CN102134067A - Method for preparing single-layer graphene - Google Patents
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Abstract
The invention discloses a method for preparing single-layer graphene. The method comprises the following steps of: 1) preparing an alloy substrate; and 2) in the hydrogen and inert atmosphere, catalyzing to grow graphene on the surface of the alloy substrate obtained in the step 1) by a chemical vapor deposition method, thereby finishing the preparation of the single-layer graphene. The method makes use of the characteristics of two or more alloy metals in the alloy substrate, realizes control on the decomposition, diffusion and precipitation processes of a carbon source, simply and efficiently restrains the precipitation process of carbon dissolved in the metal substrate to enable the graphene to be capable of growing in a surface catalytic manner to obtain the single-layer graphene with uniform layer distribution, and is suitable for industrial production and particularly for the controllable preparation of single-layer or few-layer graphene.
Description
Technical field
The invention belongs to the two-dimensional film technical field of material, relate to a kind of method for preparing single-layer graphene.
Background technology
Graphene is according to sp by carbon atom
2The two-dimentional monoatomic layer material that becomes key to form.Graphene has a lot of good character, has such as it to show long-range ballistic transport character under very high electronic mobility, the room temperature, and band gap can be regulated and control, and is considered to construct the strong rival of electronic device material of new generation.Conductivity that Graphene is good and light transmission make it in that extraordinary application prospect is arranged aspect the transparent conductance electrode, are expected to be widely used in fields such as touch-screen, liquid-crystal display, organic photovoltaic battery, Organic Light Emitting Diode.The two-dirnentional structure of Graphene uniqueness makes it have bright application prospect in sensor field, and huge surface-area makes it very responsive to environment on every side, even a gas molecule adsorbs or discharges can detect.Exactly because have the character of numerous excellences, Graphene becomes the nova that gets most of the attention in Condensed Matter Physics and the material science, has caused the extensive concern of academia, industry member.The discoverer Britain physicist An Deliehaimu and the Constantine Nuo Woxiaoluofu of Graphene have just obtained Nobel Prize in physics in 2010 after Graphene only is found 6 years.
Method about the Graphene preparation has much at present, peel off highly oriented pyrolytic graphite (HOPG) as mechanical process, liquid phase is peeled off graphite, the chemical reduction graphite oxide, the single-crystal metal epitaxy, the SiC epitaxy, chemical vapor deposition (CVD) is grown on metallic nickel or copper, under the vacuum by metal base segregation growth etc.Wherein, mechanical process is peeled off HOPG, and to obtain the procedure of Graphene uncontrollable, and efficient is low, and the common area of Graphene that obtains is less, and shape, structure are also not reproducible.Causing by the Graphene that the mechanically peel method prepares is one of the most expensive material in the world, and the tiny sampler of human hair's sectional dimension need spend 1000 dollars.At present, higher SiC epitaxy and the CVD method of Graphene preparation efficiency gets most of the attention.But the former experiment condition harshness, substrate costs an arm and a leg, and the Graphene of preparation is difficult to separate, and its thickness determines by Heating temperature, and the Graphene that the preparation big area has single thickness is difficulty relatively; The latter has realized tentatively that at present efficient, qurer prepares large-area Graphene, but often in uneven thickness, the difficult control of the number of plies of Graphene of adopting this method to obtain, and the experiment condition control accuracy requires high.
The Graphene of the different numbers of plies has different character, such as single-layer graphene is high conductive semi-metal, double-layer graphite alkene has the band gap that can be regulated and control by electric field, and the overlapping degree of the conduction band of three layer graphenes and valence band can change by electric field adjusting, and multi-layer graphene (＞10 layers) then has the energy band structure similar with graphite.If the Graphene number of plies skewness of preparation, the character of the Graphene of gained can mix the different qualities of different number of plies Graphenes so, for next step application is made troubles.Therefore, the number of plies how effectively to control Graphene is the key issue in the Graphene preparation.
In existing bibliographical information, in order effectively to control the number of plies of Graphene, people have attempted different metal base and have grown, Low Pressure Chemical Vapor Deposition on Copper Foil can prepare and all once reaching 95% single-layer graphene, yet preparation condition requires harsh, and the generation of multi-layer graphene can't be avoided fully.The metal base of monocrystalline also is used to control the homogeneity of Graphene, the monocrystalline of metals such as nickel cobalt can grow equally distributed Graphene, yet the single-crystal metal substrate costs an arm and a leg, being difficult to recycling after the experience etching in the transfer process of Graphene, is not to be fit to mass preparation and application and industrial method.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing single-layer graphene.
The method for preparing single-layer graphene provided by the invention comprises the steps:
1) preparation alloy substrates;
2) in hydrogen and inert atmosphere, feed the utilization of carbon source chemical gaseous phase depositing process at described step 1) gained alloy substrates surface catalysis growth Graphene, finish the preparation of described single-layer graphene.
The described method for preparing alloy substrates of the described step 1) of aforesaid method is following method a or method b, and wherein, described method a comprises the steps: to prepare one deck metallic film at least on metal base, obtain described alloy substrates;
Described method b comprises the steps: to prepare double layer of metal film at least on non metallic substrate, obtain described alloy substrates.
Among the described method a, the number of plies of described metallic film is one deck or two-layer, preferred one deck; The material that constitutes described metal base and metallic film all is selected from least a in nickel, cobalt, iron, aluminium, gold and silver, copper, zinc, molybdenum, tungsten, titanium, vanadium, chromium, ruthenium, rhodium, platinum, palladium and the iridium, at least a in preferred nickel, cobalt, iron, tungsten and the molybdenum; The thickness of described metal base is 1 μ m～1000 μ m, preferred 25 μ m～200 μ m; The thickness of described metallic film is 5nm～1 μ m, preferred 200nm～500nm, more preferably 200nm;
Among the described method b, the material that constitutes described non metallic substrate is silicon chip, silicon oxide, glass, quartz, silicon carbide or aluminum oxide; The number of plies of described metallic film is two-layer or three layers, and is preferably two-layer; The material that constitutes described metallic film is selected from least a in nickel, cobalt, iron, aluminium, gold and silver, copper, zinc, molybdenum, tungsten, titanium, vanadium, chromium, ruthenium, rhodium, platinum, palladium and the iridium, at least a in preferred nickel, cobalt, iron, tungsten and the molybdenum; The thickness of described non metallic substrate is 1 μ m～1000 μ m, preferred 25 μ m～500 μ m; The thickness of described every layer of metallic film is 5nm～1 μ m, preferred 200nm～500nm, more preferably 200nm.
The method for preparing metallic film among aforesaid method a and the method b is vapour deposition method; In the described vapour deposition method, temperature is 20～100 ℃, preferred 25 ℃; Pressure is 1 * 10
-5Mbar～1 * 10
-8Mbar, preferred 1 * 10
-7Mbar.
Described step 2) step of chemical gaseous phase depositing process is: in hydrogen and inert atmosphere, after described step 1) gained alloy substrates risen to annealing temperature annealing by room temperature, feed carbon source again and rise to growth temperature at described step 1) gained alloy substrates surface catalysis growth Graphene; In the described annealing steps, temperature is 800-1000 ℃, and preferred 900 ℃, the time is 15-60 minute, preferred 20 minutes; In the described catalytic growth step, temperature is 800～1200 ℃, and preferred 900～1100 ℃, more preferably 1000 ℃, the time is 3～180 minutes, specifically can be 5-30 minute, preferred 5～60 minutes; The heating-up time that is risen to the temperature of described annealing steps by room temperature is 25-40 minute, and preferred 5-10 minute, the time that is warming up to the temperature of described catalytic growth step by the temperature of described annealing steps was 5-10 minute, preferred 5 minutes; The flow velocity of described hydrogen is 20sccm-1000sccm, preferred 100sccm-800sccm, more preferably 400sccm; The flow velocity of described rare gas element is 100sccm-1000sccm, preferred 300sccm-600sccm, more preferably 500sccm; The flow velocity of described carbon source is 3sccm-200sccm, preferred 20sccm-100sccm, more preferably 50sccm; The volume ratio of described carbon source and described hydrogen is 3: 800-1: 2, preferred 1: 16-1: 2, and more preferably 1: 16.Described carbon source is selected from least a in carbon monoxide, methane, ethane, propane, butane, pentane, hexane, hexanaphthene, ethene, propylene, divinyl, amylene, cyclopentadiene, acetylene, methyl alcohol, ethanol, benzene, toluene and the phthalocyanine, at least a in optimization methane, ethanol, ethene and the hexanaphthene; Described rare gas element is selected from least a in nitrogen and the argon gas, preferred argon gas.
The method for preparing single-layer graphene that the invention described above provides, also comprise the steps: in described step 2) afterwards, with the described metallic film of etching agent etching, and with polymeric membrane as support membrane, make described single-layer graphene under the support of described polymeric membrane with after described metallic film separates, remove described support membrane with organic solvent again.Wherein, to be selected from dilute hydrochloric acid, concentration that mass percentage concentration is 30%-60% be the FeCl of 0.5M-1M to described etching agent
3The aqueous solution, mass percentage concentration are at least a in rare nitric acid of 30%-60% and the rare chloroazotic acid that mass percentage concentration is 30%-40%, and this etching agent is the metal etch agent of available various commercializations also, and preferred concentration is the FeCl of 0.5M-1M
3The aqueous solution; Described polymeric membrane is polymethyl methacrylate film or polydimethylsiloxane film, preferred polymethyl methacrylate film, and thickness is 100nm-500nm, preferred 200nm-250nm; Described organic solvent is selected from least a in acetone, chloroform, ethyl acetate and the toluene.
In addition, the single-layer graphene for preparing according to the method described above also belongs to protection scope of the present invention.
The invention provides the method for preparation 100% single-layer graphene, have following feature and advantage:
1, the present invention discloses for the first time and has utilized in the alloyed metal for the control of carbon source precipitation process in metal in the chemical vapor deposition growth Graphene process, controlledly prepares that thickness is strict evenly, the method for big area graphene film.This method is utilized in the alloy substrates characteristic of two kinds or above different-alloy metal, realized the control of decomposition, diffusion and precipitation process to carbon source, retrained the precipitation process that is dissolved in carbon in the metal base simply, efficiently, make Graphene to have obtained the single-layer graphene of number of plies distribution homogeneous with the form growth of surface catalysis.Specifically, the surface catalysis metal that the present invention uses, as nickel, and the lattice mismatch between the Graphene is very little, has higher carbon dissolution degree, can be used as catalyst substrate and prepares the multiwalled graphene film.Simultaneously, another component metals in the binary alloy as molybdenum, has high melt point, at high temperature can form stable molybdenum carbon compound with carbon, can play the effect of fixing extra carbon source.For example, the present invention in the molybdenum foil substrate, utilizes molybdenum to go up catalytic decomposition and the graphitizing of nickel for carbon for the fixed action and the surface of carbon the nickel evaporation, surface catalysis growth single-layer graphene film in the chemical vapour deposition system.Adopt easy CVD system, by the design of growth substrate being realized strictness control, thereby realized the big area controllable growth of high quality monolayer Graphene the single-layer graphene preparation.
2, the inventive method has universality, for most of alloyed metals, but as long as wherein contain the graphited composition of catalyzed carbon, all can grow Graphene in chemical vapor deposition processes.
3, method disclosed by the invention has changed to innovative the preparation present situation of Graphene.Compare other graphene preparation methods, it has overcome the randomness that the mechanically peel legal system is equipped with Graphene, the Graphene monocrystalline size that obtains than the liquid phase method separation is big, and more even, more controlled with respect to the CVD method of having reported, strong to the growth conditions fault-tolerance, thin foil substrate conveniently is used for mass preparation.
4, the Graphene of the present invention's preparation can not be subjected to the restriction of substrate lattice size.Need not monocrystalline can the uniform Graphene of the growing large-area number of plies.
5, the method for preparing Graphene provided by the invention, condition is simple, need not harsh control heat-up rate, temperature, pressure, additional carbon kind and carbon source amount and cooling rate, more need not to consider the directivity of substrate, so can carry out the scale batch preparations of chip-scale Graphene.Simultaneously, Experiment Preparation parameter (as heat-up rate, temperature, pressure, additional carbon kind and carbon source amount and cooling rate etc.) control fault-tolerance is strong, preparation gained Graphene is 100% individual layer, number of plies strictness is controlled, be evenly distributed, the good reproducibility of product, substrate is cheap and easy to get, be particularly suitable for being applied to suitability for industrialized production, be particularly useful for the controlled preparation of individual layer or few layer graphene.
Description of drawings
Fig. 1 prepares the schema of Graphene for chemical vapour deposition.
Fig. 2 is transferred to optical photograph (embodiment 1) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Fig. 3 is transferred to number of plies analysis chart (embodiment 1) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Fig. 4 is transferred to Raman spectrogram (embodiment 1) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Fig. 5 is transferred to atomic force microscope images (embodiment 1) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Fig. 6 is transferred to transmission electron microscope image and selected area electron diffraction image (embodiment 1) on little grid copper mesh for Graphene that will preparation.
Fig. 7 is transferred to optical photograph (embodiment 2) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Fig. 8 is transferred to Raman spectrogram (embodiment 2) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Fig. 9 is transferred to optical photograph (embodiment 3) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Figure 10 is transferred to Raman spectrogram (embodiment 3) on the silicon base that has the 300nm thermal oxide layer for Graphene that will preparation.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can get from open commercial sources if no special instructions.Preparation gained graphene film among the following embodiment, its number of plies is Graphene to be shifted getting by directly perceived resolution of the color distortion under the opticmicroscope on the silicon base that has the 300nm thermal oxide layer, by difference by Red Green Blue value under the green glow, can obtain Graphene number of plies distribution plan exactly, the thickness of this graphene film characterizes by Raman spectrum, atomic force microscope (AFM) and transmission electron microscope (TEM).
Embodiment 1, preparation single-layer graphene
1) select thickness be the molybdenum foil of 200 μ m as metal base, and utilize the electron beam evaporation plating method, be 1 * 10 in vacuum tightness
-7Mbar, temperature be under 25 ℃ the condition on this molybdenum foil metal base evaporation one layer thickness be the polycrystalline nickel film of 200nm, obtain alloy substrates;
2) in hydrogen (flow velocity is 400sccm) and argon gas (flow velocity is 500sccm); in tube furnace, step 1) gained alloy substrates was annealed by room temperature constant temperature after being heated to 900 ℃ in 25 minutes in 20 minutes; then be warming up to 1000 ℃ of catalytic growth temperature again through 5 minutes; feed carbon source methane (flow velocity is 50sccm) stop this moment grew in 5 minutes; the volume ratio of the methane gas scale of construction and hydrogen gas amount is 16: 1; reduce to 700 ℃ with the cooling rate of 15 ℃/min again; turn off well heater; naturally cooling; when being lower than 200 ℃, temperature closes the shielding gas argon gas; take out sample, promptly obtain single-layer graphene provided by the invention on step 1) gained alloy substrates surface.
3) spin coating one deck PMMA (thickness is 200nm) transparent flexible macromolecule membrane is as support base on the gained single-layer graphene, and 170 ℃ of heating 15min are immersed in the FeCl that concentration is 1M then
330min in the aqueous solution is corroded the nickel thin layer in the sample, and Graphene separates with molybdenum foil together with the PMMA film.The PMMA film is supporting this single-layer graphene and is transferring on the silicon chip that has the 300nm zone of oxidation, and the PMMA film as support base is removed in dissolving in organic solvent-acetone.Obtain result as shown in Figure 2.As shown in Figure 2, this embodiment area of preparing the gained single-layer graphene reaches 100%.
As shown in Figure 3, the optical microscope image that shifts the Graphene on silicon base the Color Channel analysis of RGB (RGB), (Reina, A. have been carried out; Thiele, S.; Jia, X.T.; Bhaviripudi, S.; Dresselhaus, M.S.; Schaefer, J.A.; Kong, J., Growth of Large-Area Single-and Bi-Layer Graphene byControlled Carbon Precipitation on Polycrystalline Ni Surfaces.Nano Research.2009,2 (6), 509-516) by the difference of Red Green Blue value under the green glow, can obtain Graphene number of plies distribution plan exactly, wherein redness is represented single-layer graphene, and black is represented substrate.From the analysis of Fig. 3 as can be seen, the area of the single-layer graphene that this embodiment is prepared can reach 100%.
As shown in Figure 4, the Graphene of transfer on silicon base carried out the sign of Raman spectrum.Raman spectrum is advantageous methods (Ferrari, the A.C. that characterizes the Graphene number of plies and quality; Meyer, J.C.; Scardaci, V; Casiraghi, C.; Lazzeri, M.; Mauri, F.; Piscanec, S.; Jiang, D.; Novoselov, K.S.; Roth, S.; Physical Review Letters 2006,97,187401).The Graphene that as can be seen from the figure utilizes the present invention to prepare possesses peak width at half height～35cm
-1G ' peak, G ' peak meets the match at single Lorentz peak, and the D peak of defective and relative intensity ratio＜0.3 at G peak are represented in the relative contrast＜0.5 by force at G peak and G ' peak, can prove that according to the raman spectral characteristics of Graphene the Graphene of preparation is superior in quality single-layer graphene.
As shown in Figure 5, the Graphene of transfer on silicon base carried out the sign of atomic force microscope.It is generally acknowledged, because the existence of water layer in Van der Waals interaction and the transfer process is transferred at Graphene thickness on the silicon base between 0.7～1.5nm.Represent as can be seen that from figure the difference of altitude of Graphene and substrate confirms further that at 1.0nm prepared graphene is a single-layer graphene.Simultaneously, the Graphene for preparing is evenly distributed, the thickness homogeneous.
As shown in Figure 6, the Graphene of transfer on silicon base carried out the sign of transmission electron microscope.Big figure among Fig. 6 has showed the single-layer graphene of burst, little figure is the selected area electron diffraction (SAED that single-layer graphene is carried out, selected area electron diffraction) characterize, the hexagonal lattice structure among the figure has proved the crystallization degree of Graphene.
In sum, utilize the various alloyed metal substrates of patent utilization of the present invention, in chemical vapor deposition processes easy and simple to handle, realize the strictness of single-layer graphene preparation is controlled by design to growth substrate, thus the big area controllable growth of realization high quality, single-layer graphene.This method for preparing thickness homogeneous single-layer graphene requires not harsh, simple and easy to do to preparation condition, be suitable for large-scale industrialization production.
Embodiment 2, preparation single-layer graphene (thickness of attenuate metal base is to 1/8 of embodiment 1, and carbon source concentration prolongs growth time 6 times to embodiment 1 to 8 times of embodiment 1 when improving growth)
1) select thickness be the molybdenum foil of 25 μ m as metal base, and utilize the electron beam evaporation plating method, be 1 * 10 in vacuum tightness
-7Mbar, temperature be under 25 ℃ the condition on this molybdenum foil metal base evaporation one layer thickness be the polycrystalline nickel film of 200nm, obtain alloy substrates;
2) in hydrogen (flow velocity is 400sccm) and argon gas (flow velocity is 500sccm); in tube furnace, step 1) gained alloy substrates was annealed by room temperature constant temperature after being heated to 900 ℃ in 25 minutes in 20 minutes; then be warming up to 1000 ℃ of catalytic growth temperature again through 5 minutes; feed carbon source methane (flow velocity is 50sccm) stop this moment grew in 30 minutes; the volume ratio of the methane gas scale of construction and hydrogen gas amount is 2: 1; reduce to 700 ℃ with the cooling rate of 15 ℃/min again; turn off well heater; naturally cooling; when being lower than 200 ℃, temperature closes the shielding gas argon gas; take out sample, promptly obtain single-layer graphene provided by the invention on step 1) gained alloy substrates surface.
3) spin coating one deck PMMA (thickness is 200nm) transparent flexible macromolecule membrane is as support base on the gained single-layer graphene, and 170 ℃ are heated 15min, are immersed in the FeCl of 1M then
330min in the aqueous solution is corroded the nickel thin layer in the sample, and Graphene separates with molybdenum foil together with the PMMA film.The PMMA film is supporting this single-layer graphene and is transferring on the silicon chip that has the 300nm zone of oxidation, and the PMMA film as support base is removed in dissolving in organic solvent-acetone.Obtain result as shown in Figure 7.As shown in Figure 7, this embodiment area of preparing the gained single-layer graphene reaches 100%.
As shown in Figure 8, the Graphene of transfer on silicon base carried out the sign of Raman spectrum.The Graphene that as can be seen from the figure utilizes the present invention to prepare possesses peak width at half height～35cm
-1G ' peak, G ' peak meets the match at single Lorentz peak, and the D peak of defective and relative intensity ratio＜0.3 at G peak are represented in the relative contrast＜0.5 by force at G peak and G ' peak, can prove that according to the raman spectral characteristics of Graphene the Graphene of preparation is superior in quality single-layer graphene.
Embodiment 3, preparation single-layer graphene (thickness of attenuate metal base is to 1/8 of embodiment 1, when improving growth carbon source concentration to 8 times of embodiment 1, lower cooling rate to embodiment 1～1/4)
1) select thickness be the molybdenum foil of 25 μ m as metal base, and utilize the electron beam evaporation plating method, be 1 * 10 in vacuum tightness
-7Mbar, temperature be under 25 ℃ the condition on this molybdenum foil metal base evaporation one layer thickness be the polycrystalline nickel film of 200nm, obtain alloy substrates;
2) in hydrogen (flow velocity is 400sccm) and argon gas (flow velocity is 500sccm); constant temperature was annealed in 20 minutes after in tube furnace step 1) gained alloy substrates being heated to 900 ℃; then be warming up to 1000 ℃ of catalytic growth temperature; feed carbon source methane (flow velocity is 50sccm) stop this moment grew in 5 minutes; the volume ratio of the methane gas scale of construction and hydrogen gas amount is 2: 1; reduce to 500 ℃ with the cooling rate of 4 ℃/min again; turn off well heater; naturally cooling; when being lower than 200 ℃, temperature closes the shielding gas argon gas; take out sample, promptly obtain single-layer graphene provided by the invention on step 1) gained alloy substrates surface.
3) spin coating one deck PMMA (thickness is 200nm) transparent flexible macromolecule membrane is as support base on the gained single-layer graphene, and 170 ℃ are heated 15min, are immersed in the FeCl of 1M then
330min in the aqueous solution is corroded the nickel thin layer in the sample, and Graphene separates with molybdenum foil together with the PMMA film.The PMMA film is supporting this single-layer graphene and is transferring on the silicon chip that has the 300nm zone of oxidation, and the PMMA film as support base is removed in dissolving in organic solvent-acetone.Obtain result as shown in Figure 9.As shown in Figure 9, this embodiment area of preparing the gained single-layer graphene reaches 100%.
As shown in figure 10, the Graphene of transfer on silicon base carried out the sign of Raman spectrum.The Graphene that as can be seen from the figure utilizes the present invention to prepare possesses peak width at half height～34cm
-1G ' peak, G ' peak meets the match at single Lorentz peak, and the relative contrast＜0.5 by force at G peak and G ' peak, can prove that according to the raman spectral characteristics of Graphene the Graphene of preparation is superior in quality single-layer graphene.
Claims (10)
1. a method for preparing single-layer graphene comprises the steps:
1) preparation alloy substrates;
2) in hydrogen and inert atmosphere, feed the utilization of carbon source chemical gaseous phase depositing process at described step 1) gained alloy substrates surface catalysis growth Graphene, finish the preparation of described single-layer graphene.
2. method according to claim 1, it is characterized in that: in the described step 1), the described method for preparing alloy substrates is following method a or method b, wherein, described method a comprises the steps: to prepare one deck metallic film at least on metal base, obtain described alloy substrates;
Described method b comprises the steps: to prepare double layer of metal film at least on non metallic substrate, obtain described alloy substrates.
3. method according to claim 2 is characterized in that: among the described method a, the number of plies of described metallic film is one deck or two-layer, preferred one deck; The material that constitutes described metal base and metallic film all is selected from least a in nickel, cobalt, iron, aluminium, gold and silver, copper, zinc, molybdenum, tungsten, titanium, vanadium, chromium, ruthenium, rhodium, platinum, palladium and the iridium, at least a in preferred nickel, cobalt, iron, tungsten and the molybdenum; The thickness of described metal base is 1 μ m～1000 μ m, preferred 25 μ m～200 μ m; The thickness of described metallic film is 5nm～1 μ m, preferred 200nm～500nm, more preferably 200nm;
Among the described method b, the material that constitutes described non metallic substrate is silicon chip, silicon oxide, glass, quartz, silicon carbide or aluminum oxide; The number of plies of described metallic film is two-layer or three layers, and is preferably two-layer; The material that constitutes described metallic film is selected from least a in nickel, cobalt, iron, aluminium, gold and silver, copper, zinc, molybdenum, tungsten, titanium, vanadium, chromium, ruthenium, rhodium, platinum, palladium and the iridium, at least a in preferred nickel, cobalt, iron, tungsten and the molybdenum; The thickness of described non metallic substrate is 1 μ m～1000 μ m, preferred 25 μ m～500 μ m; The thickness of described every layer of metallic film is 5nm～1 μ m, preferred 200nm～500nm, more preferably 200nm.
4. according to claim 2 or 3 arbitrary described methods, it is characterized in that: the method for preparing metallic film among described method a and the method b is vapour deposition method.
5. method according to claim 4 is characterized in that: in the described vapour deposition method, temperature is 20-100 ℃, preferred 25 ℃; Pressure is 1 * 10
-5Mbar-1 * 10
-8Mbar, preferred 1 * 10
-7Mbar.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: described step 2) in the chemical gaseous phase depositing process, carbon source is selected from least a in carbon monoxide, methane, ethane, propane, butane, pentane, hexane, hexanaphthene, ethene, propylene, divinyl, amylene, cyclopentadiene, acetylene, methyl alcohol, ethanol, benzene, toluene and the phthalocyanine, at least a in optimization methane, ethanol, ethene and the hexanaphthene; Described rare gas element is selected from least a in nitrogen and the argon gas, preferred argon gas.
7. according to the arbitrary described method of claim 1-6, it is characterized in that: described step 2) step of chemical gaseous phase depositing process is: in hydrogen and inert atmosphere, after described step 1) gained alloy substrates risen to annealing temperature annealing by room temperature, feed carbon source again and rise to growth temperature at described step 1) gained alloy substrates surface catalysis growth Graphene; In the described annealing steps, temperature is 800-1000 ℃, and preferred 900 ℃, the time is 15-60 minute, preferred 20 minutes; In the described catalytic growth step, temperature is 800～1200 ℃, and preferred 900～1100 ℃, the time is 3～180 minutes, preferred 5～60 minutes; The heating-up time that is risen to the temperature of described annealing steps by room temperature is 25-40 minute, and preferred 5-10 minute, the time that is warming up to the temperature of described catalytic growth step by the temperature of described annealing steps was 5-10 minute, preferred 5 minutes; The flow velocity of described hydrogen is 20sccm-1000sccm, preferred 100sccm-800sccm; The flow velocity of described rare gas element is 100sccm-1000sccm, preferred 300sccm-600sccm; The flow velocity of described carbon source is 3sccm-200sccm, preferred 20sccm-100sccm; The volume ratio of described carbon source and described hydrogen is 3: 800-1: 2, preferred 1: 16-1: 2.
8. according to the arbitrary described method of claim 1-7, it is characterized in that: the described method for preparing single-layer graphene also comprises the steps:
In described step 2) afterwards, with etching agent etching described metallic film, and with polymeric membrane as support membrane, make described single-layer graphene under the support of described polymeric membrane with after described metallic film separates, remove described support membrane with organic solvent again.
9. method according to claim 8 is characterized in that: it is the FeCl of 0.5M-1M that described etching agent is selected from dilute hydrochloric acid, the concentration that mass percentage concentration is 30%-60%
3The aqueous solution, mass percentage concentration are at least a in rare nitric acid of 30%-60% and the rare chloroazotic acid that mass percentage concentration is 30%-40%, and preferred concentration is the FeCl of 0.5M-1M
3The aqueous solution; Described polymeric membrane is polymethyl methacrylate film or polydimethylsiloxane film, preferred polymethyl methacrylate film, and thickness is 100nm-500nm, preferred 200nm-250nm; Described organic solvent is selected from least a in acetone, chloroform, ethyl acetate and the toluene.
10. the single-layer graphene for preparing of the arbitrary described method of claim 1-9.
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