CN113840801A - Method for ultra-fast growth of graphene - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C01B32/182—Graphene
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Abstract
The invention provides a method for ultra-fast growing graphene on a large area on the surfaces of a metal plane, a nonmetal plane and a needle point substrate, wherein the metal substrate is preferably Fe, Ni, W and the like, and the nonmetal substrate is preferably glass, silicon nitride, a high polymer material and the like. According to the invention, aiming at the properties of different materials, pulse current, induction current or converged microwave energy and the like are utilized to act on the carbonized substrate material, and a large amount of heat is generated in situ through the current on the surface of the substrate, so that the instant quenching of the material is realized, and continuous single-layer or multi-layer graphene in a large range is generated on the surface of the material. According to the method, good graphene can be contacted with the growth interface on the surface of the material which does not resist high temperature for a long time; the method provided by the invention is not limited by the size of the vacuum tube furnace, and the growth of graphene on a large-size substrate material is realized. The graphene growth method provided by the invention has the characteristics of wide material and environment application range, rapidness, low energy consumption and the like.
Description
The invention belongs to the field of material surface functionalization, and particularly relates to a method for ultra-fast growth of graphene on a metal plane, a nonmetal plane and a needle point substrate surface in a large area range.
Graphene is a two-dimensional mesh material formed by stacking single-layer carbon atoms in a honeycomb-like configuration plane, has excellent physical properties such as optics, electricity, heat and mechanics and unique chemical properties, and can be applied to the fields of multifunctional composite materials, organic optoelectronic materials, hydrogen storage materials, supercapacitors, microelectronic devices and the like. Graphene has attracted considerable attention in recent years by researchers. The controllable preparation of high-quality large-area graphene is a prerequisite condition for the application of the graphene, and the expansion of the preparation method of the graphene to meet the application requirements of different fields is the first problem to be solved in the field research. The main methods for preparing graphene at present comprise a mechanical stripping method, a redox method, an epitaxial growth method, a chemical vapor deposition method and the like. 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 environment, and controls the conditions of temperature gradient, gas flow rate, etc. to obtain high-quality graphene.
The current method for realizing graphene functionalization on the surface of a target material mainly comprises a graphene transfer method and a CVD direct growth method. Since CVD growth of graphene generally uses a single-crystal Cu, Ni, or alloy substrate of both, the synthesized graphene is transferred to a target material, defects and contaminants of graphene are easily caused during the transfer process, and interface contact between graphene and the target is not controllable; in addition, the CVD method is limited by a furnace body, cannot obtain graphene with larger size, and has the defects of long high-temperature growth time and high energy consumption.
Glass substrate growth of graphene is one of the hot spots in the field of graphene growth today. The glass is used as a transparent amorphous oxide, has low preparation cost, is widely applied to daily life, has the same transparent characteristic as graphene, and is complementary in the aspects of electrical conductivity, thermal conductivity and liquid wettability. Therefore, the graphene glass and the glass are combined together to form the graphene glass, so that the transparency of the graphene glass and the glass can be kept, and the graphene glass has excellent electric conductivity, thermal conductivity and high hydrophobicity and is expected to become a new material for replacing common glass. In order to completely replace common glass with graphene glass, firstly, the problem of large-scale manufacturing of the common glass needs to be solved, and the graphene glass prepared in a laboratory at present is mainly prepared by two methods, wherein the first method is a transfer method, a liquid-phase coating mode is adopted for preparing graphene slurry on the surface of the glass, or the graphene slurry is prepared on a metal substrate by a CVD method and then transferred to the surface of the glass, and the other method is that the graphene is directly grown on the surface of the glass by the CVD method. As mentioned above, the first transfer method has a small graphene size and many defects, and also causes problems such as contamination during the transfer process, so that the prepared graphene glass has poor performance. The graphene glass prepared by the second CVD method is good in performance, but the size of the graphene glass is limited by the size of the inner diameter of the tube furnace, and the graphene glass with larger size cannot be prepared.
In addition, the CVD direct growth method is not suitable for growing graphene on the surface of a material (for example, a polymer material, a nanoprobe tip, or the like) which cannot withstand high temperature for a long time. The graphene flexible high polymer material has special electrical and mechanical properties, and can be used for flexible display screens and intelligent sensorsAnd the like, has unique application prospect. However, since the substrate material cannot withstand high temperatures for a long time, graphene functionalization of flexible materials is currently mainly prepared by physical coating methods. Detection H was made by ink jet printing of a solution of graphene oxide flakes (rGO) chemically reduced on polyethylene terephthalate (PET) film by Dua and Ruoff et al2And the like atmosphere sensor. However, graphene sprayed with the rGO solution has more defects in a sheet, and the sheet-to-sheet electric resistance is larger, so that the application of the graphene in a sensor is limited. Bae et al make G/PEF displays by wet transfer of high quality graphene grown on a metal substrate by CVD, but the transfer process usually causes breakage of the graphene and some inevitable organic impurities. On the other hand, the graphene functionalized nanometer needle tip has enhanced electrical and mechanical properties and has prominent application prospect in the fields of scanning probe imaging, nanometer electrical measurement, sensors and the like. At present, researches on graphene modified nanoprobes can be divided into a graphene transfer method and a direct CVD growth method. Duan et al reported that the fabrication of graphene functionalized AFM tips by growing graphene on copper foil and transferring it to commercial Atomic Force Microscope (AFM) tips showed higher conductivity and lifetime; however, the transfer process of the graphene is not controllable, and the transferred graphene is small in acting force with the AFM probe body and not tightly attached. Martin-Olmos et al, using semiconductor processing techniques, form a pyramidal groove array on the surface of a silicon wafer and plate a layer of copper on the surface, and then grow a continuous graphene layer on the copper coating (including in the pyramidal grooves) by CVD; and further spin-coating a substrate material SU-8 on the graphene layer to obtain the graphene functionalized AFM probe. However, during the CVD growth process, the tips of the pyramidal grooves are passivated by the high temperature for a long time, resulting in a final AFM probe tip size of more than 1um and a resulting AFM probe with reduced spatial resolution. In summary, the physical adsorption method is not controllable and cannot ensure good contact between the tip surface and the graphene layer, while the CVD method causes the probe tip nano-size to be damaged due to the long-time high-temperature environment required for growth.
In summary, the methods for realizing graphene functionalization on the surface of a material mainly include a transfer method and a CVD direct growth method. The transfer method easily causes defects and pollutants of the graphene in the transfer process, and the interface contact between the graphene and the target substrate is uncontrollable; the CVD direct growth method has high requirements on the temperature resistance of the substrate, long time, high energy consumption and limited product size, and blocks the mass production and application expansion of graphene functional products. In addition to the above method, Xiong et al report a method for generating a graphene pattern on the surface of an insulating substrate material such as glass or a Si sheet by using micro-nano laser direct writing equipment. In the method, the laser spot is focused on the surface of the substrate to heat the irradiation area of the surface of the substrate to reach the growth temperature and the growth condition of the graphene, so that the rapid growth of the graphene is realized while the long-time high temperature of the surface of the substrate is avoided. However, in addition to the limitation of complicated equipment, the laser spot size used in this method is very small (about 800 nm), and only a small range (micrometer scale) of graphene growth can be realized, but the large-area graphene rapid growth on the surface of the macroscopic substrate cannot be realized. Aiming at the problems, the invention provides a novel ultra-fast graphene growth method, which adopts pulse current, induction current or converged microwave energy and the like to act on a carbonized substrate material, generates a large amount of heat in situ through the current on the surface of the substrate, realizes instant quenching of the material and further generates continuous single-layer or multi-layer graphene (as shown in figure 1) in a large range on the surface of the material. The ultrafast growth method provided by the invention is not limited by the size of the vacuum tube furnace, realizes the growth of graphene on a large-size substrate material, and has the characteristics of wide application range, rapidness, low energy consumption and the like of the material (type and size) and the environment (vacuum, inert atmosphere or atmosphere).
Reference documents:
1.Paton,K.R.；Varrla,E.；Backes,C.；Smith,R.J.；Khan,U.；O’Neill,A.；Boland,C.；Lotya,M.；Istrate,O.M.；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 vapour deposition growth of uniform single-layer graphene.Nature communications 2011,2(1),1-6.
3.Dua,V.；Surwade,S.P.；Ammu,S.；Agnihotra,J.；Jain S.；Roberts,K.E.；Park,S.；Ruoff,R.S.,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,H.R.；Song,Y.I.；Kim,Y.-J.；Kim,K.S.；Ozyilmaz,B.；Hong,B.H.；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,G.Y.；Zhang,Y.F.；Liu,Z.F.；Duan,H.L.,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,Y.S.；Hou,W.J.；Jiang,L.J.；Gao,Y.；Fan,L.S.；Jiang,L.；Silvain,J.F.；Lu,Y.F.,Direct writing of graphene patterns on insulating substrates under ambient conditions.Scientific Reports 2014,4,4892.
disclosure of Invention
Aiming at the defects that the existing method for preparing the graphene functionalized material is too long in time, high in energy consumption and incapable of large-area growth, the invention aims to provide a preparation method for realizing large-area ultrafast graphene functionalization on the surfaces of different materials.
In order to achieve the above object, the present invention provides a method for ultrafast growth of graphene, comprising the steps of:
1) carbonizing the substrate material to form a carbon layer or a metallized carbon layer on the surface;
2) quenching the carbonized substrate material; the quenching treatment is specifically to raise the temperature of the substrate material to 500-; the temperature rise time of the quenching treatment is 1 us-10 s.
The substrate is heated to a high temperature suitable for the growth of graphene by controlling the heating time, the cooling is not particularly limited, and the substrate material is naturally cooled immediately after the heating is finished.
Preferably, in step 1), the base material is cleaned to remove surface impurities before the carbonization treatment.
The base material in the step 1) comprises some common metal, non-metal plane and needle point materials, preferably, the metal material is Fe, Ni, W, etc., and the non-metal base is preferably glass, silicon nitride, polymer material, etc.
In one embodiment of the invention, the substrate material is a silicon wafer, a glass sheet, an iron foil, a Ni tip, a commercial AFM probe, or the like.
Wherein the carbonization treatment of the surface of the substrate material in the step 1) is completed by one or more of the following methods: carbon powder slurry coating method, high temperature carbonization method and vacuum evaporation method.
Preferably, the carbon powder slurry coating method comprises the following steps: adding carbon powder into a Cyrene solvent to obtain carbon powder slurry, coating the carbon powder slurry on the surface of the substrate to enable the carbon powder slurry to form a film on the surface of the substrate uniformly, and then heating the substrate with the film formed on the surface to enable the solvent to be completely volatilized to obtain a continuous carbon film; preferably, the thickness of the continuous carbon film is 1-100 um.
Preferably, the high temperature carbonization method comprises the steps of: dripping a PMMA glacial acetic acid solution on the substrate, homogenizing to obtain a PMMA film, heating the substrate with the PMMA film on the surface to 350-400 ℃, and obtaining a substrate subjected to surface carbonization treatment; preferably, the thickness of the PMMA thin film is 10nm to 100 mu m.
Preferably, the vacuum evaporation method comprises the following steps: fixing a substrate in a vacuum cavity, and then heating a carbon rod by electrifying or bombarding a target material by utilizing high-energy ions to coat a carbon film or a metal/carbon composite film on the surface of the substrate; preferably, the thickness of the carbon film or the metal/carbon composite film is 1nm to 1 um.
Wherein the quenching treatment in the step 2) is performed in vacuum, inert atmosphere or atmospheric environment.
Wherein, in the step 2), the quenching treatment is completed by a pulse current quenching method, an induction current quenching method or a convergent microwave energy quenching method.
Preferably, the pulse current quenching method comprises the steps of: and placing the carbonized substrate in a vacuum cavity, and applying pulse current to two ends of the conductive substrate in a vacuum or inert atmosphere environment to ensure that the substrate is naturally cooled after rapidly reaching a red hot state. Preferably, the pulse width range of the pulse current is 1 us-10 s, and the current magnitude range is 1-50A.
Preferably, the induction hardening method includes a bulk induction heating and a moving induction heating method.
Preferably, the bulk induction current quenching method comprises the steps of: and placing the carbonized substrate in a quartz tube, placing the quartz tube in a copper induction coil, starting electromagnetic induction in a vacuum or inert atmosphere environment to excite eddy current in a surface conductive layer of the substrate to generate self-heating to a red hot state, and naturally cooling the sample after heating. Preferably, the output power of the electromagnetic induction power supply is 0.1kW-10kW, and the heating time is 0.1-10 s.
Preferably, the moving induction current quenching method comprises the following steps: placing the carbonized substrate on a two-dimensional electric translation table, arranging an electromagnetic induction copper ring 5-10 mm above the substrate, starting the electric translation table and the electromagnetic induction copper ring, enabling the electric translation table to drive the substrate to move, and enabling a local area of the substrate below the electromagnetic induction copper ring to be heated to a red hot state; the substrate heating zone was then moved out of the copper coil induction range to allow it to cool.
Preferably, the concentrated microwave energy quenching comprises the steps of: and gathering microwave energy on the carbonized substrate to generate instantaneous high temperature of the substrate to reach a red hot state, and then cooling the substrate.
In a specific embodiment of the present invention, the method for ultrafast-growth of graphene comprises the following specific steps:
1) carbonizing the clean substrate material to form a carbon layer or a metallized carbon layer on the surface;
2) and in a vacuum, inert atmosphere or atmospheric environment, pulse current, induction current or converged microwave energy is utilized to act on the whole or local area of the carbonized material, so that the temperature of the substrate is instantly increased to 500-2000 ℃ and is rapidly cooled, and the graphene functionalization on the surface of the material is realized. The temperature rise time of the single quenching process ranges from 1us to 10 s.
In a preferred embodiment of the present invention, the toner slurry coating method comprises the steps of: adding carbon powder into Cyrene solvent (dihydrovinyl glucosone), and sequentially performing ultrasonic treatment for 1h and 30min (duty ratio of 33%) by using an ultrasonic cleaning machine and a probe to obtain black viscous solution. And dripping the prepared carbon powder slurry on the surface of the substrate, and treating by using a spin coater or a film scraper until the carbon powder slurry is uniformly formed into a film on the surface of the substrate. And (3) placing the substrate subjected to spin coating on a heating plate at 80 ℃ for processing for 24h until the solvent is completely volatilized, so as to obtain a continuous carbon film with a certain thickness, wherein the thickness is preferably 1-100 um.
In another preferred embodiment of the present invention, the high temperature carbonization method comprises the steps of: preparing a PMMA (polymethyl methacrylate) glacial acetic acid solution, placing a clean substrate on a rotary table of a spin coater, dropwise adding the PMMA solution, and spin coating to obtain a uniform PMMA film with a certain thickness. And (3) putting the substrate with the PMMA film on the surface into a vacuum tube furnace for heating, and keeping the temperature at 350-400 ℃ for 2h to obtain the substrate with the surface carbonized treatment, wherein the thickness is preferably 10 nm-100 mu m.
In another preferred embodiment of the present invention, the vacuum evaporation method comprises the steps of: fixing a clean substrate on a sample table in a vacuum cavity, covering the cavity and vacuumizing; after the vacuum degree meets the requirement, a carbon rod (direct current evaporation equipment) is heated by electrifying current or a target material (magnetron sputtering equipment) is bombarded by high-energy ions, and a carbon film or a metal/carbon (such as Ni/C) composite film with a certain thickness is plated on the surface of the substrate, wherein the thickness is preferably 1 nm-1 um.
In a preferred embodiment of the present invention, the preferred scheme for quenching with pulsed current is as follows:
placing 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 cavity, vacuumizing or replacing the cavity with an inert atmosphere environment, applying a voltage pulse (as shown in figure 2a) at two ends of the substrate, allowing a pulse current to pass through the substrate or the conductive metal/carbon composite layer on the surface of the substrate, and naturally cooling the substrate after the substrate rapidly reaches a red hot state. The pulse width range of the pulse current is 1 us-10 s, and the current magnitude range is 1-50A. The current generates a large amount of joule heat through the conductive substrate or surface coating to rapidly bring the substrate or surface thereof to a red hot state. The magnitude and duration of the applied current is closely related to the resistivity and dimensional specifications of the base material. When the resistivity of the metal material is larger, the thickness and the width are smaller, and the length is larger, the current is correspondingly smaller, and the duration is correspondingly shorter; when the resistivity of the metal material is small, the thickness and the width are large, and the length is small, the current is correspondingly large, and the duration is correspondingly long.
In another preferred embodiment of the present invention, the quenching is performed using induction current quenching, which is divided into a bulk induction heating and a moving induction heating method.
In still another preferred embodiment of the present invention, if the bulk induction method is used, a metal substrate having a carbon layer on the surface thereof or a non-metal substrate having a metal/carbon composite layer on the surface thereof is placed in a quartz tube; the quartz tube was placed in the copper induction coil of an electromagnetic induction power supply apparatus (Dongda DDCGP-06-III) and the quartz tube was evacuated or replaced with an inert atmosphere (as shown in FIG. 3). Setting the output power and the heating time of an electromagnetic induction power supply, wherein the power range is 0.1kW-6kW, the heating time is set to 0.1-10s, starting the electromagnetic induction power supply, exciting a vortex in a surface conductive layer of a metal substrate or a non-metal substrate to generate a self-heating phenomenon, rapidly heating the sample to a red hot state, and naturally cooling the sample after heating. The output power and heating time of the electromagnetic induction power supply are related to the working frequency of the power supply, the material and the size of the substrate.
In another preferred embodiment of the present invention, if the motion induction method is used, the metal substrate with the carbon layer on the surface is sandwiched between two pieces of clean flat glass, and the four corners of the glass are clamped; or two nonmetal substrates with the same size are clamped by a graphite sheet with the equivalent size and thickness of 1mm to form a sandwich structure, and four corners of the substrate are clamped tightly. The sample is placed on a sample seat of a two-dimensional electric translation table, an electromagnetic induction copper ring is located 5-10 mm above the sample (as shown in figure 4), and the whole device is located in the atmosphere. The control software of the electric translation stage is used for setting the running path and the running speed of the electric translation stage, the speed range is 10-40mm/s, and the output power range of the electromagnetic induction power supply is 0.5-6 kW. After the electromagnetic induction power supply is started, the electric translation table is started to drive the sample to move along a set path, and under an optimized condition, the sample area below the electromagnetic induction copper ring is rapidly heated to a red hot state; the sample area can be rapidly cooled after moving out of the copper coil induction range.
In yet another preferred embodiment of the present invention, the preferred embodiment of quenching using concentrated microwave energy is as follows:
the schematic diagram of the apparatus used in this scheme is shown in fig. 5, and comprises 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 is stabilized in a standing wave state, and a point with the maximum electric field intensity appears at 1/4 wavelengths on the central line of the wide surface of the waveguide cavity to form a microwave energy hot spot. And inserting a metal lead at the maximum point of the electric field intensity, and feeding the gathered microwave energy into the lead. Fixing the substrate with the carbon layer or the metal/carbon composite layer on the surface on the metal lead. The wave guide cavity is vacuumized or replaced by inert atmosphere environment, the wave number generated by the magnetron is controlled by a program-controlled high-voltage pulse power supply to accurately control the microwave output time, under the condition of the invention, the loss of the converged microwave energy accurately occurs at the metal sample or the surface coating thereof, the microwave energy is converted into a large amount of heat energy, the instantaneous high temperature generated on the surface of the sample reaches a red hot state, and then the sample is naturally cooled. The temperature rise time of the single quenching is 0.001-10 seconds. The fuse is made of metal, such as Ni, W, Fe, stainless steel wire, etc., and has a diameter of 0.2-5 mm. Wherein, clips or other fixers which are matched with the shape of the sample can be welded at different positions of the lead wire to fix the sample. The microwave output time is related to the size of the lead wire, the material and the size of the substrate and the like.
The ultrafast graphene growth method provided by the invention has the following beneficial effects.
Under the method and the condition, eddy current and converged microwave energy excited by pulse current and electromagnetic induction directly act on the metal substrate or a coating on the surface of the substrate, a large amount of heat is generated in situ to rapidly heat the surface of the substrate to high temperature (500-2000 ℃) at a large heating rate (which can be more than 1000 ℃/s), and then the substrate is rapidly and naturally cooled, wherein the heating time in the whole single quenching process is 1-10 s. In the ultra-fast quenching process, the carbon layer on the surface of the substrate infiltrates into the metal substrate or the metal coating on the surface of the substrate under the high-temperature condition, then the substrate is rapidly cooled, and the infiltrated carbon is precipitated on the surface of the substrate to form graphene. In the reported graphene preparation method, an electric furnace or an induction current is generally used to heat a sample stage (such as a tungsten boat, etc.) and then conduct heat energy to the sample to achieve the purpose of heating the sample, and the temperature rise and drop process of the sample is long (Piner R, Li H, Kong X, et al. ACS Nano,2013,7(9): 7495). In the microwave-assisted CVD method, microwaves form a uniform microwave field by continuous reflection in a multi-cavity upstream of a CVD tube furnace to crack a carbon source precursor, and do not directly interact with a growth substrate of graphene, and the substrate is raised by electric furnace heating and then thermal conduction and maintained at a high temperature condition suitable for graphene growth (Li x.s., Cai w., An j.et al. science,2009,324(5932): 1312).
The ultrafast graphene method provided by the invention is characterized in that a substrate is directly heated by using eddy currents excited by pulse current and electromagnetic induction and a microwave alternating electromagnetic field, and graphene growth on the surface of the substrate is completed in a very short time. The method provided by the invention ensures that large-area graphene is generated on the surface of the substrate, avoids the damage of melting, oxidation and the like to the substrate caused by high temperature, expands the variety of graphene functionalized substrate materials, is not limited by the size of the tube furnace, and can be used for rapid graphene functionalization of large-size substrate materials; meanwhile, the production speed can be effectively accelerated, and the energy consumption and the cost are reduced.
Fig. 1 is a schematic diagram of an ultrafast graphene growth method according to the present invention. The electromagnetic energy on the surface of the substrate material generates a large amount of heat, so that the surface of the substrate is rapidly quenched, and continuous graphene in a large range is generated on the surface of the material.
FIG. 2a is a schematic view of an apparatus for holding a substrate during a process of instantaneously high-temperature quenching a sample using a pulse current; FIG. 2b is a single pulse recorded by an oscilloscope with current set through the sample heating; the arrows on the figures 2c, 2d and 2e are a series of photographs of the red heat of the surface of the instantaneous high-temperature quenching treatment silicon wafer; the left arrow is a series of pictures of the surface cooling of the instantaneous high-temperature quenching treatment silicon wafer.
Fig. 3 is a schematic view of an induction heating apparatus. Wherein a is a schematic view of a vacuum device; b is a drawing diagram of an induction coil and a quartz tube; and c is a schematic diagram of the whole experimental device (no cold water taking and temperature measuring device is added).
FIG. 4 is a schematic view of a moving induction heating apparatus for glass substrates, wherein a is a schematic view of an experimental apparatus for moving an induction heating part; b is a schematic diagram of an induction coil and a quartz glass device.
Fig. 5 is a schematic diagram of a microwave ultrafast quenching system, which is composed of a program-controlled high-voltage pulse power supply, a magnetron (an electric vacuum device for generating microwave energy), a coaxial line (a microwave transmission line formed by coaxial cylindrical conductors), an excitation cavity (for receiving microwave energy and transmitting the microwave energy to a circulator), a three-port circulator (only allowing microwave to be delayed in the excitation cavity → a waveguide → a load to transmit in a single direction for protecting the magnetron), a waveguide (for concentrating and binding the microwave in a space to serve as a sample quenching chamber), a load (for consuming redundant microwave energy), and a pump set (a combined pump set of a mechanical pump and a molecular pump for providing a vacuum environment for the waveguide), wherein an observation window and a sample inlet matched with an adapter are designed at the waveguide.
FIG. 6a is a photograph of a sample stage with a Si substrate fixed in a vacuum chamber during an instantaneous high temperature quenching process using a pulse current; FIG. 6b is a series of Raman spectra corresponding to graphene grown at different positions (dispersed at 8 points) on a silicon wafer after quenching; FIG. 6c is a photograph of a sample stage with a glass substrate fixed in a vacuum chamber during an instantaneous high temperature quenching process using a pulsed current; fig. 6d is a series of raman spectra corresponding to graphene grown at different positions (dispersed at 13 points) on the silicon wafer after quenching.
FIG. 7a is a photograph of a sample stage in which a flexible substrate PDMS is fixed in a vacuum chamber during an instantaneous high-temperature quenching process using a pulse current; fig. 7b is a series of raman spectra corresponding to graphene grown at different positions (dispersed at 4 points) on PDMS after quenching.
FIG. 8 is a vacuum induction heating experimental image of a metallic iron substrate, wherein a and c are Raman spectra of the carbon-coated iron substrate before and after quenching; b is a photo of the instant red heat of the iron substrate under the action of electromagnetic induction; and d is an AFM image of the graphene on the surface of the iron base after quenching.
Fig. 9 is a photograph of a carbon-coated glass substrate and its raman spectrum after vacuum induction quenching.
FIG. 10 is an image of a moving induction heating experiment of a glass substrate, wherein a is a schematic diagram of a moving path of an electric translation stage in the moving induction heating experiment; b is the state of local red heat in the moving induction heating process of the glass substrate; and c is a Raman spectrum of graphene on the surface of the glass substrate after moving induction heating.
Fig. 11 is a photograph of a carbon coated iron substrate and its raman spectrum after moving induction heating.
FIG. 12a is a transmission electron microscope image of a nickel needle with tip size less than 50 nm; FIG. 12b shows a fixing manner of a nickel needle sample, wherein a gold-plated wire welded with a gold-plated stainless steel tube (inner diameter 0.26mm) is fixed on the adapter, and a nickel needle is inserted into the stainless steel tube for fixing; FIG. 12c is a photograph showing the red heat of the nickel pin at the moment of microwave quenching; FIG. 12d is a transmission electron microscope photograph corresponding to the graphene-coated nickel needle prepared by microwave instantaneous high-temperature quenching, wherein the tip size of the needle tip is still kept at about 100 nm; FIG. 12e is a Raman spectrum measured at the tip of the quenched nickel tip, wherein the spectra show the positions of 1350cm respectively-1、1580cm -1And 2700cm-1NearbyCharacteristic peak of graphene, wherein the peak is located at 1350cm-1The nearby D peak is from the defect of graphene and is positioned at 1600cm-1The near G peak is sharp and indicates higher crystallinity, and is located at 2700cm-1The intensity of the nearby 2D peak is lower relative to the G peak, and the half-peak width is more than 50cm-1Consistent with the characteristics of multilayer graphene.
FIG. 13a is a scanning electron micrograph of a typical graphene-modified AFM probe prepared by microwave instant high temperature quenching, wherein the tip is clean and remains sharp; fig. 13b is a transmission electron microscope photograph corresponding to the graphene-modified AFM probe, where about 7 and 8 layers of continuous multi-layer graphene along the tip profile are located at the red line mark, the tip size is only about 30nm, and the graphene and the tip surface form a good interface contact; FIG. 13c is a red hot photograph of the AFM probe at the instant of microwave high temperature quenching; fig. 13D is a raman spectrum corresponding to the graphene-modified AFM probe, and the presence of graphene is confirmed by a D peak, a G peak, and a 2D peak, which are characteristic of graphene.
FIG. 14 shows the red thermal photograph of the silicon wafer sample at the moment of microwave high-temperature quenching and the Raman spectrum measured after quenching at 1350cm respectively-1、1580cm -1And 2700cm-1The characteristic D peak, G peak and 2D of graphene appear nearby, and the relative intensity of each peak of Raman signals measured at different positions on the silicon wafer is different, which indicates that the silicon wafer is coated by single-layer and multi-layer graphene in a mixed manner.
Exemplary embodiments of the invention are provided in the following examples. The following examples are given by way of illustration only and are presented to assist one of ordinary skill in the art in utilizing the present invention. The examples are not intended to limit the scope of the invention in any way.
Example 1
The silicon slice cut into 10 x10 mm is treated with a large amount of alcohol, acetone and water by ultrasonic treatment, then washed with a large amount of water, and dried by nitrogen. The silicon wafer is subjected to magnetron sputtering to generate a 5nm carbon layer (purity of magnetron sputtering carbon target: 99.99%) and a 30nm nickel layer (purity of magnetron sputtering nickel target: 99.999%) on the surface in sequence. Or a 30nm nickel carbide layer is generated on the surface by a magnetron sputtering method (purity of a magnetron sputtering nickel carbide target: 99.99%).
Fixing the coated silicon wafer in the middle of a metal Cu electrode (shown in a schematic diagram of figure 2a) with the length of 30mm, the width of 1mm and the thickness of 0.1mm, and fixing two ends of the silicon wafer on a ceramic base by nuts or dovetail clamps respectively to prevent the surface of the silicon wafer from being damaged in the fixing process; the Cu electrode is connected with an external power supply through a vacuum electrode flange. The cavity is vacuumized to 10 degrees by a molecular pump-5Pa. The substrate Si wafer reaches red heat state instantly by outputting an instant current with a magnitude of 10A and duration of 2 seconds by using a direct current power supply (as shown in FIGS. 2c, d and e). And after the sample is cooled, taking out the Si sheet.
Wherein, fig. 6a is a photo of a real object with a Si substrate fixed in a vacuum chamber. Performing Raman characterization on the quenched Si sheet, wherein a Raman spectrum of graphene under 514nm laser excitation is shown in FIG. 6 b; it was found to be at 1580cm-1Near G peak and a peak at 2675cm-1Is shifted towards a high wavenumber, I2D/I G1 is approximately distributed, and the 2D peak has an obvious peak separation phenomenon, which can prove that the number of generated graphene layers is double, wherein the D peak is lower, and the defects of graphene are few; based on the existing microscopic observation conditions, the double-layer continuous graphene is generated on most areas of the surface of the Si sheet, and the coverage rate reaches 75% -100%.
Example 2:
the glass pieces cut to 10X 10mm were treated with a large amount of alcohol, acetone, water with ultrasound, rinsed with a large amount of water, and blown dry with nitrogen. The above glass substrate was subjected to magnetron sputtering to form a 5nm carbon layer (purity of magnetron sputtering carbon target: 99.99%) and a 30nm nickel layer (purity of magnetron sputtering nickel target: 99.999%) on the surface in this order. Or a 30nm nickel carbide layer is generated on the surface by a magnetron sputtering method (purity of a magnetron sputtering nickel carbide target: 99.99%).
Fixing the coated glass substrate in the middle of a metal Cu electrode (shown in a schematic diagram of figure 2a) with the length of 30mm, the width of 1mm and the thickness of 0.1mm, and fixing two ends of the coated glass substrate on a ceramic base by nuts or dovetail clamps respectively to prevent the surface of a silicon wafer from being damaged in the fixing process; cu electrode passing through vacuumThe polar flange is connected to an external power supply, and fig. 6c shows a physical photograph of the glass substrate in the vacuum chamber. The cavity is vacuumized to 10 degrees by a molecular pump-5Pa. The glass substrate reaches red heat instantaneously by outputting an instantaneous current with a magnitude of 10A and a duration of 2 seconds by using a direct current power supply (as shown in FIGS. 2c, d and e). After the sample was cooled, the glass substrate was taken out.
The quenched glass substrate was subjected to Raman characterization, and the Raman spectrum of FIG. 6d was found to be 1582cm under excitation of 514nm laser-1Near G peak and a peak at 2680cm-1Graphene of the 2D peak of (a) shifts to a high wavenumber, I2D/I G1 is approximately distributed, and the 2D peak has an obvious peak separation phenomenon, which can prove that the number of generated graphene layers is double, wherein the D peak is lower, and the defects of graphene are few; based on the existing microscopic observation conditions, double-layer continuous graphene is generated in most areas of the surface of the glass substrate, and the coverage rate reaches 75% -100%.
Example 3:
uniformly mixing Polydimethylsiloxane (PDMS) reagent A and B according to the proportion of 1:10, removing bubbles, preparing a PDMS film of a flexible material with the thickness of 0.45mm, and cutting the PDMS film into PDMS sheets with the thickness of 10 multiplied by 10mm after the film is dried thoroughly.
The clean PDMS slides were adsorbed onto a 10X 10mm glass slide. The above glass substrate was subjected to magnetron sputtering to form a 5nm carbon layer (purity of magnetron sputtering carbon target: 99.99%) and a 30nm nickel layer (purity of magnetron sputtering nickel target: 99.999%) on the surface in this order. Or a 30nm nickel carbide layer is generated on the surface by a magnetron sputtering method (purity of a magnetron sputtering nickel carbide target: 99.99%).
Fixing the coated PDMS sheet and glass sheet in the middle of a metal Cu electrode (shown in a schematic diagram of figure 2a) with the length of 30mm, the width of 1mm and the thickness of 0.1mm, and fixing two ends of the coated PDMS sheet and glass sheet on a ceramic base by nuts or dovetail clips respectively to prevent the surface of a silicon wafer from being damaged in the fixing process; the Cu electrode was flanged to an external power supply via a vacuum electrode, and fig. 7a shows a real photograph of the PDMS substrate in the vacuum chamber. The cavity is vacuumized to 10 degrees by a molecular pump-5Pa. Utilizes a direct current power supply to output an instantaneous current with the magnitude of 10A and the duration of 2 secondsThe PDMS substrate reaches a red hot state instantly. After the sample was cooled, the PDMS substrate was taken out.
Raman characterization is carried out on the quenched PDMS substrate, and the Raman spectrum shown in FIG. 7b is located at 1582cm under excitation of 514nm laser-1The nearby G peak shifts to a high wave number and the peak at the D position has an obvious peak separation phenomenon, so that the generated graphene layers are multilayer and have more defects; based on the existing microscopic observation conditions, the surface of the PDMS substrate generates a plurality of layers of graphene in most areas, and the coverage rate reaches 75% -100%.
Example 4:
the iron foil (Alfa Aesar 40493) was cut into a square shape of 12.5 × 12.5mm in size, and ultrasonically cleaned with pure water for 30 min. And continuously using alcohol and acetone to respectively perform ultrasonic cleaning for 30min to remove oil stains on the surface. Measuring 95mL of alcohol by using a measuring cylinder, pouring the alcohol into a 200mL beaker, sucking 5mL of perchloric acid solution by using a pipette, slowly dripping the perchloric acid solution along the inner wall of the beaker, stirring while dripping, standing the solution, and cooling the solution. Selecting a Pt sheet as a cathode to be connected with a direct current power supply cathode, taking an iron foil to be polished as an anode to be connected with a direct current power supply anode, putting the two electrodes into electrolyte to carry out electrochemical polishing, wherein the constant current is 0.05A, and the polishing time is 120 s.
Weighing 3.0g of graphite powder, measuring 25mL of a Cyrene solution (dihydrovinyl glucosone) by using a measuring cylinder, pouring the graphite powder into the Cyrene solution, firstly treating for 1h by using an ultrasonic cleaning machine, then treating for 30min by using a high-power ultrasonic probe (duty ratio is 33%), and finally obtaining a black viscous solution. Putting a square iron foil with the thickness of 0.1mm and the side length of 12.5mm on a rotary table of a spin coater, performing vacuum adsorption, and sucking 30 mu L of prepared carbon film slurry by using a pipette, and dripping the carbon film slurry at the center of the iron foil. And starting a rotary switch of the spin coater, adjusting the revolution to 2000r/min, and preparing a uniform carbon film with the thickness of 20-30 μm on the surface of the iron foil. And (3) placing the coated iron sheet on a heating plate for 24 hours at the temperature of 80 ℃, so that the solvent is fully volatilized and is completely dried.
An iron foil coated with a carbon film was placed on the bottom of a quartz tube, which was connected to a vacuum system (see fig. 3). When the vacuum gauge reading reaches 1x10-4When pa is below, the water-cooling circulator is started first and then the water-cooling circulator is startedAnd turning on an electromagnetic induction heating power supply. The heating power is set to be 0.5kW, the heating time is set to be 2.9s, the switch is pressed after the setting is finished, and the switch is automatically switched off after 2.9s, so that the heating is stopped. After the sample was cooled, the iron foil was removed. And (3) putting the iron foil into alcohol, and ultrasonically cleaning for 30min each time for 3 times to remove the residual graphite powder adhered to the surface.
FIG. 8a is a characteristic peak of Raman spectrum of graphite powder before induction heating, FIG. 8c is a characteristic peak of graphene after reaction, and the ratio I of 2D peak intensity and G peak intensity before and after reaction can be seen through comparison2D/I GThe peak values are increased, the 2D peak position is shifted to the left, and the peak splitting phenomenon is avoided. The change of substances before and after the reaction can be illustrated, and the graphite powder is changed from graphite to the graphene with low layer number. The graphene generation on the surface of the iron base after electromagnetic induction heating is proved. From the ratio I of the 2D peak to the G peak2D/I GSlightly less than 1, the number of layers of the graphene is 2-3, and the existence of a D peak indicates that the graphene has partial defects. As can be seen from the AFM image of fig. 8d, 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 since the surface of the graphene is up-down, it can be concluded that the number of layers of the graphene is 1-2, which is consistent with the above raman characterization.
Example 5:
the quartz glass was cut into a square having a size of 12.5 × 12.5mm, and ultrasonically cleaned with pure water for 30 min. And continuously using alcohol and acetone to respectively perform ultrasonic cleaning for 30min to remove oil stains on the surface. And (3) performing carboxylation treatment on the quartz glass by using the piranha solution to enhance the adsorption force on the surface of the quartz glass.
Weighing 3.0g of graphite powder, measuring 25mL of a Cyrene solution (dihydrovinyl glucosone) by using a measuring cylinder, pouring the graphite powder into the Cyrene solution, treating for 1 hour by using an ultrasonic cleaning machine, treating for 30min by using a high-power ultrasonic probe (duty ratio is 33%), and finally obtaining a black viscous solution. Square quartz glass with the thickness of 1mm and the side length of 12.5mm is placed on a rotary table of a spin coater, vacuum adsorption is carried out, 30 mu L of prepared carbon film slurry is absorbed by a liquid transfer gun and is dripped at the center of the glass. And starting a rotary switch of the spin coater, adjusting the revolution number to 2000r/min, and preparing a uniform carbon film with the thickness of 20-30 mu m on the surface of the glass. And (3) placing the coated glass on a heating plate for 24 hours at the temperature of 80 ℃ to fully volatilize the solvent and completely dry the solvent.
And putting the quartz coated with the carbon film at the bottom of a quartz tube, and connecting the quartz tube with a vacuum system. When the vacuum gauge reading reaches 1x10-4And when the power is below pa, the water-cooling circulator is started, and then the electromagnetic induction heating power supply is started. Heating power sets up to 1kW, and the heat time sets up to 3.2s, presses the switch after setting up, and 3.2s back switch automatic disconnection stops the heating. After the sample was cooled, the iron foil was removed. And (3) putting the iron foil into alcohol, and ultrasonically cleaning for 30min each time for 3 times to remove the residual graphite powder adhered to the surface.
Fig. 9 is a raman image of the surface of the glass substrate after vacuum induction heating of the quartz glass substrate, and it can be seen that peak positions of D, G and 2D peaks thereof are the same as a raman characteristic peak of standard graphene, which proves that graphene is actually generated, and it can be seen that a graphene D peak is lower, which proves that defects of graphene are few. I is2D/I GAnd 1, the graphene is proved to be double-layer graphene.
Example 6:
putting 100X100mm quartz glass into a 5L super large beaker, and ultrasonically cleaning with acetone alcohol for 30min to remove oil stains on the surface. And (3) performing carboxylation treatment on the quartz glass by using the piranha solution to enhance the adsorption force on the surface of the quartz glass.
Weighing 3.0g of graphite powder, measuring 25mL of a Cyrene solution (dihydrovinyl glucosone) by using a measuring cylinder, pouring the graphite powder into the Cyrene solution, firstly treating for 1h by using an ultrasonic cleaning machine, then treating for 30min by using a high-power ultrasonic probe (duty ratio is 33%), and finally obtaining a black viscous solution. And dripping the prepared carbon film slurry onto the surface of the quartz glass, and moving for multiple times from top to bottom in a single direction by using a film scraper until the carbon film slurry on the surface of the quartz glass is uniformly formed. Taking 2 quartz glass sheets with carbon films on the surfaces of 100x100mm, wherein the carbon films face inwards, a graphite sheet with the thickness of 1mm is placed in the middle to form a sandwich structure, and the periphery of the quartz glass is clamped by a clamp.
The sample is placed on the table top of the two-position electric translation stage (see fig. 4), the electric translation stage control software is opened, the running path of the electric translation stage is set, and the schematic route is shown in fig. 10 a. The operation rate of the motor-driven translation stage was set to 20 mm/s. Set up induction heating power and be 3.3kW, press induction heating device switch and heat, open electronic translation platform operation switch simultaneously, treat after electronic translation platform operation, the stop heating. And after cooling the quartz glass, putting the quartz glass into alcohol for ultrasonic cleaning for 3 times, wherein each time is 30min, and removing the residual graphite powder on the surface.
FIG. 10a is a schematic view of the glass substrate heated by induction heating, wherein the glass substrate is moved by the electric translation stage in an "s-shaped" manner for a plurality of times, so that all the carbon film portions are heated by the induction coil; 10b is a heating picture during induction moving heating, and the graphite flake is in a red hot state and is measured to be about 1500 ℃; and 10c is a Raman image of graphene on the surface of the glass substrate, and the characteristic peak of the Raman image is consistent with that of the graphene, so that the generation of the graphene is proved, and the D peak in the spectrum is lower, so that the defect of the graphene is proved to be less. Intensity ratio of 2D peak to G peak I2D/I GSlightly less than 1 proves that the number of layers of the graphene is 2-3. Compared with graphene generated by glass substrate vacuum induction heating, the defect is increased, and the number of layers of the graphene is increased.
Example 7:
iron foil (Alfa Aesar 40493) 100x100mm was placed in a beaker and ultrasonically cleaned with acetone alcohol for 30min to remove oil stains on the surface. Measuring 95mL of alcohol by using a measuring cylinder, pouring the alcohol into a 200mL beaker, sucking 5mL of perchloric acid solution by using a pipette, slowly dripping the perchloric acid solution along the inner wall of the beaker, stirring while dripping, standing the solution after the dripping is finished, and cooling the solution. Selecting a Pt sheet as a cathode to be connected with a direct current power supply cathode, taking an iron foil to be polished as an anode to be connected with a direct current power supply anode, putting the two electrodes into electrolyte to carry out electrochemical polishing, wherein the constant current is 0.05A, and the polishing time is 120 s.
Weighing 3.0g of graphite powder, measuring 25mL of a Cyrene solution (dihydrovinyl glucosone) by using a measuring cylinder, pouring the graphite powder into the Cyrene solution, firstly treating for 1h by using an ultrasonic cleaning machine, then treating for 30min by using a high-power ultrasonic probe (duty ratio is 33%), and finally obtaining a black viscous solution. And dripping the prepared carbon film slurry onto the surface of the iron foil, and moving for many times from top to bottom in a single direction by using a film scraper until the carbon film slurry on two sides of the iron foil is uniformly formed. Two pieces of quartz glass are used for clamping the iron foil in the middle to form a sandwich structure, and the periphery of the quartz glass is clamped by clamps.
The sample is placed on the table top of the two-dimensional electric translation stage (see fig. 4), the electric translation stage control software is opened, the running path of the electric translation stage is set, and the schematic route is shown in fig. 10 a. The operation rate of the motor-driven translation stage was set to 30 mm/s. Set up induction heating power and be 2.0kW, press induction heating device switch and heat, open electronic translation platform operation switch simultaneously, treat after electronic translation platform operation, the stop heating. And after cooling the quartz glass, putting the quartz glass into alcohol for ultrasonic cleaning for 3 times, wherein each time is 30min, and removing the residual graphite powder on the surface.
Fig. 11 is a raman spectrum of the iron substrate surface after induction moving heating, and each peak value of the raman spectrum is consistent with a characteristic peak of a standard graphene raman spectrum, which proves that graphene is generated. And the D peak of the graphene is lower, which proves that the graphene has defects but has less defects. From the intensity ratio I of the 2D peak to the G peak2D/I GSlightly less than 1 may prove that the number of graphene layers is 2-3. Compared with graphene generated by iron substrate vacuum induction heating, the defect is increased, but the number of layers of the graphene is consistent.
Example 8:
a nickel needle is prepared by electrochemical etching with high-purity nickel-kneading wire with diameter of 0.25mm as raw material and KCl solution as electrolyte (as shown in FIG. 12 a). Immersing the nickel needle into 1-butyl-3-methylimidazolium acetate ionic liquid, and heating at 200 ℃ for 35min to carbonize the surface of the nickel needle.
The Ni needle tip was removed, rinsed with copious amounts of water, blown dry with nitrogen, and then inserted into a 0.26mm inside diameter stainless steel barrel welded to a lead (0.5mm) (the surface was treated by spraying gold to reduce microwave loss of the lead and the barrel), and the lead was fixed to a waveguide adapter (fig. 12 b). The adapter is loaded into the vacuum waveguide cavity as shown in fig. 5. Starting a pump set to vacuumize the waveguide to 10-4After Pa, a program-controlled high-voltage power supply is used for controlling a magnetron to generate microwaves with the duration of 1.2 seconds, and the microwaves are not rustedThe steel cylinder and the Ni needle inserted therein instantaneously reached a red hot state as shown in fig. 12 c. And after the sample is cooled, taking out the metal needle tip.
The corresponding transmission electron micrograph and the corresponding Raman spectrum of the quenched nickel needle tip are shown in FIG. 12. The electron microscope photo shows that the nickel needle tip is melted into a sphere after quenching under the condition, but the surface is flat and smooth, and the size is about 60 nm; the raman test results confirmed the presence of the graphene structure.
Example 9
A5 nm thick carbon film and a 25nm thick nickel film were magnetron sputtered successively from the front of an AFM probe (Sunano, NSG10) using a high purity carbon target (99.99%) and a high purity nickel target (99.999%).
And fixing the AFM probe tip plated with the carbon-nickel coating on a lead wire by using a clamping piece, and fixing the lead wire on a waveguide adapter. The adapter is loaded into the vacuum waveguide cavity as shown in fig. 5. Starting a pump set to vacuumize the waveguide to 10-4After Pa, a magnetron is controlled by a program-controlled high-voltage power supply to generate microwaves with the duration of 0.17 second, and the AFM probe fixed at the clamping piece instantly reaches a red hot state. And taking out the sample after the sample is cooled to obtain the graphene modified AFM probe.
Fig. 13 is scanning and transmission electron micrographs corresponding to the quenched graphene functionalized AFM probe and the corresponding raman spectra. Scanning electron microscope photos show that the probe tip is coated by a wrinkled film, and the most pointed end of the needle tip is very clean; the high-resolution transmission image shows that the tip of the needle tip is wrapped by continuous multi-layer graphene, the size of the tip is only about 30nm, and the graphene and the surface of the tip form good interface contact. Raman test results of the tip region of the tip also confirmed the presence of the graphene structure.
Example 10
A carbon film with the thickness of 5nm and a nickel film with the thickness of 25nm are sequentially sputtered on the surface of a silicon wafer with the size of 8 multiplied by 8mm by magnetron sputtering by using a high-purity carbon target (99.99%) and a high-purity nickel target (99.999%).
Fixing the silicon wafer plated with the carbon-nickel coating on a lead wire by using a clamping piece, fixing the lead wire on a waveguide adapter, and installing the adapter into a vacuum waveguide cavity. Starting a pump set to vacuumize the waveguide to 10-4After Pa, a program-controlled high-voltage power supply is utilized to control a magnetron to generate microwaves with the duration of 0.3 second, and the silicon wafer fixed at the clamping piece reaches a red hot state instantly. And taking out the sample after the sample is cooled.
FIG. 14 is a photograph of the instantaneous red heat of a silicon wafer during microwave ultrafast processing and a Raman spectrum after quenching. Raman test results corresponding to different positions of the silicon wafer prove that single-layer and multi-layer graphene structures exist on the silicon wafer in a mixed mode.
The above examples are only for describing the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
The invention provides a method for ultra-fast growing graphene on a large area on the surfaces of a metal plane, a nonmetal plane and a needle point substrate, wherein the metal substrate is preferably Fe, Ni, W and the like, and the nonmetal substrate is preferably glass, silicon nitride, a high polymer material and the like. According to the invention, aiming at the properties of different materials, pulse current, induction current or converged microwave energy and the like are utilized to act on the carbonized substrate material, and a large amount of heat is generated in situ through the current on the surface of the substrate, so that the instant quenching of the material is realized, and continuous single-layer or multi-layer graphene in a large range is generated on the surface of the material. The invention provides an ultrafast synthesis method for realizing graphene functionalization on the surfaces of different materials, which can grow graphene with good interface contact on the surface of a material (such as a flexible high polymer material and a needle tip) which cannot bear high temperature for a long time; the method provided by the invention is not limited by the size of the vacuum tube furnace, and the growth of graphene on a large-size substrate material is realized. The graphene growth method provided by the invention has the characteristics of wide application range of materials (types and sizes) and environments (vacuum, inert atmosphere or atmosphere), rapidness, low energy consumption and the like.
Claims (10)
- A method for ultra-fast growth of graphene is characterized by comprising the following steps:1) carbonizing the substrate material to form a carbon layer or a metallized carbon layer on the surface;2) quenching the carbonized substrate material; the quenching treatment is specifically to raise the temperature of the substrate material to 500-; the temperature rise time of the quenching treatment is 1 us-10 s.
- The method of claim 1, wherein the base material is a metallic, non-metallic planar or needle-tip material; preferably, the metal material is Fe, Ni or W, and the non-metal substrate is glass, silicon nitride or a polymer material.
- The method according to claim 1 or 2, wherein in step 2), the quenching process is performed by a pulse current quenching method, a bulk induction current quenching method, a moving induction current quenching method, or a focused microwave energy quenching method.
- The method of claim 3, wherein the pulsed current quenching method comprises the steps of: and applying pulse current to two ends of the carbonized substrate to enable the substrate to quickly reach a red hot state and then naturally cool.
- The method of claim 4, wherein the pulse width of the pulse current is in the range of 1us to 10s and the current magnitude is in the range of 1 to 50A.
- The method of claim 3, wherein the bulk induction quenching process comprises the steps of: and placing the carbonized substrate in a quartz tube, placing the quartz tube in a copper induction coil, starting electromagnetic induction to excite eddy current in a surface conductive layer of the substrate to generate self-heating to a red hot state, and naturally cooling the sample after heating.
- The method according to claim 6, wherein the electromagnetic induction power supply outputs a power of 0.1kW to 10kW and the heating time is 0.1 to 10 s.
- The method of claim 3, wherein the moving induction current quenching method comprises the steps of: placing the carbonized substrate on a two-dimensional electric translation table, arranging an electromagnetic induction copper ring 5-10 mm above the substrate, starting the electric translation table and the electromagnetic induction copper ring, driving the substrate to move by the electric translation table, and heating the substrate below the electromagnetic induction copper ring to a red hot state; the substrate is then moved out of the copper coil induction range to allow the substrate to cool.
- The method of claim 3 wherein the focused microwave energy quenching comprises the steps of: microwave energy is converged on the carbonized substrate, so that the substrate generates instantaneous high temperature to reach a red hot state, and then the substrate is naturally cooled.
- A graphene product prepared according to the method of any one of claims 1-9.
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| PCT/CN2020/086682 WO2021212469A1 (en) | 2020-04-24 | 2020-04-24 | Method for ultra-fast growth of graphene |
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| CN115650600A (en) * | 2022-10-14 | 2023-01-31 | 国家纳米科学中心 | Graphene glass and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114620716A (en) * | 2022-03-25 | 2022-06-14 | 西南交通大学 | Fluorinated graphene and preparation method and application thereof |
| CN114620716B (en) * | 2022-03-25 | 2023-02-28 | 西南交通大学 | Fluorinated graphene and preparation method and application thereof |
| CN115385328A (en) * | 2022-09-22 | 2022-11-25 | 北京石墨烯技术研究院有限公司 | Graphene composite material and preparation method and application thereof |
| CN115385328B (en) * | 2022-09-22 | 2023-10-17 | 北京石墨烯技术研究院有限公司 | Graphene composite material and preparation method and application thereof |
| CN115650600A (en) * | 2022-10-14 | 2023-01-31 | 国家纳米科学中心 | Graphene glass and preparation method thereof |
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