WO2021212469A1

WO2021212469A1 - Method for ultra-fast growth of graphene

Info

Publication number: WO2021212469A1
Application number: PCT/CN2020/086682
Authority: WO
Inventors: 徐建勋; 赵宇亮; 梁建波; 葛逸飞; 王鲁峰; 杨宜
Original assignee: 国家纳米科学中心
Priority date: 2020-04-24
Filing date: 2020-04-24
Publication date: 2021-10-28
Also published as: CN113840801A; CN113840801B

Abstract

Provided by the present invention is a class of methods for ultra-fast growth of graphene in large areas on the surface of metal and non-metal planes as well as pinpoint substrates, the metal substrates preferably being Fe, Ni, W, or the like, and non-metal substrates preferably being glass, silicon, silicon nitride, polymer materials, or the like. The present invention uses pulsed current, induction current or converging microwave energy, or the like to act on a carbonized substrate material according to different material properties, and generates a large amount of heat in situ by means of the current on the substrate surface to achieve instantaneous quenching of the material and then generate a large range of continuous single or multi-layer graphene on the material surface. The method according to the present invention allows the growth of graphene, having good interfacial contact, on the surface of materials that do not tolerate high temperature for long a period of time. The method provided by the present invention is not limited by the size of a vacuum tube furnace, and enables the growth of the graphene on large-size substrate materials. The graphene growth method provided by the present invention is characterized advantages such as having a wide range of material and environmental adaptations, being rapid, and having a low energy consumption.

Description

A method for ultra-fast growth of graphene

Technical field

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.

Background technique

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. At present, the main methods for preparing graphene include mechanical exfoliation, oxidation-reduction, epitaxial growth, and chemical vapor deposition. Among them, 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.

At present, the functionalization of graphene on the surface of the target material mainly includes the graphene transfer method and the CVD direct growth method. Because 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 growth of graphene on glass substrates is one of the hotspots in the field of graphene growth. As a transparent amorphous oxide, glass has a low production cost and is now widely used in daily life. It has the same transparent characteristics as graphene and is complementary in terms of electrical conductivity, thermal conductivity and liquid wettability. Therefore, the two are combined to form graphene glass, which can maintain the transparency of the two, but also has excellent electrical conductivity, thermal conductivity and high hydrophobicity. It is expected to become a new material to replace ordinary glass. In order to completely replace ordinary glass with graphene glass, it is first necessary to solve its large-scale production problem. Nowadays, there are two main methods for preparing graphene glass in the laboratory. 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. As mentioned above, 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.

In addition, 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. However, since 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.} However, rGO solution sprayed graphene sheets have many defects and large contact resistance between sheets, which limits the application in sensors. Bae et al. used the CVD method to produce high-quality graphene on a metal substrate by wet transfer to PET to make a G/PEF display. However, the transfer process usually causes the damage of the graphene and brings some unavoidable organic impurities. . On the other hand, graphene functionalized nano-tips have enhanced electrical and mechanical properties, and have outstanding application prospects in scanning probe imaging, nano electrical measurement and sensors. At present, the research on graphene-modified nano-tips can be divided into graphene transfer method and direct CVD growth method. Duan et al. reported that 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. However, during the CVD growth process, 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. In short, 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.

In summary, 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. In addition to the above methods, 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. In this method, 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. However, in addition to the limitations caused by complicated equipment, 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. In view of the above problems, 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.

references:

1.Paton, KR; Varrla, E.; Backes, C.; Smith, RJ; Khan, U.; O'Neill, A.; Boland, C.; Lotya, M.; Istrate, OM; King, P. ,Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids.Nature materials 2014,13(6),624

2.Dai,B.;Fu,L.;Zou,Z.;Wang,M.;Xu,H.;Wang,S.;Liu,Z.,Rational design of a binary metal alloy for chemical vapor deposition growth of uniform single-layer graphene. Nature communications 2011, 2(1), 1-6.

3. Dua, V.; Surwade, SP; Ammu, S.; Agnihotra, J.; Jain S.; Roberts, KE; Park, S.; Ruoff, RS, All-Organic Vapor Sensor Using Inkjet-Printed Reduced Graphene Oxide .Angew.Chem.Int.Ed.2010,49,2154.

4. Bae, S.; Kim, H.; Lee, Y.; Balakrishnan, J.; Lei, T.; Kim, HR; Song, YI; Kim, Y.-J.; Kim, KS; Ozyilmaz, B .;Hong,BH;Iijima,S.,Roll-to-roll production of 30-inch graphene films for transparent electrodes.Nat.Nanotechnol.2010,5,574

5.Lanza,M.;Bayerl,A.;Gao,T.;Porti,M.;Nafria,M;Jing,GY;Zhang,YF;Liu,ZF;Duan,HL,Graphene-Coated Atomic Force Microscopy Tips for Reliable Nanoscale Electrical Characteriztion. Adv Mater 2013, 25, 1440-1444.

6. Martin-Olmos, C.; Rasool, H.M.; Weiller, B.H.; Gimzewski, J.K., Graphene MEMS: AFM Probe Performance Improvement. Acs Nano 2013, 7, 4164-4170.

7.Xiong,W.;Zhou,YS;Hou,WJ;Jiang,LJ;Gao,Y.;Fan,LS;Jiang,L.;Silvain,JF;Lu,YF,Direct writing of graphene patterns on insulating substrates ambient conditions. Scientific Reports 2014, 4,4892.

Summary of the invention

In view of the shortcomings of the current methods for preparing graphene functionalized materials that are too long, high energy consumption, and unable to grow in a large area, 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.

In order to achieve the above objective, the present invention provides a method for ultra-fast growth of graphene. The method includes the following steps:

1) Carburize the base material to form a carbon layer or a metalized carbon layer on the surface;

2) Perform a quenching treatment on the base material after the carbonization treatment; 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.

Wherein, in the present invention, by controlling the heating time to make the substrate reach a high temperature suitable for graphene growth, the cooling is not particularly limited, and the substrate material is naturally cooled immediately after the heating is completed.

Preferably, in step 1), before the carbonization treatment, the base material is cleaned to remove surface impurities.

Wherein, 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.

In a specific embodiment of the present invention, the base material is silicon wafer, glass wafer, iron foil, Ni tip, commercial AFM probe, and the like.

Wherein, 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.

Preferably, 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.

Preferably, 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-100μm.

Preferably, 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; Preferably, the thickness of the carbon film or the metal/carbon composite film is 1 nm to 1 um.

Wherein, the quenching treatment in step 2) is performed in a vacuum, an inert atmosphere or an atmospheric environment.

Wherein, in 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.

Preferably, 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. Preferably, the pulse width of the pulse current ranges from 1 us to 10 s, and the current magnitude ranges from 1 to 50A.

Preferably, the induction current quenching method includes integral induction heating and movement induction heating.

Preferably, 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. Preferably, the output power of the electromagnetic induction power supply is 0.1 kW-10 kW, and the heating time is 0.1-10 s.

Preferably, 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.

Preferably, 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.

In a specific embodiment of the present invention, the method for ultra-fast graphene growth includes the following specific steps:

1) Carburize the clean base material to form a carbon layer or metalized carbon layer on the surface;

2) In a vacuum, inert atmosphere or atmospheric environment, 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 ℃ 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.

In a preferred embodiment of the present invention, 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.

In another preferred embodiment of the present invention, 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 The 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 μm.

In another preferred embodiment of the present invention, 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.

In a preferred embodiment of the present invention, the preferred solution for quenching using pulsed current is as follows:

Place a metal substrate with a carbon layer on the surface or a non-metal substrate with a metal/carbon composite layer on the surface in a vacuum chamber, vacuum or replace the chamber with an inert atmosphere, and apply a voltage pulse across the substrate (as shown in Figure 2a) ), 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. When 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. When the length is smaller, the current passed is correspondingly larger, and the duration is correspondingly longer.

In another preferred embodiment of the present invention, the quenching is accomplished by induction current quenching, and the induction current quenching method is divided into integral induction heating and mobile induction heating.

In another preferred embodiment of the present invention, if the overall induction method is used, 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). Set the output power and heating time of the electromagnetic induction power supply. The power range is 0.1kW-6kW, and the heating time is set to 0.1-10s. 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.

In another preferred embodiment of the present invention, if the movement induction method is used, 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. Place the above-mentioned sample on the sample holder of a two-dimensional electric translation stage, the electromagnetic induction copper ring is located 5-10mm above the sample (as shown in Figure 4), and the whole device is located in the atmosphere. Use the control software of the electric translation table to set the running path and speed of the electric translation table, the speed range is 10-40mm/s, and the output power range of the electromagnetic induction power supply is 0.5-6kW. After starting the electromagnetic induction power supply, turn on the electric translation stage to drive the sample to move along the set path. Under optimized conditions, the sample area under the electromagnetic induction copper ring is quickly heated to a red hot state; when the sample area moves out of the copper ring sensing range, it will Can be cooled quickly.

In another preferred embodiment of the present invention, the preferred solution for quenching using convergent microwave energy is as follows:

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. Insert the metal lead wire at the point where the electric field intensity is the highest, and feed the concentrated microwave energy into the lead wire. Fix the substrate with a carbon layer or a metal/carbon composite layer on the metal lead wire. 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. Under the conditions of the present invention, the concentrated microwave energy loss occurs accurately on the metal sample or its surface coating At this point, 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 beneficial effects of the ultra-fast graphene growth method provided by the present invention are as follows.

Under the method and conditions of the present invention, 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. (Can be greater than 1000°C/s) quickly heat to high temperature (500-2000°C), and then quickly cool naturally, the heating time in the entire single quenching process time is 1us-10s. In this ultra-rapid quenching process, 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. In the reported preparation methods of 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). In the microwave-assisted CVD method, 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.

Description of the drawings

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. Among them, 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.

Figure 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.

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; FIG. 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.

Detailed ways

Exemplary embodiments of the invention are provided in the following examples. The following embodiments are only given by way of example, and are used to help ordinary technicians to use the present invention. The described embodiments do not limit the scope of the present invention in any way.

Example 1

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. Alternatively, a 30nm nickel carbide layer is formed on the surface by magnetron sputtering (magnetron sputtering nickel carbide target purity: 99.99%).

Fix the above-mentioned coated silicon wafer in the middle of the metal Cu electrode of length 30mm×width 1mm×thickness 0.1mm (as shown in the schematic diagram of Figure 2a), and fix both ends on the ceramic base with nuts or dovetail clips. During the fixing process Prevent damage to the surface of the silicon wafer; the Cu electrode is connected to an external power source through a vacuum electrode flange. Use a molecular pump to pump the cavity vacuum to 10 ^-5 Pa. Using a DC power supply to output an instantaneous current with a magnitude of 10A and a duration of 2 seconds, 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.

Among them, Fig. 6a is a physical photo of the Si substrate fixed in the vacuum chamber. After quenching the Si wafer Raman characterization, 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%.

Example 2:

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. Alternatively, a 30nm nickel carbide layer is formed on the surface by magnetron sputtering (magnetron sputtering nickel carbide target purity: 99.99%).

Fix the above-mentioned coated glass substrate in the middle of the metal Cu electrode of length 30mm×width 1mm×thickness 0.1mm (as shown in the schematic diagram of Figure 2a), and fix both ends on the ceramic base with nuts or dovetail clips. During the fixing process Prevent damage to the surface of the silicon wafer; the Cu electrode is connected to an external power source through the vacuum electrode flange. Figure 6c shows the actual photo of the glass substrate in the vacuum chamber. Use a molecular pump to pump the cavity vacuum to 10 ^-5 Pa. Using a DC power supply to output an instantaneous current with a magnitude of 10A and a duration of 2 seconds, the glass substrate instantly reaches a red hot state (as shown in Figure 2c, d, and e). After the sample has cooled, remove the glass substrate.

The glass substrate after the quenching characterized by Raman, Raman spectra of FIG. 6d found at 514nm laser excitation, is located in the vicinity of 1582cm G peak located at 2680cm ^-1 and ^-1 graphene 2D peak shift to higher wave number, I _2D /I _G ≈1 and the peak at 2D has obvious peak separation, which can prove that the number of graphene layers produced is double-layered, and the D peak is lower, which proves that the graphene has fewer defects; based on the existing microscopic observation conditions , The double-layer continuous graphene is formed in most areas of the surface of the glass substrate, with a coverage rate of 75% to 100%.

Example 3:

Mix polydimethylsiloxane (PDMS, Dow Corning) reagents A:B at a ratio of 1:10, and defoam to prepare a 0.45mm thick flexible material PDMS film. When the film is dry, cut it into 10×10mm PDMS tablets.

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. Alternatively, a 30nm nickel carbide layer is formed on the surface by magnetron sputtering (magnetron sputtering nickel carbide target purity: 99.99%).

Fix the above-mentioned coated PDMS sheet and glass slide in the middle of a metal Cu electrode of length 30mm×width 1mm×thickness 0.1mm (as shown in the schematic diagram of Figure 2a), and fix both ends on the ceramic base with nuts or dovetail clips. During the fixing process, the surface of the silicon wafer is prevented from being damaged; the Cu electrode is connected to an external power source through the vacuum electrode flange. Figure 7a shows the actual photo of the PDMS substrate in the vacuum chamber. Use a molecular pump to pump the cavity vacuum to 10 ^-5 Pa. Using a DC power supply to output an instantaneous current with a magnitude of 10A and a duration of 2 seconds, the PDMS substrate instantly reaches a red hot state. After the sample has cooled, remove the PDMS substrate.

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%.

Example 4:

Cut the iron foil (Alfa Aesar 40493) into a square with a size of 12.5x12.5mm, and ultrasonically clean with pure water for 30 minutes. Continue to use alcohol and acetone to ultrasonically clean for 30 minutes to remove oil stains on the surface. Measure 95mL of alcohol with a graduated cylinder and pour it into a 200mL beaker, and then use a pipette to draw 5mL of perchloric acid solution and slowly drop it along the inner wall of the beaker. Stir while dripping. After the dripping is completed, let the solution stand and wait for it to cool. 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.

Weigh 3.0 g of graphite powder, measure 25 mL of Cyrene solution (dihydrovinyl glucone) in a graduated cylinder, pour the graphite powder into the Cyrene solution, first treat with an ultrasonic cleaner for 1 hour, and then use a high-power ultrasonic probe for 30 minutes (accounting for The air ratio is 33%), and finally a black viscous solution is obtained. Place a square iron foil with a thickness of 0.1mm and a side length of 12.5mm on the turntable of the homogenizer, vacuum suction, and then use a pipette to suck up 30μL of the previously prepared carbon film slurry and drop it on the center of the iron foil. Turn on the rotary switch of the homogenizer, adjust the number of revolutions to 2000r/min, and prepare a uniform carbon film with a thickness of 20-30μm on the surface of the iron foil. Put the coated iron sheet on the heating plate for 24h, set the temperature to 80℃, so that the solvent is fully volatilized and completely dried.

Place the iron foil coated with carbon film on the bottom of the quartz tube, and the quartz tube is connected to the vacuum system (see Figure 3). When 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 0.5kW, and the heating time is set to 2.9s. After setting, press the switch. After 2.9s, the switch will automatically disconnect and stop heating. After the sample has cooled, 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.

Fig. 8a is the Raman spectrum before induction heating showing the characteristic peaks of the Raman image of graphite powder, and 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. From the ratio of the 2D peak to the G peak I _2D /I _{G is} slightly less than 1, it can be seen that the number of graphene layers is 2-3 layers, and the presence of the D peak indicates that there are some defects. The AFM image in Figure 8d shows that the thickness of the graphene grown on the surface of the iron substrate is 0.78nm, while the thickness of the single-layer graphene is 0.33nm, but because the graphene surface is up and down, it can be concluded that the graphene layer The number is 1-2 layers, which is consistent with the Raman characterization above.

Example 5:

Cut the quartz glass into a square with a size of 12.5x12.5mm, and ultrasonically clean with pure water for 30 minutes. Continue to use alcohol and acetone to ultrasonically clean 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.

Weigh 3.0 g of graphite powder, measure 25 mL of Cyrene solution (dihydrovinyl glucone) in a graduated cylinder, pour the graphite powder into the Cyrene solution, first treat with an ultrasonic cleaner for 1 hour, and then use a high-power ultrasonic probe for 30 minutes (Duty ratio 33%), and finally a black viscous solution is obtained. Place a square quartz glass with a thickness of 1mm and a side length of 12.5mm on the turntable of the homogenizer, vacuum adsorption, and a pipette to suck 30μL of the previously prepared carbon film slurry and drop it on the center of the glass. Turn on the rotary switch of the homogenizer, adjust the number of revolutions to 2000r/min, and prepare a uniform carbon film with a thickness of 20-30μm on the glass surface. Put the coated glass on the heating plate for 24 hours, set the temperature to 80°C, so that the solvent is fully volatilized and completely dried.

Place the quartz coated with carbon film on the bottom of the quartz tube, and the quartz tube is connected to the vacuum system. When 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. After the sample has cooled, 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.

Example 6:

Put 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.

Weigh 3.0 grams of graphite powder, measure 25 mL of Cyrene solution (dihydrovinyl glucone) in a graduated cylinder, pour the graphite powder into the Cyrene solution, first treat with an ultrasonic cleaner for 1 hour, and then use a high-power ultrasonic probe for 30 minutes (accounting for The air ratio is 33%), and finally a black viscous solution is obtained. The prepared carbon film slurry is dripped onto the surface of the quartz glass, and a film wiper is used to move it in a single direction from top to bottom for multiple times until the carbon film slurry on the surface of the quartz glass is uniformly formed into a film. Take 2 pieces of 100x100mm quartz glass with carbon film on the surface, with the carbon film facing inward, and place a 1mm thick graphite sheet in the middle to form a sandwich structure. The quartz glass is clamped around with a clamp.

Place the sample on the surface of the two-position electric translation stage (see Figure 4), open the control software of the electric translation stage, and set the running path of the electric translation stage. 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. 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 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℃; 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.

Example 7:

Put a 100x100mm iron foil (Alfa Aesar 40493) in a beaker, and ultrasonically clean it with acetone alcohol for 30 minutes to remove oil stains on the surface. Measure 95mL of alcohol with a graduated cylinder and pour it into a 200mL beaker, then use a pipette to draw 5mL of perchloric acid solution and slowly drop it along the inner wall of the beaker. Stir while dripping. After the dripping is completed, let the solution stand and wait for it to cool. 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.

Weigh 3.0 g of graphite powder, measure 25 mL of Cyrene solution (dihydrovinyl glucone) in a graduated cylinder, pour the graphite powder into the Cyrene solution, first treat with an ultrasonic cleaner for 1 hour, and then use a high-power ultrasonic probe for 30 minutes (accounting for The air ratio is 33%), and finally a black viscous solution is obtained. Add the prepared carbon film slurry dropwise to the surface of the iron foil, and use a film wiper to move from top to bottom in a single direction several times until the carbon film slurry on both sides of the iron foil is evenly formed. Take two pieces of quartz glass and sandwich the iron foil in the middle to form a sandwich structure, and clamp around the quartz glass with clamps.

Place the sample on the surface of the two-dimensional electric translation stage (see Figure 4), open the control software of the electric translation stage, and set the running path of the electric translation stage. 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. After the operation of the electric translation table is finished, stop heating. 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.

Example 8:

Using 0.25mm diameter high-purity kneaded nickel wire as raw material, KCl solution as electrolyte, electrochemical corrosion method is used to prepare 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.

Take out the above Ni needle tip, rinse it with plenty of water, dry it with nitrogen, and insert a stainless steel needle barrel with an inner diameter of 0.26mm welded on the wire (0.5mm) (in order to reduce the microwave loss of the wire and the barrel itself, the surface After spraying gold treatment), then fix the guide wire on the waveguide adapter (Figure 12b). Install the adapter into the vacuum waveguide cavity, as shown in Figure 5. After starting the pump set to pump the waveguide vacuum to 10 ^-4 Pa, the magnetron is controlled by the program-controlled high-voltage power supply to generate microwaves with a duration of 1.2 seconds. The stainless steel syringe and the Ni needle inserted in it instantly reach a red hot state, as shown in Figure 12c Shown. After the sample has cooled, remove the metal needle tip.

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.

Example 9

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.

Fix the above-mentioned AFM probe tip coated with carbon nickel coating on the guide wire with a clip, and then fix the guide wire on the waveguide adapter. Install the adapter into the vacuum waveguide cavity, as shown in Figure 5. After starting the pumping unit to pump the waveguide vacuum to 10 ^-4 Pa, 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.

Example 10

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. After starting the pump group to pump the waveguide vacuum to 10 ^-4 Pa, 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 above embodiments only describe the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications made by ordinary engineers in the art to the technical solutions of the present invention The improvements and improvements should fall within the scope of protection determined by the claims of the present invention.

Industrial applicability

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., and the non-metal substrate is preferably glass, silicon, silicon nitride. , Polymer materials, etc. According to the properties of different materials, 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. A range of continuous single-layer or multi-layer graphene. 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.

Claims

A method for ultra-fast graphene growth, which is characterized in that it comprises the following steps:

1) Carburize the base material to form a carbon layer or a metalized carbon layer on the surface;

2) Perform a quenching treatment on the base material after the carbonization treatment; 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 method according to claim 1, wherein the base material is a metal, a non-metallic plane or a needle tip material; preferably, the metal material is Fe, Ni or W, and the non-metal base is glass, silicon , Silicon nitride or polymer materials.
The method according to claim 1 or 2, characterized in that, in step 2), the quenching treatment is completed by a pulse current quenching method, an overall induction current quenching method, a mobile induction current quenching method or a concentrated microwave energy quenching method.
The method according to claim 3, wherein the pulse current quenching method comprises the following steps: applying pulse current to both ends of the carbonized substrate, so that the substrate quickly reaches a red hot state and then naturally cools.
The method according to claim 4, wherein the pulse width of the pulse current is in the range of 1 us to 10 s, and the current magnitude is in the range of 1 to 50A.
The method according to claim 3, wherein the overall induction current quenching method comprises the following steps: placing the carbonized substrate in a quartz tube, placing the quartz tube in a copper induction coil, The electromagnetic induction is activated to excite eddy currents in the conductive layer on the surface of the substrate to generate self-heating to a red hot state, and the sample is naturally cooled after the heating is completed.
The method according to claim 6, wherein 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 method according to claim 3, wherein the mobile induction current quenching method comprises the following steps: placing the carbonized substrate on a two-dimensional electric translation table, and setting an electromagnetic induction copper ring on the substrate Above 5-10mm, start the electric translation stage and the electromagnetic induction copper ring, so that the electric translation stage drives the substrate to move, and the substrate under the electromagnetic induction copper ring is heated to red heat State; then move the substrate out of the copper ring sensing range to cool the substrate.
The method according to claim 3, wherein the convergent microwave energy quenching comprises the following steps: converge microwave energy on the carbonized substrate to make the substrate generate an instantaneous high temperature to reach a red hot state, and then Natural cooling.
A graphene product prepared according to the method of any one of claims 1-9.