CN113840801B - Method for ultra-fast growth of graphene - Google Patents
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The invention provides a method for growing graphene on a metal substrate, a nonmetal plane and a needle tip substrate surface in a large area in an ultrafast manner, 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. Aiming at the properties of different materials, the invention utilizes pulse current, induced current or converged microwave energy and the like to act on the carbonized substrate material, generates a large amount of heat in situ through the current on the surface of the substrate, realizes the instant quenching of the material and further generates a large-range continuous single-layer or multi-layer graphene on the surface of the material. According to the method disclosed by the invention, the graphene with good interface contact can be grown on the surface of a material which does not resist long-time high temperature; the method provided by the invention is not limited by the size of the vacuum tube furnace, and can realize the growth of graphene on a large-size substrate material. 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
Technical Field
The invention belongs to the field of material surface functionalization, and particularly relates to a method for ultra-fast growth of graphene in a large area range of metal, nonmetal planes and the surface of a needle point substrate.
Background
Graphene is a two-dimensional net-shaped material formed by stacking single-layer carbon atoms in a honeycomb-like configuration plane, has excellent physical properties such as optics, electricity, heat, mechanics and the like, and unique chemical properties, and can be applied to the fields such as multifunctional composite materials, organic optoelectronic materials, hydrogen storage materials, supercapacitors, microelectronic devices and the like. Graphene has attracted considerable attention from researchers in recent years. The controllable preparation of high-quality large-area graphene is a prerequisite for application, and expanding the preparation method of graphene to meet the application requirements of different fields is a primary problem to be solved in the research of the fields. The main methods for preparing the 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 (Chemical vapor deposition, CVD) method generally uses a specific gaseous carbon source, grows on a metal substrate (Ni or Cu) in a suitable atmosphere, and obtains graphene with high quality by controlling conditions such as temperature gradient, gas flow rate, etc.
At present, the realization of graphene functionalization on the surface of a target material mainly comprises a graphene transfer method and a CVD direct growth method. Since CVD grown graphene typically uses an alloy substrate of single crystal Cu, ni, or both, the synthesized graphene is re-transferred to the target material, defects and contaminants of the graphene are easily caused during transfer, and interface contact between the graphene and the target is not controllable; in addition, the CVD method is limited by a furnace body, so that larger-size graphene cannot be obtained, and meanwhile, the defects of long high-temperature growth time and high energy consumption exist.
Glass substrate growth of graphene is one of the hot spots of research in the field of graphene growth today. 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 electrical conductivity, thermal conductivity and wettability of liquid. Therefore, the graphene glass can keep the transparency of the graphene glass and has excellent electric conduction, thermal conduction and high hydrophobicity, and is hopeful to be a new material for replacing common glass. In order to completely replace common glass with graphene glass, the problem of large-scale production of the graphene glass needs to be solved, and the graphene glass is prepared in a laboratory at present mainly by two methods, namely a transfer method, a method of using graphene slurry to coat a liquid phase on the surface of the glass or a method of using a CVD method to prepare the graphene glass on a metal substrate and then transferring the graphene glass to the surface of the glass, and a method of using the CVD method to directly grow graphene on the surface of the glass. As described above, the graphene prepared by the first transfer method has small size, many defects, pollution and other problems in the transfer process, so that 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, so that the graphene glass with larger size cannot be prepared.
In addition, the CVD direct growth method is also unsuitable for growing graphene on the surface of materials (e.g., polymer materials, nanotip tips, etc.) that cannot withstand high temperatures for a long period of time. The graphene flexible polymer material has special electrical and mechanical properties and has unique application prospects in the fields of flexible display screens, intelligent sensors and the like. However, since the substrate material cannot withstand high temperatures for a long time, graphene functionalization of the flexible material is currently mainly prepared by a physical coating method. Detection H was made by inkjet printing of a rGO solution of Dua and Ruoff et al chemically reduced graphene oxide flakes (rGO) on polyethylene terephthalate (PET) film 2 An atmosphere sensor. However, the rGO solution sprayed graphene has more defects in the sheet, and has larger electric shock resistance between sheets, so that the application of the rGO solution sprayed graphene in a sensor is limited. Bae et al make G/PEF displays by wet transfer of high quality graphene produced on a metal substrate by CVD to PET, but the transfer process typically causes breakage of the graphene and brings about some unavoidable organic impurities. On the other hand, the graphene functionalized nano needle tip has enhanced electrical and mechanical properties, and has outstanding application in the fields of scanning probe imaging, nano electrical measurement, sensors and the like And (3) prospect. Currently, studies on graphene-modified nanotips can be classified into a graphene transfer method and a direct CVD growth method. Duan et al reported that fabricating graphene functionalized Atomic Force Microscope (AFM) tips by growing graphene on copper foil and transferring it to a commercial AFM probe tip, exhibited higher conductivity and lifetime; however, the transfer process of the graphene is uncontrollable, and the acting force between the transferred graphene and the AFM probe body is small and the adhesion is not tight. Martin-Olmos et al formed a pyramid-shaped groove array on the surface of a silicon wafer using a semiconductor processing technique and plated a layer of copper on the surface, and grown a continuous graphene layer on the copper coating (including in the pyramid-shaped grooves) by CVD; and further spin coating a matrix material SU-8 on the graphene layer to obtain the graphene-functionalized AFM probe. However, during CVD growth, the tips of the pyramid shaped grooves are passivated due to the high temperature for a long time, resulting in a final AFM probe tip size of greater than 1um, resulting in reduced spatial resolution of the AFM probe. In summary, the physical adsorption method is not controllable and cannot ensure good contact between the surface of the tip and the graphene layer, whereas the CVD method causes the nano-size damage of the probe tip due to the long-time high-temperature environment required for growth.
In summary, the current methods for implementing graphene functionalization on the surface of the material mainly include a transfer method and a CVD direct growth method. The transfer method is easy to cause 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 prevents the mass production and application expansion of graphene functionalized products. In addition to the above method, xiong et al report a method of generating a graphene pattern on the surface of an insulating base material such as glass or Si sheet using a micro-nano laser direct writing device. In the method, laser spots are focused on the surface of the substrate to heat the irradiation area of the surface of the substrate to reach the growth temperature and conditions 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 limitations of complex equipment, the laser spot size used in the method is very small (about 800 nm), and only graphene growth in a small range (micron level) can be realized, but rapid growth of large-area graphene on the surface of a macroscopic substrate cannot be realized. Aiming at the problems, the invention provides a novel ultra-fast graphene growth method, which adopts pulse current, induced current or convergent microwave energy and the like to act on carbonized substrate materials, generates a large amount of heat in situ through the current on the surface of the substrate, realizes the instant quenching of the materials and further generates a large-scale continuous single-layer or multi-layer graphene on the surface of the materials (as shown in figure 1). The ultra-fast growth method provided by the invention can realize the growth of graphene on a large-size substrate material without being limited by the size of a vacuum tube furnace, and 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.
Reference is made to:
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 functional material is overlong in time, high in energy consumption and incapable of growing in a large area, 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 growing graphene, comprising the steps of:
1) Carbonizing a base 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 500-2000 ℃ and then immediately cool; the temperature rise time of the quenching treatment is 1 us-10 s.
According to the invention, the substrate is enabled to reach the high temperature for proper graphene growth 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 prior to the carbonization treatment.
Wherein, the substrate material in the step 1) comprises common metal, nonmetal plane and needle point materials, preferably, the metal materials are Fe, ni, W and the like, and the nonmetal substrate is preferably glass, silicon nitride, high polymer materials and the like.
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 base material in step 1) is accomplished by one or several 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 form a film uniformly on the surface of the substrate, and then heating the substrate with the film formed on the surface to completely volatilize the solvent to obtain a continuous carbon film; preferably, the thickness of the continuous carbon film is 1 to 100um.
Preferably, the high temperature carbonization method comprises the steps of: dripping PMMA glacial acetic acid solution on the substrate, uniformly sizing to obtain a PMMA film, and heating the substrate with the PMMA film on the surface to 350-400 ℃ to obtain a surface carbonization-treated substrate; preferably, the PMMA film has a thickness of 10nm to 100. Mu.m.
Preferably, the vacuum evaporation method comprises the steps of: fixing a substrate in a vacuum cavity, and then, heating a carbon rod by current or bombarding a target material by using high-energy ions so as 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 1um.
Wherein the quenching treatment in step 2) is performed in a vacuum, inert atmosphere or an atmospheric environment.
Wherein, in the step 2), the quenching treatment is completed by a pulse current quenching method, an induced current quenching method or a focused microwave energy quenching method.
Preferably, the pulse current quenching method comprises the following steps: and placing the carbonized substrate in a vacuum cavity, applying pulse current to two ends of the conductive substrate in a vacuum or inert atmosphere environment, and naturally cooling the substrate after the substrate rapidly reaches a red-hot state. Preferably, the pulse width of the pulse current ranges from 1us to 10s, and the current size ranges from 1 to 50A.
Preferably, the induction current quenching method includes a bulk induction heating method and a mobile induction heating method.
Preferably, the overall induced 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 currents in a surface conductive layer of the substrate to generate self-heating to a red-hot state, and naturally cooling a sample after heating is completed. Preferably, the output power of the electromagnetic induction power supply is 0.1kW-10kW, and the heating time is 0.1-10s.
Preferably, the mobile induction current quenching method comprises the following steps: placing the carbonized substrate on a two-dimensional electric translation table, setting an electromagnetic induction copper ring at a position 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 area is then moved out of the copper coil induction range to cool it.
Preferably, the converging microwave energy quench comprises the steps of: and converging microwave energy on the carbonized substrate to enable the substrate to generate instant high temperature to reach a red-hot state, and then naturally cooling.
In one specific embodiment of the invention, the method for growing graphene ultrafast 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) In vacuum, inert atmosphere or atmosphere, pulse current, induced current or convergent microwave energy is utilized to act on the whole or partial area of the carbonized material, so that the temperature of the substrate is instantaneously raised to 500-2000 ℃ and rapidly cooled, thereby realizing the functionalization of graphene on the surface of the material. The temperature rise time of the single quenching process is 1 us-10 s.
In a preferred embodiment of the present invention, the carbon powder slurry coating method comprises the steps of: carbon powder is added into Cyrene solvent (dihydro vinyl glucose ketone), and ultrasonic treatment is carried out for 1h and 30min (duty ratio is 33%) by using an ultrasonic cleaner and a probe in sequence, so that black sticky solution is obtained. And (3) dripping the prepared carbon powder slurry on the surface of the substrate, and treating by using a spin coater or a film scraping device until the carbon powder slurry is uniformly formed on the surface of the substrate. And (3) placing the spin-coated substrate on a heating plate at 80 ℃ for 24 hours until the solvent is completely volatilized, and obtaining 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 PMMA (polymethyl methacrylate) glacial acetic acid solution, placing a clean substrate on a spin stand of a spin coater, dripping 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 preserving heat for 2 hours at 350-400 ℃ to obtain the substrate with the carbonized surface, 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 reaches the requirement, a carbon rod (direct current evaporation equipment) is heated by current or a high-energy ion is utilized to bombard a target material (magnetron sputtering equipment), 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, applying a voltage pulse (shown in figure 2 a) at two ends of the substrate, allowing 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 of the pulse current ranges from 1us to 10s, and the current size ranges from 1A to 50A. The current passes through the conductive substrate or surface coating to generate a significant amount of joule heat to rapidly reach the red-hot state on the substrate or surface. The magnitude and duration of the current passed is closely related to the resistivity and dimensional specification of the base material. When the resistivity of the used 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 used metal material is smaller, the thickness and width are larger, and the length is smaller, the current is correspondingly larger, and the duration is correspondingly longer.
In another preferred embodiment of the present invention, the quenching is accomplished using induction current quenching, which is classified into a bulk induction heating and a moving induction heating method.
In still another preferred embodiment of the present invention, if a bulk induction method is used, a metal substrate having a carbon layer on the surface or a non-metal substrate having a metal/carbon composite layer on the surface is placed in a quartz tube; the quartz tube was placed in a copper induction coil of an electromagnetic induction power supply device (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 heating time of the electromagnetic induction power supply, wherein the power range is 0.1kW-6kW, the heating time is 0.1-10s, starting the electromagnetic induction power supply, exciting eddy currents in the surface conductive layer of the metal substrate surface layer or the non-metal substrate surface conductive layer to generate 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 of the substrate and the size of the substrate.
In a further preferred embodiment of the invention, if a mobile induction method is used, the metal substrate with the carbon layer on the surface is clamped between two clean and flat glass sheets, and four corners of the glass sheets are clamped; or two nonmetallic substrates with the same size are clamped by a graphite sheet with the same size and the same thickness as 1mm to form a sandwich structure, and four corners of the substrates are clamped. The sample is placed on a sample seat of a two-dimensional electric translation table, an electromagnetic induction copper ring is positioned at a position 5-10 mm above the sample (as shown in figure 4), and the whole device is positioned in the atmosphere. And setting the running path and running speed of the electric translation stage by using electric translation stage control software, wherein the speed range is 10-40mm/s, and the output power range of the electromagnetic induction power supply is 0.5-6kW. After the electromagnetic induction power supply is started, the electric translation stage is started to drive the sample to move along a set path, and under the optimized condition, the sample area below the electromagnetic induction copper ring is rapidly heated to a red-hot state; the sample area is rapidly cooled after it moves out of the copper coil sensing range.
In yet another preferred embodiment of the present invention, the preferred scheme for quenching using focused 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 (SanxingOM 74P,1000W,2450 MHz), a circulator, a load and a stainless steel vacuum waveguide cavity (BJ 22 type). Microwave generated by the magnetron enters the waveguide cavity through the circulator and is stabilized to be in a standing wave state, and a maximum point of electric field intensity appears at 1/4 wavelength on the central line of the broad surface of the waveguide cavity to form a microwave energy hot spot. Inserting a metal guide wire at the maximum electric field intensity point, and feeding the converged microwave energy into the guide wire. And fixing the substrate with the carbon layer or the metal/carbon composite layer on the surface on the metal guide wire. The waveguide cavity is vacuumized or replaced by an inert atmosphere environment, a program-controlled high-voltage pulse power supply is used for controlling a magnetron to generate wave numbers to accurately control microwave output time, under the condition of the invention, the loss of converged microwave energy accurately occurs at a metal sample or a surface coating thereof, the microwave energy is converted into a large amount of heat energy, the surface of the sample is enabled to generate instant high temperature to reach a red-hot state, and then natural cooling is carried out. The temperature rise time of the single quenching is in the range of 0.001 to 10 seconds. The guide wire is made of metal, such as Ni, W, fe, stainless steel wire and the like, and has a diameter of 0.2-5mm. Wherein different positions of the guide wire may be welded with clips or other holders adapted to the shape of the sample to secure the sample. The microwave output time is related to the size of the guide wire, the material and the size of the substrate, etc.
The ultra-fast graphene growth method provided by the invention has the following beneficial effects.
Under the method and the condition, the eddy current excited by pulse current and electromagnetic induction and the converged microwave energy directly act on the metal substrate or the coating on the surface of the substrate, a great amount of heat is generated in situ to rapidly heat the surface of the substrate to high temperature (500-2000 ℃) at a great heating rate (which can be more than 1000 ℃/s), then the substrate is rapidly and naturally cooled, and the heating time in the whole single quenching process time is 1 us-10 s. In the ultra-fast quenching process, a carbon layer on the surface of a substrate permeates into a metal substrate or a metal coating on the surface of the substrate at a high temperature, the substrate is rapidly cooled, and the permeated carbon is separated out 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 for heating a sample stage (such as a tungsten boat and the like) and then heat energy is conducted to the sample to heat the sample, so that the temperature of the sample is increased and decreased (Piner R, li H, kong X, et al ACS Nano,2013,7 (9): 7495). In the microwave-assisted CVD process, microwaves form a uniform microwave field by continuous reflection in a multi-cavity upstream of a CVD tube furnace to cleave a carbon source precursor, without directly acting on a growth substrate of graphene, which is still heated by An electric furnace and then raised and maintained at a high temperature suitable for growth of graphene by means of thermal conduction (Li x.s., cai w., an j.et al science,2009,324 (5932):1312).
The ultra-fast graphene method provided by the invention directly heats the substrate by utilizing the eddy current excited by pulse current and electromagnetic induction and the microwave alternating electromagnetic field, and completes the graphene growth on the surface of the substrate in an extremely short time. The method ensures that large-area graphene is generated on the surface of the substrate, simultaneously avoids the damage of high temperature to the substrate such as melting, oxidation and the like, expands the types of graphene functionalized substrate materials, ensures that the substrate size is not limited by the size of a tube furnace, and can be used for rapid graphene functionalization of large-size substrate materials; meanwhile, the production speed can be effectively increased, and the energy consumption and the cost are reduced.
Drawings
Fig. 1 is a schematic diagram of an ultrafast graphene growth method of the present invention. A large amount of heat is generated by electromagnetic energy on the surface of the substrate material, so that the rapid quenching of the surface of the substrate is realized, and a large-range continuous graphene is generated on the surface of the material.
FIG. 2a is a schematic diagram of an apparatus for holding a substrate during a sample transient high temperature quench treatment with pulsed current; FIG. 2b is a single pulse recorded by an oscilloscope with a set current being passed through the sample for heating; 2c, 2d and 2e are a series of photographs of red heat on the surface of the silicon wafer subjected to instantaneous high-temperature quenching; the left arrow is a series of photographs of the surface of the instantaneously high-temperature quenched silicon wafer.
Fig. 3 is a schematic diagram of an induction heating apparatus. Wherein a is a schematic diagram of vacuum equipment; b is a schematic diagram of an induction coil and a quartz tube; and c is a schematic diagram of the whole experimental device (the water taking and temperature measuring device is not cooled).
FIG. 4 is a schematic diagram of a moving induction heating apparatus for glass substrates, wherein a is a schematic diagram of a moving induction heating section experimental apparatus; b is a schematic diagram of an induction coil and 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 to a circulator), a three-port circulator (only allowing microwave to extend from the excitation cavity to the waveguide to carry out unidirectional transmission for protecting the magnetron), a waveguide (for intensively confining microwaves in a space as a sample quenching cabin), a load (for consuming excessive microwave energy), a pump unit (a combined pump unit of a mechanical pump and a molecular pump for providing a vacuum environment for the waveguide), and a viewing 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 held within a vacuum chamber during an instantaneous high temperature quenching process using a pulsed current; FIG. 6b is a series of Raman spectra corresponding to graphene grown at different positions (8 points dispersed) on a silicon wafer after quenching; FIG. 6c is a photograph of a sample stage with a glass substrate held 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 (13 points dispersed) on a silicon wafer after quenching.
FIG. 7a is a photograph of a sample stage with a flexible substrate PDMS fixed in a vacuum chamber during a transient high temperature quenching process using a pulsed current; fig. 7b is a series of raman spectra corresponding to graphene grown at different positions (4 points dispersed) 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-plated iron substrate before and after quenching; b is a photograph of instant red heat of the iron matrix under the electromagnetic induction effect; d is 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 a raman spectrum after vacuum induction quenching.
FIG. 10 is an image of a glass substrate moving induction heating experiment, wherein a is a schematic diagram of a moving path of an electric translation stage in the moving induction heating experiment; b is a state of local red heat in the moving induction heating process of the glass substrate; and c, carrying out mobile induction heating on the graphene Raman spectrum on the surface of the glass substrate.
Fig. 11 is a photograph of a carbon-iron plated substrate and a raman spectrum after mobile induction heating.
FIG. 12a is a transmission electron microscope image of a nickel needle with tip dimensions less than 50nm; FIG. 12b shows a nickel needle sample mounting and fixing mode, wherein a gold-plated metal lead wire welded with a gold-plated stainless steel tube (with an inner diameter of 0.26 mm) is fixed on an adapter, and a nickel needle is inserted into the stainless steel tube for fixing; FIG. 12c is a photograph of a nickel needle red heat at the moment of microwave quenching; FIG. 12d is a transmission electron micrograph of a nickel needle coated with graphene prepared by microwave instantaneous high-temperature quenching, wherein the tip size of the needle tip is still kept around 100 nm; FIG. 12e is a Raman spectrum of a nickel tip after quenching, showing the presence of a probe at 1350cm -1 、1580cm -1 And 2700cm -1 A nearby graphene characteristic peak, located at 1350cm -1 The nearby D peak comes from a defect in graphene, and is located at 1600cm -1 The sharp G peak in the vicinity indicates a higher crystallinity, while at 2700cm -1 The intensity of the nearby 2D peak relative to the G peak is low, and the half-width is larger than 50cm -1 Is in accordance with the characteristics of the multilayer graphene.
FIG. 13a is a scanning electron microscope photograph corresponding to a typical graphene-modified AFM probe prepared by microwave transient Gao Wencui pyrogenicity, with a clean and sharp tip; FIG. 13b is a transmission electron microscope photograph corresponding to a graphene-modified AFM probe, wherein about 7 and 8 layers of continuous multi-layer graphene along the outline of the needle tip are arranged at the red line mark, the tip size is only about 30nm, and good interface contact is formed between the graphene and the tip surface; FIG. 13c is a red thermal photograph of a microwave high temperature quenching instant AFM probe; fig. 13D shows a raman spectrum corresponding to the graphene-modified AFM probe, and the D peak, G peak, and 2D peak of the graphene characteristic confirm the presence of graphene.
FIG. 14 is a red-thermal photograph of a sample of a silicon wafer at the instant of microwave high-temperature quenching and a Raman spectrum measured after quenching, respectively at 1350cm -1 、1580cm -1 And 2700cm -1 Characteristic D peak, G peak and 2D of graphene appear nearby, and the relative intensities of the peaks of Raman signals measured at different positions on the silicon wafer are different, which indicates that the silicon wafer is coated by single-layer and multi-layer graphene.
Detailed Description
Exemplary embodiments of the present invention are provided in the following examples. The following examples are given by way of illustration only and are intended 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
And (3) ultrasonically treating the silicon wafer cut into 10 multiplied by 10mm by using a large amount of alcohol, acetone and water, flushing with a large amount of water and drying with nitrogen. The silicon wafer is subjected to magnetron sputtering to sequentially generate a 5nm carbon layer (the purity of a magnetron sputtering carbon target is 99.99%) and a 30nm nickel layer (the purity of a magnetron sputtering nickel target is 99.999%) on the surface. Or by a magnetron sputtering method, a 30nm nickel carbide layer is generated on the surface (the purity of the magnetron sputtering nickel carbide target is 99.99%).
Fixing the silicon chip plated with the film in the middle of a metal Cu electrode (shown in a schematic diagram of figure 2 a) with the length of 30mm multiplied by the width of 1mm multiplied by the thickness of 0.1mm, and fixing the two ends of the silicon chip on a ceramic base by nuts or dovetail clamps respectively to prevent the surface of the silicon chip from being damaged in the fixing process; the Cu electrode is connected with an external power supply through a vacuum electrode flange. Vacuum pumping the cavity to 10 by using molecular pump -5 Pa. The substrate Si sheet instantaneously reaches a red-hot state by outputting an instantaneous current of 10A for 2 seconds using a dc power supply (see fig. 2c, d, e). And taking out the Si sheet after the sample is cooled.
Fig. 6a is a photograph of a real object of the Si substrate fixed in the vacuum chamber. Carrying out Raman characterization on the quenched Si sheet, wherein FIG. 6b is a graphene Raman spectrum under 514nm laser excitation; it was found that the length of the membrane was 1580cm -1 Near the G peak and at 2675cm -1 2D peak to high wavenumber shift of (2D)，I 2D /I G The peaks at the positions of approximately 1 and 2D have obvious peak separation phenomenon, and the number of the generated graphene layers is proved to be double-layer, wherein the D peak is lower, and the defect of graphene is proved to be less; based on the existing microscopic observation conditions, the majority of areas on the surface of the Si sheet generate double-layer continuous graphene, and the coverage rate reaches 75% -100%.
Example 2:
the glass sheet cut into 10X 10mm is treated by ultrasonic treatment with a large amount of alcohol, acetone and water, then rinsed with a large amount of water and dried by nitrogen. The glass substrate is subjected to magnetron sputtering to sequentially generate a 5nm carbon layer (the purity of a magnetron sputtering carbon target is 99.99%) and a 30nm nickel layer (the purity of a magnetron sputtering nickel target is 99.999%) on the surface. Or by a magnetron sputtering method, a 30nm nickel carbide layer is generated on the surface (the purity of the magnetron sputtering nickel carbide target is 99.99%).
Fixing the glass substrate plated with the film in the middle of a metal Cu electrode (shown in a schematic diagram of figure 2 a) with the length of 30mm multiplied by the width of 1mm multiplied by the thickness of 0.1mm, and fixing the two ends of the metal Cu electrode 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; the Cu electrode is connected with an external power supply through a vacuum electrode flange, and a physical photo of the glass substrate in the vacuum cavity is shown in FIG. 6 c. Vacuum pumping the cavity to 10 by using molecular pump -5 Pa. The glass substrate instantaneously reaches a red-hot state (see fig. 2c, d, e) by outputting an instantaneous current of 10A for 2 seconds using a dc power supply. After the sample cooled, the glass substrate was removed.
The quenched glass substrate was subjected to Raman characterization, and the Raman spectrum of FIG. 6d was found to be 1582cm under excitation by 514nm laser -1 Near the G peak and at 2680cm -1 Is shifted to Gao Boshu by graphene of 2D peak of (2D), I 2D /I G The peaks at the positions of approximately 1 and 2D have obvious peak separation phenomenon, and the number of the generated graphene layers is proved to be double-layer, wherein the D peak is lower, and the defect of graphene is proved to be less; based on the existing microscopic observation conditions, the majority of areas on the surface of the glass substrate generate double-layer continuous graphene, and the coverage rate reaches 75% -100%.
Example 3:
and uniformly mixing polydimethylsiloxane (PDMS, dakangning) reagent A and B according to the proportion of 1:10, removing bubbles, preparing a flexible material PDMS film with the thickness of 0.45mm, and cutting the film into PDMS sheets with the thickness of 10 multiplied by 10mm after the film is dried.
The above clean PDMS sheet was adsorbed onto a 10×10mm slide. The glass substrate is subjected to magnetron sputtering to sequentially generate a 5nm carbon layer (the purity of a magnetron sputtering carbon target is 99.99%) and a 30nm nickel layer (the purity of a magnetron sputtering nickel target is 99.999%) on the surface. Or by a magnetron sputtering method, a 30nm nickel carbide layer is generated on the surface (the purity of the magnetron sputtering nickel carbide target is 99.99%).
Fixing the PDMS sheet and glass slide with the plated film in the middle of a metal Cu electrode (shown in the schematic diagram of figure 2 a) with the length of 30mm multiplied by the width of 1mm multiplied by the thickness of 0.1mm, and fixing the two ends of the metal Cu electrode on a ceramic base by nuts or dovetail clamps respectively to prevent the surface of the silicon sheet from being damaged in the fixing process; the Cu electrode is connected with an external power supply through a vacuum electrode flange, and a physical photo of the PDMS substrate in the vacuum cavity is shown in FIG. 7 a. Vacuum pumping the cavity to 10 by using molecular pump -5 Pa. And outputting an instant current with the size of 10A and the duration of 2 seconds by using a direct current power supply, wherein the PDMS substrate instantly reaches a red-hot state. After the sample cooled, the PDMS substrate was removed.
The quenched PDMS substrate was subjected to Raman characterization, and the Raman spectrum of FIG. 7b was found to be 1582cm under 514nm laser excitation -1 The G peak near the graphene layer shifts to a high wave number, and the peak at the D position has obvious peak separation phenomenon, so that the generated graphene layer has multiple layers and more defects; based on the existing microscopic observation conditions, the majority of areas on the surface of the PDMS substrate generate multilayer graphene, and the coverage rate reaches 75% -100%.
Example 4:
the iron foil (Alfa Aesar 40493) was cut into squares of 12.5x12.5 mm size and cleaned by pure water ultrasound for 30min. And continuously using alcohol and acetone to ultrasonically clean for 30min respectively, and removing greasy dirt on the surface. The measuring cylinder is used for measuring 95mL of alcohol, the alcohol is poured into a 200mL beaker, 5mL of perchloric acid solution is sucked by a pipette and slowly dripped along the inner wall of the beaker, the solution is placed still after the dripping is completed while the dripping is stirred, and the solution is cooled. The Pt sheet is selected as a cathode to be connected with a negative electrode of a direct current power supply, the iron foil to be polished is used as an anode to be connected with a positive electrode of the direct current power supply, and the two electrodes are put into electrolyte to be subjected to electrochemical polishing, wherein the constant current is 0.05A, and the polishing time is 120s.
3.0g of graphite powder is weighed, 25mL of Cyrene solution (dihydrovinyl glucose ketone) is measured by a measuring cylinder, the graphite powder is poured into the Cyrene solution, the graphite powder is firstly treated by an ultrasonic cleaner for 1h, then is treated by a high-power ultrasonic probe for 30min (duty ratio is 33%), and finally, a black viscous solution is obtained. Square iron foil with the thickness of 0.1mm and the side length of 12.5mm is placed on a spin stand of a spin coater, vacuum adsorption is carried out, 30 mu L of carbon film slurry prepared before is sucked by a pipetting gun, and the carbon film slurry is dripped at the center of the iron foil. Turning on a spin switch of a spin coater, regulating the revolution to 2000r/min, and preparing a layer of uniform carbon film with the thickness of 20-30 mu m on the surface of the iron foil. And placing the coated iron sheet on a heating plate for 24 hours, setting the temperature to 80 ℃ to fully volatilize the solvent and completely dry the solvent.
An iron foil coated with a carbon film was placed on the bottom of a quartz tube connected to a vacuum system (see fig. 3). When the vacuum gauge indication number reaches 1x10 -4 And when pa is less than or equal to pa, the water cooling circulation machine is started first, and then the electromagnetic induction heating power supply is started. The heating power is set to be 0.5kW, the heating time is set to be 2.9s, the switch is pressed down after the setting, and the switch is automatically disconnected after 2.9s, so that the heating is stopped. After the sample cooled, the iron foil was removed. And (3) placing the iron foil into alcohol for ultrasonic cleaning for 3 times, each time for 30 minutes, and removing graphite powder adhered on the surface.
FIG. 8a shows characteristic peaks of Raman spectrum of graphite powder before induction heating, FIG. 8c shows characteristic peaks of graphene after reaction, and comparison shows that the ratio I of 2D peak intensity to G peak intensity before and after reaction 2D /I G And the two peaks are increased, the 2D peak position is shifted leftwards, and no peak separation phenomenon exists. It can be shown that the substances are changed before and after the reaction, and the graphite powder is changed into graphene with a low layer number from graphite. It is proved that graphene is generated on the surface of the iron-based substrate after electromagnetic induction heating. From the ratio I of 2D peak to G peak 2D /I G Slightly less than 1, the number of layers of graphene can be seen to be 2-3, and the presence of the D peak indicates that the graphene has a partial defect. As can be seen from the AFM image of FIG. 8d, the thickness of graphene grown on the surface of the iron substrate is 0.78nm, while the thickness of single-layer graphene is 0.33nm, but due to grapheneThe surface is up-and-down undulating, so it can be concluded that the number of graphene layers is 1-2, consistent with the raman characterization above.
Example 5:
the quartz glass was cut into squares of 12.5x12.5mm in size and ultrasonically cleaned with pure water for 30min. And continuously using alcohol and acetone to ultrasonically clean for 30min respectively, and removing greasy dirt on the surface. Carboxylation treatment is carried out on the quartz glass by using the piranha solution, so that the adsorption force of the surface of the quartz glass is enhanced.
3.0g of graphite powder is weighed, 25mL of Cyrene solution (dihydrovinyl glucose ketone) is measured by a measuring cylinder, the graphite powder is poured into the Cyrene solution, the graphite powder is firstly treated by an ultrasonic cleaner for 1 hour, then is treated by a high-power ultrasonic probe for 30min (duty ratio is 33%), and finally, a black sticky solution is obtained. Square quartz glass with the thickness of 1mm and the side length of 12.5mm is placed on a spin stand of a spin coater, vacuum adsorption is carried out, a pipetting gun sucks 30 mu L of the previously prepared carbon film slurry, and the slurry is dripped at the center of the glass. Turning on a spin switch of a spin coater, regulating the revolution to 2000r/min, and preparing a layer of uniform carbon film with the thickness of 20-30 mu m on the surface of glass. And placing the coated glass on a heating plate for 24 hours, setting the temperature to 80 ℃ to fully volatilize the solvent and completely dry the solvent.
And placing quartz coated with the carbon film at the bottom of a quartz tube, wherein the quartz tube is connected with a vacuum system. When the vacuum gauge indication number reaches 1x10 -4 And when pa is less than or equal to pa, the water cooling circulation machine is started first, and then the electromagnetic induction heating power supply is started. The heating power is set to be 1kW, the heating time is set to be 3.2s, the switch is pressed down after the setting, and the switch is automatically disconnected after the setting for 3.2s, so that the heating is stopped. After the sample cooled, the iron foil was removed. And (3) placing the iron foil into alcohol for ultrasonic cleaning for 3 times, each time for 30 minutes, and removing graphite powder adhered on 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 shows that the peak positions of D, G and 2D peaks are the same as the raman characteristic peaks of standard graphene, which proves that graphene is indeed generated, and that the graphene D peak is lower, which proves that the defect of graphene is less. I 2D /I G And (3) proving that the graphene is double-layer graphene.
Example 6:
quartz glass of 100×100 mm is placed in a 5L oversized beaker and ultrasonically cleaned with acetone alcohol for 30min to remove surface oil stains. Carboxylation treatment is carried out on the quartz glass by using the piranha solution, so that the adsorption force of the surface of the quartz glass is enhanced.
3.0 g of graphite powder is weighed, 25mL of Cyrene solution (dihydrovinyl glucose ketone) is measured by a measuring cylinder, the graphite powder is poured into the Cyrene solution, the graphite powder is firstly treated by an ultrasonic cleaner for 1h, then is treated by a high-power ultrasonic probe for 30min (duty ratio is 33%), and finally, a black viscous solution is obtained. And (3) dripping the prepared carbon film slurry on the surface of the quartz glass, and repeatedly moving the prepared carbon film slurry from top to bottom by using a film scraping device until the carbon film slurry on the surface of the quartz glass is uniformly formed into a film. 2 quartz glass sheets with 100x100 mm surfaces provided with carbon films are taken, 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 table (see fig. 4), the electric translation table control software is opened, the running path of the electric translation table is set, and the route schematic diagram is shown in fig. 10 a. The running speed of the motorized translation stage was set at 20mm/s. Setting the induction heating power to be 3.3kW, pressing the switch of the induction heating device to heat, starting the operation switch of the electric translation stage, and stopping heating after the operation of the electric translation stage is finished. After the quartz glass is cooled, the quartz glass is put into alcohol to be ultrasonically cleaned for 3 times, 30 minutes each time, and the graphite powder remained on the surface is removed.
FIG. 10a illustrates a movement path set by an electric translation stage in an experiment of induction movement of a glass substrate, wherein the movement path is moved back and forth in an s-shape for a plurality of times, so that the carbon film part is heated by an induction coil; 10b is a heating picture in induction mobile heating, and the graphite flake is in a red-hot state, and is measured to be about 1500 ℃;10c is a Raman image of graphene on the surface of the glass substrate, and the characteristic peak of the Raman image accords with the graphene, so that the generation of the graphene is proved, and the D peak in the map is lower, so that the defect of the graphene is proved to be less. Intensity ratio of 2D peak to G peak I 2D /I G A slightly smaller than 1 demonstrates that the number of graphene layers is 2-3. Defect enhancement compared to glass substrate vacuum induction heated graphene The number of layers of graphene increases.
Example 7:
100×100 mm iron foil (Alfa Aesar 40493) was placed in a beaker and ultrasonically cleaned with acetone alcohol for 30min to remove surface oil stains. The measuring cylinder is used for measuring 95mL of alcohol, the alcohol is poured into a 200mL beaker, 5mL of perchloric acid solution is sucked by a pipette and slowly dripped along the inner wall of the beaker, the solution is placed still after the dripping is completed while the dripping is stirred, and the solution is cooled. The Pt sheet is selected as a cathode to be connected with a negative electrode of a direct current power supply, the iron foil to be polished is used as an anode to be connected with a positive electrode of the direct current power supply, and the two electrodes are put into electrolyte to be subjected to electrochemical polishing, wherein the constant current is 0.05A, and the polishing time is 120s.
3.0g of graphite powder is weighed, 25mL of Cyrene solution (dihydrovinyl glucose ketone) is measured by a measuring cylinder, the graphite powder is poured into the Cyrene solution, the graphite powder is firstly treated by an ultrasonic cleaner for 1h, then is treated by a high-power ultrasonic probe for 30min (duty ratio is 33%), and finally, a black viscous solution is obtained. And (3) dripping the prepared carbon film slurry on the surface of the iron foil, and repeatedly moving the prepared carbon film slurry from top to bottom by using a film scraping device until the carbon film slurry on the two sides of the iron foil is uniformly formed into films. And clamping the iron foil by two pieces of quartz glass to form a sandwich structure, and clamping the periphery of the quartz glass by using a clamp.
The sample is placed on the table top of the two-dimensional electric translation table (see fig. 4), the control software of the electric translation table is opened, the running path of the electric translation table is set, and the route schematic diagram is shown in fig. 10 a. The running speed of the motorized translation stage was set at 30mm/s. Setting the induction heating power to be 2.0kW, pressing the switch of the induction heating device to heat, starting the operation switch of the electric translation stage, and stopping heating after the operation of the electric translation stage is finished. After the quartz glass is cooled, the quartz glass is put into alcohol to be ultrasonically cleaned for 3 times, 30 minutes each time, and the graphite powder remained on the surface is removed.
Fig. 11 shows a raman spectrum of the iron-based substrate surface after induction mobile 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 graphene D peak is lower, which proves that the graphene has defects but fewer defects. From the intensity ratio I of 2D peak to G peak 2D /I G A few less than 1 may prove that the number of graphene layers is 2-3. With iron baseCompared with graphene generated by bottom vacuum induction heating, the defects are increased, but the layers of the graphene are consistent.
Example 8:
the nickel needle was prepared by electrochemical corrosion using 0.25mm diameter high purity nickel wire as the starting material and KCl solution as the electrolyte (see fig. 12 a). Immersing the nickel needle into 1-butyl-3-methylimidazole acetate ionic liquid, and heating at 200 ℃ for 35min to carbonize the surface of the nickel needle.
The Ni needle tip was taken out, rinsed with a large amount of water, dried with nitrogen, and then inserted into a stainless steel needle cylinder (the surface of which was subjected to a metal spraying treatment in order to reduce microwave loss of the guide wire and the needle cylinder itself) welded on the guide wire (0.5 mm) and having an inner diameter of 0.26mm, and the guide wire was fixed to the waveguide adapter (FIG. 12 b). The adapter is loaded into the vacuum waveguide cavity as shown in fig. 5. The pump group is started to vacuumize the waveguide to 10 -4 After Pa, the magnetron was controlled to generate microwaves with a duration of 1.2 seconds using a program-controlled high-voltage power supply, and the stainless steel cylinder and the Ni needle inserted therein were instantaneously brought to a red-hot state as shown in fig. 12 c. And taking out the metal needle tip after the sample is cooled.
The corresponding transmission electron microscope photograph after quenching the nickel needle point and the corresponding Raman spectrum are shown in figure 12. Electron microscope pictures show that the nickel needle tip after quenching under the condition is melted into a sphere, but the surface is flat and smooth, and the size is about 60nm; raman test results confirm the presence of graphene structures.
Example 9
A5 nm thick carbon film and a 25nm thick nickel film were sequentially magnetron sputtered on the front of an AFM probe (Sunano, NSG 10) 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 the guide wire by using a clamping piece, and fixing the guide wire on the waveguide adapter. The adapter is loaded into the vacuum waveguide cavity as shown in fig. 5. The pump group is started to vacuumize the waveguide to 10 -4 After Pa, the magnetron is controlled by a program control high-voltage power supply to generate microwaves with the duration of 0.17 seconds, and an AFM probe fixed at the clamping piece instantaneously reaches a red-hot state. And taking out the sample after the sample is cooled, and obtaining the graphene modified AFM probe.
Fig. 13 is a scanning and transmission electron microscope photograph and corresponding raman spectrum corresponding to the quenched graphene functionalized AFM probe. Scanning electron microscope pictures show that the tip of the probe is covered by the wrinkled film, and the most tip of the needle point is quite 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 needle tip also confirm the presence of graphene structures.
Example 10
A layer of carbon film with the thickness of 5nm and a layer of nickel film with the thickness of 25nm are sequentially and magnetically sputtered on the surface of a silicon wafer with the size of 8 multiplied by 8mm by using a high-purity carbon target (99.99%) and a high-purity nickel target (99.999%).
And fixing the silicon chip plated with the carbon-nickel coating on the guide wire by using a clamping piece, fixing the guide wire on a waveguide adapter, and loading the adapter into a vacuum waveguide cavity. The pump group is started to vacuumize the waveguide to 10 -4 After Pa, the magnetron is controlled by a program control high-voltage power supply to generate microwaves with the duration of 0.3 seconds, and the silicon chip fixed at the clamping piece instantaneously reaches a red-hot state. And taking out the sample after the sample is cooled.
Fig. 14 is a photograph of the instant red heat of a silicon wafer and a raman spectrum after quenching during the microwave ultrafast treatment. And the Raman test results corresponding to different positions of the silicon wafer prove that a single-layer graphene structure and a multi-layer graphene structure are mixed on the silicon wafer.
The above examples are only illustrative of 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 by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the design of the present invention.
Claims (5)
1. The method for ultra-fast growth of the graphene is characterized by comprising the following steps of:
1) Carbonizing a base material to form a carbon layer or a metallized carbon layer on the surface; the substrate material is a metal plane or a nonmetal plane;
2) Carbonizing treatmentQuenching the base material; the quenching treatment is specifically to raise the temperature of the base material to 500-2000 deg.f o C, immediately cooling; the temperature rise time of the quenching treatment is 1 us-10 s;
in the step 2), the quenching treatment is finished by a whole induction current quenching method, a mobile induction current quenching method or a converging microwave energy quenching method;
The integral 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, starting electromagnetic induction to excite eddy currents in a surface conducting layer of the substrate to generate self-heating to a red-hot state, and naturally cooling a sample after heating is completed;
the mobile induction current quenching method comprises the following steps: placing the carbonized substrate on a two-dimensional electric translation table, setting an electromagnetic induction copper ring at a position 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 the substrate below the electromagnetic induction copper ring to be heated to a red-hot state; then moving the substrate out of the copper ring induction range to cool the substrate;
the converging microwave energy quenching comprises the following steps: focusing microwave energy on the carbonized substrate to enable the substrate to generate instant high temperature to reach a red-hot state, and then naturally cooling; the device consists of a program-controlled high-voltage pulse power supply, a magnetron, a coaxial line, an excitation cavity, a three-port circulator, a waveguide cavity, a load and a pump set, wherein an observation window and a sample inlet matched with an adapter are arranged at the waveguide cavity.
2. The method of claim 1, wherein the metal is Fe, ni or W and the non-metal is glass, silicon nitride or a polymeric material.
3. The method of claim 1, wherein the electromagnetic induction power source output in the bulk induction current quenching process is 0.1 kW to 10 kW and the heating time is 0.1 to 10 s.
4. The method for ultra-fast growth of the graphene is characterized by comprising the following steps of:
1) Carbonizing a base material to form a carbon layer or a metallized carbon layer on the surface;
the substrate material is a Ni tip, a W tip or a commercial AFM probe;
2) Quenching the carbonized substrate material; the quenching treatment is specifically to raise the temperature of the base material to 500-2000 deg.f o C, immediately cooling; the temperature rise time of the quenching treatment is 1 us-10 s;
in the step 2), the quenching treatment is completed by a converging microwave energy quenching method; the converging microwave energy quenching comprises the following steps: focusing microwave energy on the carbonized substrate to enable the substrate to generate instant high temperature to reach a red-hot state, and then naturally cooling; the device consists of a program-controlled high-voltage pulse power supply, a magnetron, a coaxial line, an excitation cavity, a three-port circulator, a waveguide, a load and a pump set, wherein an observation window and a sample inlet matched with an adapter are arranged at the waveguide.
5. A graphene product prepared by the method of any one of claims 1-4.
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