WO2012167738A1 - 一种低成本无损转移石墨烯的方法 - Google Patents

一种低成本无损转移石墨烯的方法 Download PDF

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WO2012167738A1
WO2012167738A1 PCT/CN2012/076622 CN2012076622W WO2012167738A1 WO 2012167738 A1 WO2012167738 A1 WO 2012167738A1 CN 2012076622 W CN2012076622 W CN 2012076622W WO 2012167738 A1 WO2012167738 A1 WO 2012167738A1
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graphene
pmma
transfer
transfer medium
platinum foil
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English (en)
French (fr)
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任文才
高力波
马来鹏
成会明
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Priority to JP2014513048A priority Critical patent/JP5840772B2/ja
Priority to EP12797578.7A priority patent/EP2719797B1/en
Priority to ES12797578T priority patent/ES2571602T3/es
Priority to US14/124,072 priority patent/US9216559B2/en
Priority to KR1020147000101A priority patent/KR101529012B1/ko
Publication of WO2012167738A1 publication Critical patent/WO2012167738A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • C01B32/194—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene

Definitions

  • the invention relates to a low-cost non-destructive transfer technology of graphene, in particular to a new method for low-cost non-destructive transfer of graphene from an initial substrate to an arbitrary target substrate by utilizing the driving action of bubbles generated during electrolysis and gas intercalation.
  • Single-layer, low-layer graphene suitable for non-destructive transfer of conductor or semiconductor substrate surfaces.
  • Graphene is a two-dimensional honeycomb crystal structure composed of a single layer of carbon atoms, which is a basic structural unit for constructing other dimensional carbon materials (zero-dimensional fullerene, one-dimensional carbon nanotubes, three-dimensional graphite).
  • the unique crystal structure of graphene gives it excellent electrical, thermal and mechanical properties, such as electron mobility of up to 200,000 cm 2 /V's at room temperature and thermal conductivity of up to 5300 W/mk, which is expected to be used in multifunctional nanoelectronic devices. Widely used in transparent conductive films, composite materials, catalytic materials, energy storage materials, field emission materials, gas sensors and gas storage.
  • the CVD method and the epitaxial growth method are currently the main methods for controlling the preparation of high quality graphene.
  • the preparation conditions such as temperature, carbon source and pressure
  • the preparation conditions such as temperature, carbon source and pressure
  • metal and non-metal metal and non-metal
  • the currently developed graphene transfer technology can be divided into two categories: corrosion matrix method and direct transfer method.
  • corrosion matrix method For graphene with only atomic or several nanometer thickness, the non-destructive separation from the initial matrix is a major problem to be overcome in the transfer process due to its low macroscopic strength and easy breakage during transfer.
  • graphene prepared by a CVD method or an epitaxial growth method on a surface such as a transition metal the problem can be solved by a method of etching a substrate.
  • the method loses the metal matrix material at the expense of the metal substrate at the expense of the metal matrix, the production cost of the graphene is significantly increased (especially for an expensive substrate), and the process steps are cumbersome, the preparation cycle is long, and the environment serious pollution.
  • the method is not suitable for the transfer of graphene on noble metal matrix materials with high chemical stability, such as ruthenium (Ru) and platinum (Pt).
  • ruthenium (Ru) and platinum (Pt) For graphene grown on a high-cost substrate, a direct transfer method can be used, that is, a transfer medium with strong binding ability to graphene is used. The quality (such as tape, adhesive, etc.) peels the graphene directly from the surface of the substrate.
  • This method does not require loss of the matrix material, nor does it use corrosive and contaminating chemicals. However, this method is liable to cause breakage of graphene, and thus it is impossible to achieve non-destructive transfer of high quality graphene.
  • there is an urgent need to develop the non-destructive transfer technology of graphene (the matrix material and graphene are not damaged), which determines the development prospect of high quality graphene to some extent.
  • the transfer method has no damage and loss to graphene and its initial matrix, and is easy to operate, fast, easy to control, and non-polluting, and is expected to achieve large-scale amplification, so it can be used as an ideal for transferring high-quality graphene at low cost. method.
  • the present invention provides a new method for low cost lossless transfer of graphene.
  • the method adopts an initial substrate covered with surface or covered with graphene as an electrode, and graphene is arbitrarily covered on the surface of the initial substrate, and the graphene is combined by the driving force of bubbles generated on the surface of the electrolysis process and the gas intercalation.
  • Non-destructive separation from the initial substrate and lossless bonding of graphene to the surface of any target substrate. Specific steps are as follows:
  • Coating of the transfer medium layer coating a transfer medium on the initial substrate grown or covered with graphene to prevent the graphene from being damaged in subsequent processing;
  • Transfer medium / combination of graphene composite layer and target substrate The transfer medium / graphene composite layer is placed on the surface of the target substrate by direct contact or the like;
  • the graphene is graphene grown by a chemical vapor deposition method, or graphene obtained by an epitaxial growth method, or graphene grown by a precipitation method, or graphene obtained by a tape stripping method, or graphite obtained by a chemical stripping method.
  • the polymer is used as a transfer medium layer to consolidate and protect the graphene to prevent the graphene from being damaged during the operation.
  • These high molecular polymers are one or more of polymethyl methacrylate (PMMA), polyethylene, polystyrene, and polypropylene.
  • the thickness of the transfer medium layer is from 1 nm to 1 mm, and preferably ranges from 20 ⁇ to 500 ⁇ .
  • the graphene and the initial substrate covered with the transfer medium are used as a cathode or an anode during electrolysis.
  • the initial matrix of graphene is a conductor such as a metal such as Pt, Ni, Cu, Co, Ir, Ru, Au, or Ag, or an alloy thereof, or a semiconductor such as Si, Si0 2 or A1 2 0 3 or both.
  • Composite material such as a metal such as Pt, Ni, Cu, Co, Ir, Ru, Au, or Ag, or an alloy thereof, or a semiconductor such as Si, Si0 2 or A1 2 0 3 or both.
  • the solution used in the electrolysis process is an aqueous solution of a single electrolyte (acid, alkali or salt), or an aqueous solution of one or more electrolytes (acid, alkali or salt), or a single electrolyte (acid, alkali or salt) and a mixed solution of an organic substance (an alkene, an alkene, a block, an aromatic hydrocarbon, an alcohol, an aldehyde, a carboxylic acid, an ester or two or more), or one or more electrolytes (acid, alkali, salt) and an organic substance (alkane, alkene) a mixed solution of one or more of a block, an aromatic hydrocarbon, an alcohol, an aldehyde, a carboxylic acid, an ester, or two or more.
  • a solution that does not chemically or electrochemically react with the initial substrate is selected as the electrolyte.
  • the concentration of the electrolyte in the solution is 0.01 mol/L to 10 mol/L, preferably 0.1 mol/L to 4 in the present invention, and the operating temperature of the electrolysis process is -10 ° C to 100 ° C, preferably The range is 10 ⁇ 50 °C.
  • the voltage used in the electrolysis process is in the range of 1 to 100 volts, preferably in the range of 2 to 20 volts; the current is in the range of 0.01 to 100 amps, preferably in the range of 1 to 10 amps.
  • the organic solvent used is acetone, ethyl lactate, dichloroethane, trichloroethylene, chloroform or the like, chlorinated hydrocarbon, halogenated hydrocarbon, aromatic hydrocarbon.
  • the dissolution temperature is in the range of 0 to 200 ° C, preferably in the range of 20 to 80 ° C.
  • the heating temperature is 50 ° C to 600. C, preferably in the range of 100 to 350. C.
  • the target substrate used is a conductor such as Pt, M, Cu, Co, Ir, Ru, Au, Ag, or a semiconductor such as Si, BN, Si0 2 or A1 2 0 3 , or an insulator such as glass or quartz. Any material such as a polymer such as ethylene terephthalate or a substrate having an arbitrary shape such as a flat surface, a curved surface, or a mesh surface.
  • the invention adopts graphene covered with a transfer medium and an initial substrate as an electrode to be placed in a solution, generates gas on the surface by electrolysis, and uses the driving force of the bubble and the gas intercalation to damage the graphene and the initial substrate. Separation.
  • the invention utilizes a common high molecular polymer as a transfer medium for graphene, which is cheap and durable, and is easy to remove after transfer is completed.
  • the present invention uses a constant voltage or constant current power supply.
  • the voltage is usually 5 volts in the constant voltage mode, and the current is usually 1 amp in the constant current mode.
  • the electrolysis time is usually within a few minutes, so the transfer period is short and the energy consumption is low.
  • the graphene and the initial matrix in the present invention since only as an electrode in the electrolysis reaction, do not use any chemical agent having a corrosive action as an electrolyte, so that there is no damage to the graphene and the initial matrix, and the initial matrix can be Multiple or even repeated use, greatly reducing costs and no environmental pollution. 5.
  • the process of the invention is simple and easy to operate, and it is expected to realize the low-cost and large-scale rapid transfer of graphene compared to the transfer of graphene by the corrosion matrix method.
  • the graphene can be transferred from the substrate by the driving force of the bubble generated by the electrolysis process and the intercalation of the gas, and transferred to the arbitrary On the substrate.
  • the driving force of the bubble generated by the electrolysis process and the intercalation of the gas there is no damage to graphene and the matrix, so graphene can maintain high quality, and the matrix can be reused many times or even indefinitely, which significantly reduces the transfer cost caused by matrix loss, especially suitable for growth on metal substrates.
  • Transfer of graphene has a fast transfer speed and less environmental pollution, and has been technically supported in order to realize the use of graphene in the field of unconventional conductive films and nanoelectronic devices.
  • FIG. 1 Schematic diagram of the process of lossless transfer of graphene to a substrate. Wherein (a) coating a transfer medium PMMA layer on a platinum substrate initial substrate coated with or coated with graphene; (b) using a transfer medium PMMA/graphene/platinum foil as a cathode of the electrolytic cell, and utilizing a piece of platinum is used as the anode; (c) under the action of applying a constant current of 1 amp, the hydrogen gas bubble generated by the electrolyzed water gradually peels off the transfer medium PMMA/graphene composite layer from the initial base platinum foil; After a few seconds of bubbling, the transfer medium PMMA/graphene composite layer was completely separated from the initial base platinum foil.
  • the transfer medium PMMA/graphene composite layer is indicated by arrows in the figure.
  • Figure 2 Graphene film transferred from a metal platinum foil.
  • (a) is an optical photograph of graphene transferred onto a Si/SiO 2 substrate, the inset is a single crystal P ⁇ 111) substrate (left image) after growth of the graphene film and transferred therefrom to Si/Si0 Graphene film on 2 (right); optical micrograph of graphene transferred to the surface of Si/SiO 2 , showing that graphene is mostly monolayer, and a small portion is a double layer and a few layers.
  • the illustration shows the TEM image of the single-layer graphene boundary;
  • Raman spectroscopy comparison of single-layer graphene graphene and lossless transfer method obtained by tape stripping method are transferred to Si/Si0 2 and Si/Al 2 respectively Graphene on 0 3 , where the weak D mode represents a high quality of graphene after transfer. It can be seen that the transfer process does not cause any damage or damage to the graphene.
  • FIG. 3 Structural features of graphene single crystal grown in metallic platinum foil before and after lossless transfer.
  • (ab) is an SEM image of a graphene single crystal grown on a metal platinum foil;
  • (cd) is an optical photograph of the graphene single crystal transferred to the Si/SiO 2 substrate, respectively. It can be seen that the transfer process does not cause any damage or damage to the graphene single crystal.
  • FIG. 4 Non-destructive transfer of graphene single crystal grown on metal platinum foil onto different substrates.
  • (d) is an optical photograph of graphene transferred onto a Si/SiO 2 substrate with a channel on the surface;
  • (e) is an optical photograph of graphene transferred to the Au electrode on the surface of Si/SiO 2 . It can be seen that this transfer method is equally applicable to an uneven substrate having a channel, an electrode, or the like on its surface.
  • (a) is the AFM image of the surface of the single crystal Pt(lll) on which the graphene is grown, the pleats indicate the presence of graphene on the surface;
  • FIG. 6 Morphology of a graphene film grown on a polycrystalline platinum foil substrate after lossless transfer.
  • (ad) is the SEM image of the graphene film grown under the same conditions at the same position, without loss of 1 time, 5 times, 15 times and more than 100 times. It can be seen that there is no obvious change in the surface, indicating that after lossless transfer The substrate can be reused.
  • FIG. 7 Characteristics of single crystal graphene islands grown on a polycrystalline platinum foil substrate after lossless transfer.
  • (a-b) is an SEM image after 120 minutes of growth;
  • (c-d) is an SEM image after 180 minutes of growth. It can be seen that after repeated use, the platinum foil can still maintain its growth matrix function, and the grown single crystal graphene island is not significantly different.
  • the polycrystalline platinum foil substrate has been reused more than 500 times.
  • the method for low-cost non-destructive transfer of graphene of the invention adopts an initial substrate which is surface-grown or covered with graphene as an electrode, and graphene is arbitrarily covered on the surface of the initial substrate, and uses the driving force and gas of bubbles generated on the surface of the electrolysis process.
  • the intercalation action combines the lossless separation of graphene from the initial matrix and the lossless bonding of graphene to the surface of any target substrate. Specific steps are as follows:
  • Coating of the transfer medium layer coating a transfer medium on the initial substrate grown or covered with graphene to prevent the graphene from being damaged in subsequent processing;
  • Transfer medium / combination of graphene composite layer and target substrate The transfer medium / graphene composite layer is placed on the surface of the target substrate by direct contact or the like;
  • the coating time is 1 minute. Place in an oven, hold at 180 ° C for 30 minutes, then take out the natural cooling, the thickness of the transfer medium layer is 500 ⁇ 1000nm.
  • the PMMA/graphene/platinum foil is used as the cathode to connect the negative electrode of the constant current power source, and the other platinum plate is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH
  • the PMMA/graphene/ After the platinum foil is completely immersed in the solution, a current of 1 amp is applied, the voltage is 8 to 16 volts, the operating temperature is 30 to 40 ° C, and hydrogen is generated on the PMMA/graphene/platinum foil connected to the negative electrode of the power supply during the electrolysis process. (3 ⁇ 4), the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of hydrogen gas and intercalation.
  • the time required for stripping varies, depending on the separation of PMMA/graphene and platinum foil, generally 1 cm x 3 cm PMMA/graphene/platinum foil, The required peel time is 30 seconds to 1 minute.
  • the PMMA/graphene and platinum foil were both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is washed several times with water for a long time, PMMA/graphene is taken from the water by using a cut target substrate such as Si/Si0 2 , Si/Al 2 0 3 BN, PET, glass, copper mesh, etc.
  • Graphene transferred to the target substrate, the layer distribution, uniformity and damage degree of the surface were observed by optical microscope.
  • the microcracks, wrinkles and other details of graphene were observed by atomic force microscopy.
  • the crystal quality of graphene was determined by Raman spectroscopy. .
  • Embodiment 1 The difference from Embodiment 1 is that:
  • the graphene is grown on the metal platinum foil by the atmospheric pressure CVD method, and after cooling the platinum foil to which the graphene is grown, a layer of PMMA is coated on both sides of the platinum foil by a spin coater (in this embodiment, both sides are both Coated with PMMA), the spin coating rate was 2000 rpm, and the spin coating time was 1 minute. It was placed in an oven, kept at 180 ° C for 30 minutes, then taken out and then naturally cooled, and the thickness of the transfer medium layer was 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as a cathode to connect the negative electrode of the constant current power source, and another platinum plate is used as the anode to connect the positive electrode of the power source.
  • the electrolyte solution is an aqueous solution of NaOH having a concentration of 0.1 mol/L to 4 mol/L.
  • a current of 1 amp is applied (in this embodiment, the electrolysis current is 0.1 amp to 4 amps), the voltage is 8 to 16 volts, and the operating temperature is 20 to 30.
  • hydrogen (3 ⁇ 4) is generated on the PMMA/graphene/platinum foil connected to the negative electrode of the power supply during the electrolysis process, and the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of hydrogen gas and intercalation.
  • the electrolysis time is 30 minutes to 20 seconds, respectively
  • the PMMA/graphene and the platinum foil are both removed from the NaOH solution and placed in the purified water.
  • PMMA/graphene is rinsed several times with water for a long time
  • PMMA/graphene is removed from the water and dried by using a silicon wafer to fix PMMA/graphene on the surface of the silicon wafer.
  • PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as a cathode to connect the negative electrode of the constant current power source, and another platinum plate is used as the anode to connect the positive electrode of the power source, and the electrolyte is a 1 mol/L aqueous solution of NaOH (in this embodiment, the electrolyte can be replaced by KOH, Different alkali, acid or salt solutions such as H 2 S0 4 and Na 2 S0 4 , the solution concentration is from 0.1 mol/L to lj 5 mol/L), after the PMMA/graphene/platinum foil is completely immersed in the solution Applying 1 amp current (in this embodiment, the electrolysis current is 0.1 amp to 4 amps), the voltage is 8 to 16 volts, the operating temperature is 30 to 40 ° C, and the PMMA/graphene of the negative electrode of the power source is connected during the electrolysis process.
  • the electrolyte can be replaced by KOH, Different alkali, acid or salt solutions such as H 2 S
  • Hydrogen gas (3 ⁇ 4) is produced on the platinum foil, and the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of hydrogen gas and intercalation.
  • the electrolysis time is 60 minutes to 60 seconds, respectively
  • the PMMA/graphene and the platinum foil are both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is rinsed several times with water for a long time
  • PMMA/graphene is removed from the water and dried by using a silicon wafer to fix PMMA/graphene on the surface of the silicon wafer. Finally, PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • the graphene is grown on the single crystal metal platinum by the atmospheric pressure CVD method (in the present embodiment, the metal platinum foil can be replaced with a platinum plate or a platinum foil of different specifications, a single crystal or a polycrystal, and the thickness is larger than ⁇ ).
  • the metal platinum foil can be replaced with a platinum plate or a platinum foil of different specifications, a single crystal or a polycrystal, and the thickness is larger than ⁇ ).
  • a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as the cathode to connect the negative electrode of the constant current power source, and the other platinum plate is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH
  • the PMMA/graphene/ After the platinum foil is completely immersed in the solution, a current of 1 amp is applied, the voltage is 8 to 16 volts, and the operating temperature is 40 to 50 ° C. Hydrogen is generated on the PMMA/graphene/platinum foil connected to the negative electrode of the power supply during electrolysis ( 3 ⁇ 4), the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of hydrogen and intercalation. After PMMA/graphene and platinum foil are completely separated, PMMA/graphene and platinum foil are all removed from NaOH. Remove from the solution and place in purified water.
  • PMMA/graphene is rinsed several times with water for a long time, PMMA/graphene is removed from the water and dried by using a silicon wafer to fix PMMA/graphene on the surface of the silicon wafer. Finally, PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on different metals by different methods (in this embodiment, the platinum foil may be replaced by a metal foil such as tantalum, niobium, nickel, or copper, or a metal thin film stably bonded on the silicon wafer).
  • a layer of PMMA is coated on one side of the metal foil or the metal film by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/metal foil or metal film is used as a cathode to connect the negative electrode of the constant current power source, and another piece of platinum is used as the anode to connect the positive electrode of the power source, and the electrolyte is a 1 mol/L aqueous solution of NaOH (in this embodiment, the electrolyte can be exchanged)
  • a solution of a base, acid or salt that does not easily corrode a specific metal) after immersing the PMMA/graphene/metal foil or metal film completely in the solution, applying a current of 1 amp, a voltage of 8 to 16 volts, and an operating temperature of 30 At ⁇ 40 °C, hydrogen (3 ⁇ 4) is generated on the PMMA/graphene/platinum foil connected to the negative electrode of the power supply during electrolysis.
  • the PMMA/graphene composite layer is gradually stripped from the platinum foil under the action of hydrogen and intercalation. .
  • the PMMA/graphene and the metal foil or the silicon wafer stably bonded with the metal film are taken out from the solution and placed in purified water.
  • PMMA/graphene is washed several times with water for a long time, PMMA/graphene is removed from the water by silicon wafer and dried to fix PMMA/graphene on the surface of the silicon wafer. Finally, PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is prepared on different semiconductor substrates by different methods (in this embodiment, the metal substrate can be replaced with a semiconductor substrate such as SiC). After the semiconductor substrate to which graphene is grown is cooled, a layer of PMMA is coated on one side of the semiconductor substrate by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/semiconductor substrate is used as a cathode to connect the negative electrode of the constant current power source, and another platinum plate is used as the anode to connect the positive electrode of the power source, and the electrolyte is a 1 mol/L aqueous solution of H 2 S0 4 (in this embodiment, the electrolyte can be exchanged)
  • An acid or salt solution that does not corrode the substrate An acid or salt solution that does not corrode the substrate, in the PMMA/graphene/semiconductor base After the body is completely immersed in the solution, a current of 1 amp is applied, the voltage is 8 to 16 volts, and the operating temperature is 20 to 30 ° C.
  • Hydrogen is generated on the PMMA/graphene/platinum foil connected to the negative electrode of the power supply during electrolysis (3 ⁇ 4
  • the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of hydrogen gas and intercalation.
  • the PMMA/graphene and the semiconductor substrate are both removed from the solution and placed in purified water.
  • PMMA/graphene is rinsed several times with water for a long time, PMMA/graphene is removed from the water and dried by using a silicon wafer to fix PMMA/graphene on the surface of the silicon wafer. Finally, PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater and then dried, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • PMMA/graphene/platinum foil was used as the cathode to connect the negative electrode of the constant current power source, and another piece of platinum was used as the anode to connect the positive electrode of the power supply.
  • the electrolyte was a 1 mol/L NaOH aqueous solution, and the PMMA/graphene/platinum foil was partially immersed.
  • PMMA/graphene/platinum foil is slowly immersed in the solution during the electrolysis process, which coincides with the time of separation of the platinum foil from PMMA/graphene), and a current of 1 amp is applied, and the voltage is 8 ⁇ 16. Volt, operating temperature is 10 ⁇ 20 °C, hydrogen (3 ⁇ 4) is generated on the PMMA/graphene/platinum foil connected to the negative electrode of the power supply during electrolysis, and the PMMA/graphene composite layer is driven by hydrogen and intercalated. The platinum foil is gradually peeled off. After the PMMA/graphene is completely separated from the platinum foil, the PMMA/graphene and platinum foil are both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is washed several times with water for a long time, PMMA/graphene is removed from the water by silicon wafer and dried to fix PMMA/graphene on the surface of the silicon wafer. Finally, PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of transfer medium is coated on one side of the platinum foil by a spin coater (in this embodiment, photoresist, PDMS, metal film, etc. can be easily formed by film formation, Strong adhesion to the substrate, easy to remove, etc. as a transfer medium) drying, the thickness of the transfer medium layer is 500 ⁇ 1000nm.
  • a spin coater in this embodiment, photoresist, PDMS, metal film, etc. can be easily formed by film formation, Strong adhesion to the substrate, easy to remove, etc. as a transfer medium
  • the transfer medium/graphene/platinum foil is used as a cathode to connect the negative electrode of the constant current power source, and another piece of platinum is used as the anode to connect the positive electrode of the power source, and the electrolyte is a 1 mol/L aqueous solution of NaOH (in this embodiment, the use of the medium without damage to the transfer medium) Electrolyte), immersing the transfer medium/graphene/platinum foil portion into the solution, applying a current of 1 amp, the voltage is 8 to 16 volts, the operating temperature is 20 to 30 ° C, and the negative electrode of the power source is connected during the electrolysis process.
  • Hydrogen gas (3 ⁇ 4) is produced on the PMMA/graphene/platinum foil, and the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of hydrogen gas and intercalation.
  • the transfer medium/graphene and platinum foil are both removed from the NaOH solution and placed in purified water.
  • the transfer medium/graphene is washed several times and for a long time, the transfer medium/graphene is removed from the water by a silicon wafer and dried to fix the transfer medium graphene on the surface of the silicon wafer. Finally, the transfer medium is removed.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater and then dried, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as the anode to connect the positive electrode of the constant current power source, and the other platinum plate is used as the cathode to connect the negative electrode of the power source, and the electrolyte is a specific electrolyte of 1 mol/L (in this embodiment, no oxygen is generated at the anode).
  • a solution such as a solution such as NaCl or HCl
  • a current of 1 amp is applied
  • the voltage is 8 to 16 volts
  • the operating temperature is 30 to 40 ° C.
  • chlorine gas (Cl 2 ) is generated on the PMMA/graphene/platinum foil connected to the positive electrode of the power source, and the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of chlorine gas and intercalation.
  • PMMA/graphene and platinum foil are both removed from the electrolytic solution and placed in purified water.
  • PMMA/graphene is rinsed several times with water for a long time, PMMA/graphene is removed from the water by silicon wafer and dried to fix PMMA/graphene on the surface of the silicon wafer. Finally, PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater and then dried, and the thickness of the transfer medium layer is 500 to 1000 nm. Put two pieces of PMMA/ The graphene/platinum foil is respectively connected to the positive electrode and the negative electrode of the constant current power source, and the electrolyte is a specific electrolyte of 1 mol/L (in the present embodiment, a solution which does not generate oxygen at the anode, such as a solution such as NaCl or HC1) is used.
  • a solution which does not generate oxygen at the anode such as a solution such as NaCl or HC1
  • PMMA/graphene/platinum foil is fully immersed in the solution, applying 1 amp of current, voltage is 8 ⁇ 16 volts, operating temperature is 50 ⁇ 60 °C, and PMMA/graphene/positive of positive and negative electrodes are connected during electrolysis.
  • Chlorine gas (Cl 2 ) and hydrogen gas (3 ⁇ 4) are respectively generated on the platinum foil, and the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of chlorine gas and hydrogen gas and intercalation.
  • the PMMA/graphene and the platinum foil are both removed from the electrolytic solution (in this embodiment, the two poles are separated from the PMMA/graphene and the platinum foil) and placed in the pure In the water.
  • PMMA/graphene is rinsed several times with water for a long time, PMMA/graphene is removed from the water by silicon wafer and dried to fix PMMA/graphene on the surface of the silicon wafer. Finally, PMMA was dissolved using acetone.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and the crystal of graphene was determined by Raman spectroscopy. quality.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as the cathode to connect the negative electrode of the constant current power source, and the other platinum plate is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH
  • the PMMA/graphene/ After the platinum foil is completely immersed in the solution, a current of 1 amp is applied to the port, the voltage is 8 to 16 volts, the operating temperature is 40 to 50 ° C, and the PMMA/graphene/platinum foil is connected to the negative electrode of the power source during the electrolysis process.
  • Hydrogen (H 2 ) the PMMA/graphene composite layer is gradually stripped from the platinum foil under the action of hydrogen and intercalation. After the PMMA/graphene was completely separated from the platinum foil, the PMMA/graphene and platinum foil were both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is removed from the water by using the cut target substrate (in this embodiment, glass is used as the target substrate), under a low temperature heating station or a heat lamp. (50 to 80 ° C), keep the remaining moisture for 30 minutes or more, and then use a high temperature heating table (100 to 180 ° C) for 30 minutes or more to fix PMMA/graphene on the glass surface. Finally, PMMA was dissolved using acetone, and the dissolution time was more than 10 minutes.
  • Embodiment 1 After the transfer of graphene/glass, the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope. The micro-cracks and wrinkles of graphene were observed by atomic force microscopy, and the crystal quality of graphene was determined by Raman spectroscopy. .
  • the difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as the cathode to connect the negative electrode of the constant current power source, and the other platinum plate is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH
  • the PMMA/graphene/ After the platinum foil is completely immersed in the solution, a current of 1 amp is applied to the port, the voltage is 8 to 16 volts, the operating temperature is 40 to 50 ° C, and the PMMA/graphene/platinum foil is connected to the negative electrode of the power source during the electrolysis process.
  • Hydrogen (H 2 ) the PMMA/graphene composite layer is gradually stripped from the platinum foil under the action of hydrogen and intercalation. After the PMMA/graphene was completely separated from the platinum foil, the PMMA/graphene and platinum foil were both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is washed several times with water for a long time
  • PMMA/graphene is removed from the water by using the cut target substrate (in this embodiment, PET is used as the target substrate), under a low temperature heating station or a heat lamp. (50 ⁇ 80 °C), keep it for more than 30 minutes, dry the remaining moisture, and fix PMMA/graphene on the PET surface.
  • PMMA was dissolved using acetone, and the dissolution time was more than 10 minutes.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as the cathode to connect the negative electrode of the constant current power source, and the other platinum plate is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH
  • the PMMA/graphene/ After the platinum foil is completely immersed in the solution, a current of 1 amp is applied to the port, the voltage is 8 to 16 volts, the operating temperature is 40 to 50 ° C, and the PMMA/graphene/platinum foil is connected to the negative electrode of the power source during the electrolysis process.
  • Hydrogen (H 2 ) the PMMA/graphene composite layer is gradually stripped from the platinum foil under the action of hydrogen and intercalation. After the PMMA/graphene was completely separated from the platinum foil, the PMMA/graphene and platinum foil were both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is removed from the water by using the cut target substrate (in this embodiment, a small layer of hexagonal boron nitride/Si0 2 /Si is used as the target substrate). ), keep it at a low temperature heating station or a heat lamp (50 ⁇ 80 °C) for more than 30 minutes, and then dry the remaining water, and then use a high temperature heating station (100 ⁇ 180 °C) for more than 30 minutes, PMMA / Graphene is fixed on the BN surface. Finally, PMMA was dissolved using acetone, and the dissolution time was more than 10 minutes.
  • the cut target substrate in this embodiment, a small layer of hexagonal boron nitride/Si0 2 /Si is used as the target substrate.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as the cathode to connect the negative electrode of the constant current power source, and the other platinum plate is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH
  • the PMMA/graphene/ After the platinum foil is completely immersed in the solution, a current of 1 amp is applied to the port, the voltage is 8 to 16 volts, the operating temperature is 40 to 50 ° C, and the PMMA/graphene/platinum foil is connected to the negative electrode of the power source during the electrolysis process.
  • Hydrogen (H 2 ) the PMMA/graphene composite layer is gradually stripped from the platinum foil under the action of hydrogen and intercalation. After the PMMA/graphene was completely separated from the platinum foil, the PMMA/graphene and platinum foil were both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is washed several times with water for a long time, PMMA/graphene is removed from the water by using the cut target substrate (in this embodiment, a copper mesh micro-gate film is used as the target substrate, 200 mesh), Under low temperature heating table or under heat lamp (50 ⁇ 80 °C), keep the residual moisture for more than 30 minutes, then use high temperature heating table (100 ⁇ 180 °C) for more than 30 minutes, PMMA/graphene It is fixed on the surface of the copper mesh micro-gate film. Finally, PMMA was dissolved using acetone, and the dissolution time was more than 10 minutes.
  • the graphene/copper mesh micro-gate film was observed, and the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope.
  • the micro-cracks, wrinkles and other details of the graphene were observed by atomic force microscopy, and the graphite was judged by Raman spectroscopy.
  • the crystal quality of the ene was judged by Raman spectroscopy.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as a cathode to connect the negative electrode of the constant current power source, and another piece of platinum is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH, and the PMMA/graphene is used.
  • the platinum foil After the platinum foil is completely immersed in the solution, a current of 1 amp is applied, the voltage is 8 to 16 volts, and the operating temperature is 40 to 50 ° C. Hydrogen is generated on the PMMA/graphene/platinum foil connected to the negative electrode of the power supply during the electrolysis process. (3 ⁇ 4), the PMMA/graphene composite layer is gradually peeled off from the platinum foil under the action of hydrogen gas and intercalation. After the PMMA/graphene was completely separated from the platinum foil, the PMMA/graphene and platinum foil were both removed from the NaOH solution and placed in purified water.
  • PMMA/graphene is removed from the water by using the cut target substrate (in this embodiment, Si0 2 /Si with channel on the surface is used as the target substrate) , Under low temperature heating table or heat lamp (50 ⁇ 80 °C), keep it for more than 30 minutes, dry the remaining water, and then use high temperature heating table (100 ⁇ 180 °C) for more than 30 minutes, PMMA/graphite The ene is fixed to the surface of the SiO 2 /Si substrate with a channel on the surface. Finally, PMMA was dissolved using acetone, and the dissolution time was more than 10 minutes.
  • the cut target substrate in this embodiment, Si0 2 /Si with channel on the surface is used as the target substrate
  • high temperature heating table 100 ⁇ 180 °C
  • the graphene/Si0 2 /Si substrate with a channel on the surface was observed, and the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by an atomic force microscope.
  • the crystal quality of graphene was judged by Raman spectroscopy.
  • Embodiment 1 The difference from Embodiment 1 is that:
  • Graphene is grown on a metal platinum foil by atmospheric pressure CVD. After the platinum foil to be grown with graphene is cooled, a layer of PMMA is coated on one side of the platinum foil by a spin coater, and the thickness of the transfer medium layer is 500 to 1000 nm.
  • the PMMA/graphene/platinum foil is used as a cathode to connect the negative electrode of the constant current power source, and another piece of platinum is used as the anode to connect the positive electrode of the power source.
  • the electrolyte is a 1 mol/L aqueous solution of NaOH, and the PMMA/graphene is used.
  • PMMA/graphene is removed from the water by using a cut copper metal substrate (in this embodiment, a metal substrate such as silver or aluminum may be used, and the thickness is 1 ⁇ m ⁇ Lmm), keep it at a low temperature heating station or under a heat lamp (50 ⁇ 80 °C) for more than 30 minutes, then dry the remaining water, and then use a high temperature heating station (100 ⁇ 180 °C) for more than 30 minutes.
  • PMMA/graphene is fixed on the surface of the copper metal substrate. Finally, the PMMA was dissolved by acetone, and the dissolution time was more than 10 minutes.
  • the layer distribution, uniformity and damage degree of the surface were observed by an optical microscope, and detailed information such as microcracks and wrinkles of graphene was observed by atomic force microscopy, and graphene was judged by Raman spectroscopy. Crystal quality.
  • a flow chart of transferring graphene grown on a platinum foil from a non-destructive transfer method can be seen, wherein (a) is a PMMA layer coated on a platinum foil coated with or coated with graphene; b) In order to use PMMA/graphene/platinum foil as the cathode of the electrolytic cell, another piece of platinum is used as the anode; (c) for the application of a constant current of 1 amp, the hydrogen bubble generated by the electrolyzed water will PMMA/graphite The olefin is gradually stripped from the metal matrix platinum foil; (d) is the complete separation of PMMA/graphene from the metal platinum foil after escaping for several tens of seconds. The figure indicates the PMMA/graphene with arrows.
  • FIG. 2 (a) is a photograph of graphene transferred onto a Si/SiO 2 substrate, the inset is a single crystal Pt (lll) substrate after growth of graphene (left) and transferred therefrom to Si/ Graphene film on Si0 2 (right); (b) transfer to Si/Si0 2 surface
  • the optical micrograph of the graphene on the graph shows that the graphene is mostly monolayer, and a small portion is a double layer and a few layers.
  • the illustration shows the TEM image of the single-layer graphene boundary;
  • (ab) is an SEM image of a graphene single crystal grown on a metal platinum foil;
  • (cd) is an optical photograph of the graphene single crystal transferred to the Si/SiO 2 substrate, respectively. It can be seen that the transfer process does not cause any damage or damage to the graphene single crystal.
  • FIG. 5 (a) is an AFM image of the surface of a single crystal Pt(ll) on which graphene is grown, and wrinkles indicate the presence of graphene on the surface; (b) AFM on the surface of Pt(lll) after lossless transfer of graphene
  • the figure shows that only the original atomic step of the surface of Pt(l 11) is left, and there is no wrinkle of graphene, and Pt(lll) retains its original morphology and structure after transfer. Comparing the surface of single crystal platinum before and after non-destructive transfer, it can be found that there is no graphene residue on the platinum surface after transfer, and the atomic step on the platinum surface has not changed, which proves that the transfer method is not damaged to the platinum matrix.
  • FIG. 6 (ad) is an SEM image of a graphene film grown under the same conditions after lossless transfer of 1, 5, 15 and more than 100 times on the polycrystalline platinum, respectively, showing the graphene structure. No significant change, indicating that the matrix after lossless transfer can be reused.
  • the SEM image of the graphene film grown on the non-destructively transferred polycrystalline platinum shows that the graphene film grown on the polycrystalline platinum does not exist after the first, fifth, fifteenth or even more than 100 transfers. Significant changes, demonstrating that the substrate can be reused after transfer.
  • (a-b) is the SEM image after 120 minutes of growth; (c-d) is after 180 minutes of growth, respectively.
  • the growth substrate can still be maintained, and the grown single crystal graphene island is not significantly different.
  • the polycrystalline platinum foil substrate has been transferred more than 500 times.
  • the structure of the single crystal graphene island grown on the polycrystalline platinum after non-destructive transfer, the platinum foil substrate has been transferred more than 500 times, and the structure and original matrix growth of the single crystal graphene island grown by the substrate after multiple transfer can be found.
  • the single crystal graphene has no significant difference, which proves that the matrix can be reused after multiple transfers.

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Abstract

一种低成本无损转移石墨烯的方法，该方法采用表面覆盖有转移介质的石墨烯和初始基体作为电极，将其放置于电解液中，利用电解过程中在石墨烯电极表面所产生的气泡的推动力及气体插层作用将石墨烯与初始基体无损分离，然后将覆盖有转移介质的石墨烯无损结合到目标基体表面，取出转移介质后实现石墨烯到目标基体的无损转移。该转移方法对石墨烯及其初始基体均无任何破坏和损耗，基体可重复使用，并且操作简便、速度快、易于控制、无污染。

Description

一种低成本无损转移石墨烯的方法
技术领域：
本发明涉及石墨烯的低成本无损转移技术， 具体为一种利用电解过程中产生的气泡的推 动作用及气体插层作用将石墨烯从初始基体向任意目标基体上低成本无损转移的新方法， 适 用于无损转移导体或半导体基体表面的单层、 少层石墨烯。
背景技术：
石墨烯是由单层碳原子紧密堆积成的二维蜂窝状晶体结构， 是构建其他维数炭材料 （零 维富勒烯、 一维纳米碳管、 三维石墨） 的基本结构单元。 石墨烯独特的晶体结构使它具有优 异的电学、 热学和力学性能， 如室温下其电子迁移率高达 200,000 cm2/V's， 热导率高达 5300 W/m-k, 可望在多功能纳电子器件、 透明导电膜、 复合材料、 催化材料、 储能材料、 场发射 材料、 气体传感器及气体存储等领域获得广泛应用。 为了综合利用石墨烯的众多优异特性， 高质量石墨烯的制备及将石墨烯转移到特定基体上变得至关重要。自 2004年英国曼彻斯特大 学的研究组采用胶带剥离法 （或微机械剥离法）首次分离获得稳定存在的石墨烯后， 很多制 备石墨烯的方法陆续被发展起来，包括化学氧化剥离法、外延生长法和化学气相沉积 (CVD) 法。 由于相对简单的制备过程， 且产量较大， 化学氧化剥离法制得的石墨烯已经被广泛用于 复合材料、 柔性透明导电薄膜以及储能电极材料等。 但是， 化学剥离石墨烯的质量较差， 存 在大量结构缺陷，而且难以控制石墨烯的尺寸和层数等结构特征。 CVD方法和外延生长法是 目前可控制备高质量石墨烯的主要方法。 通过控制温度、 碳源和压力等制备条件， 可以实现 在多种基体材料表面 （金属和非金属） 生长出高结晶度的石墨烯， 并可在一定范围内对石墨 烯的层数和尺寸进行控制。 对于石墨烯的表征、 物性测量以及应用研究而言， 通常需要将石 墨烯放置在除制备基体之外的特定基体上， 因此发展高质量石墨烯的转移技术对于推动石墨 烯材料的研究乃至应用具有重要的作用和意义。
目前发展的石墨烯转移技术可以分为两大类： 腐蚀基体法与直接转移法。 对于仅有原子 级或者数纳米厚度的石墨烯而言， 由于其宏观强度低， 转移过程中极易破损， 因此与初始基 体的无损分离是转移过程所须克服的主要问题。 对于在过渡金属等表面采用 CVD方法或者 外延生长方法制备的石墨烯， 可以通过腐蚀基体的方法解决该问题。 但是， 由于该方法以牺 牲金属基体为代价， 在转移过程中损耗了金属基体材料， 因此显著增加了石墨烯的制备成本 (尤其对于价格昂贵的基体)， 并且工艺步骤繁琐， 制备周期长， 环境污染严重。而且该方法 并不适用于化学稳定性高的贵金属基体材料上石墨烯的转移， 如钌 （Ru)和铂 （Pt)等。 对 于在高成本基体上生长的石墨烯， 可采用直接转移法， 即利用与石墨烯结合力较强的转移介 质 （如胶带、 粘结剂等）将石墨烯直接从基体表面剥离下来。 该方法无需损耗基体材料， 也 不采用具有腐蚀性和污染性的化学试剂。 但是， 该方法易于造成石墨烯的破损， 因此无法实 现高质量石墨烯的无损转移。 综上， 目前亟需发展石墨烯的无损转移技术 （基体材料、 石墨 烯均无损）， 这在一定程度上决定了高质量石墨烯的发展前景。
发明内容：
本发明的目的在于提供一种利用电解过程中产生的气泡的推动力及气体插层作用低成 本无损转移石墨烯的新方法， 可将石墨烯从初始基体转移到任意目标基体上。 该转移方法对 石墨烯及其初始基体均无任何破坏和损耗， 并且操作简便、 速度快、 易于调控、 无污染， 有 望实现规模化放大， 因此可作为一种低成本转移高质量石墨烯的理想方法。
本发明的技术方案是：
本发明提供了一种低成本无损转移石墨烯的新方法。 该方法以表面生长或覆盖有石墨烯 的初始基体作为电极， 石墨烯任意覆盖在初始基体表面， 利用电解过程中在其表面所产生的 气泡的推动力及气体插层作用相结合， 将石墨烯与初始基体无损分离， 并将石墨烯无损结合 到任意目标基体表面。 具体步骤如下：
(1)转移介质层的涂覆： 在生长有或覆盖有石墨烯的初始基体上涂覆一层转移介质， 以防止石墨烯在后续处理中损坏；
(2)转移介质 /石墨烯复合层与初始基体的分离： 将覆盖有转移介质的石墨烯和初始基 体作为电极置于溶液中， 通过电解的方法在其表面产生气体， 并利用气泡的推动力和气体的 插层作用将石墨烯与初始基体无损分离；
(3)转移介质 /石墨烯复合层与目标基体的结合： 采用直接接触等方法将转移介质 /石墨 烯复合层置于目标基体表面；
(4)转移介质的去除： 采用溶剂溶解或者加热等方法将覆盖在石墨烯表面的转移介质去 除。
本发明中， 石墨烯为采用化学气相沉积方法生长的石墨烯， 或外延生长方法获得的石墨 烯， 或析出方法生长的石墨烯， 或胶带剥离法获得的石墨烯， 或化学剥离法获得的石墨烯， 或组装方法组装的石墨烯薄膜。
本发明中， 采用高分子聚合物作为转移介质层对石墨烯进行巩固保护， 防止石墨烯在操 作过程中被损坏。 这些高分子聚合物为聚甲基丙烯酸甲酯 （PMMA)、 聚乙烯、 聚苯乙烯、 聚丙烯之一种或两种以上。 转移介质层厚度为 lnm〜lmm， 优选范围为 20ηιη〜500μηι。
本发明中， 覆盖有转移介质的石墨烯和初始基体在电解过程中作为阴极或阳极使用。 本发明中， 石墨烯的初始基体为 Pt、 Ni、 Cu、 Co、 Ir、 Ru、 Au、 Ag等金属及其合金等 导体、 或者 Si、 Si02、 A1203等半导体、 或者两者的复合材料。
本发明中， 电解过程所用溶液为单一电解质 （酸、 碱或盐类） 的水溶液， 或一种以上电 解质 （酸、 碱或盐类） 的水溶液， 或单一电解质 （酸、 碱或盐类）与有机物 （烷、 烯、 块、 芳香烃、 醇、 醛、 羧酸、 酯之一种或两种以上） 的混合溶液， 或一种以上电解质 （酸、 碱、 盐类）与有机物（烷、 烯、 块、 芳香烃、 醇、 醛、 羧酸、 酯之一种或两种以上） 的混合溶液。 在特定操作条件下， 需选用与初始基体不发生化学或电化学反应的溶液作为电解液。
本发明中， 电解质在溶液中的浓度在 0.01 mol/L〜10 mol/L， 优选范围为 0.1 mol/L〜4 本发明中， 电解过程的操作温度在- 10°C〜100°C， 优选范围为 10〜50°C。
本发明中， 电解过程所用电压在 1〜100伏特， 优选范围为 2〜20伏特； 电流在 0.01〜100 安培， 优选范围为 1〜10安培。
本发明中， 采用有机溶剂去除高分子聚合物转移介质时， 采用的有机溶剂为丙酮、 乳酸 乙酯、二氯乙烷、三氯乙烯、氯仿等酮类、氯代烃、 卤代烃、芳烃类试剂之一种或两种以上。 溶解温度在 0〜200°C， 优选范围为 20〜80°C。
本发明中， 采用加热方法去除高分子聚合物转移介质时， 采用的加热温度在 50°C 〜600。C， 优选范围为 100〜350。C。
本发明中， 采用的目标基体为 Pt、 M、 Cu、 Co、 Ir、 Ru、 Au、 Ag等导体， 或 Si、 BN、 Si02、 A1203等半导体， 或玻璃、石英等绝缘体， 聚对苯二甲酸乙二醇酯等高分子聚合物等任 意材料和平面、 曲面、 网面等任意形状的基体。
本发明的特点及有益效果是：
1.本发明采用覆盖有转移介质的石墨烯和初始基体作为电极置于溶液中，通过电解的方 法在其表面产生气体， 并利用气泡的推动力和气体插层作用将石墨烯与初始基体无损分离。
2.本发明利用常见高分子聚合物作为石墨烯的转移介质，便宜耐用，转移完成后易于去 除。
3.本发明使用恒压或者恒流电源， 恒压模式时电压通常为 5伏特， 恒流模式时电流通常 为 1安培， 电解时间一般在数分钟以内， 因此转移周期短， 能源消耗低。
4.本发明中石墨烯和初始基体， 由于仅作为电解反应中的电极， 不采用任何对其具有腐 蚀作用的化学试剂作为电解液， 因此对石墨烯和初始基体均无任何损伤， 初始基体可以多次 甚至无限次重复使用， 极大降低了成本， 并且无环境污染。 5.本发明工艺流程简单， 操作容易， 相比于腐蚀基体法转移石墨烯， 可有望真正实现石 墨烯的低成本、 规模化快速转移。
总之， 对于基体上生长或放置的石墨烯， 在转移介质的保护下， 石墨烯可以通过电解过 程产生的气泡的推动力及气体的插层作用，无损地从基体上转移下来，并转移到任意基体上。 此过程中， 石墨烯与基体均无任何损伤， 因此石墨烯可以保持高质量， 而基体可以多次甚至 无限次重复利用， 显著降低了基体损耗带来的转移成本， 尤其适合金属基体上生长的石墨烯 的转移。 此外， 该方法转移速度快， 在环境污染少， 为实现石墨烯在未総明导电薄膜、 纳电 子器件等领域的规赚用搬了技术上的支持。
附图说明：
图 1.基体无损转移石墨烯过程的示意图。 其中， （a)为在表面生长或覆盖有石墨烯的铂 箔初始基体上涂覆转移介质 PMMA层； （b)为将转移介质 PMMA/石墨烯 /铂箔作为电解池的 阴极， 而利用另外一片铂片作为阳极； （c)为在施加恒定电流 1安培的作用下， 电解水产生的 氢气气泡将转移介质 PMMA/石墨烯复合层从初始基体铂箔上逐渐剥离下来； （d)为在冒泡数 十秒后转移介质 PMMA/石墨烯复合层与初始基体铂箔彻底分离。 图中用箭头指示转移介质 PMMA/石墨烯复合层。
图 2. 从金属铂箔上转移下来的石墨烯薄膜。 其中， （a)为转移到 Si/Si02基体上的石墨烯 的光学照片，插图是生长完石墨烯薄膜后的单晶 P<111)基体 (左图)和从其上转移到 Si/Si02上 的石墨烯薄膜 (右图)； 为转移到 Si/Si02表面上的石墨烯的光学显微照片， 显示石墨烯大部 分为单层，并有一小部分区域为双层和少数层，插图给出了单层石墨烯边界的 TEM照片； (c) 单层石墨烯的拉曼光谱对比：胶带剥离法得到的石墨烯、无损转移法分别转移到 Si/Si02上和 Si/Al203上的石墨烯， 其中微弱的 D模代表了转移后石墨烯具有很高的质量。 可以看出， 该 转移过程对石墨烯没有任何损坏和破坏。
图 3. 金属铂箔生长的石墨烯单晶无损转移前后的结构特征。 其中， （a-b)为金属铂箔上 生长的石墨烯单晶的 SEM图； （c-d)分别为该石墨烯单晶转移到 Si/Si02基体上的光学照片。 可以看出， 该转移过程对石墨烯单晶没有任何损坏和破坏。
图 4.将金属铂箔上生长的石墨烯单晶无损转移到不同基体上。 其中， （d)为转移到表面 带有沟道的 Si/Si02基体上的石墨烯光学照片； （e)为转移到 Si/Si02表面 Au电极上的石墨烯 的光学照片。 可以看出， 此种转移方法对于表面带有沟道和电极等的不平整基体同样适用。
图 5.石墨烯无损转移前后的基体表面变化。 其中， （a)为生长完石墨烯的单晶 Pt(lll)表 面的 AFM图， 褶皱表明其表面存在石墨烯； （b)为无损转移石墨烯后 Pt(lll)表面的 AFM图， 仅观察到 Pt(lll)表面原始的原子台阶， 而并无石墨烯的褶皱， 并且转移后的 Pt(lll)完整保留 了其原有形貌和结构。
图 6. 无损转移后的多晶铂箔基体生长的石墨烯薄膜的形貌特征。 其中， （a-d)分别为在 同一位置， 无损转移 1次、 5次、 15次和超过 100次后， 同样条件生长的石墨烯薄膜的 SEM 图， 可以看出表面无明显变化， 表明无损转移后的基体可重复使用。
图 7.无损转移后的多晶铂箔基体生长的单晶石墨烯岛的特征。 其中， （a-b)分别为生长 120分钟后的 SEM图； (c-d)分别为生长 180分钟后的 SEM图。可以看出， 在多次重复使用 后， 铂箔仍能保持其生长基体的作用， 生长的单晶石墨烯岛无明显不同， 该多晶铂箔基体已 经被重复使用超过 500次。
具体实施方式：
本发明低成本无损转移石墨烯的方法，以表面生长或覆盖有石墨烯的初始基体作为电极， 石墨烯任意覆盖在初始基体表面， 利用电解过程中在其表面所产生的气泡的推动力及气体插 层作用相结合， 将石墨烯与初始基体无损分离， 并将石墨烯无损结合到任意目标基体表面。 具体步骤如下：
(1)转移介质层的涂覆： 在生长有或覆盖有石墨烯的初始基体上涂覆一层转移介质， 以防止石墨烯在后续处理中损坏；
(2)转移介质 /石墨烯复合层与初始基体的分离： 将覆盖有转移介质的石墨烯和初始基 体作为电极置于溶液中， 通过电解的方法在其表面产生气体， 并利用气泡的推动力和气体的 插层作用将石墨烯与初始基体无损分离；
(3)转移介质 /石墨烯复合层与目标基体的结合： 采用直接接触等方法将转移介质 /石墨 烯复合层置于目标基体表面；
(4)转移介质的去除： 采用溶剂溶解或者加热等方法将覆盖在石墨烯表面的转移介质去 除。
实施例 1
利用常压化学气相沉积 (CVD)法在金属铂箔上生长石墨烯 [ "常压 CVD法"请参见文 献： Gao, L. B.; Ren, W. C; Zhao, J. P.; Ma, L. P.; Chen, Z. P.; Cheng, H. M. Efficient growth of high-quality graphene films on Cu foils by ambient pressure chemical vapor deposition. Appl. Phys. Lett. 2010, 97, 183109.]。 待生长有石墨烯的铂箔冷却后， 利用旋涂机在铂箔单面上涂覆一层 PMMA (PMMA溶解在乳酸乙酯中， PMMA浓度为 4wt.%) ， 旋涂速率为 2000rpm， 旋涂 时间 1分钟。 放入烘箱中， 180°C下保持 30分钟， 然后取出自然冷却， 转移介质层厚度为 500〜1000nm。将 PMMA/石墨烯 /铂箔作为阴极连接恒流电源的负极， 用另一片铂片作为阳极 连接电源正极，本实施例中， 电解液为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔完 全浸入所述溶液中后， 施加 1安培的电流， 电压为 8〜16伏特， 操作温度在 30〜40°C， 在电解 过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用 下 PMMA/石墨烯复合层从铂箔上逐渐剥离下来。 由于金属铂箔的表面粗糙度、 尺寸等因素 的影响， 剥离需要的时间有所不同， 具体根据 PMMA/石墨烯与铂箔的分离状况决定， 一般 lcm X 3cm的 PMMA/石墨烯 /铂箔， 需要的剥离时间为 30秒到 1分钟。 待 PMMA/石墨烯与 铂箔完全分离后， 将 PMMA/石墨烯和铂箔均从 NaOH溶液中捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用切割好的目标基体， 例如 Si/Si02、 Si/Al203 BN、PET、玻璃、铜网等，将 PMMA/石墨烯从水中捞出，在低温加热台或者热灯下（50〜80°C)， 保持 30分钟以上， 使残存的水分烘干， 进而将 PMMA/石墨烯固定在目标基体表面。 最后利 用丙酮将 PMMA溶解， 溶解时间 10分钟。
转移到目标基体上的石墨烯，利用光学显微镜观察表面的层数分布、均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 2
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯， 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔双面上分别涂覆一层 PMMA (本实施例中， 双面均涂覆 PMMA) ， 旋涂速率为 2000rpm, 旋涂时间 1分钟。 放入烘箱中， 180°C下保持 30分钟， 然后取出后自然冷却， 转 移介质层厚度为 500〜1000nm。将 PMMA/石墨烯 /铂箔作为阴极连接恒流电源的负极，用另一 片铂片作为阳极连接电源正极， 本实施例中， 电解液为浓度 O.lmol/L到 4mol/L的 NaOH水 溶液， 在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后， 施加 1安培电流 （本实施例中， 电 解电流为 0.1安培到 4安培） ， 电压为 8〜16伏特， 操作温度为 20〜30°C， 在电解过程中连接 电源负极的 PMMA/石墨烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用下 PMMA/ 石墨烯复合层从铂箔上逐渐剥离下来。 待 PMMA/石墨烯与铂箔完全分离后 （本实施例中， 电解时间分别为 30分钟到〜 20秒） ， 将 PMMA/石墨烯和铂箔均从 NaOH溶液中捞出， 并放 置在纯净水中。将 PMMA/石墨烯多次和长时间用水冲洗后， 利用硅片将 PMMA/石墨烯从水 中捞出并烘干， 固定 PMMA/石墨烯在硅片表面。 最后利用丙酮将 PMMA溶解。 转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 3
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /铂箔 作为阴极连接恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 电解液为 lmol/L 的 NaOH水溶液（本实施例中， 电解液可以换为 KOH、 H2S04、 Na2S04等不同的碱、 酸或者盐 溶液， 溶液浓度为 O.lmol/L至 lj 5mol/L) ， 在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后， 施加 1安培电流（本实施例中， 电解电流为 0.1安培到 4安培） ， 电压为 8〜16伏特， 操作温 度为 30〜40°C， 在电解过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 (¾) ， 在氢 气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐剥离下来。待 PMMA/石墨烯与 铂箔完全分离后 （本实施例中， 电解时间分别为 60分钟到〜 60秒） ， 将 PMMA/石墨烯和铂 箔均从 NaOH溶液中捞出， 并放置在纯净水中。将 PMMA/石墨烯多次和长时间用水冲洗后， 利用硅片将 PMMA/石墨烯从水中捞出并烘干， 固定 PMMA/石墨烯在硅片表面。最后利用丙 酮将 PMMA溶解。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 4
与实施例 1不同之处在于：
利用常压 CVD法在单晶金属铂上 （本实施例中， 金属铂箔可以换成不同规格的铂片或 者铂箔， 单晶或者多晶， 厚度大于 ΙΟμιη即可）生长石墨烯。待生长有石墨烯的铂箔冷却后， 利用旋涂机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石 墨烯 /铂箔作为阴极连接恒流电源的负极，用另一片铂片作为阳极连接电源正极，本实施例中， 电解液为 lmol/L的 NaOH水溶液， 在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后， 施加 1 安培电流， 电压为 8〜16伏特， 操作温度为 40〜50°C， 在电解过程中连接电源负极的 PMMA/ 石墨烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔 上逐渐剥离下来。 待 PMMA/石墨烯与铂箔完全分离后， 将 PMMA/石墨烯和铂箔均从 NaOH 溶液中捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用硅片将 PMMA/石墨烯从水中捞出并烘干， 固定 PMMA/石墨烯在硅片表面。最后利用丙酮将 PMMA 溶解。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 5
与实施例 1不同之处在于：
利用不同方法在不同金属上 （本实施例中， 铂箔可以换成钌、 铱、 镍、 铜等金属箔， 或 其在硅片上稳定结合的金属薄膜）生长石墨烯。待生长有石墨烯的金属箔或金属薄膜冷却后， 利用旋涂机在金属箔或金属薄膜单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /金属箔或金属薄膜作为阴极连接恒流电源的负极， 用另一片铂片作为阳极 连接电源正极， 电解液为 lmol/L的 NaOH水溶液（本实施例中， 电解液可以换成不易腐蚀 特定金属的碱、 酸或者盐溶液） ， 在将 PMMA/石墨烯 /金属箔或金属薄膜完全浸入所述溶液 中后， 施加 1安培电流， 电压为 8〜16伏特， 操作温度为 30〜40°C， 在电解过程中连接电源负 极的 PMMA/石墨烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯 复合层从铂箔上逐渐剥离下来。 待 PMMA/石墨烯与金属箔或金属薄膜完全分离后， 将 PMMA/石墨烯和金属箔或稳定结合有金属薄膜的硅片均从溶液中捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用硅片将 PMMA/石墨烯从水中捞出并烘干， 固定 PMMA/石墨烯在硅片表面。 最后利用丙酮将 PMMA溶解。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 6
与实施例 1不同之处在于：
利用不同方法在不同半导体基体上（本实施例中，金属基体可以换成 SiC等半导体基体) 制备石墨烯。 待生长有石墨烯的半导体基体冷却后， 利用旋涂机在半导体基体单面上涂覆一 层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /半导体基体作为阴极连接恒 流电源的负极，用另一片铂片作为阳极连接电源正极， 电解液为 lmol/L的 H2S04水溶液（本 实施例中， 电解液可以换成不易腐蚀基体的酸或者盐溶液） ， 在将 PMMA/石墨烯 /半导体基 体完全浸入所述溶液中后， 施加 1安培电流， 电压为 8〜16伏特， 操作温度为 20〜30°C， 在电 解过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作 用下 PMMA/石墨烯复合层从铂箔上逐渐剥离下来。待 PMMA/石墨烯与半导体基体完全分离 后， 将 PMMA/石墨烯和半导体基体均从溶液中捞出， 并放置在纯净水中。将 PMMA/石墨烯 多次和长时间用水冲洗后， 利用硅片将 PMMA/石墨烯从水中捞出并烘干， 固定 PMMA/石墨 烯在硅片表面。 最后利用丙酮将 PMMA溶解。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 Ί
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA后烘干， 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨 烯 /铂箔作为阴极连接恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 电解液为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔部分浸入所述溶液中（本实施例中， PMMA/ 石墨烯 /铂箔在电解过程中， 慢慢浸入溶液中， 与 PMMA/石墨烯分离铂箔的时间吻合） ， 施 加 1安培电流，电压为 8〜16伏特，操作温度为 10〜20°C，在电解过程中连接电源负极的 PMMA/ 石墨烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔 上逐渐剥离下来。 待 PMMA/石墨烯与铂箔完全分离后， 将 PMMA/石墨烯和铂箔均从 NaOH 溶液中捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用硅片将 PMMA/石墨烯从水中捞出并烘干， 固定 PMMA/石墨烯在硅片表面。最后利用丙酮将 PMMA 溶解。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 8
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层转移介质后 （本实施例中， 可以利用光刻胶、 PDMS、 金属薄膜等 易于成膜固化、 与基体结合力强、 易于去除等作为转移介质） 烘干， 转移介质层厚度为 500〜1000nm。 将转移介质 /石墨烯 /铂箔作为阴极连接恒流电源的负极， 用另一片铂片作为阳 极连接电源正极， 电解液为 lmol/L的 NaOH水溶液（本实施例中， 利用不伤害转移介质的 电解液） ， 在将转移介质 /石墨烯 /铂箔部分浸入所述溶液中， 施加 1安培电流， 电压为 8〜16 伏特， 操作温度为 20〜30°C， 在电解过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐剥离下来。 待转 移介质 /石墨烯与铂箔完全分离后， 将转移介质 /石墨烯和铂箔均从 NaOH溶液中捞出， 并放 置在纯净水中。 将转移介质 /石墨烯多次和长时间用水冲洗后， 利用硅片将转移介质 /石墨烯 从水中捞出并烘干， 固定转移介质石墨烯在硅片表面。 最后将转移介质去除。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 9
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA后烘干， 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨 烯 /铂箔作为阳极连接恒流电源的正极， 用另一片铂片作为阴极连接电源负极， 电解液为 lmol/L的特定电解液（本实施例中， 使用在阳极不产生氧气的溶液， 例如 NaCl或 HC1等溶 液） ， 在将 PMMA/石墨烯 /铂箔全部浸入所述溶液中， 施加 1安培电流， 电压为 8〜16伏特， 操作温度为 30〜40°C，在电解过程中连接电源正极的 PMMA/石墨烯 /铂箔上产生氯气 (Cl2) ， 在氯气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐剥离下来。待 PMMA/石墨 烯与铂箔完全分离后， 将 PMMA/石墨烯和铂箔均从电解溶液中捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗干净后，利用硅片将 PMMA/石墨烯从水中捞出并烘 干， 固定 PMMA/石墨烯在硅片表面。 最后利用丙酮将 PMMA溶解。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 10
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA后烘干， 转移介质层厚度为 500〜1000nm。 将两片 PMMA/ 石墨烯 /铂箔分别连接恒流电源的正极和负极， 电解液为 lmol/L的特定电解液（本实施例中， 使用在阳极不产生氧气的溶液， 例如 NaCl或 HC1等溶液） ， 在将 PMMA/石墨烯 /铂箔全部 浸入所述溶液中， 施加 1安培电流， 电压为 8〜16伏特， 操作温度为 50〜60°C， 在电解过程中 连接电源正、 负极的 PMMA/石墨烯 /铂箔上分别产生氯气 (Cl2)和氢气（¾) ， 在氯气和氢 气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐剥离下来。待 PMMA/石墨烯与 铂箔完全分离后， 将 PMMA/石墨烯和铂箔均从电解溶液中捞出 （本实施例中， 两极都在分 离 PMMA/石墨烯与铂箔）， 并放置在纯净水中。将 PMMA/石墨烯多次和长时间用水冲洗干 净后， 利用硅片将 PMMA/石墨烯从水中捞出并烘干， 固定 PMMA/石墨烯在硅片表面。最后 利用丙酮将 PMMA溶解。
转移完成后的石墨烯 /硅片， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 11
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /铂箔 作为阴极连接恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 本实施例中， 电解液 为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后，施力口 1安培电 流， 电压为 8〜16伏特， 操作温度为 40〜50°C， 在电解过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 （H2) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐 剥离下来。待 PMMA/石墨烯与铂箔完全分离后，将 PMMA/石墨烯和铂箔均从 NaOH溶液中 捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用切割好的目标 基体将 PMMA/石墨烯从水中捞出 （本实施例中， 采用玻璃为目标基体)， 在低温加热台或者 热灯下（50〜80°C)，保持 30分钟以上，使残存的水分烘干，再用高温加热台（100〜180°C) ， 保持 30分钟以上， 将 PMMA/石墨烯固定在玻璃表面。 最后利用丙酮将 PMMA溶解， 溶解 时间大于 10分钟。
转移完成后的石墨烯 /玻璃， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。 与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /铂箔 作为阴极连接恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 本实施例中， 电解液 为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后，施力口 1安培电 流， 电压为 8〜16伏特， 操作温度为 40〜50°C， 在电解过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 （H2) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐 剥离下来。待 PMMA/石墨烯与铂箔完全分离后，将 PMMA/石墨烯和铂箔均从 NaOH溶液中 捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用切割好的目标 基体将 PMMA/石墨烯从水中捞出 （本实施例中， 采用 PET为目标基体)， 在低温加热台或者 热灯下 （50〜80°C) ， 保持 30分钟以上， 使残存的水分烘干， 将 PMMA/石墨烯固定在 PET 表面。 最后利用丙酮将 PMMA溶解， 溶解时间大于 10分钟。
转移完成后的石墨烯 /PET， 利用光学显微镜观察表面的层数分布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯的晶体 质量。
实施例 13
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /铂箔 作为阴极连接恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 本实施例中， 电解液 为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后，施力口 1安培电 流， 电压为 8〜16伏特， 操作温度为 40〜50°C， 在电解过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 （H2) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐 剥离下来。待 PMMA/石墨烯与铂箔完全分离后，将 PMMA/石墨烯和铂箔均从 NaOH溶液中 捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用切割好的目标 基体将 PMMA/石墨烯从水中捞出 （本实施例中， 采用少层六方氮化硼 /Si02/Si为目标基体)， 在低温加热台或者热灯下（50〜80°C) ， 保持 30分钟以上， 使残存的水分烘干， 再用高温加 热台 （100〜180°C) ， 保持 30分钟以上， 将 PMMA/石墨烯固定在 BN表面。 最后利用丙酮 将 PMMA溶解， 溶解时间大于 10分钟。
转移完成后的石墨烯 /BN/Si02/Si， 利用光学显微镜观察表面的层数分布、 均匀性与破损 程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯 的晶体质量。
实施例 14
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /铂箔 作为阴极连接恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 本实施例中， 电解液 为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后，施力口 1安培电 流， 电压为 8〜16伏特， 操作温度为 40〜50°C， 在电解过程中连接电源负极的 PMMA/石墨烯 /铂箔上产生氢气 （H2) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐渐 剥离下来。待 PMMA/石墨烯与铂箔完全分离后，将 PMMA/石墨烯和铂箔均从 NaOH溶液中 捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用切割好的目标 基体将 PMMA/石墨烯从水中捞出 （本实施例中， 采用铜网微栅膜为目标基体， 200 目)， 在 低温加热台或者热灯下（50〜80°C) ， 保持 30分钟以上， 使残存的水分烘干， 再用高温加热 台 （100〜180°C) ， 保持 30分钟以上， 将 PMMA/石墨烯固定在铜网微栅膜表面。 最后利用 丙酮将 PMMA溶解， 溶解时间大于 10分钟。
转移完成后的石墨烯 /铜网微栅膜， 利用光学显微镜观察表面的层数分布、均匀性与破损 程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯 的晶体质量。
实施例 15
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /铂箔 作为阴极连接上恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 本实施例中， 电解 液为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后，施加 1安培 电流， 电压为 8〜16伏特， 操作温度为 40〜50°C， 在电解过程中连接电源负极的 PMMA/石墨 烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐 渐剥离下来。待 PMMA/石墨烯与铂箔完全分离后，将 PMMA/石墨烯和铂箔均从 NaOH溶液 中捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用切割好的目 标基体将 PMMA/石墨烯从水中捞出 （本实施例中，采用表面带有沟道的 Si02/Si为目标基体)， 在低温加热台或者热灯下（50〜80°C) ， 保持 30分钟以上， 使残存的水分烘干， 再用高温加 热台 （100〜180°C)， 保持 30分钟以上， 将 PMMA/石墨烯固定在表面带有沟道的 Si02/Si基 体表面。 最后利用丙酮将 PMMA溶解， 溶解时间大于 10分钟。
转移完成后的石墨烯 /表面带有沟道的 Si02/Si基体， 利用光学显微镜观察表面的层数分 布、 均匀性与破损程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉 曼光谱判断石墨烯的晶体质量。
实施例 16
与实施例 1不同之处在于：
利用常压 CVD法在金属铂箔上生长石墨烯。 待生长有石墨烯的铂箔冷却后， 利用旋涂 机在铂箔单面上涂覆一层 PMMA, 转移介质层厚度为 500〜1000nm。 将 PMMA/石墨烯 /铂箔 作为阴极连接上恒流电源的负极， 用另一片铂片作为阳极连接电源正极， 本实施例中， 电解 液为 lmol/L的 NaOH水溶液，在将 PMMA/石墨烯 /铂箔完全浸入所述溶液中后，施加 1安培 电流， 电压为 8〜16伏特， 操作温度为 40〜50°C， 在电解过程中连接电源负极的 PMMA/石墨 烯 /铂箔上产生氢气 (¾) ， 在氢气的驱动下和插层作用下 PMMA/石墨烯复合层从铂箔上逐 渐剥离下来。待 PMMA/石墨烯与铂箔完全分离后，将 PMMA/石墨烯和铂箔均从 NaOH溶液 中捞出， 并放置在纯净水中。 将 PMMA/石墨烯多次和长时间用水冲洗后， 利用切割好的铜 金属基体将 PMMA/石墨烯从水中捞出 （本实施例中， 可采用银、 铝等金属基体， 厚度 1 μ m〜lmm)， 在低温加热台或者热灯下 （50〜80°C) ， 保持 30分钟以上， 使残存的水分烘干， 再用高温加热台 （100〜180°C) ， 保持 30分钟以上， 将 PMMA/石墨烯固定在铜金属基体表 面。 最后利用丙酮将 PMMA溶解， 溶解时间大于 10分钟。
转移完成后的石墨烯 /铜金属基体， 利用光学显微镜观察表面的层数分布、均匀性与破损 程度， 利用原子力显微镜观察石墨烯的微裂痕、 褶皱等细节信息， 利用拉曼光谱判断石墨烯 的晶体质量。
如图 1 所示， 从无损转移法转移生长在铂箔上的石墨烯的流程图可以看出， 其中， （a) 为在表面生长或覆盖有石墨烯的铂箔上涂覆 PMMA层； （b)为将 PMMA/石墨烯 /铂箔作为电 解池的阴极， 而利用另外一片铂片作为阳极； （c)为在施加恒定电流 1安培的作用下， 电解水 产生的氢气气泡将 PMMA/石墨烯从金属基体铂箔上逐渐剥离;（d)为在冒泡数十秒后 PMMA/ 石墨烯与金属铂箔彻底分离。 图中用箭头指示 PMMA/石墨烯。
如图 2所示， （a)为转移到 Si/Si02基体上的石墨烯光学照片， 插图是生长石墨烯后的单 晶 Pt(lll)基体 (左图)和从其上转移到 Si/Si02上的石墨烯薄膜 (右图)；（b)为转移到 Si/Si02表面 上的石墨烯的光学显微照片， 显示出石墨烯大部分为单层， 并有一小部分区域为双层和少数 层， 插图给出了单层石墨烯边界的 TEM照片； （c)单层石墨烯的拉曼光谱对比： 胶带剥离法 得到的石墨烯、 无损转移法分别转移到 Si/Si02上和 Si/Al203上的石墨烯， 其中微弱的 D模 (拉曼散射峰）代表了转移后石墨烯具有很高的质量。 可以看出， 该转移过程对石墨烯没有 任何损坏和破坏。 无损转移后的石墨烯薄膜， 无明显破损， 并且呈现处较高的晶体质量， 证 明此种转移方法对于石墨烯是无损伤的。
如图 3所示， （a-b)为金属铂箔上生长的石墨烯单晶的 SEM图； （c-d)分别为该石墨烯单 晶转移到 Si/Si02基体上的光学照片。可以看出，该转移过程对石墨烯单晶没有任何损坏和破 坏。
如图 4所示， （d)为转移到表面带有沟道的 Si/Si02基体上的石墨烯光学照片； （e)为转移 到 Si/Si02表面 Au电极上的石墨烯的光学照片。 可以看出， 此种转移方法对于表面带有沟道 和电极等的不平整基体同样适用。
如图 5所示， （a)为生长完石墨烯的单晶 Pt(lll)表面的 AFM图， 褶皱表明其表面存在石 墨烯； （b)为无损转移石墨烯后 Pt(lll)表面的 AFM图， 显示仅剩下 Pt(l 11)表面原始的原子台 阶， 而并无石墨烯的褶皱， 并且转移后 Pt(lll)保持了其原有形貌和结构。 对比无损转移前后 的单晶铂表面， 可以发现转移后铂表面无石墨烯残留， 铂表面的原子台阶也未发生变化， 证 明此种转移方法对于铂基体是无损伤的。
如图 6所示， （a-d)分别为在多晶铂上同一位置， 无损转移 1次、 5次、 15次和超过 100 次后， 同样条件生长的石墨烯薄膜的 SEM图， 可见石墨烯结构无明显变化， 表明无损转移 后的基体可重复使用。 从无损转移后的多晶铂上生长的石墨烯薄膜的 SEM 图可以发现， 在 第 1次、 第 5次、 第 15次乃至超过 100次转移后， 多晶铂上长出的石墨烯薄膜无明显变化， 证明转移后基体可以重复使用。
如图 7所示， (a-b)分别为生长 120分钟后的 SEM图； （c-d)分别为生长 180分钟后的
SEM图。在铂箔多次重复使用后， 仍能保持其生长基体的作用， 生长的单晶石墨烯岛无明显 不同， 该多晶铂箔基体已经被转移超过 500次。 无损转移后的多晶铂上生长的单晶石墨烯岛 的结构， 此铂箔基体已经转移超过 500次， 可以发现转移多次后的基体生长出的单晶石墨烯 岛的结构与原始基体生长的单晶石墨烯无明显差别， 证明多次转移后基体可以重复使用。

Claims

权 利 要 求
1、一种低成本无损转移石墨烯的方法，其特征在于： 该方法采用覆盖有转移介质的石墨 烯和初始基体作为电极， 石墨烯任意覆盖在初始基体表面， 将其放置于电解液中， 利用电解 过程中在石墨烯电极表面所产生的气泡的推动力及气体插层作用将石墨烯与初始基体无损分 离， 然后将覆盖有转移介质的石墨烯结合到目标基体表面， 在去除转移介质后实现石墨烯无 损转移到目标基体上;该转移方法在实施过程中对石墨烯及其初始基体均无任何破坏和损耗， 初始基体可重复使用； 具体步骤如下：
(1)转移介质层的涂覆： 在表面生长有或放置有石墨烯的初始基体涂覆一层转移介质， 以防止石墨烯在后续处理中损坏；
(2)转移介质 /石墨烯复合层与初始基体的分离： 将覆盖有转移介质的石墨烯和初始基体 作为电极置于电解溶液中， 通过电解的方法在其表面产生气体， 利用气泡的推动力及其插层 作用将石墨烯与初始基体无损分离；
(3)转移介质 /石墨烯复合层与目标基体的结合： 采用直接接触方法将转移介质 /石墨烯复 合层置于目标基体表面；
(4)转移介质的去除： 采用溶剂溶解或者加热方法将覆盖在石墨烯表面的转移介质去除。
2、按照权利要求 1所述的无损转移石墨烯的方法，其特征在于： 石墨烯为采用化学气相 沉积方法生长的石墨烯， 或夕卜延生长方法获得的石墨烯， 或析出方法生长的石墨烯， 或胶带 剥离法获得的石墨烯， 或化学剥离法获得的石墨烯， 或组装方法组装的石墨烯薄膜。
3、按照权利要求 1所述的无损转移石墨烯的方法，其特征在于： 采用高分子聚合物作为 转移介质层对石墨烯进行巩固保护， 防止石墨烯在操作过程中被损坏； 这些高分子聚合物为 聚甲基丙烯酸甲酯、 聚乙烯、 聚苯乙烯、 聚丙烯之一种或两种以上， 转移介质层厚度为
4、 按照权利要求 1 所述的无损转移石墨烯的方法， 其特征在于： 覆盖有转移介质的石 墨烯和初始基体在电解过程中作为阴极或阳极使用。
5、 按照权利要求 1 所述的无损转移石墨烯的方法， 其特征在于： 石墨烯的初始基体为
Pt、 M、 Cu、 Co、 Ir、 Ru、 Au、 Ag金属或其合金导体之一或两种以上复合， 或者 Si、 Si02、 A1203半导体之一或两种以上复合， 或者导体与半导体两者的复合材料。
6、 按照权利要求 1 所述的无损转移石墨烯的方法， 其特征在于： 电解过程所用溶液为 单一电解质酸、 碱或盐类的水溶液， 或一种以上电解质酸、 碱或盐类的水溶液， 或单一电解 质酸、 碱、 盐类与有机物烷、 烯、 块、 芳香烃、 醇、 醛、 羧酸、 酯之一种或两种以上的混合 溶液， 或一种以上电解质酸、 碱或盐类与有机物烷、 烯、 块、 芳香烃、 醇、 醛、 羧酸、 酯之 一种或两种以上的混合溶液； 选用与初始基体不发生化学或电化学反应的溶液作为电解液。
7、 按照权利要求 1 所述的无损转移石墨烯的方法， 其特征在于： 电解质在溶液中的浓 度在 0.01 mol/L〜10 mol/L， 电解过程的操作温度在- 10。C 〜100。C， 电解过程所用电压在 1〜100伏特， 电流在 0.01〜100安培。
8、 按照权利要求 1 所述的无损转移石墨烯的方法， 其特征在于： 采用有机溶剂去除高 分子聚合物转移介质时， 采用的有机溶剂为酮类、 氯代烃、 卤代烃、 芳烃类试剂之一种或两 种以上， 溶解温度在 0〜200°C; 采用加热方法去除高分子聚合物转移介质时， 采用的加热温 度在 50。C〜600。C。
9、 按照权利要求 1 所述的无损转移石墨烯的方法， 其特征在于： 采用的目标基体为导 体： Pt、 Ni、 Cu、 Co、 Ir、 Ru、 Au或 Ag， 或者目标基体为半导体： Si、 BN、 Si02或 A1203， 或者目标基体为绝缘体： 玻璃或石英， 或者目标基体为高分子聚合物： 聚对苯二甲酸乙二醇 酯， 目标基体的形状为平面、 曲面或网面。
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