析出形成石墨烯。在已报道的石墨烯制备方法中，通常使用电炉或感应电流加热样品台(如钨舟等)再将热能传导给样品实现加热样品的目的，样品的升温和降温过程较长(Piner R,Li H,Kong X,et al.ACS Nano,2013,7(9):7495)。在微波辅助CVD方法中，微波在CVD管式炉上游的多模腔内通过不断反射形成均匀的微波场以裂解碳源前驱体，与石墨烯的生长基底没有直接作用，基底仍是使用电炉加热再通过热传导的方式让基底上升并维持在一个适宜石墨烯生长的高温条件(Li X.S.,Cai W.,An J.et al.Science,2009,324(5932):1312)。
本发明所提出的超快石墨烯方法是利用脉冲电流、电磁感应所激发的涡流和微波交变电磁场直接加热基底，在极短的时间内完成了基底表面的石墨烯生长。本发明的方法保证了在基底表面生成大面积石墨烯的同时避免了高温对基底造成熔融和氧化等损伤，拓展了石墨烯功能化基底材料的 种类，且基底尺寸不受管式炉的尺寸限制，可用于大尺寸基底材料的快速石墨烯功能化；同时可有效加快生产速度，降低能耗和成本。
附图说明
图1为本发明的超快石墨烯生长法示意图。通过基底材料表面的电磁能产生大量的热，实现基底表面的快速淬火进而在材料表面生成大范围的连续石墨烯。
图2a为利用脉冲电流瞬时高温淬火处理样品过程中用于固定基底的装置示意图；图2b为设置电流通过样品加热时，示波器记录的单个脉冲；图2c、图2d、图2e上向右箭头为瞬时高温淬火处理硅片表面红热的一系列照片；向左箭头为瞬时高温淬火处理硅片表面降温的一系列照片。
图3为感应加热装置示意图。其中a为真空设备示意图；b为感应线圈与石英管示意图；c为整体实验装置示意简图(未加冷取水和测温装置)。
图4为玻璃基底移动感应加热装置示意图，其中a为移动感应加热部分实验装置示意图；b为感应线圈与石英玻璃装置示意图。
图5为微波超快淬火***装置示意图，装置由程控高压脉冲电源、磁控管(产生微波能的电真空器件)、同轴线(同轴圆柱导体构成的一种微波传输线)、激励腔(接收微波能并向环形器传播)、三端口环形器(仅允许微波延激励腔→波导→负载单方向传输，用以保护磁控管)、波导(将微波集中束缚在空间内，作为样品淬火舱室)、负载(消耗多余微波能量)、泵组(机械泵和分子泵的组合泵组，用以为波导提供真空环境)组成，波导处设计有观察窗和配合适配器使用的进样口。
图6a为利用脉冲电流瞬时高温淬火处理时，Si基底固定在真空腔体内的样品台照片；图6b为淬火后，硅片上不同位置(分散8个点)生长石墨烯相应的一系列拉曼图谱；图6c为利用脉冲电流瞬时高温淬火处理时，玻璃基底固定在真空腔体内的样品台照片；图6d为淬火后，硅片上不同位置(分散13个点)生长石墨烯相应的一系列拉曼图谱。
图7a为利用脉冲电流瞬时高温淬火处理时，柔性基底PDMS固定在真空腔体内的样品台照片；图7b为淬火后，PDMS上不同位置(分散4个点)生长石墨烯相应的一系列拉曼图谱。
图8为金属铁基底真空感应加热实验图像，其中a、c为镀碳铁基底在淬火前后的拉曼图谱；b为铁基底在电磁感应作用下瞬间红热的照片； d为淬火后铁基底表面石墨烯的AFM图像。
图9为镀碳玻璃基底的照片及其在真空感应淬火后的拉曼图谱。
图10为玻璃基底移动感应加热实验图像，其中a为移动感应加热实验中电动平移台移动路径示意图；b为玻璃基底移动感应加热过程中局域红热的状态；c为移动感应加热后玻璃基底表面石墨烯拉曼图谱。
图11为镀碳铁基底的照片及其在移动感应加热后的拉曼图谱。
图12a为镍针的透射电镜图像，尖端尺寸小于50nm；图12b为镍针装样固定方式，焊有镀金不锈钢管(内径0.26mm)的镀金金属引丝固定在适配器上，镍针插于不锈钢管中固定；图12c为微波淬火瞬间镍针红热照片；图12d为微波瞬时高温淬火处理制备的有石墨烯包覆的镍针所对应的透射电镜照片，针尖尖端尺寸依然保持在100nm左右；图12e为淬火后镍针尖处测得的拉曼图谱,谱图中出现了分别位于1350cm -1、1580cm -1和2700cm -1附近的石墨烯特征峰，其中位于1350cm -1附近的D峰来自石墨烯的缺陷，位于1600cm -1附近的G峰尖锐表示较高的结晶度，而位于2700cm -1附近2D峰相对G峰强度较低，半峰宽大于50cm -1，与多层石墨烯的特征符合。
图13a为微波瞬时高温淬火法制备的一种典型的石墨烯修饰的AFM探针所对应的扫描电镜照片，针尖尖端洁净且保持尖锐；图13b为石墨烯修饰的AFM探针所对应的透射电镜照片，红线标记处有约7、8层沿针尖轮廓的连续的多层石墨烯，尖端尺寸仅有30nm左右，石墨烯和尖端表面形成良好的界面接触；图13c为微波高温淬火瞬间AFM探针红热照片；图13d为石墨烯修饰的AFM探针所对应的拉曼图谱，石墨烯特征的D峰、G峰、2D峰，证实了石墨烯的存在。
图14为微波高温淬火瞬间硅片样品红热照片及淬火后测得的拉曼图谱，分别在1350cm -1、1580cm -1和2700cm -1附近出现了石墨烯的特征D峰、G峰和2D，硅片上不同位置测得的拉曼信号各峰的相对强度有所差异，表明了硅片被单层和多层石墨烯混合包覆。
具体实施方式
在以下的实施例中提供了本发明的示例性的实施方案。以下的实施例仅通过示例的方式给出，并用于帮助普通技术人员使用本发明。所述实施例并不能以任何方式来限制本发明的范围。
实施例1
将切割为10×10mm的硅片用大量酒精、丙酮、水超声处理，再用大量水冲洗，氮气吹干。将上述硅片通过磁控溅射的方法，在表面上先后生成5nm碳层(磁控溅射碳靶纯度：99.99％)和30nm镍层(磁控溅射镍靶纯度：99.999％)。或者通过磁控溅射的方法，在表面上生成30nm碳化镍层(磁控溅射碳化镍靶纯度：99.99％)。
将上述镀好膜的硅片固定在长30mm×宽1mm×厚0.1mm的金属Cu电极中间(如图2a示意图所示)，两端分别用螺母或燕尾夹固定在陶瓷底座上，固定过程中防硅片表面损伤；Cu电极通过真空电极法兰连接外部电源。利用分子泵将腔体真空抽至10 -5Pa。利用直流电源输出一个大小为10A、持续时间2秒的瞬间电流，基底Si片瞬间达到红热状态(如图2c、d、e)。待样品冷却后，取出Si片。
其中，图6a为Si基底固定在真空腔体内的实物照片。将上述淬火后的Si片进行拉曼表征，图6b为514nm激光激发下的石墨烯拉曼图谱；从中发现，位于1580cm -1附近的G峰和位于2675cm -1的2D峰向高波数偏移，I 2D/I G≈1且2D处峰有明显分峰现象，可证明生成的石墨烯层数为双层，其中D峰较低，证明石墨烯的缺陷少；基于现有的显微观察条件，Si片表面大部分区域生成双层连续石墨烯，覆盖率达75％～100％。
实施例2：
将切割为10×10mm的玻璃片用大量酒精、丙酮、水超声处理，再用大量水冲洗，氮气吹干。将上述玻璃基底通过磁控溅射的方法，在表面上先后生成5nm碳层(磁控溅射碳靶纯度：99.99％)和30nm镍层(磁控溅射镍靶纯度：99.999％)。或者通过磁控溅射的方法，在表面上生成30nm碳化镍层(磁控溅射碳化镍靶纯度：99.99％)。
将上述镀好膜的玻璃基底固定在长30mm×宽1mm×厚0.1mm的金属Cu电极中间(如图2a示意图所示)，两端分别用螺母或燕尾夹固定在陶瓷底座上，固定过程中防硅片表面损伤；Cu电极通过真空电极法兰连接外部电源，图6c所示为玻璃基底在真空腔体内的实物照片。利用分子泵将腔体真空抽至10 -5Pa。利用直流电源输出一个大小为10A、持续时间2秒的瞬间电流，玻璃基底瞬间达到红热状态(如图2c、d、e)。待样品冷却后，取出玻璃基底。
将上述淬火后的玻璃基底进行拉曼表征，图6d的拉曼图谱发现于514nm激光激发下，位于1582cm -1附近的G峰和位于2680cm -1的2D峰的石墨烯向高波数偏移，I 2D/I G≈1且2D处峰有明显分峰现象，可证明生成的石墨烯层数为双层，其中D峰较低，证明石墨烯的缺陷少；基于现有的显微观察条件，玻璃基底表面大部分区域生成双层连续石墨烯，覆盖率达75％～100％。
实施例3:
将聚二甲基硅氧烷(PDMS，道康宁)试剂A:B按1:10的比例混合均匀，除泡，制成0.45mm厚的柔性材料PDMS膜，待膜干透切割成10×10mm的PDMS片。
将上述洁净的PDMS片吸附于10×10mm的玻片上。将上述玻璃基底通过磁控溅射的方法，在表面上先后生成5nm碳层(磁控溅射碳靶纯度：99.99％)和30nm镍层(磁控溅射镍靶纯度：99.999％)。或者通过磁控溅射的方法，在表面上生成30nm碳化镍层(磁控溅射碳化镍靶纯度：99.99％)。
将上述镀好膜的PDMS片和玻片固定在长30mm×宽1mm×厚0.1mm的金属Cu电极中间(如图2a示意图所示)，两端分别用螺母或燕尾夹固定在陶瓷底座上，固定过程中防硅片表面损伤；Cu电极通过真空电极法兰连接外部电源，图7a所示为PDMS基底在真空腔体内的实物照片。利用分子泵将腔体真空抽至10 -5Pa。利用直流电源输出一个大小为10A、持续时间2秒的瞬间电流，PDMS基底瞬间达到红热状态。待样品冷却后，取出PDMS基底。
将上述淬火后的PDMS基底进行拉曼表征，图7b的拉曼图谱发现于514nm激光激发下，位于1582cm -1附近的G峰向高波数偏移且D处峰有明显分峰现象，可证明生成的石墨烯层数为多层且缺陷较多；其中基于现有的显微观察条件，PDMS基底表面大部分区域生成多层石墨烯，覆盖率达75％～100％。
实施例4：
将铁箔(Alfa Aesar 40493)切割成尺寸为12.5x12.5mm的正方形，纯水超声清洗30min。继续使用酒精、丙酮分别超声清洗30min，除去表面的油污。量筒量取95mL酒精倒入200mL烧杯中，再用移液管吸取高氯酸溶液5mL沿烧杯内壁缓慢滴入，边滴加边搅拌滴加完成后静置溶 液，待其冷却。选取Pt片作为阴极与直流电源负极相连，将待抛光铁箔作为阳极与直流电源正极相连，将两电极放入电解液中进行电化学抛光，恒电流0.05A，抛光时间120s。
称取石墨粉3.0g，量筒量取Cyrene溶液(二氢乙烯基葡萄糖酮)25mL，将石墨粉倒入Cyrene溶液中，先用超声清洗机处理1h，再使用高功率的超声探头处理30min(占空比33％)，最后得到黑色粘稠状溶液。将厚度0.1mm边长12.5mm的正方形铁箔放在匀胶机转台上，真空吸附，再用移液枪吸取之前已制备好的碳膜浆料30μL，滴在铁箔中心处。开启匀胶机旋转开关，调节转数为2000r/min，在铁箔表面制备一层厚度为20-30μm的均匀碳膜。将镀膜后的铁片放在加热板上24h，温度设置为80℃，使溶剂充分挥发，完全干燥.
将镀有碳膜的铁箔放在石英管底部，石英管连接真空***(见图3)。待真空计示数达到1x10 -4pa以下时，先打开水冷循环机，再打开电磁感应加热电源。加热功率设置为0.5kW，加热时间设置为2.9s，设置好后按下开关，2.9s后开关自动断开，停止加热。样品冷却后，取出铁箔。将铁箔放入酒精中超声清洗3次，每次30min，除去表面粘附残留的石墨粉。
图8a为感应加热前的拉曼图谱显示石墨粉拉曼图像的特征峰，图8c为反应后拉曼图谱显示石墨烯的特征峰，经对比可看出反应前后的2D峰强度与G峰强度的比值I 2D/I G均增大，2D峰位置左移且无分峰现象。可以说明反应前后物质发生了变化，石墨粉由石墨变成了低层数的石墨烯。证明了电磁感应加热后在铁基底表面有石墨烯生成。由2D峰与G峰的比值I 2D/I G略小于1，可以看出石墨烯的层数为2-3层，存在D峰说明有部分缺陷。图8d的AFM图像可以看出，铁基底表面生长的石墨烯的厚度为0.78nm，而单层石墨烯的厚度为0.33nm，但由于石墨烯表面是上下起伏的，因此可以断定石墨烯的层数为1-2层，与上面拉曼表征相一致。
实施例5：
将石英玻璃切割成尺寸为12.5x12.5mm的正方形，纯水超声清洗30min。继续使用酒精、丙酮分别超声清洗30min，除去表面的油污。使用食人鱼溶液对石英玻璃进行羧基化处理，增强石英玻璃表面的吸附力。
称取石墨粉3.0g，量筒量取Cyrene溶液(二氢乙烯基葡萄糖酮)25 mL，将石墨粉倒入Cyrene溶液中，先用超声清洗机处理1小时，再使用高功率的超声探头处理30min(占空比33％)，最后得到黑色粘稠状溶液。将厚度1mm边长12.5mm的正方形石英玻璃放在匀胶机转台上，真空吸附，移液枪吸取之前已制备好的碳膜浆料30μL，滴在玻璃中心处。开启匀胶机旋转开关，调节转数为2000r/min，在玻璃表面制备一层厚度为20-30μm的均匀碳膜。将镀膜后的玻璃放在加热板上24h，温度设置为80℃，使溶剂充分挥发，完全干燥.
将镀有碳膜的石英放在石英管底部，石英管连接真空***。待真空计示数达到1x10 -4pa以下时，先打开水冷循环机，再打开电磁感应加热电源。加热功率设置为1kW，加热时间设置为3.2s，设置好后按下开关，3.2s后开关自动断开，停止加热。样品冷却后，取出铁箔。将铁箔放入酒精中超声清洗3次，每次30min，除去表面粘附残留的石墨粉。
图9为石英玻璃基底真空感应加热后的玻璃基底表面的拉曼图像，可以看出其D、G和2D峰的峰位置与标准石墨烯的拉曼特征峰相同，证明确实有石墨烯生成，可以看出石墨烯D峰较低，证明石墨烯的缺陷少。I 2D/I G≈1证明石墨烯为双层石墨烯。
实施例6：
将100x100mm的石英玻璃放在5L的超大烧杯中，用丙酮酒精超声清洗30min，去除表面油污。使用食人鱼溶液对石英玻璃进行羧基化处理，增强石英玻璃表面的吸附力。
称取石墨粉3.0克，量筒量取Cyrene溶液(二氢乙烯基葡萄糖酮)25mL，将石墨粉倒入Cyrene溶液中，先用超声清洗机处理1h，再使用高功率的超声探头处理30min(占空比33％)，最后得到黑色粘稠状溶液。将制备好的碳膜浆料滴加到石英玻璃表面，使用刮膜器由上到下单一方向多次移动，直至石英玻璃表面碳膜浆料均匀成膜。取100x100mm表面有碳膜的石英玻璃2片，碳膜面朝内，并在中间放一块1mm厚的石墨片形成三明治结构，石英玻璃四周用夹子夹紧。
将样品放在二位电动平移台的台面上(见图4)，打开电动平移台控制软件，设置电动平移台的运行路径，路线示意图如图10a所示。电动平移台的运行速率设为20mm/s。设置感应加热功率为3.3kW，按下感应加热装置开关进行加热，同时开启电动平移台运行开关，待电动平移台运行结 束后，停止加热。待石英玻璃冷却后将其放入酒精中超声清洗3次，每次30min，除去表面残留的石墨粉。
图10a玻璃基底感应移动加热实验中电动平移台设定的移动路径，多次来回“s型”移动，使有碳膜部分全都被感应线圈加热；10b为感应移动加热时加热图片，石墨片呈现红热状态，经测量为1500℃左右；10c为玻璃基底表面上石墨烯的拉曼图像，可以看出其特征峰与石墨烯相符，证明有石墨烯生成，并且图谱中D峰较低，证明石墨烯的缺陷少。2D峰与G峰的强度比值I 2D/I G略小于1证明石墨烯的层数为2-3层。与玻璃基底真空感应加热生成的石墨烯相比缺陷增大，石墨烯的层数增加。
实施例7：
将100x100mm的铁箔(Alfa Aesar 40493)放在烧杯中，用丙酮酒精超声清洗30min，去除表面油污。量筒量取95mL酒精倒入200mL烧杯中，再用移液管吸取高氯酸溶液5mL沿烧杯内壁缓慢滴入，边滴加边搅拌滴加完成后静置溶液，待其冷却。选取Pt片作为阴极与直流电源负极相连，将待抛光铁箔作为阳极与直流电源正极相连，将两电极放入电解液中进行电化学抛光，恒电流0.05A，抛光时间120s。
称取石墨粉3.0g，量筒量取Cyrene溶液(二氢乙烯基葡萄糖酮)25mL，将石墨粉倒入Cyrene溶液中，先用超声清洗机处理1h，再使用高功率的超声探头处理30min(占空比33％)，最后得到黑色粘稠状溶液。将制备好的碳膜浆料滴加到铁箔表面，使用刮膜器由上到下单一方向多次移动，直至铁箔两面碳膜浆料均匀成膜。取两块石英玻璃将铁箔夹在中间形成三明治结构，石英玻璃四周用夹子夹紧。
将样品放在二维电动平移台的台面上(见图4)，打开电动平移台控制软件，设置电动平移台的运行路径，路线示意图如图10a所示。电动平移台的运行速率设为30mm/s。设置感应加热功率为2.0kW，按下感应加热装置开关进行加热，同时开启电动平移台运行开关，待电动平移台运行结束后，停止加热。待石英玻璃冷却后将其放入酒精中超声清洗3次，每次30min，除去表面残留的石墨粉。
图11为铁基底表面感应移动加热后的拉曼图谱，其各峰值与标准石墨烯拉曼图谱特征峰一致，证明有石墨烯生成。并且石墨烯D峰较低，证明石墨烯存在缺陷但缺陷较少。由2D峰与G峰强度比值I 2D/I G略小于 1可证明石墨烯的层数为2-3层。与铁基底真空感应加热生成的石墨烯相比，缺陷增大，但石墨烯的层数一致。
实施例8：
以0.25mm直径的高纯捏镍丝为原料，KCl溶液为电解液，用电化学腐蚀法制备镍针(如图12a)。将镍针浸入1-丁基-3-甲基咪唑醋酸盐离子液中，200℃下加热35min对镍针表面进行碳化。
将上述Ni针尖取出，用大量水冲洗，氮气吹干后，***焊接在引丝(0.5mm)上的内径为0.26mm的不锈钢针筒(为减小引丝和针筒自身的微波损耗，表面进行了喷金处理)，再将引丝固定在波导适配器上(图12b)。将适配器装入真空波导腔，如图5所示。启动泵组将波导真空抽至10 -4Pa后，利用程控高压电源控制磁控管产生持续时间为1.2秒的微波，不锈钢针筒和插于其中的Ni针瞬间达到红热状态，如图12c所示。待样品冷却后，取出金属针尖。
镍针尖淬火后所对应的透射电镜照片以及相应的拉曼图谱见图12。电镜照片显示，这种条件淬火后镍针尖端熔化成球状，但表面平整光滑，尺寸约60nm；拉曼测试结果证实了石墨烯结构的存在。
实施例9
用高纯碳靶(99.99％)和高纯镍靶(99.999％)在AFM探针(Sunano，NSG10)正面先后磁控溅射上一层5nm厚的碳膜和25nm厚的镍膜。
将上述镀有碳镍镀层的AFM探针尖用夹片固定于引丝上，再将引丝固定在波导适配器上。将适配器装入真空波导腔，如图5所示。启动泵组将波导真空抽至10 -4Pa后，利用程控高压电源控制磁控管产生持续时间为0.17秒的微波，固定于夹片处的AFM探针瞬间达到红热状态。待样品冷却后取出，得到石墨烯修饰的AFM探针。
图13为淬火后石墨烯功能化AFM探针所对应的扫描和透射电镜照片以及相应的拉曼图谱。扫描电镜照片显示，探针尖端被皱褶的薄膜包覆，针尖的最尖端是十分洁净；高分辨透射图像显示针尖尖端被连续的多层石墨烯包裹，尖端尺寸仅有30nm左右，石墨烯和尖端表面形成良好的界面接触。针尖尖端区域的拉曼测试结果也证实了石墨烯结构的存在。
实施例10
用高纯碳靶(99.99％)和高纯镍靶(99.999％)在8×8mm尺寸的硅片表 面先后磁控溅射上一层5nm厚的碳膜和25nm厚的镍膜。
将上述镀有碳镍镀层的硅片用夹片固定于引丝上，再将引丝固定在波导适配器上，将适配器装入真空波导腔。启动泵组将波导真空抽至10 -4Pa后，利用程控高压电源控制磁控管产生持续时间为0.3秒的微波，固定于夹片处的硅片瞬间达到红热状态。待样品冷却后取出。
图14为微波超快法处理时硅片瞬间红热的照片及淬火后的拉曼图谱。硅片不同位置对应的拉曼测试结果，证实了硅片上混合存在单层和多层石墨烯结构。
以上的实施例仅仅是对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通工程技术人员对本发明的技术方案作出的各种变型和改进，均应落入本发明的权利要求书确定的保护范围内。
工业实用性
本发明提供一类在金属、非金属平面以及针尖基底表面大面积超快生长石墨烯的方法，所述金属基底优选为Fe、Ni、W等，非金属基底优选为玻璃、硅、氮化硅、高分子材料等。本发明针对不同材料的性质，利用脉冲电流、感应电流或汇聚微波能等作用于碳化后的基底材料，通过基底表面的电流原位产生大量的热，实现材料的瞬间淬火进而在材料表面生成大范围的连续单层或多层石墨烯。本发明提供了在不同材料表面实现石墨烯功能化的超快合成方法，可在不耐受长时间高温的材料(如柔性高分子材料、针尖尖端)表面生长界面接触良好的石墨烯；本发明提供的方法可不受真空管式炉的尺寸限制，实现大尺寸基底材料上的石墨烯生长。本发明提供的石墨烯生长方法具有材料(种类、尺寸)和环境(真空、惰性气氛或大气)适应范围广、快速、能耗低等特点。

Claims (10)

  1. 一种超快生长石墨烯的方法，其特征在于，其包括如下步骤：
    1)将基底材料进行碳化处理，以在表面形成碳层或金属化碳层；
    2)将碳化处理后的所述基底材料进行淬火处理；所述淬火处理具体为将所述基底材料的温度升高到500-2000℃，然后立即冷却；所述淬火处理的升温时间为1us～10s。
  2. 根据权利要求1所述的方法，其特征在于，所述基底材料为金属、非金属平面或针尖材料；优选地，所述金属材料为Fe、Ni或W，所述非金属基底为玻璃、硅、氮化硅或高分子材料。
  3. 根据权利要求1或2所述的方法，其特征在于，在步骤2)中，所述淬火处理通过脉冲电流淬火法、整体感应电流淬火法、移动感应电流淬火法或汇聚微波能淬火法完成。
  4. 根据权利要求3所述的方法，其特征在于，所述脉冲电流淬火法包括如下步骤：将碳化处理后的基底两端施加脉冲电流，使基底迅速达到红热状态后自然冷却。
  5. 根据权利要求4所述的方法，其特征在于，所述脉冲电流脉宽范围为1us～10s，电流大小范围为1～50A。
  6. 根据权利要求3所述的方法，其特征在于，所述整体感应电流淬火法包括如下步骤：将碳化处理后的所述基底置于石英管中，将所述石英管置于铜感应线圈内，启动电磁感应，以在基底的表面导电层内激发出涡流产生自加热至红热状态，加热完成后样品自然冷却。
  7. 根据权利要求6所述的方法，其特征在于，所述电磁感应电源输出功率为0.1kW-10kW，所述加热时间为0.1-10s。
  8. 根据权利要求3所述的方法，其特征在于，所述移动感应电流淬火法包括如下步骤：将碳化处理后的所述基底置于二维电动平移台上，设置电磁感应铜圈位于所述基底上方5～10mm处，启动所述电动平移台以及所述电磁感应铜圈，使所述电动平移台带动所述基底移动，并使所述电 磁感应铜圈下方的所述基底被加热至红热状态；然后将所述基底移出铜圈感应范围以使所述基底冷却。
  9. 根据权利要求3所述的方法，其特征在于，所述汇聚微波能淬火包括如下步骤：通过微波能量汇聚于碳化处理后的所述基底上，使所述基底产生瞬时高温达到红热状态，随后自然冷却。
  10. 根据权利要求1-9中任一项所述的方法制备得到的石墨烯产品。
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