WO2013104141A1 - 一种利用多苯环碳源低温化学气相沉积生长大面积石墨烯的方法 - Google Patents

一种利用多苯环碳源低温化学气相沉积生长大面积石墨烯的方法 Download PDF

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WO2013104141A1
WO2013104141A1 PCT/CN2012/071965 CN2012071965W WO2013104141A1 WO 2013104141 A1 WO2013104141 A1 WO 2013104141A1 CN 2012071965 W CN2012071965 W CN 2012071965W WO 2013104141 A1 WO2013104141 A1 WO 2013104141A1
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graphene
copper foil
carbon source
chemical vapor
vapor deposition
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PCT/CN2012/071965
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English (en)
French (fr)
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谢晓明
沈鸿烈
吴天如
丁古巧
孙雷
唐述杰
江绵恒
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中国科学院上海微系统与信息技术研究所
南京航空航天大学
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Publication of WO2013104141A1 publication Critical patent/WO2013104141A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • 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
    • C01B32/186—Preparation by chemical vapour deposition [CVD]

Definitions

  • the present invention relates to a method for producing graphene, and more particularly to a method for producing a long-area graphene by low-temperature chemical vapor deposition using a polyphenylene ring carbon source.
  • Graphene is a single layer of atomic thickness graphite having a two-dimensional honeycomb grid structure. Due to the presence of the ⁇ orbital in the plane of the graphene sheet, electrons can move freely in the crystal, making graphene have excellent electron transport properties. Due to its excellent mechanical, thermal, electrical and magnetic properties, graphene is expected to find wide application in high performance nanoelectronic devices, composite materials, field emission materials, gas sensors, energy storage and other fields. Graphene is structurally malleable, and its electrical, optical, and acoustic properties can be greatly adjusted by stress and deformation. Even the bandwidth structure of graphene can be changed, and research on curved, folded, and curled graphene is beginning to accelerate.
  • Graphene has an unparalleled high electron mobility, and the charge transfer rate in graphene can reach an unprecedented 200000 cm 2 /vs, more than 100 times more than silicon. This advantage makes it possible for graphene to replace silicon as the base material for next-generation ultra-high-frequency transistors and is widely used in high-performance integrated circuits and new nanoelectronic devices. It is expected that a full-carbon circuit composed entirely of graphene will soon appear and is widely used in people's daily lives.
  • the conventional preparation method requires a substrate temperature of at most 1000 ° C in the process of preparing graphene, and the price of the high purity gas source is relatively expensive. This undoubtedly brings great limitations to the application of materials. Therefore, finding a suitable experimental technique to realize the low-temperature growth of graphene on a relatively low temperature substrate has become a very important direction in the field.
  • the main method for preparing the low temperature substrate is plasma assisted chemical reaction vapor deposition, chemical reduction graphene oxide, and the like.
  • the graphene directly deposited by these methods has a small area, a poor crystal quality, and many defects.
  • the object of the present invention is to overcome the above deficiencies of the prior art, and provide a method for growing large-area graphene by low-temperature chemical vapor deposition using a polyphenylene ring carbon source to solve the problem of small graphene and crystallization in the prior art.
  • Technical problems with poor quality and many defects In order to solve the above technical problems, the present invention uses a solid or liquid polyphenylene aromatic hydrocarbon to replace methane as a carbon source, and controls the decomposition rate of the carbon source to achieve a sufficiently low partial pressure of the carbon active element in the chamber to achieve The number of layers of graphene grown was controllable; and it was successfully transferred to various flexible substrates with virtually no macroscopic damage.
  • a method for growing large-area graphene by low-temperature chemical vapor deposition characterized in that: by using a polyphenylene aromatic hydrocarbon as a carbon source, a graphene is grown on a copper foil surface by a carbon source decomposition method or a carbon source spin coating method. .
  • the polyphenylene aromatic hydrocarbon is benzene or a fused aromatic hydrocarbon.
  • the fused ring aromatic hydrocarbon is selected from the group consisting of naphthalene, anthracene, phenanthrene, anthracene, anthracene and hexacene.
  • the copper foil is an oxygen-free copper foil having a purity of not less than 99.99%, and has a typical thickness of 50 to 200 ⁇ m.
  • the copper foil has a surface roughness of 50 nm or less, preferably 30 nm or less.
  • the copper foil is annealed under a protective atmosphere to grow the Cu crystal grains, the surface is flat and free from defects, and the surface stress of the copper foil is released.
  • the temperature of the annealing process is maintained at 900-1050 ° C, the gas pressure is between 4000-1000 Pa, and the annealing time is controlled between 30-90 min.
  • the protective atmosphere is a mixture of argon and hydrogen. More preferably, the volume flow ratio of argon to hydrogen is 10-20:1. The purity of the gas used is not less than 99.999%.
  • the specific steps include: placing the carbon source at the inlet end of the tube furnace, and placing the copper foil in the center of the tube furnace, the control station
  • the central temperature of the tube furnace is 400-700 ° C; the carrier gas is introduced, and the temperature of the carbon source is raised to 80-350 ° C, and graphene is grown on the surface of the copper foil; then, the heating is stopped, and the furnace is cooled to The copper foil on which graphene was grown was taken out at room temperature.
  • the carbon source has a weight of 15-150 mg.
  • the specific steps include: dissolving a carbon source in toluene to prepare a mixture, and then spin-coating the copper foil, and the copper is The foil is placed in the center of the tube furnace; the carrier gas is introduced, and the furnace temperature of the tube furnace is raised to 400-700 ° C to grow graphene on the surface of the copper foil; then, the heating is stopped, and the furnace is cooled to room temperature and taken out.
  • the weight ratio of the carbon source to the toluene is 5-20 mg/ml.
  • the temperature rise rate of the tube furnace is 20-50 ° C / m in.
  • the furnace temperature rises to the temperature required to grow graphene it is kept for 20-40 minutes.
  • the working pressure during the growth of the graphene is 4000-10000 Pa.
  • the carrier gas is a mixed gas of argon gas and hydrogen gas. More preferably, the volume flow ratio of argon to hydrogen is 10-20:1. The purity of the gas used is not less than 99.999%.
  • the flow rate of the carrier gas is 300-500 sccm.
  • the above method for growing large-area graphene further comprises the following steps of transferring the prepared graphene to a target substrate:
  • the PMMA film has a thickness of 200-400 nm.
  • the annealing treatment is carried out in a reducing or inert atmosphere, the annealing temperature is 300-450 V, and the annealing time is 40-90 min.
  • the reducing or inert atmosphere is selected from the group consisting of hydrogen, argon or a mixture of hydrogen and argon.
  • the invention adopts solid or liquid polyphenylene aromatic hydrocarbon as a carbon source, and low-temperature preparation of layer-controlled graphene technology is of great significance for the industrial application of graphene, and is a large-area graphene with great potential.
  • New technology for growth. Compared with the existing graphene preparation technology, the present invention has the following advantages:
  • the method uses a polyphenylene ring solid state and a liquid carbon source to prepare a layer of controllable graphene.
  • the active element containing a benzene ring is used as a basic unit of graphene.
  • the present invention pretreats the substrate by mechanical polishing and chemical polishing to achieve a flatness of the substrate surface. !!! ⁇
  • the graphene obtained thereon by catalytic deposition of copper metal has less defects and good crystallization properties.
  • the method of the invention can reduce the consumption of high-purity gas, reduce the preparation temperature and greatly shorten the preparation time, and can reduce the production cost of large-sized graphene, thereby achieving excellent electrical properties and preparation for realizing development and development on a flexible substrate.
  • Low cost and The environmentally-friendly new generation of graphene microelectronic devices provides experimental basis and guiding ideas, and ultimately realizes the large-scale application of graphene-based microelectronic devices.
  • FIG. 1 is a schematic view of a device for growing graphene by low temperature chemical vapor deposition according to the present invention
  • Figure 2 is an AFM photograph of the surface of the copper foil after mechanical polishing and electrochemical polishing
  • Fig. 3 is an optical micrograph of catalytically growing graphene on the surface of a copper foil in the present invention.
  • FIG. 4 is a graph of a graphene Raman diagram prepared by a low-temperature chemical vapor phase method of a polyphenylene ring carbon source of the present invention.
  • Fig. 5 is a graph showing the transmittance of graphene obtained by low-temperature preparation of a benzene carbon source of the present invention to a quartz substrate.
  • Fig. 6 is a SEM photograph of graphene produced by low temperature of a polyphenylene ring carbon source of the present invention.
  • Fig. 7 is a graph showing the transmittance of graphene obtained by low-temperature preparation of a naphthalene carbon source of the present invention after transfer to a quartz substrate.
  • Fig. 8 is a graph showing the transmittance of graphene obtained by low-temperature preparation of a phenanthrene carbon source of the present invention after transfer to a quartz substrate.
  • Fig. 9 is a graph showing the transmittance of graphene obtained by low temperature preparation of a ruthenium carbon source of the present invention after transfer to a quartz substrate.
  • Fig. 10 is a graph showing the transmittance of graphene obtained by low-temperature preparation of a ruthenium carbon source to a quartz substrate.
  • Fig. 11 is a graph showing the transmittance of graphene obtained by low-temperature preparation of a hexacenebenzene carbon source of the present invention after transfer to a quartz substrate.
  • the main innovation of the present invention is to prepare a layer of controllable graphene under the catalysis of a copper substrate by a polyphenylene aromatic hydrocarbon as a carbon source decomposing active benzene ring monomer at a lower temperature.
  • the present invention provides a method for growing large-area graphene by low-temperature chemical vapor deposition, which uses a polyphenylene aromatic hydrocarbon as a carbon source, using a carbon source decomposition method or a carbon source spin coating method in a copper foil. Graphene is grown on the surface.
  • the solid or liquid polyphenylene aromatic hydrocarbon used in the present invention is decomposed by heat to form a benzene ring-containing active element necessary for preparing graphene, and these benzene ring-containing active units are used as a basic unit constituting graphene. It is easy to form a large-area layer-controlled graphene by the catalysis of a metal substrate and the action of hydrogen at a low temperature.
  • the polyphenylene aromatic hydrocarbon described in the present invention means a hydrocarbon which is liquid or solid at normal temperature and contains at least one benzene ring in its molecular formula.
  • the polyphenylene aromatic hydrocarbon is benzene or a fused aromatic hydrocarbon. More preferably, the fused ring aromatic hydrocarbon is selected from the group consisting of naphthalene, anthracene, phenanthrene, ⁇ , ⁇ and hexacene benzene and other substances.
  • the copper foil is an oxygen-free copper foil having a purity of not less than 99.99%, and a typical thickness thereof is 50 to 200 ⁇ m.
  • Alfa Aesar 99.99% high purity oxygen free copper foil can be used.
  • the copper foil has a surface roughness of 50 nm or less, preferably 30 nm or less.
  • the surface of the copper-platinum can be treated by mechanical polishing and electrochemical polishing to achieve a surface roughness of 50 nm or less.
  • the methods of mechanical polishing and electrochemical polishing are well known to those skilled in the art. For example, the following process conditions can be employed: 800 rpm can be used for the mechanical polishing speed; 85% phosphoric acid can be selected for the electrochemical polishing solution with a volume ratio of 3:1.
  • electrochemical polishing voltage is 1 ⁇ 2V, polishing time 1800s; after electrochemical polishing, the copper foil is ultrasonically cleaned by acetone for 10 minutes, then ultrasonically washed with 25% hydrochloric acid for 10 minutes, and finally with alcohol The copper foil is cleaned.
  • the copper foil having a surface roughness of 50 nm or less (preferably 30 nm or less) is first annealed under a protective atmosphere to grow the Cu crystal grains.
  • the surface is flat and defect-free, releasing the surface stress of the copper foil.
  • the temperature of the annealing process is maintained at 900-1050 ° C
  • the gas pressure is between 4000-1000 Pa
  • the annealing time is controlled between 30-90 min.
  • the protective atmosphere is a mixture of argon and hydrogen. More preferably, the volume flow ratio of argon to hydrogen is 10:1.
  • the purity of the gas used is not less than 99.999%.
  • the specific steps include: placing a carbon source at the inlet end of the tube furnace, and placing the copper foil on the tube type In the center of the furnace, the temperature of the central portion of the tube furnace is controlled to be 400-700 ° C; a carrier gas of a certain flow rate is introduced, and the temperature of the carbon source is raised to 80-350 ° C to grow graphene on the surface of the copper foil; Then, the heating was stopped, and the graphene-grown copper foil was taken out after the furnace was cooled to room temperature.
  • the weight of the carbon source used to grow graphene per furnace is 15-150 mg.
  • the specific steps include: dissolving the carbon source in toluene to prepare a mixed solution and then spin-coating the copper foil. And placing the copper foil in the center of the tube furnace; introducing a carrier gas of a certain flow rate, and raising the temperature of the tube furnace to 400-700 ° C to grow graphene on the surface of the copper foil; then, stopping After heating, the graphene-grown copper foil was taken out after the furnace was cooled to room temperature.
  • the weight ratio of the carbon source to the toluene is 5-20 mg/ml.
  • the spin coating was carried out using a spin coater at a rotational speed of 1000-2000 r/min.
  • the heating rate of the tube furnace is 20-50 ° C / m in.
  • the furnace temperature rises to the temperature required to grow graphene, it is kept for 20-40 minutes.
  • the working gas pressure during the growth of graphene is 4000-10000 Pa.
  • the carrier gas is a mixed gas of argon gas and hydrogen gas. More preferably, the volume flow ratio of argon to hydrogen is 10-20:1, preferably 10:1. The purity of the gas used is not less than 99.999%.
  • the flow rate of the carrier gas is 300-500 sccm.
  • the method further includes the following steps of transferring the prepared graphene to the target substrate:
  • PMMA can be dissolved in an organic solvent (e.g., phenol, anisole, etc.) and spin-coated on a copper foil by a spin coater.
  • organic solvent e.g., phenol, anisole, etc.
  • the PMMA film has a thickness of 200-400 nm.
  • the annealing treatment is carried out in a reducing or inert atmosphere, the annealing temperature is 300-450 V, and the annealing time is 40-90 min.
  • the reducing or inert atmosphere is selected from the group consisting of hydrogen, argon or a mixture of hydrogen and argon.
  • the target substrate includes, but is not limited to, various metal substrates, and may also be various substrates for semiconductor devices, such as silicon, silicon dioxide, silicon-on-insulator (soi), ⁇ - ⁇ or Mv compound semiconductor substrate, etc. (for example
  • FIG. 1 is a schematic diagram of a device for growing graphene by low temperature chemical vapor deposition according to the present invention.
  • the direction of the arrow in the figure is the flow direction of the carrier, wherein: 1 is the inlet end, 2 is the outlet end, 3 is the tube heating furnace, 4 is the carbon source, 5 is the copper foil, and 6 is the rotary pump. Since the chemical vapor deposition process and the devices used therein are well known to those skilled in the art, they are not described herein.
  • Example 1 Low-temperature growth of large-area single-layer graphene by benzene liquid carbon source
  • the surface of the copper substrate was treated by mechanical polishing and electrochemical polishing to achieve a surface roughness of 50 nm or less.
  • the mechanical polishing speed is 800 rpm.
  • the electrochemical workstation is used as the polishing power source, and the Ag/AgCl electrode is used as the reference electrode.
  • the 85% phosphoric acid and polyethylene glycol mixture with a volume ratio of 3:1 is used as the electrochemical polishing liquid; the copper foil to be polished is placed.
  • a copper plate is used as a negative electrode; an electrochemical polishing voltage is 1 to 2 V, and a polishing time is 1800 s.
  • the copper foil was ultrasonically cleaned by acetone for 10 min, ultrasonically washed with 25% hydrochloric acid for 10 min, and finally the copper foil was cleaned with alcohol.
  • Annealing the copper foil The copper foil is heated to 1035 ° C under the protection of a mixture of hydrogen and argon gas to make Cu crystal grains Growing up, the surface is flat and defect-free, releasing the surface stress of the copper substrate.
  • the working pressure of the chamber is between 4000 and 1000 Pa
  • the flow rate of hydrogen is 30 sccm
  • the flow rate of argon is 300 sccm.
  • the purity of the gas used for annealing the copper foil is 99.999%, and the annealing time is 30 min;
  • the annealed copper foil is placed in a high temperature heating zone of the tube furnace.
  • 15 mg of benzene liquid carbon source was weighed into a quartz tube closed at one end, and placed in a low temperature heating zone of the tube furnace.
  • the furnace temperature is raised to 500-700 V, while the benzene liquid carbon source is heated to 150-200 ° C, the hydrogen flow rate is 30 sccm, the argon flow rate is 300 sccm, the reaction time is 30 min, and the working pressure is between 4000 and 1000 Pa.
  • the liquid source and the tube furnace were stopped, and the sample was taken out after the chamber was lowered to room temperature.
  • the purity of the carrier gas used in the chemical vapor phase reaction is higher than 99.999%.
  • a layer of PMMA/anisole solvent is spin-coated on the graphene/copper foil surface by a spin coater.
  • the PMMA film thickness is 200-400 nm. Then, it was dried in a vacuum oven at 150 ° C for 5 minutes to remove the organic solvent.
  • the copper foil was floated in an ammonium persulfate solution with a concentration of 0.1 mol/L to remove copper and react for 5 hours. Then rinse with deionized water for 3-5 times to wash the copper ions in the solution.
  • Figure 4 is a Raman diagram of graphene prepared at 600 °C.
  • the Raman test shows that the graphene has good crystallinity, and the peak intensity ratio of I2D/IG of the 2D peak and the G peak is 1.75. The D defect peak is small; the crystallinity of the graphene prepared at 500 ° C and 700 ° C is basically the same.
  • Figure 5 is a light transmittance test chart of graphene prepared at 600 ° C, showing that benzene is used as a liquid carbon source to obtain a graphene transmittance of 96.6%, which is a single layer of graphene; at 500 ° C and 700 The transmittance of graphene prepared under °C conditions is basically the same. As shown in Fig. 6, the optical photographs show that the large-area graphene transferred to the glass substrate by chemical means has no significant macroscopic breakage and is a complete large-area single-layer graphene.
  • Example 2 The benzene liquid carbon source in Example 1 was changed to a naphthalene solid carbon source of 15 mg.
  • the heating temperature of the naphthalene solid source during the growth of graphene is 80-120 ° C, and the other processes are the same as in the first embodiment.
  • Fig. 4 is a Raman diagram of graphene prepared at 600 ° C. Raman test shows that the graphene has good crystallinity, and the peak intensity ratio of 2D peak and G peak is 1.9, and I2D/IG is 1.9. D defect peak is small; at 500 ° C and The crystallinity of the graphene prepared at 700 ° C is basically the same.
  • Figure 7 is a light transmittance test chart of graphene prepared at 600 ° C, showing that the use of naphthalene as a solid carbon source yields a graphene transmittance of 96.7%, which is a single layer of graphene; at 500 ° C and 700
  • the transmittance of graphene prepared under °C conditions is basically the same.
  • the optical photographs show that the large-area graphene transferred by chemical means onto the glass substrate has no significant macroscopic damage and is a complete large-area single-layer graphene.
  • Example 3 The benzene liquid carbon source in Example 1 was changed to a phenanthrene solid carbon source of 15 mg.
  • the phenanthrene solid source heating temperature is 100-150 V, and other processes are the same as in the first embodiment.
  • Fig. 4 is a Raman diagram of graphene prepared at 600 ° C. Raman test shows that the graphene has good crystallinity, and the peak intensity ratio of I2D/IG of the 2D peak and the G peak is 1.65. The D defect peak is small; the crystallinity of the graphene prepared at 500 ° C and 700 ° C is basically the same.
  • Figure 8 is a light transmittance test chart of graphene prepared at 600 ° C, showing that the transmittance of graphene is 96.5% using phenanthrene as a solid carbon source; it is a single layer graphene; at 500 ° C and 700 The transmittance of graphene prepared under °C conditions is basically the same.
  • the optical photographs show that the large-area graphene transferred by chemical means to the glass substrate has no significant macroscopic damage and is a complete large-area single-layer graphene.
  • Example 4 The benzene liquid carbon source in Example 1 was changed to a solid carbon source of 15 mg.
  • the phenanthrene solid source heating temperature is 150-200 V, and other processes are the same as in the first embodiment.
  • Fig. 4 is a Raman diagram of graphene prepared at 600 ° C.
  • the Raman test shows that the graphene has good crystallinity, and the peak intensity ratio I 2 / Ifj of the 2D peak and the G peak is 2.0. At the same time, the D defect peak is small; the crystallinity of the graphene prepared at 500 ° C and 700 ° C is basically the same.
  • Figure 9 is a light transmittance test chart of graphene prepared at 600 ° C, showing that the ruthenium is used as a solid carbon source to obtain a graphene transmittance of 96.5%, which is a single layer of graphene; at 500 ° C and 700
  • the transmittance of graphene prepared under °C conditions is basically the same. Its optical photographs show that large-area graphene that is chemically transferred to a glass substrate has no significant macroscopic damage and is a complete large-area single-layer graphene.
  • Example 5 The benzene liquid carbon source of Example 1 was changed to 15 mg of a solid carbon source.
  • the heating temperature of the phenanthrene solid source is 280-350 ° C, and other processes are the same as in the first embodiment.
  • FIG. 4 is a Raman diagram of graphene prepared at 600 ° C. The Raman test shows that the graphene has good crystallinity, and the peak intensity ratio I ⁇ /Ifj of the 2D peak and the G peak is 1.94. At the same time, the D defect peak is small; the crystallinity of the graphene prepared at 500 ° C and 700 ° C is basically the same.
  • Figure 10 is a light transmittance test chart of graphene prepared at 600 ° C, showing that the ruthenium is used as a solid carbon source to obtain a graphene transmittance of 96.7%, which is a single layer of graphene; at 500 ° C and 700
  • the transmittance of graphene prepared under °C conditions is basically the same.
  • the optical photographs show that the large-area graphene transferred by chemical means onto the glass substrate has no significant macroscopic damage and is a complete large-area single-layer graphene.
  • Example 6 Growth of graphene using hexacene as a carbon source.
  • the hexacene benzene/toluene mixed solution was spin-coated on the surface of the copper foil, followed by low temperature heating of the copper foil substrate to catalyze the growth of graphene.
  • the surface of the copper substrate was treated by mechanical polishing and electrochemical polishing to achieve a surface roughness of 50 nm or less; the mechanical polishing speed was 800 rpm.
  • the electrochemical workstation was used as the polishing power source, and the Ag/AgCl electrode was used as the reference electrode.
  • the 85% phosphoric acid and polyethylene glycol mixture with a volume ratio of 3:1 was used as the electrochemical polishing solution.
  • the copper foil to be polished is placed on the positive electrode, and the copper plate is used as the negative electrode. Electrochemical polishing voltage 1 ⁇ 2V, polishing time 1800s;
  • the copper foil is ultrasonically cleaned by acetone for 10 min, ultrasonically washed with 25% hydrochloric acid for 10 min, and finally the copper foil is rinsed with deionized water;
  • Annealing the copper foil The copper foil is heated to 1035 °C under the protection of a mixed gas of hydrogen and argon to grow the Cu crystal grains, the surface is flat and free from defects, and the surface stress of the copper substrate is released.
  • the working pressure of the chamber is between 4000 and 1000 Pa
  • the flow of hydrogen is 30 sccm
  • the flow of argon is 300 sccm.
  • the purity of the gas used for annealing the copper foil is 99.999%, and the annealing time is 30 min;
  • the hexabenzophenone/toluene solution is spin-coated on the annealed and destressed copper foil substrate by a spin coater at a solution concentration of 5-20 mg/mL.
  • the speed of the spin coater is 1200 rpm, the spin coating time is 30 s, and then it is placed in a heating furnace at 150 ° C for drying;
  • the working pressure is between 4000 and 1000 Pa.
  • the purity of the carrier gas used in the chemical vapor phase reaction is higher than 99.999%;
  • a layer of PMMA/anisole solvent is spin-coated on the surface of graphene/copper with a spin coater.
  • the PMMA has a thickness of 200-400 nm. Then, it was dried in a vacuum drying oven at 150 ° C for 5 min to remove the organic solvent; (7)
  • the copper foil was floated in an ammonium persulfate solution having a concentration of 0.1 mol/L to remove copper and react for 5 hours. Subsequently, it is washed 3-5 times with deionized water to wash the copper ions in the solution;
  • Figure 4 is a Raman diagram of graphene prepared at 600 ° C.
  • the Raman test shows that the hexacene benzene can be directly coated on the surface of the Cu foil by chemical vapor phase reaction.
  • Crystalline quality graphene, the peak intensity ratio of 2D peak and G peak is I 2D /I (i is 1.6, and the D defect peak is small; the crystallinity of graphene prepared at 500 ° C and 700 ° C is Basically the same.
  • Figure 11 is a light transmittance test chart of graphene prepared at 600 ° C, the transmittance of which is 96.5%, is a single layer of graphene; prepared at 500 ° C and 700 ° C
  • the transmittance of graphene is basically the same.
  • the optical photographs show that the large-area graphene transferred to the glass substrate by chemical method has no obvious macroscopic damage, and is a complete large-area single-layer graphene.

Abstract

一种多苯环碳源低温化学气相沉积生长大面积石墨烯的制备方法，以多苯环芳香族碳氢化合物作为碳源，采用碳源分解法或碳源旋涂法在铜箔表面生长出石墨烯；所述多苯环芳香族碳氢化合物为苯或稠环芳烃。

Description

一种利用多苯环碳源低温化学气相沉积生长大面积石墨烯的方法
技术领域 本发明涉及一种石墨烯的制备方法， 具体涉及一种利用多苯环碳源低温化学气相沉积生 长大面积石墨烯的方法。
背景技术 石墨烯是单层原子厚度的石墨， 具有二维蜂窝状网格结构。 由于石墨烯片平面内 π轨道 的存在， 电子可在晶体中自由移动， 使得石墨烯具有十分优异的电子传输性能。 由于具有优 异的力学、 热学、 电学和磁学性能， 石墨烯有望在高性能纳电子器件、 复合材料、 场发射材 料、 气体传感器、 能量储存等领域获得广泛应用。 石墨烯在结构上具有延展性， 其电学、 光 学以及声学特性都可以通过应力和形变进行大幅调整。 甚至可以改变石墨烯的带宽结构， 对 弯曲、 折叠以及卷曲的石墨烯的研究也正开始加速。 石墨烯拥有无与伦比的高电子迁移率， 电荷在石墨烯中的迁移速率可以到达前所未有的 200000 cm2/vs， 超过硅 100倍以上。 这一优 势使得石墨烯很有可能取代硅成为下一代超高频率晶体管的基础材料而广泛应用于高性能集 成电路和新型纳米电子器件中。 预计不久就会出现全由石墨烯构成的全碳电路并广泛应用于 人们的日常生活中。
传统制备方法在制备石墨烯过程中所需要的衬底温度大都在 1000°C的高温下， 而且高纯 气源价格均比较昂贵。 这无疑为材料的应用带来了很大的限制。 因此寻找合适的实验技术在 较低温的衬底上实现石墨烯的低温生长的研究成为当前该领域人们极为关注的方向。 目前主 流的低温衬底制备方法有等离子体辅助增强化学反应气相沉积法， 化学还原氧化石墨烯法等。 但是采用这些方法直接沉积的石墨烯面积很小， 结晶质量差， 而且缺陷很多。
发明内容 本发明的目的在于克服以上现有技术的不足， 提供一种利用多苯环碳源低温化学气相沉 积生长大面积石墨烯的方法， 以解决现有技术中制备的石墨烯面积小、 结晶质量差、 缺陷多 的技术问题。 为解决上述技术问题，本发明采用固态或液态的多苯环芳香族碳氢化合物取代甲烷作为碳 源， 控制碳源的分解速率从而使腔室内碳活性基元达到足够低的分压， 以实现使生长出的石 墨烯的层数可控； 并成功将其完整地转移至各种柔性衬底上， 几乎没有任何宏观破损。
本发明具体采用如下技术方案：
一种低温化学气相沉积生长大面积石墨烯的方法， 其特征在于： 以多苯环芳香族碳氢化合 物作为碳源， 采用碳源分解法或碳源旋涂法在铜箔表面生长出石墨烯。
优选的， 所述多苯环芳香族碳氢化合物为苯或稠环芳烃。 优选的， 所述稠环芳烃选自萘、 蒽、 菲、 芘、 茈和六苯并苯等物质。
较佳的， 所述铜箔为纯度不小于 99.99%的无氧铜箔， 其典型厚度为 50-200微米。
较佳的， 所述铜箔的表面粗糙度在 50nm以下， 优选为 30nm以下。
较佳的， 在生长石墨烯之前， 先将铜箔在保护气氛下进行退火处理， 以使 Cu晶粒长大， 表面平坦无缺陷， 释放铜箔表面应力。 优选的， 所述退火过程的温度保持在 900-1050°C， 气 压在 4000-lOOOOPa之间， 退火时间控制在 30-90min之间。
优选的， 所述保护气氛为氩气和氢气的混合气。 更优选的， 所述氩气与氢气的体积流量比 为 10-20: 1。 所用气体纯度均不小于 99.999%。
较佳的， 采用碳源分解法在铜箔表面生长石墨烯时， 具体步骤包括： 将碳源放置在管式炉 的进气端， 将铜箔放置于所述管式炉的中央， 控制所述管式炉中央区域温度为 400-700°C ; 通 入载气， 并将碳源温度升至 80-350°C， 在铜箔表面生长出石墨烯； 然后， 停止加热， 随炉冷 却至室温后取出生长有石墨烯的铜箔。
优选的， 采用碳源分解法在铜箔表面生长石墨烯时， 所述碳源的重量为 15-150mg。
较佳的， 采用碳源旋涂法在铜箔表面生长出石墨烯时， 具体步骤包括： 将碳源溶于甲苯中 制成混合液再旋涂于所述铜箔上， 并将所述铜箔放置于管式炉中央； 通入载气， 并将管式炉 的炉温升至 400-700°C， 在铜箔表面生长出石墨烯； 然后， 停止加热， 随炉冷却至室温后取出 生长有石墨烯的铜箔。
优选的， 所述混合溶液中， 碳源与甲苯的重量体积比为 5-20mg/ml。
优选的， 上述技术方案中， 所述管式炉的升温速度为 20-50°C/min。 当炉温升至生长石墨 烯所需的温度时， 保温 20_40min。
优选的， 上述技术方案中， 石墨烯生长期间的工作气压为 4000-10000Pa。 优选的， 上述技术方案中， 所述载气为氩气和氢气的混合气。 更优选的， 所述氩气与氢气 的体积流量比为 10-20: 1。 所用气体纯度均不小于 99.999%。
优选的， 上述技术方案中， 所述载气的流量为 300-500sccm。
进一步的， 本发明所提供的上述生长大面积石墨烯的方法， 还包括将制备出的石墨烯转移 至目标衬底上的如下步骤：
( 1 )在生长有石墨烯的铜箔表面旋涂一层 PMMA (聚甲基丙烯酸甲酯） 薄膜； 将其漂浮 于过硫酸铵水溶液中腐蚀去除铜箔， 随后用去离子水清掉溶液中的铜离子；
(2) 将去除铜箔后的 PMMA/石墨烯转移到目标衬底上， 再整体浸泡于丙酮中溶解去除 PMMA, 采用酒精清洗去除残留的丙酮， 最后退火处理去除残留的 PMMA。
优选的， 所述 PMMA薄膜的厚度为 200-400 nm。
优选的， 步骤 （2) 中， 所述退火处理于还原或者惰性气氛中进行， 退火温度为 300-450 V , 退火时间为 40-90min。
优选的， 所述还原或者惰性气氛选自氢气、 氩气或者氢气和氩气的混合气。
本发明采用固态或液态的多苯环芳香族碳氢化合物作为碳源， 低温制备层数可控石墨烯技 术对于石墨烯产业化应用具有重要意义， 是一种具有很大潜力的大面积石墨烯生长的新技术。 与现有石墨烯制备技术相比， 本发明有如下优点：
1) 本方法采用多苯环固态、 液态碳源的方法制备层数可控石墨烯。 含苯环的活性基元作为组 成石墨烯的基本单元， 通过控制固态、 液态碳源的质量和气体流量， 制备得到单层大面积 石墨烯， 并可以通过 PMMA化学转移的方法转移至包括柔性衬底在内的各种衬底上， 且 几乎没有任何宏观破损。
2) 相对于传统化学气相法制备石墨烯。本方法采用固态或液态的多苯环芳香族碳氢化合物取 代甲烷作为碳源， 在较低温度下通过多苯环芳香族碳氢化合物 分解产生的含苯环的活性 单体在铜衬底催化下制备大面积石墨烯。 控制固态、 液态源分解速率使腔室内碳活性基元 达到足够低的分压低温下得到高质量石墨烯， 极大的降低了制备石墨烯的成本。
3) 本发明采用机械抛光和化学抛光的方法对衬底进行预处理，使衬底表面平整度达到 。!!!^ 使得在其上通过铜金属催化沉积得到的石墨烯具有较少的缺陷和良好的结晶性能。
4) 本发明的方法可减少高纯气体的消耗， 降低制备温度并大大縮短制备时间， 可降低大尺寸 石墨烯的生产成本， 从而为实现在柔性衬底上研制与开发出电学性能优异、 制备成本低且 环保的新一代石墨烯微电子器件提供实验依据和指导思路， 最终实现以石墨烯为基础的微 电子器件的大规模应用。
附图说明
图 1为本发明的低温化学气相沉积生长石墨烯的装置示意图；
图 2为机械抛光和电化学抛光后的铜箔表面的 AFM照片；
图 3为本发明中铜箔表面催化生长石墨烯的光学显微镜照片。
图 4 为本发明的多苯环碳源低温化学气相法制备石墨烯拉曼图。
图 5 为本发明的苯碳源低温制备的到的石墨烯转移至石英衬底后的透过率图。
图 6 为本发明的多苯环碳源低温制备石墨烯 SEM照片。
图 7 为本发明的萘碳源低温制备的到的石墨烯转移至石英衬底后的透过率图。
图 8为本发明的菲碳源低温制备的到的石墨烯转移至石英衬底后的透过率图。
图 9为本发明的芘碳源低温制备的到的石墨烯转移至石英衬底后的透过率图。
图 10为本发明的茈碳源低温制备的到的石墨烯转移至石英衬底后的透过率图。
图 11为本发明的六苯并苯碳源低温制备的到的石墨烯转移至石英衬底后的透过率图。
具体实施方式 本发明的主要创新之处在于在较低温度下通过多苯环芳香族碳氢化合物作为碳源分解产 生的活性含苯环单体在铜衬底催化下制备层数可控石墨烯， 以解决现有技术中制备的石墨烯 面积小、 结晶质量差、 缺陷多的技术问题。 为此， 本发明提供了一种低温化学气相沉积生长 大面积石墨烯的方法， 该方法以多苯环芳香族碳氢化合物作为碳源， 采用碳源分解法或碳源 旋涂法在铜箔表面生长出石墨烯。
本发明采用的固态或液态的多苯环芳香族碳氢化合物受热会分解成制备石墨烯所必须的 含苯环活性基元， 这些含苯环的活性基元作为组成石墨烯的基本单元， 很容易在低温下通过 金属衬底的催化和氢气的作用， 形成大面积层数可控的石墨烯。 本发明中所述的多苯环芳香 族碳氢化合物是指常温下呈液态或固态且分子式中含有至少一个苯环的碳氢化合物。优选的， 所述多苯环芳香族碳氢化合物为苯或稠环芳烃。 更优选的， 所述稠环芳烃选自萘、 蒽、 菲、 芘、 茈和六苯并苯等物质。
可选地， 在上述技术方案中， 所述铜箔为纯度不小于 99.99%的无氧铜箔， 其典型厚度为 50-200微米。 例如可选用 Alfa Aesar 99.99% 高纯无氧铜箔。
可选地， 在上述技术方案中， 所述铜箔的表面粗糙度在 50nm以下， 优选为 30nm以下。 可通过先后采用机械抛光和电化学抛光的方法处理铜铂表面，达到使表面粗糙度达到 50nm以 下。 机械抛光和电化学抛光的方法均为本领域技术人员所熟知， 例如可采用如下工艺条件： 机械抛光转速可选用 800转 /min; 电化学抛光液可选用体积比为 3: 1的 85%磷酸和聚乙二醇的 混合液； 电化学抛光的电压为 1〜2V， 抛光时间 1800s; 电化学抛光结束后将铜箔经丙酮超声 清洗 lOmin, 再用 25%盐酸超声清洗 lOmin, 最后用酒精将铜箔清洗干净。
可选地， 在上述技术方案中， 在生长石墨烯之前， 需先将表面粗糙度在 50nm以下 （优选 为 30nm以下） 的铜箔在保护气氛下进行退火处理， 以使 Cu晶粒长大， 表面平坦无缺陷， 释 放铜箔表面应力。 优选的， 所述退火过程的温度保持在 900-1050°C， 气压在 4000-lOOOOPa之 间， 退火时间控制在 30-90min之间。 优选的， 所述保护气氛为氩气和氢气的混合气。 更优选 的， 所述氩气与氢气的体积流量比为 10: 1。 所用气体纯度均不小于 99.999%。
可选地， 在上述技术方案中， 采用碳源分解法在铜箔表面生长石墨烯时， 具体步骤包括： 将碳源放置在管式炉的进气端， 将铜箔放置于所述管式炉的中央， 控制所述管式炉中央区域 温度为 400-700°C ; 通入一定流量的载气， 并将碳源温度升至 80-350°C， 在铜箔表面生长出石 墨烯； 然后， 停止加热， 随炉冷却至室温后取出生长有石墨烯的铜箔。 每炉生长石墨烯所用 的碳源的重量为 15-150mg。
可选地，在上述技术方案中，采用碳源旋涂法在铜箔表面生长出石墨烯时，具体步骤包括: 将碳源溶于甲苯中制成混合液再旋涂于所述铜箔上， 并将所述铜箔放置于管式炉中央； 通入 一定流量的载气， 并将管式炉的炉温升至 400-700°C， 在铜箔表面生长出石墨烯； 然后， 停止 加热， 随炉冷却至室温后取出生长有石墨烯的铜箔。 优选的， 所述混合溶液中， 碳源与甲苯 的重量体积比为 5-20mg/ml。 所述旋涂采用旋涂机进行， 其转速为 1000-2000r/min。
可选地， 上述技术方案中， 所述管式炉的升温速度为 20-50°C/min。 当炉温升至生长石墨 烯所需的温度时， 保温 20_40min。 石墨烯生长期间的工作气压为 4000-10000Pa。
可选地， 上述技术方案中， 所述载气为氩气和氢气的混合气。 更优选的， 所述氩气与氢气 的体积流量比为 10-20: 1， 优选为 10: 1。 所用气体纯度均不小于 99.999%。
可选地， 上述技术方案中， 所述载气的流量为 300-500sccm。 可选地，上述技术方案中，还进一步包括将制备出的石墨烯转移至目标衬底上的如下步骤：
( 1 ) 在生长有石墨烯的铜箔表面旋涂一层 PMMA (聚甲基丙烯酸甲酯， 又称有机玻璃） 薄膜； 将其漂浮于过硫酸铵水溶液中腐蚀去除铜箔， 随后用去离子水清掉溶液中的铜离子；
(2) 将去除铜箔后的 PMMA/石墨烯转移到目标衬底上， 再整体浸泡于丙酮中溶解去除 PMMA, 采用酒精清洗去除残留的丙酮， 最后退火处理去除残留的 PMMA。
所述旋涂 PMMA薄膜的方法为本领域的技术人员所熟知，例如可将 PMMA溶于有机溶剂 (如苯酚， 苯甲醚等） 中， 通过旋涂机旋涂于铜箔上。
优选的， 所述 PMMA薄膜的厚度为 200-400 nm。
优选的， 步骤 （2) 中， 所述退火处理于还原或者惰性气氛中进行， 退火温度为 300-450 V , 退火时间为 40-90min。
优选的， 所述还原或者惰性气氛选自氢气、 氩气或者氢气和氩气的混合气。
本发明中， 所述目标衬底包括但不限于各种金属衬底， 还可以为用于半导体器件的各种衬 底， 例如硅、 二氧化硅、 绝缘体上硅 （soi)、 ιι-νι或者 m-v族化合物半导体衬底等 （例如
Ge、 GaAs、 GaN、 InP等）。 下面结合图示更完整的描述本发明， 本发明提供的优选实施例， 不应被认为仅限于在此 阐述的实施例中。 参考图是本发明的示意图， 图中的表示只是示意性质的， 不应该被认为限 制本发明的范围。
请参见图 1， 其为本发明的低温化学气相沉积生长石墨烯的装置示意图。 图中箭头方向为 载体流动方向， 其中： 1为进气端， 2为出气端， 3为管式加热炉， 4为碳源， 5为铜箔， 6为 回转泵。 由于化学气相沉积工艺及其所用装置均为本领域技术人员所熟知， 故在此不再赘述。 实施例 1： 苯液态碳源低温生长大面积单层石墨烯
(1) 采用铜箔作为衬底， 先后采用机械抛光和电化学抛光的方法处理铜衬底表面， 使表面粗糙 度达到 50nm以下。机械抛光转速 800转 /min。采用电化学工作站为抛光电源，选用 Ag/AgCl 电极作为参比电极， 选用体积比为 3:1的 85%磷酸和聚乙二醇混合液为电化学抛光液； 将 所需抛光的铜箔放置于正极，采用铜片作为负极； 电化学抛光电压 1〜2V，抛光时间 1800s。
(2) 电化学抛光结束后将铜箔经丙酮超声清洗 lOmin, 再用 25%盐酸超声清洗 lOmin, 最后用 酒精将铜箔清洗干净。
(3) 将铜箔进行退火处理： 将铜箔在氢气和氩气混合气体的保护下升温至 1035°C， 使 Cu晶粒 长大， 表面平坦无缺陷， 释放铜衬底表面应力。退火过程中腔室工作气压在 4000-lOOOOPa 之间， 氢气流量为 30sccm， 氩气流量 300sccm。 铜箔退火所用气体纯度均为 99.999% ， 退火时间 30min;
(4) 待炉温降至室温后， 将经过退火处理的铜箔放入管式炉高温加热区。 同时称取苯液态碳源 15mg于一端封闭的石英试管中， 并将其放置于管式炉低温加热区。 将炉温升至 500-700 V , 同时加热苯液态碳源至 150-200 °C， 氢气流量为 30sccm氩气流量为 300sccm， 反应时 间 30 min， 工作气压为 4000-lOOOOPa之间。 最后停止加热液态源和管式炉， 腔室降至室 温后取出样品。 化学气相反应所用载气纯度高于 99.999%。
(5) 采用旋涂机在石墨烯 /铜箔表面旋涂一层 PMMA/苯甲醚溶剂， 溶剂配比为： PMMA:苯甲 醚 =1 :9 (体积比）， 旋涂机转速 3000转 /min， 旋涂时间 45s。 PMMA膜厚度为 200-400 nm。 然后置于真空干燥箱中 150°C干燥 5min， 去除有机溶剂。
(6) 将铜箔漂浮于浓度为 0.1 mol/L的过硫酸铵溶液中腐蚀去除铜， 反应 5h。 随后选用去离子 水清洗 3-5遍， 洗净溶液中的铜离子。
(7) 将去除铜箔后的 PMMA/石墨烯转移到目标衬底上， 再整体浸泡于丙酮中 3h溶解去除 PMMA, 采用酒精缓慢清洗去除残留的丙酮， 最后于 450°C下在氢气和氩气混合气中退火 处理衬底 /石墨烯去除残留的 PMMA。 氢气、 氩气的流量分别为 lOOsccm和 300sccm， 退 火时间为 40-90min。
实施例结果： 图 4为在 600°C条件下制备得到的石墨烯的拉曼图， Raman测试表明该 石墨烯结晶性较好， 2D峰和 G峰的峰强比 I2D/IG为 1.75， 同时 D缺陷峰很小； 在 500°C 和 700°C条件下制备得到的石墨烯的结晶性能与之基本相同。 图 5为在 600°C条件下制备 得到的石墨烯的透光率测试图， 说明采用苯作为液态碳源得到石墨烯透过率达到 96.6%， 为单层石墨烯； 在 500°C和 700°C条件下制备得到的石墨烯的透过率与之基本相同。 如图 6所示， 光学照片表明， 通过化学方法转移至玻璃衬底上的大面积石墨烯没有明显的宏观 破损， 为完整的大面积单层石墨烯。
实施例 2: 将实施例 1 中的苯液态碳源改为萘固态碳源 15mg。 生长石墨烯过程中萘固态 源加热温度为 80-120°C， 其他工艺与实施例 1相同。
实施例结果： 图 4为在 600°C条件下制备得到的石墨烯的拉曼图， Raman测试表明该 石墨烯结晶性较好， 2D峰和 G峰的峰强比 I2D/IG为 1.9， 同时 D缺陷峰很小； 在 500°C和 700°C条件下制备得到的石墨烯的结晶性能与之基本相同。 图 7为在 600°C条件下制备得 到的石墨烯的透光率测试图， 说明采用萘作为固态碳源得到石墨烯透过率达到 96.7%， 为 单层石墨烯； 在 500°C和 700°C条件下制备得到的石墨烯的透过率与之基本相同。 其光学 照片表明， 通过化学方法转移至玻璃衬底上的大面积石墨烯没有明显的宏观破损， 为完整 的大面积单层石墨烯。
实施例 3: 将实施例 1 中苯液态碳源改为菲固态碳源 15mg。 生长石墨烯过程中菲固态源 加热温度为 100-150 V , 其他工艺与实施例 1相同。
实施例结果： 图 4为在 600°C条件下制备得到的石墨烯的拉曼图， Raman测试表明该 石墨烯结晶性较好， 2D峰和 G峰的峰强比 I2D/IG为 1.65， 同时 D缺陷峰很小； 在 500°C 和 700°C条件下制备得到的石墨烯的结晶性能与之基本相同。 图 8为在 600°C条件下制备 得到的石墨烯的透光率测试图， 说明采用菲作为固态碳源得到石墨烯透过率达到 96.5%， 为单层石墨烯； 在 500°C和 700°C条件下制备得到的石墨烯的透过率与之基本相同。 其光 学照片表明， 通过化学方法转移至玻璃衬底上的大面积石墨烯没有明显的宏观破损， 为完 整的大面积单层石墨烯。
实施例 4: 将实施例 1 中苯液态碳源改为芘固态碳源 15mg。 生长石墨烯过程中菲固态源 加热温度为 150-200 V , 其他工艺与实施例 1相同。
实施例结果： 图 4为在 600°C条件下制备得到的石墨烯的拉曼图， Raman测试表明该 石墨烯结晶性较好， 2D峰和 G峰的峰强比 I^/Ifj为 2.0， 同时 D缺陷峰很小； 在 500°C和 700°C条件下制备得到的石墨烯的结晶性能与之基本相同。 图 9为在 600°C条件下制备得 到的石墨烯的透光率测试图， 说明采用芘作为固态碳源得到石墨烯透过率达到 96.5%， 为 单层石墨烯； 在 500°C和 700°C条件下制备得到的石墨烯的透过率与之基本相同。 其光学 照片表明， 通过化学方法转移至玻璃衬底上的大面积石墨烯没有明显的宏观破损， 为完整 的大面积单层石墨烯。
实施例 5: 将实施例 1 中苯液态碳源改为茈固态碳源 15mg。 生长石墨烯过程中菲固态源 加热温度为 280-350°C， 其他工艺与实施例 1相同。 实施例结果： 图 4为在 600°C条件下制备得到的石墨烯的拉曼图， Raman测试表明该 石墨烯结晶性较好， 2D峰和 G峰的峰强比 I^/Ifj为 1.94， 同时 D缺陷峰很小； 在 500°C 和 700°C条件下制备得到的石墨烯的结晶性能与之基本相同。图 10为在 600°C条件下制备 得到的石墨烯的透光率测试图， 说明采用茈作为固态碳源得到石墨烯透过率达到 96.7%， 为单层石墨烯； 在 500°C和 700°C条件下制备得到的石墨烯的透过率与之基本相同。 其光 学照片表明， 通过化学方法转移至玻璃衬底上的大面积石墨烯没有明显的宏观破损， 为完 整的大面积单层石墨烯。
实施例 6:采用六苯并苯作为碳源生长石墨烯。将六苯并苯 /甲苯混合溶液旋涂于铜箔表面， 随后低温加热铜箔衬底催化生长石墨烯。
(1) 采用铜箔作为衬底， 先后采用机械抛光和电化学抛光的方法处理铜衬底表面， 使表面粗糙 度达到 50nm以下；机械抛光转速 800转 /min。采用电化学工作站为抛光电源，选用 Ag/AgCl 电极作为参比电极； 采用体积比为 3: 1的 85%磷酸和聚乙二醇混合液为电化学抛光液。所 需抛光的铜箔放置于正极， 采用铜片作为负极。 电化学抛光电压 1〜2V， 抛光时间 1800s;
(2) 电化学抛光结束后将铜箔经丙酮超声清洗 lOmin, 再用 25%盐酸超声清洗 lOmin, 最后用 去离子水将铜箔冲洗干净；
(3) 将铜箔进行退火处理： 将铜箔在氢气和氩气混合气体的保护下升温至 1035 °C， 使 Cu晶粒 长大， 表面平坦无缺陷， 释放铜衬底表面应力。退火过程中腔室工作气压在 4000-lOOOOPa 之间， 氢气流量为 30sccm， 氩气流量 300sccm。 铜箔退火所用气体纯度均为 99.999% ， 退火时间 30min;
(4) 待炉温降至室温后， 采用旋涂机在退火去应力的铜箔衬底上旋涂六苯并苯 /甲苯溶液， 溶 液浓度为 5-20 mg/mL。 旋涂机转速 1200转 /min， 旋涂时间 30s， 随后放置于 150°C的加热 炉中烘干；
(5) 将旋涂有六苯并苯固态源的铜箔衬底放入腔室中， 将炉温升温至 500-700°C， 氢气流量为
30sccm氩气流量 300sccm， 反应时间 30 min, 最后停止加热使石英管降至室温。 工作气 压为 4000-lOOOOPa之间。 化学气相反应所用载气纯度高于 99.999%;
(6) 采用旋涂机在石墨烯 /铜箔表面旋涂一层 PMMA/苯甲醚溶剂， 溶剂配比为： PMMA:苯甲 醚 =1 :9 (体积比）， 旋涂机转速为 3000转 /min， 旋涂时间 45s。 PMMA厚度为 200-400 nm。 然后置于真空干燥箱中 150°C干燥 5min， 去除有机溶剂； (7) 将铜箔漂浮于浓度为 0.1 mol/L的过硫酸铵溶液中腐蚀去除铜， 反应 5h。 随后选用去离子 水清洗 3-5遍， 洗净溶液中的铜离子；
(8) 将去除铜箔后的 PMMA/石墨烯 转移到目标衬底上， 再整体浸泡于丙酮中 3h溶解去除 PMMA, 采用酒精缓慢清洗去除残留的丙酮， 最后于 450°C下在氢气和氩气混合气中退火 处理衬底 /石墨烯去除残留的 PMMA。 氢气、 氩气的流量分别为 lOOsccm和 300sccm， 退 火时间为 40-90min。
实施例结果： 图 4为在 600°C条件下制备得到的石墨烯的拉曼图， Raman测试表明通 过直接将六苯并苯悬涂在 Cu箔表面， 利用化学气相反应同样可以制备得到的高结晶质量 石墨烯， 2D峰和 G峰的峰强比 I2D/I(i为 1.6， 同时 D缺陷峰很小； 在 500°C和 700°C条件 下制备得到的石墨烯的结晶性能与之基本相同。 图 11 为在 600°C条件下制备得到的石墨 烯的透光率测试图， 其透过率达到 96.5%， 为单层石墨烯； 在 500°C和 700°C条件下制备 得到的石墨烯的透过率与之基本相同。其光学照片表明， 通过化学方法转移至玻璃衬底上 的大面积石墨烯没有明显的宏观破损， 为完整的大面积单层石墨烯。

Claims

权利要求书
1. 一种化学气相沉积生长石墨烯的方法， 其特征在于： 以多苯环芳香族碳氢化 合物作为碳源， 采用碳源分解法或碳源旋涂法在铜箔表面生长出石墨烯。
2. 如权利要求 1所述的化学气相沉积生长石墨烯的方法， 其特征在于： 所述多 苯环芳香族碳氢化合物为苯或稠环芳烃。
3. 如权利要求 2所述的化学气相沉积生长石墨烯的方法， 其特征在于： 所述稠 环芳烃选自萘、 蒽、 菲、 芘、 茈和六苯并苯。
4. 如权利要求 1所述的化学气相沉积生长石墨烯的方法， 其特征在于： 所述铜 箔的表面粗糙度在 50nm以下。
5. 如权利要求 1或 4所述的化学气相沉积生长石墨烯的方法， 其特征在于： 在 生长石墨烯之前， 先将所述铜箔在保护气氛下进行退火处理， 所述退火过程 的温度保持在 900-1050°C， 气压在 4000-10000Pa 之间， 退火时间控制在 30-90min之间。
6. 如权利要求 1所述的化学气相沉积生长石墨烯的方法， 其特征在于： 所述保 护气氛为氩气和氢气的混合气。
7. 如权利要求 1所述的化学气相沉积生长石墨烯的方法， 其特征在于：
采用碳源分解法在铜箔表面生长石墨烯时， 具体步骤包括： 将碳源放置 在管式炉的进气端， 将铜箔放置于所述管式炉的中央， 控制所述管式炉中央 区域温度为 400-700 °C ; 通入载气， 并将碳源温度升至 80-350 °C， 在铜箔表 面生长出石墨烯； 然后， 停止加热， 随炉冷却至室温后取出生长有石墨烯的 铜箔；
采用碳源旋涂法在铜箔表面生长出石墨烯时， 具体步骤包括： 将碳源溶 于甲苯中制成混合液再旋涂于所述铜箔上， 并将所述铜箔放置于管式炉中 央； 通入载气， 并将管式炉的炉温升至 400-700°C， 在铜箔表面生长出石墨 烯； 然后， 停止加热， 随炉冷却至室温后取出生长有石墨烯的铜箔。
8. 如权利要求 7所述的化学气相沉积生长石墨烯的方法， 其特征在于：
采用碳源分解法在铜箔表面生长石墨烯时， 所述碳源的重量为 15-150mg; 采用碳源旋涂法在铜箔表面生长出石墨烯时， 所述混合溶液中， 碳源与甲苯 的重量体积比为 5-20mg/ml。
9. 如权利要求 7-8任一所述的化学气相沉积生长石墨烯的方法， 其特征在于： 当炉温升至生长石墨烯所需的温度时， 保温 20-40min; 石墨烯生长期间的工 作气压为 4000-10000Pa。
10.如权利要求 9所述的化学气相沉积生长石墨烯的方法， 其特征在于： 所述载 气为氩气和氢气的混合气。
11.如权利要求 1-4、 6-8或 10中任一所述的化学气相沉积生长石墨烯的方法， 其特征在于： 还包括将制备出的石墨烯转移至目标衬底上的如下步骤：
( 1 )在生长有石墨烯的铜箔表面旋涂一层 PMMA薄膜； 将其漂浮于过硫酸 铵水溶液中腐蚀去除铜箔， 随后用去离子水清掉溶液中的铜离子；
(2)将去除铜箔后的 PMMA/石墨烯转移到目标衬底上， 再整体浸泡于丙酮 中溶解去除 PMMA, 采用酒精清洗去除残留的丙酮， 最后退火处理去除残留的 PMMAo
12.如权利要求 11所述的化学气相沉积生长石墨烯的方法，其特征在于：步骤 (2) 中， 所述退火处理于还原或者惰性气氛中进行， 退火温度为 300-450°C， 退火 时间为 40-90min。
13.如权利要求 12所述的化学气相沉积生长石墨烯的方法，其特征在于： 所述还 原或者惰性气氛选自氢气、 氩气或者氢气和氩气的混合气。
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