WO2021212469A1 - Procédé pour la croissance ultra-rapide du graphène - Google Patents

Procédé pour la croissance ultra-rapide du graphène Download PDF

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WO2021212469A1
WO2021212469A1 PCT/CN2020/086682 CN2020086682W WO2021212469A1 WO 2021212469 A1 WO2021212469 A1 WO 2021212469A1 CN 2020086682 W CN2020086682 W CN 2020086682W WO 2021212469 A1 WO2021212469 A1 WO 2021212469A1
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graphene
substrate
quenching
current
metal
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PCT/CN2020/086682
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English (en)
Chinese (zh)
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徐建勋
赵宇亮
梁建波
葛逸飞
王鲁峰
杨宜
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国家纳米科学中心
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Priority to CN202080005008.0A priority Critical patent/CN113840801B/zh
Priority to PCT/CN2020/086682 priority patent/WO2021212469A1/fr
Publication of WO2021212469A1 publication Critical patent/WO2021212469A1/fr

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

Definitions

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

Abstract

La présente invention concerne une classe de procédés pour la croissance ultra-rapide du graphène dans de larges zones sur la surface de plans métalliques et non métalliques ainsi que des substrats ponctuels, les substrats métalliques étant de préférence du Fe, du Ni, du W ou analogues, et les substrats non métalliques étant de préférence du verre, du silicium, du nitrure de silicium, des matériaux polymères ou analogues. La présente invention utilise un courant pulsé, un courant d'induction ou une énergie micro-ondes convergente ou analogues pour agir sur un matériau de substrat carbonisé selon différentes propriétés de matériau, et génère une grande quantité de chaleur in situ au moyen du courant sur la surface du substrat pour obtenir une trempe instantanée du matériau puis générer une large gamme de graphène monocouche ou multicouche continu sur la surface du matériau. Le procédé selon la présente invention permet la croissance du graphène, ayant un bon contact interfacial, sur la surface de matériaux qui ne supportent pas de température élevée pendant une longue période de temps. Le procédé selon la présente invention n'est pas limité par la taille d'un four tubulaire sous vide et permet la croissance du graphène sur des matériaux de substrat de grande taille. Le procédé de croissance du graphène selon la présente invention est caractérisé en ce qu'il présente des avantages tels que le fait de disposer d'une large gamme de matériaux et d'adaptations environnementales, d'être rapide et de présenter une faible consommation d'énergie.
PCT/CN2020/086682 2020-04-24 2020-04-24 Procédé pour la croissance ultra-rapide du graphène WO2021212469A1 (fr)

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