CN102433544A - Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition - Google Patents
Method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition Download PDFInfo
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- CN102433544A CN102433544A CN2012100075831A CN201210007583A CN102433544A CN 102433544 A CN102433544 A CN 102433544A CN 2012100075831 A CN2012100075831 A CN 2012100075831A CN 201210007583 A CN201210007583 A CN 201210007583A CN 102433544 A CN102433544 A CN 102433544A
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- 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
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Abstract
The invention discloses a preparation method for growing large-area graphene by utilizing multi-benzene-ring carbon source low-temperature chemical vapor deposition. In the method, a multi-benzene-ring aromatic hydrocarbon is used as a carbon source, and graphene is grown on the surface of a copper foil by adopting a carbon source decomposition method or carbon source spin-coating method. Prepared graphene has smooth surface, large area and controllable layer number. Compared with the traditional method for preparing graphene by a high-temperature CVD (chemical vapor deposition) method, the method disclosed by the invention has the advantages that: the production cost is greatly reduced, and the method has great application potential in the aspects of high-temperature, high-frequency, large-power, photoelectronic and anti-radiation electronic devices and the like.
Description
Technical field
The present invention relates to a kind of preparation method of graphene, be specifically related to a kind of method of utilizing many phenyl ring carbon source low temperature chemical vapor deposition growing large-area Graphene.
Background technology
Graphene is the graphite of individual layer atomic thickness, has bi-dimensional cellular shape grid structure.Because the existence of π track in the graphene film plane, electronics can move freely in crystal, makes Graphene have very excellent electronic transmission performance.Owing to have excellent mechanics, calorifics, electricity and magnetic performance, Graphene is expected to the acquisition widespread use in fields such as high-performance nanometer electronic device, matrix material, field emmision material, gas sensor, store energy.Graphene structurally is ductile, and its electricity, optics and acoustic characteristics can significantly be adjusted through stress and deformation.Even can change the bandwidth structure of Graphene, the research of crooked, folding and the Graphene that curls is also just being begun to quicken.Graphene has impayable high electron mobility, and the rate of migration of electric charge in Graphene can arrive unprecedented 200000cm
2/ vs surpasses silicon more than 100 times.This advantage makes Graphene probably replace silicon to be become the transistorized base mateiral of ultra high frequency of future generation and is widely used in high performance integrated circuit and the novel nano electron device.Estimate to occur soon entirely the full carbon circuit that constitutes by Graphene and be widely used in the daily life.
Needed underlayer temperature is mostly under 1000 ℃ high temperature in preparation Graphene process for the traditional preparation process method, and high-purity source of the gas price is all relatively more expensive.This has brought very big restriction for the application of material undoubtedly.Therefore seek suitable experimental technique realizes the low-temperature epitaxy of Graphene on the substrate of lower temperature research and become the direction that current this field people very pay close attention to.The low-temperature substrate preparation method of main flow has auxiliary chemical reaction vapour deposition process, the chemical reduction graphene oxide method etc. of strengthening of plasma body at present.But adopt the direct sedimentary Graphene area of these methods very little, crystalline quality is poor, and defective is a lot.
Summary of the invention
The objective of the invention is to overcome the deficiency of above prior art; A kind of method of utilizing many phenyl ring carbon source low temperature chemical vapor deposition growing large-area Graphene is provided, to solve the technical problem that the Graphene area for preparing in the prior art is little, crystalline quality is poor, defective is many.
For solving the problems of the technologies described above; The present invention adopts solid-state or liquid many phenyl ring aromatic hydrocarbons to replace methane as carbon source; Active primitive reaches enough low dividing potential drop thereby the rate of decomposition of control carbon source makes the interior carbon of chamber, to realize the making number of plies of the Graphene that grows controlled; And successfully it intactly is transferred on the various flexible substrate, almost have no macroscopic view damaged.
The following technical scheme of the concrete employing of the present invention:
A kind of method of low temperature chemical vapor deposition growing large-area Graphene is characterized in that: as carbon source, adopt carbon source decomposition method or carbon source spin-coating method to grow Graphene at copper foil surface with many phenyl ring aromatic hydrocarbons.
Preferably, said many phenyl ring aromatic hydrocarbons is benzene or condensed-nuclei aromatics.Preferably, said condensed-nuclei aromatics is selected from materials such as naphthalene, anthracene, phenanthrene, Bi 、 perylene and coronene.
Preferable, said Copper Foil is that purity is not less than 99.99% anaerobic Copper Foil, its typical thickness is the 50-200 micron.
Preferable, the surfaceness of said Copper Foil is preferably below the 30nm below 50nm.
Preferable, before the growth Graphene, earlier Copper Foil is carried out anneal under protective atmosphere, so that the Cu grain growth, the zero defect that has an even surface discharges copper foil surface stress.Preferably, the temperature of said annealing process remains on 900-1050 ℃, and air pressure is between 4000-10000Pa, and annealing time is controlled between the 30-90min.
Preferably, said protective atmosphere is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of said argon gas and hydrogen is 10-20: 1.Gases used purity all is not less than 99.999%.
Preferable, adopt the carbon source decomposition method when copper foil surface growth Graphene, concrete steps comprise: carbon source is placed on the inlet end of tube furnace, Copper Foil is positioned over the central authorities of said tube furnace, controlling said tube furnace middle section temperature is 400-700 ℃; Feed carrier gas, and the carbon source temperature is risen to 80-350 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.
Preferably, adopt the carbon source decomposition method when copper foil surface growth Graphene, the weight of said carbon source is 15-150mg.
Preferable, adopt the carbon source spin-coating method when copper foil surface grows Graphene, concrete steps comprise: carbon source is dissolved in processes mixed solution in the toluene and be spun on the said Copper Foil again, and said Copper Foil is positioned over tube furnace central authorities; Feed carrier gas, and the furnace temperature of tube furnace is risen to 400-700 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.
Preferably, in the said mixing solutions, the weightmeasurement ratio of carbon source and toluene is 5-20mg/ml.
Preferably, in the technique scheme, the heat-up rate of said tube furnace is 20-50 ℃/min.When furnace temperature rises to the required temperature of growth Graphene, insulation 20-40min.
Preferably, in the technique scheme, the operating air pressure of Graphene growing period is 4000-10000Pa.
Preferably, in the technique scheme, said carrier gas is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of said argon gas and hydrogen is 10-20: 1.Gases used purity all is not less than 99.999%.
Preferably, in the technique scheme, the flow of said carrier gas is 300-500sccm.
Further, the method for above-mentioned growing large-area Graphene provided by the present invention also comprises the Graphene of preparing is transferred to the following steps on the target substrate:
(1) copper foil surface spin coating one deck PMMA (polymethylmethacrylate) film of Graphene is arranged in growth; It is floated on erosion removal Copper Foil in the ammonium persulfate aqueous solution, fall the cupric ion in the solution clearly with deionized water subsequently;
(2) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, and integral body is soaked in the acetone dissolving and removes PMMA again, adopts alcohol wash to remove residual acetone, and last anneal is removed residual PMMA.
Preferably, the thickness of said PMMA film is 200-400nm.
Preferably, in the step (2), said anneal is carried out in reduction or inert atmosphere, and annealing temperature is 300-450 ℃, and annealing time is 40-90min.
Preferably, said reduction or inert atmosphere are selected from the gas mixture of hydrogen, argon gas or hydrogen and argon gas.
The present invention adopts solid-state or liquid many phenyl ring aromatic hydrocarbons as carbon source, and it is significant for the Graphene commercial application that low temperature prepares the controlled Graphene technology of the number of plies, is a kind of new technology with big area Graphene growth of very big potentiality.Compare with existing Graphene technology of preparing, the present invention has following advantage:
1) present method adopts that many phenyl ring are solid-state, the method for liquid carbon source prepares the controlled Graphene of the number of plies.The active primitive that contains phenyl ring is as the elementary cell of forming Graphene; The quality and the gas flow of, liquid carbon source solid-state through controlling; Prepare individual layer big area Graphene; And can be transferred on the various substrates that comprise flexible substrate, and almost have no macroscopic view damaged through the method that the PMMA chemistry shifts.
2) prepare Graphene with respect to the traditional chemical vapor phase process.Present method adopts solid-state or liquid many phenyl ring aromatic hydrocarbons to replace methane as carbon source, decomposes the reactive monomer that contains phenyl ring that produces through many phenyl ring aromatic hydrocarbons at a lower temperature and under copper substrate catalysis, prepares the big area Graphene.Controlling solid-state, liquid source rate of decomposition reaches under the enough low dividing potential drop low temperature the active primitive of carbon in the chamber to obtain the high quality Graphene, greatly reduce the cost for preparing Graphene.
3) the present invention adopts the method for mechanical polishing and chemical rightenning that substrate is carried out pre-treatment, and the substrate surface planeness is reached＜50nm, makes the Graphene that obtains through copper metal catalytic deposition have less defects and good crystal property above that.
4) method of the present invention can reduce the consumption of high-purity gas; Reduce preparation temperature and shorten preparation time greatly; Can reduce the production cost of large size Graphene; Thereby for be implemented on the flexible substrate development and develop the electric property excellence, preparation cost is low and the Graphene microelectronic device of new generation of environmental protection provides experimental basis and instructs thinking, finally realizes with the Graphene being the large-scale application of basic microelectronic device.
Description of drawings
Fig. 1 is the device synoptic diagram of low temperature chemical vapor deposition growth Graphene of the present invention;
Fig. 2 is the AFM photo of the copper foil surface behind mechanical polishing and the electrochemical etching;
Fig. 3 is the optical microscope photograph of copper foil surface catalytic growth Graphene among the present invention.
Fig. 4 prepares Graphene Raman figure for many phenyl ring carbon source cryochemistry vapor phase process of the present invention.
Fig. 5 for benzene carbon source low temperature of the present invention preparation to Graphene be transferred to the transmitance figure after the quartz substrate.
Fig. 6 prepares Graphene SEM photo for many phenyl ring carbon source low temperature of the present invention.
Fig. 7 for naphthalene carbon source low temperature of the present invention preparation to Graphene be transferred to the transmitance figure after the quartz substrate.
Fig. 8 for luxuriant and rich with fragrance carbon source low temperature preparation of the present invention to Graphene be transferred to the transmitance figure after the quartz substrate.
Fig. 9 for pyrene carbon source low temperature of the present invention preparation to Graphene be transferred to the transmitance figure after the quartz substrate.
Figure 10 for De perylene carbon source low temperature of the present invention preparation to Graphene be transferred to the transmitance figure after the quartz substrate.
Figure 11 for coronene carbon source low temperature of the present invention preparation to Graphene be transferred to the transmitance figure after the quartz substrate.
Embodiment
Main innovation part of the present invention is that containing the phenyl ring monomer through many phenyl ring aromatic hydrocarbons activity that decomposition produces as carbon source at a lower temperature prepares the controlled Graphene of the number of plies under copper substrate catalysis, to solve the technical problem that the Graphene area for preparing in the prior art is little, crystalline quality is poor, defective is many.For this reason, the invention provides a kind of method of low temperature chemical vapor deposition growing large-area Graphene, this method as carbon source, adopts carbon source decomposition method or carbon source spin-coating method to grow Graphene at copper foil surface with many phenyl ring aromatic hydrocarbons.
Solid-state or liquid many phenyl ring aromatic hydrocarbons that the present invention adopts is heated and can resolves into the necessary active primitive of phenyl ring that contains of preparation Graphene; These active primitives that contain phenyl ring are as the elementary cell of forming Graphene; Be easy to form the controlled Graphene of the big area number of plies at low temperatures through the catalysis of metal substrate and the effect of hydrogen.Many phenyl ring aromatic hydrocarbons described in the present invention be meant be in a liquid state under the normal temperature or solid-state and molecular formula in contain the hydrocarbon polymer of at least one phenyl ring.Preferably, said many phenyl ring aromatic hydrocarbons is benzene or condensed-nuclei aromatics.Preferred, said condensed-nuclei aromatics is selected from materials such as naphthalene, anthracene, phenanthrene, Bi 、 perylene and coronene.
Alternatively, in technique scheme, said Copper Foil is that purity is not less than 99.99% anaerobic Copper Foil, and its typical thickness is the 50-200 micron.For example can select Alfa Aesar 99.99% high-purity anaerobic Copper Foil for use.
Alternatively, in technique scheme, the surfaceness of said Copper Foil is preferably below the 30nm below 50nm.It is surperficial to handle copper platinum through the method that successively adopts mechanical polishing and electrochemical etching, reaches surfaceness is reached below the 50nm.The method of mechanical polishing and electrochemical etching all is well known to those skilled in the art, and for example can adopt following processing condition: the mechanical polishing rotating speed can be selected 800 commentaries on classics/min for use; It is 3: 1 85% phosphoric acid and the mixed solution of polyoxyethylene glycol that electrochemical polish liquid can be selected volume ratio for use; The voltage of electrochemical etching is 1～2V, polishing time 1800s; After electrochemical etching finishes with Copper Foil through acetone ultrasonic cleaning 10min, with 25% hydrochloric ultrasonic wave cleaning 10min, with alcohol Copper Foil is cleaned up at last again.
Alternatively, in technique scheme, before the growth Graphene; Need earlier surfaceness to be carried out anneal at the Copper Foil that (is preferably below the 30nm) below the 50nm under protective atmosphere; So that the Cu grain growth, the zero defect that has an even surface discharges copper foil surface stress.Preferably, the temperature of said annealing process remains on 900-1050 ℃, and air pressure is between 4000-10000Pa, and annealing time is controlled between the 30-90min.Preferably, said protective atmosphere is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of said argon gas and hydrogen is 10: 1.Gases used purity all is not less than 99.999%.
Alternatively; In technique scheme, adopt the carbon source decomposition method when copper foil surface growth Graphene, concrete steps comprise: the inlet end that carbon source is placed on tube furnace; Copper Foil is positioned over the central authorities of said tube furnace, and controlling said tube furnace middle section temperature is 400-700 ℃; Feed the carrier gas of certain flow, and the carbon source temperature is risen to 80-350 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.The weight of the carbon source that every stove growth Graphene is used is 15-150mg.
Alternatively, in technique scheme, adopt the carbon source spin-coating method when copper foil surface grows Graphene, concrete steps comprise: carbon source is dissolved in processes mixed solution in the toluene and be spun on the said Copper Foil again, and said Copper Foil is positioned over tube furnace central authorities; Feed the carrier gas of certain flow, and the furnace temperature of tube furnace is risen to 400-700 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.Preferably, in the said mixing solutions, the weightmeasurement ratio of carbon source and toluene is 5-20mg/ml.Said spin coating adopts spin coater to carry out, and its rotating speed is 1000-2000r/min.
Alternatively, in the technique scheme, the heat-up rate of said tube furnace is 20-50 ℃/min.When furnace temperature rises to the required temperature of growth Graphene, insulation 20-40min.The operating air pressure of Graphene growing period is 4000-10000Pa.
Alternatively, in the technique scheme, said carrier gas is the gas mixture of argon gas and hydrogen.Preferred, the volume flow ratio of said argon gas and hydrogen is 10-20: 1, be preferably 10: 1.Gases used purity all is not less than 99.999%.
Alternatively, in the technique scheme, the flow of said carrier gas is 300-500sccm.
Alternatively, in the technique scheme, also further comprise the Graphene of preparing is transferred to the following steps on the target substrate:
(1) copper foil surface spin coating one deck PMMA (polymethylmethacrylate is claimed synthetic glass again) film of Graphene is arranged in growth; It is floated on erosion removal Copper Foil in the ammonium persulfate aqueous solution, fall the cupric ion in the solution clearly with deionized water subsequently;
(2) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, and integral body is soaked in the acetone dissolving and removes PMMA again, adopts alcohol wash to remove residual acetone, and last anneal is removed residual PMMA.
The method of said spin coating PMMA film is known by those skilled in the art, for example can PMMA be dissolved in the organic solvent (like phenol, methyl-phenoxide etc.), is spun on the Copper Foil through spin coater.
Preferably, the thickness of said PMMA film is 200-400nm.
Preferably, in the step (2), said anneal is carried out in reduction or inert atmosphere, and annealing temperature is 300-450 ℃, and annealing time is 40-90min.
Preferably, said reduction or inert atmosphere are selected from the gas mixture of hydrogen, argon gas or hydrogen and argon gas.
Among the present invention; Said target substrate includes but not limited to various metal substrate; Can also be for being used for the various substrates of semiconducter device, for example (for example Ge, GaAs, GaN, InP etc.) such as silicon, silicon-dioxide, silicon-on-insulator (SOI), II-VI or III-V compound semiconductor substrates.
Below in conjunction with the more complete description the present invention of diagram, preferred embodiment provided by the invention should not be considered to only limit in the embodiment of this elaboration.Reference drawing is a synoptic diagram of the present invention, and the expression among the figure is an illustrative nature, should not be considered to limit scope of the present invention.
See also Fig. 1, it is the device synoptic diagram of low temperature chemical vapor deposition growth Graphene of the present invention.The direction of arrow is the carrier flow direction among the figure, and wherein: 1 is inlet end, and 2 is the outlet side, and 3 is tubular oven, and 4 is carbon source, and 5 is Copper Foil, and 6 is rotary pump.Because chemical vapor deposition method and equipment therefor thereof all are well known to those skilled in the art, so repeat no more at this.
Embodiment 1: benzene liquid carbon source low-temperature epitaxy big area single-layer graphene
(1) adopts Copper Foil as substrate, successively adopt the method for mechanical polishing and electrochemical etching to handle the copper substrate surface, surfaceness is reached below the 50nm.Mechanical polishing rotating speed 800 commentaries on classics/min.Adopt electrochemical workstation for the polishing power supply, select for use the Ag/AgCl electrode as reference electrode, selecting volume ratio for use is that 3: 1 85% phosphoric acid and polyoxyethylene glycol mixed solution is electrochemical polish liquid; The Copper Foil of required polishing is positioned over positive pole, adopts copper sheet as negative pole; Electrochemical etching voltage 1～2V, polishing time 1800s.
(2) after electrochemical etching finishes with Copper Foil through acetone ultrasonic cleaning 10min, with 25% hydrochloric ultrasonic wave cleaning 10min, with alcohol Copper Foil is cleaned up at last again.
(3) Copper Foil is carried out anneal: Copper Foil is warming up to 1035 ℃ under the protection of hydrogen and argon gas mixed gas, makes the Cu grain growth, the zero defect that has an even surface discharges the copper substrate surface stress.Annealing process middle chamber operating air pressure is between 4000-10000Pa, and hydrogen flowing quantity is 30sccm, argon flow amount 300sccm.The gases used purity of copper foil annealing is 99.999%, annealing time 30min;
(4) treat that furnace temperature is reduced to room temperature after, the Copper Foil of annealed processing is put into tube furnace heat district.Take by weighing benzene liquid carbon source 15mg simultaneously in the quartz test tube of end sealing, and it is positioned over tube furnace low-temperature heat district.Furnace temperature is risen to 500-700 ℃, heat the benzene liquid carbon source simultaneously to 150-200 ℃, hydrogen flowing quantity is 300sccm for the 30sccm argon flow amount, and reaction times 30min, operating air pressure are between the 4000-10000Pa.Stop to heat liquid source and tube furnace at last, chamber takes out sample after reducing to room temperature.The used carrier gas purity of chemical gas phase reaction is higher than 99.999%.
(5) adopt spin coater at Graphene/copper foil surface spin coating one deck PMMA/ methyl-phenoxide solvent, solvent burden ratio is: PMMA: methyl-phenoxide=1: 9 (volume ratio), spin coater rotating speed 3000 commentaries on classics/min, spin coating time 45s.The PMMA film thickness is 200-400nm.Place 150 ℃ of dry 5min of vacuum drying oven then, remove organic solvent.
(6) Copper Foil is floated on erosion removal copper in the ammonium persulfate solution that concentration is 0.1mol/L, reaction 5h.Select for use subsequently washed with de-ionized water 3-5 time, clean the cupric ion in the solution.
(7) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate; Integral body is soaked in 3h dissolving removal PMMA in the acetone again; Adopt the slow cleaning and removing of alcohol to remove residual acetone, at last under 450 ℃ in hydrogen and argon gas gas mixture anneal substrate/residual PMMA of Graphene removal.The flow of hydrogen, argon gas is respectively 100sccm and 300sccm, and annealing time is 40-90min.
Embodiment result: Fig. 4 is the Raman figure of the Graphene that under 600 ℃ of conditions, prepares, and this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.75, D defective peak is very little simultaneously; The crystal property of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Fig. 5 is the transmittance test pattern of the Graphene that under 600 ℃ of conditions, prepares, explain that employing benzene obtains the Graphene transmitance as liquid carbon source and reaches 96.6%, is single-layer graphene; The transmitance of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.As shown in Figure 6, optical photograph shows, is transferred to the not significantly macroscopic view breakage of big area Graphene on the glass substrate through chemical process, is complete big area single-layer graphene.
Embodiment 2: change the benzene liquid carbon source among the embodiment 1 into naphthalene solid-state carbon source 15mg.Naphthalene Solid State Source Heating temperature is 80-120 ℃ in the growth Graphene process, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene that under 600 ℃ of conditions, prepares, and this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.9, D defective peak is very little simultaneously; The crystal property of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Fig. 7 is the transmittance test pattern of the Graphene that under 600 ℃ of conditions, prepares, explain that the employing naphthalene obtains the Graphene transmitance as solid-state carbon source and reaches 96.7%, is single-layer graphene; The transmitance of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Its optical photograph shows, is transferred to the not significantly macroscopic view breakage of big area Graphene on the glass substrate through chemical process, is complete big area single-layer graphene.
Embodiment 3: change benzene liquid carbon source among the embodiment 1 into luxuriant and rich with fragrance solid-state carbon source 15mg.The Sino-Philippines Solid State Source Heating temperature of growth Graphene process is 100-150 ℃, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene that under 600 ℃ of conditions, prepares, and this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.65, D defective peak is very little simultaneously; The crystal property of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Fig. 8 is the transmittance test pattern of the Graphene that under 600 ℃ of conditions, prepares, explain that adopting phenanthrene to obtain the Graphene transmitance as solid-state carbon source reaches 96.5%, is single-layer graphene; The transmitance of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Its optical photograph shows, is transferred to the not significantly macroscopic view breakage of big area Graphene on the glass substrate through chemical process, is complete big area single-layer graphene.
Embodiment 4: change benzene liquid carbon source among the embodiment 1 into pyrene solid-state carbon source 15mg.The Sino-Philippines Solid State Source Heating temperature of growth Graphene process is 150-200 ℃, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene that under 600 ℃ of conditions, prepares, and this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 2.0, D defective peak is very little simultaneously; The crystal property of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Fig. 9 is the transmittance test pattern of the Graphene that under 600 ℃ of conditions, prepares, explain that the employing pyrene obtains the Graphene transmitance as solid-state carbon source and reaches 96.5%, is single-layer graphene; The transmitance of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Its optical photograph shows, is transferred to the not significantly macroscopic view breakage of big area Graphene on the glass substrate through chemical process, is complete big area single-layer graphene.
Embodiment 5: benzene liquid carbon source among the embodiment 1 is changed be the solid-state carbon source 15mg of perylene.The Sino-Philippines Solid State Source Heating temperature of growth Graphene process is 280-350 ℃, and other technologies are identical with embodiment 1.
Embodiment result: Fig. 4 is the Raman figure of the Graphene that under 600 ℃ of conditions, prepares, and this Graphene crystallinity of Raman test shows is better, and the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.94, D defective peak is very little simultaneously; The crystal property of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Figure 10 is the transmittance test pattern of the Graphene that under 600 ℃ of conditions, prepares, explains to adopt to obtain the Graphene transmitance with perylene as solid-state carbon source and reach 96.7%, is single-layer graphene; The transmitance of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Its optical photograph shows, is transferred to the not significantly macroscopic view breakage of big area Graphene on the glass substrate through chemical process, is complete big area single-layer graphene.
Embodiment 6: adopt coronene as the carbon source for growth Graphene.Coronene/toluene mixing solutions is spun on copper foil surface, subsequently low-temperature heat Copper Foil substrate catalytic growth Graphene.
(1) adopts Copper Foil as substrate, successively adopt the method for mechanical polishing and electrochemical etching to handle the copper substrate surface, surfaceness is reached below the 50nm; Mechanical polishing rotating speed 800 commentaries on classics/min.Adopt electrochemical workstation for the polishing power supply, select for use the Ag/AgCl electrode as reference electrode; The employing volume ratio is that 3: 1 85% phosphoric acid and polyoxyethylene glycol mixed solution is electrochemical polish liquid.The Copper Foil of required polishing is positioned over positive pole, adopts copper sheet as negative pole.Electrochemical etching voltage 1～2V, polishing time 1800s;
(2) after electrochemical etching finishes with Copper Foil through acetone ultrasonic cleaning 10min, with 25% hydrochloric ultrasonic wave cleaning 10min, with deionized water Copper Foil is rinsed well at last again;
(3) Copper Foil is carried out anneal: Copper Foil is warming up to 1035 ℃ under the protection of hydrogen and argon gas mixed gas, makes the Cu grain growth, the zero defect that has an even surface discharges the copper substrate surface stress.Annealing process middle chamber operating air pressure is between 4000-10000Pa, and hydrogen flowing quantity is 30sccm, argon flow amount 300sccm.The gases used purity of copper foil annealing is 99.999%, annealing time 30min;
(4) treat that furnace temperature is reduced to room temperature after, adopt spin coater spin coating coronene/toluene solution on the Copper Foil substrate of annealing destressing, strength of solution is 5-20mg/mL.Spin coater rotating speed 1200 commentaries on classics/min, spin coating time 30s is positioned over subsequently in 150 ℃ the process furnace and dries;
(5) have the Copper Foil substrate of coronene Solid State Source to put into chamber spin coating, furnace temperature is warming up to 500-700 ℃, hydrogen flowing quantity is 30sccm argon flow amount 300sccm, and reaction times 30min stops heating at last and makes silica tube reduce to room temperature.Operating air pressure is between the 4000-10000Pa.The used carrier gas purity of chemical gas phase reaction is higher than 99.999%;
(6) adopt spin coater at Graphene/copper foil surface spin coating one deck PMMA/ methyl-phenoxide solvent, solvent burden ratio is: PMMA: methyl-phenoxide=1: 9 (volume ratio), spin coater rotating speed are 3000 commentaries on classics/min, spin coating time 45s.PMMA thickness is 200-400nm.Place 150 ℃ of dry 5min of vacuum drying oven then, remove organic solvent;
(7) Copper Foil is floated on erosion removal copper in the ammonium persulfate solution that concentration is 0.1mol/L, reaction 5h.Select for use subsequently washed with de-ionized water 3-5 time, clean the cupric ion in the solution;
(8) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate; Integral body is soaked in 3h dissolving removal PMMA in the acetone again; Adopt the slow cleaning and removing of alcohol to remove residual acetone, at last under 450 ℃ in hydrogen and argon gas gas mixture anneal substrate/residual PMMA of Graphene removal.The flow of hydrogen, argon gas is respectively 100sccm and 300sccm, and annealing time is 40-90min.
Embodiment result: Fig. 4 is the Raman figure of the Graphene that under 600 ℃ of conditions, prepares; The Raman test shows is through directly being coated with coronene on Cu paper tinsel surface; The high crystalline quality Graphene that utilizes chemical gas phase reaction can prepare equally, the peak at 2D peak and G peak is by force than I
2D/ I
GBe 1.6, D defective peak is very little simultaneously; The crystal property of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Figure 11 is the transmittance test pattern of the Graphene that under 600 ℃ of conditions, prepares, and its transmitance reaches 96.5%, is single-layer graphene; The transmitance of the Graphene that under 500 ℃ and 700 ℃ of conditions, prepares is basic identical with it.Its optical photograph shows, is transferred to the not significantly macroscopic view breakage of big area Graphene on the glass substrate through chemical process, is complete big area single-layer graphene.
Claims (13)
1. the method for a chemical vapor deposition growth Graphene is characterized in that: as carbon source, adopt carbon source decomposition method or carbon source spin-coating method to grow Graphene at copper foil surface with many phenyl ring aromatic hydrocarbons.
2. the method for chemical vapor deposition growth Graphene as claimed in claim 1 is characterized in that: said many phenyl ring aromatic hydrocarbons is benzene or condensed-nuclei aromatics.
3. the method for chemical vapor deposition growth Graphene as claimed in claim 2 is characterized in that: said condensed-nuclei aromatics is selected from naphthalene, anthracene, phenanthrene, Bi 、 perylene and coronene.
4. the method for chemical vapor deposition growth Graphene as claimed in claim 1 is characterized in that: the surfaceness of said Copper Foil is below 50nm.
5. like the method for claim 1 or 4 described chemical vapor deposition growth Graphenes; It is characterized in that: before the growth Graphene; Earlier said Copper Foil is carried out anneal under protective atmosphere; The temperature of said annealing process remains on 900-1050 ℃, and air pressure is between 4000-10000Pa, and annealing time is controlled between the 30-90min.
6. the method for chemical vapor deposition growth Graphene as claimed in claim 1 is characterized in that: said protective atmosphere is the gas mixture of argon gas and hydrogen.
7. the method for chemical vapor deposition growth Graphene as claimed in claim 1 is characterized in that:
Adopt the carbon source decomposition method when copper foil surface growth Graphene, concrete steps comprise: carbon source is placed on the inlet end of tube furnace, Copper Foil is positioned over the central authorities of said tube furnace, controlling said tube furnace middle section temperature is 400-700 ℃; Feed carrier gas, and the carbon source temperature is risen to 80-350 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature;
Adopt the carbon source spin-coating method when copper foil surface grows Graphene, concrete steps comprise: carbon source is dissolved in processes mixed solution in the toluene and be spun on the said Copper Foil again, and said Copper Foil is positioned over tube furnace central authorities; Feed carrier gas, and the furnace temperature of tube furnace is risen to 400-700 ℃, grow Graphene at copper foil surface; Then, stop heating, cool to the furnace and take out the Copper Foil that growth has Graphene after the room temperature.
8. the method for chemical vapor deposition growth Graphene as claimed in claim 7 is characterized in that:
Adopt the carbon source decomposition method when copper foil surface growth Graphene, the weight of said carbon source is 15-150mg;
Adopt the carbon source spin-coating method when copper foil surface grows Graphene, in the said mixing solutions, the weightmeasurement ratio of carbon source and toluene is 5-20mg/ml.
9. like the method for the arbitrary described chemical vapor deposition growth Graphene of claim 7-8, it is characterized in that: when furnace temperature rises to the required temperature of growth Graphene, insulation 20-40min; The operating air pressure of Graphene growing period is 4000-10000Pa.
10. the method for chemical vapor deposition growth Graphene as claimed in claim 9 is characterized in that: said carrier gas is the gas mixture of argon gas and hydrogen.
11. the method like arbitrary described chemical vapor deposition growth Graphene among claim 1-4, the 6-8 or 10 is characterized in that: also comprise the Graphene of preparing is transferred to the following steps on the target substrate:
(1) copper foil surface spin coating one deck PMMA film of Graphene is arranged in growth; It is floated on erosion removal Copper Foil in the ammonium persulfate aqueous solution, fall the cupric ion in the solution clearly with deionized water subsequently;
(2) the PMMA/ Graphene that will remove behind the Copper Foil is transferred on the target substrate, and integral body is soaked in the acetone dissolving and removes PMMA again, adopts alcohol wash to remove residual acetone, and last anneal is removed residual PMMA.
12. the method for chemical vapor deposition growth Graphene as claimed in claim 11 is characterized in that: in the step (2), said anneal is carried out in reduction or inert atmosphere, and annealing temperature is 300-450 ℃, and annealing time is 40-90min.
13. the method for chemical vapor deposition growth Graphene as claimed in claim 12 is characterized in that: said reduction or inert atmosphere are selected from the gas mixture of hydrogen, argon gas or hydrogen and argon gas.
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