CN104495829A - Method for preparing graphene film on low-temperature substrate - Google Patents
Method for preparing graphene film on low-temperature substrate Download PDFInfo
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Abstract
The invention discloses a method for preparing graphene on a low-temperature metal copper film substrate by adopting a hot wire CVD method. A prepared graphene film is a graphene nanocrystal. The method comprises the following processes of: (1) depositing a copper film on a quartz substrate by adopting a magnetron sputtering method; (2) annealing the deposited copper film; (3) growing the graphene film on the annealed copper film at the substrate temperature of 350-450 DEG C by adopting the hot wire CVD method; (4) transferring graphene. The method disclosed by the invention can be used for preparing the graphene film with a controllable layer number on the magnetron sputtering deposited low-cost copper film under the condition of the low-temperature substrate by adopting an ethyne gas-state carbon source or a polyphenylether solid-state carbon source and plays a guiding role on the popularization, application and industrialized production of the graphene.
Description
Technical field
That the present invention relates to is a kind of preparation method of graphene film, a kind of specifically method adopting filament CVD to prepare graphene film in low-temperature substrate.
Background technology
The basic substance that material develops as human survival and social stability, plays irreplaceable vital role from ancient times to the present always.Meanwhile, in the acquisition of material and the course of processing, the impact that environment causes also is increasingly sharpened.Therefore develop some environmental friendliness, that the novel material of rich reserves carrys out more alternative starting material is deficient or be easily the trend of the times of Materials to the old material of environment.
Graphene has very excellent electricity, optics and mechanical property, from its find by the mankind since just receive and pay close attention to widely.This bi-dimensional cellular shape structure by the tight stacking of carbon atom has the characteristic that high carrier mobility, high-specific surface area, high permeability and high heat conductance etc. have application prospect.At present, scientists is successfully applied to solar cell, matrix material, photochemical catalysis, sensor field.
Process for preparing graphenes by chemical vapour deposition has developed into the main method preparing large-area high-quality Graphene in recent years.Be mainly in reaction process after carbon compound is transported to substrate surface and obtained Graphene by growth after substrate pyrolytic decomposition.In the research of current Graphene, the normal growth mechanism utilized mainly contains substrate catalyst mechanism and substrate solution modeling mechanism 2 kinds.Wherein the machine-processed metal substrate stronger with the molten carbon such as Ni, Co ability of substrate solution modeling is for representative, relies on hot conditions carbon source is decomposed and is dissolved in substrate.After diffusion process after a while, substrate is lowered the temperature with certain rate of cooling.The change of its molten carbon amounts makes oversaturated carbon separate out also forming core at metal substrate surface and grows into graphene film.Surface catalysis mechanism is the growth mechanism using the low molten carbon amounts metal such as Cu, Mo as substrate.Main dependence carbon source pyrolytic decomposition and under substrate katalysis dehydrogenation form carbonaceous active group.When carbonaceous active group just grows at substrate surface forming core after accumulative arrival finite concentration on substrate, form graphene film.Wherein copper substrate is cheaper with price, and the Graphene that catalysis obtains is easy to the advantages such as transfer, is widely applied.
During conventional chemical vapor deposition method growing graphene, underlayer temperature is all up to about 1000 DEG C.In order to reduce the growth temperature of Graphene, carry out much research both at home and abroad, and successfully utilize solid-state carbon source to obtain high-quality Graphene under middle temperature (500 DEG C ~ 700 DEG C).But because the gaseous carbon source such as methane, acetylene is difficult to be cracked into carbonaceous active group at low temperatures, conventional chemical gaseous phase depositing process cannot use gaseous carbon source to prepare Graphene under low-temperature substrate condition.It is high that hot filament CVD (HF CVD) has filament temperature, the feature that underlayer temperature is low, can utilize high temperature filament decomposition gas state carbon source, avoid substrate to be subject to the impact of high temperature simultaneously.And filament CVD also has the advantage such as low cost, fast growth.Filament CVD has been used to the carbon materials such as depositing diamond-like film and carbon nanotube.Although the research report of external more existing use filament CVD growing graphenes, the underlayer temperature that they use still very high (800 ~ 1000 DEG C), is not suitable for the suitability for industrialized production of Graphene.People [the Synthesis and Characterization ofGraphene Films by Hot Filament Chemical Vapor Deposition such as such as D.Stojanovic, Physica Scripta, 2012, T149:014068-(1-3)] be exactly when underlayer temperature is 800 ~ 1000 DEG C filament CVD prepared Graphene, the people such as S.Kataria are then that filament CVD has prepared Graphene [Raman Imaging on High-quality Graphene Grown by Hot-filament Chemical VaporDeposition when underlayer temperature is 1000 DEG C, Journal of Raman Spectroscopy, 2012, 43 (12): 1864-1867].
Summary of the invention
The present invention proposes metal copper film that a kind of filament CVD deposits with magnetron sputtering method at low temperatures on high purity quartz for substrate and prepares the method for Graphene, and the graphene film of preparation is that graphene nano is brilliant.The present invention can adopt gaseous state acetylene or solid-state polystyrene to make carbon source under low-temperature substrate condition, with cheap Copper thin film for substrate obtains individual layer or multi-layer graphene film, has directive function to the suitability for industrialized production of Graphene and popularization.
Filament CVD involved in the present invention is that the method that substrate prepares Graphene is achieved through the following technical solutions with metal copper film under low-temperature substrate condition, specifically comprises following step:
Filament CVD prepares a method for individual layer or multi-layer graphene film in low-temperature substrate, and its feature comprises the steps:
(1). first to substrate acetone, alcohol and deionized water ultrasonic cleaning, then be placed in magnetron sputtering cavity.After vacuum tightness in chamber to be sputtered is evacuated to background vacuum, to copper target pre-sputtering to remove surface oxidation and contamination.Then the Copper thin film of baffle plate deposit film 1-5 μm of thickness is opened;
(2). the Copper thin film substrate that step (1) obtains is put into tube furnace and anneals at hydrogen and rare gas element mixed atmosphere; During annealing, inert gas flow is 300sccm ~ 500sccm, and hydrogen flowing quantity is 50sccm ~ 100sccm, and annealing temperature is 900 DEG C ~ 1050 DEG C, and annealing time is 30min ~ 60min, obtains polycrystalline copper film-substrate;
(3). the polycrystalline copper film-substrate that step (2) obtains is put into the chamber of HF CVD equipment, Chamber vacuum degree is evacuated to 8 × 10
-4pa ~ 1 × 10
-4pa Heated Copper film to 350 DEG C ~ 450 DEG C of temperature, pass into carbon-source gas afterwards and hydrogen ratio is the mixed gas of 2% ~ 5%, and air pressure is adjusted to 2Pa ~ 20Pa, open heater supply and regulate filament temperature to 1600 DEG C ~ 2100 DEG C, be 0W ~ 100W by the power regulation of radio-frequency power supply, substrate bias is adjusted to 0V ~-800V, carries out the growth of Graphene, and growth time is 1min ~ 10min;
(4). the graphene film that step (3) obtains is shifted; First at film surface spin coating one deck PMMA, spin coating solution used is the PMMA solution of massfraction 10%, and solvent is methyl-phenoxide, and during spin coating, rotating speed is 3000r/min.Then Copper thin film is eroded, then after the graphene film with PMMA is transferred to target substrate, the PMMA on removing surface.
Substrate described in step (1) can be high purity quartz or polished silicon slice.
Rare gas element described in step (2) can be argon gas or nitrogen.
In step (3), the purity of acetylene carbon source is 99.999%, and the purity of polystyrene carbon source is 99.9%.
Filament in step (3) is tantalum wire or tungsten filament.
In step (4), the method for removing PMMA is hot acetone dissolution method or thermal degradation method.
The principle of the invention:
Filament CVD can utilize high temperature filament decomposition gas state carbon source, avoids substrate to be subject to temperatures involved simultaneously.In graphene growth process, carbon source molecule in chamber is decomposed into carbonaceous active group under the effect of high temperature filament, by carbonaceous active group after the enrichment of Copper thin film substrate surface, under the katalysis of substrate, form graphene-structured and grow up, forming graphene film.Be equipped with RF-assisted ionization carbon active group and substrate DC bias during growing graphene film, growth velocity and Graphene quality can be improved comprehensively.
Beneficial effect
Compared with the existing technology preparing graphene film, the present invention has following several beneficial effect: the filament CVD that the present invention adopts has the advantage such as low cost, fast growth.Traditional C VD method growing graphene needs 30min ~ 60min usually, and this technology only needs 1min-10min, shortens the time needed for preparation; Generally adopt the Copper Foil of about 200 micron thickness during traditional CVD method growing graphene, the present invention utilizes the Copper thin film of magnetron sputtering deposition less than 5 microns thickness to carry out low-temperature catalyzed growing graphene, can save a large amount of copper resources; Current filament CVD to prepare in the technique of Graphene underlayer temperature all more than 600 DEG C; and present method is by regulating filament temperature and optimizing carbon source concentration; add that radio-frequency power supply assists ionization and substrate DC bias technology; graphene film can be obtained under underlayer temperature is the condition of 350 ~ 450 DEG C; reduce the energy consumption needed for substrate heat, be convenient to the large-scale production of Graphene big area.
Accompanying drawing explanation
Fig. 1 is the HF CVD device structure schematic diagram of deposited graphite alkene film in low-temperature substrate.Wherein 1 is acetylene gaseous carbon source, and 2 is the solid-state carbon source of polystyrene and well heater, and 3 is hydrogen cylinder, 4 is mixing chamber, and 5 to hold concurrently electric pole plate for even gas dish, and 6 is the filament of HF CVD, 7 is carbonaceous active group, 8 to hold concurrently lower electrode plate for substrate support, and 9 is substrate heater, and 10 is molecular pump, 11 is mechanical pump, 12 is vapor pipe, and 13 is negative bias power supply, and 14 is substrate.
Fig. 2 is the Raman collection of illustrative plates of graphene film prepared in embodiment 1.The wherein sp of D representative
3defect peak, G represents sp
2hydridization peak, 2D represents biphonon resonance peak.
Fig. 3 is the transmitance collection of illustrative plates of graphene film prepared in embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1:
(1) adopt 4cm × 4cm high purity quartz to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 2 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, argon flow amount is 300sccm, and hydrogen flowing quantity is 100sccm, and annealing temperature is 1050 DEG C, and annealing time is 30min;
(3) the polycrystalline copper film-substrate after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 5 × 10
-4pa heated substrate to 450 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.The ratio passing into mass flow controller monitoring is afterwards the acetylene gas of 2% and the mixed gas of hydrogen, and with valve, growth air pressure is adjusted to 5Pa, opens heater supply and regulates tantalum wire temperature to 2000 DEG C, opening the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after 2min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by the polycrystalline copper thin film corrosive between quartz substrate and Graphene, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue quartz substrate can be reused.Graphene film with PMMA is turned and adheres to after in glass substrate, whole composite structure is soaked 1h in 55 DEG C of hot acetones, the PMMA of removing graphenic surface.
The Raman collection of illustrative plates of prepared graphene film and transmitance collection of illustrative plates are as shown in Figures 2 and 3.Prepared Graphene is that graphene nano is brilliant, and Raman 2D peak fits to single Lorentz lorentz peak, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 0.94, the transmitance of film at 550nm place is 97.5%, is single-layer graphene film.
Embodiment 2
(1) adopt 4cm × 4cm high purity quartz to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 5 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, argon flow amount is 500sccm, and hydrogen flowing quantity is 50sccm, and annealing temperature is 900 DEG C, and annealing time is 60min;
(3) the polycrystalline copper film after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 1 × 10
-4pa heated substrate to 350 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.The ratio passing into mass flow controller monitoring is afterwards the acetylene gas of 2% and the mixed gas of hydrogen, and with valve, growth air pressure is adjusted to 8Pa, opens heater supply and regulates tungsten filament temperature to 1800 DEG C, opening the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after 10min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by polycrystalline copper thin film corrosive, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue quartz substrate can be reused.After graphene film with PMMA is transferred to target substrate, at 500 DEG C, be incubated 30min, the PMMA of removing graphenic surface.
Prepared graphene film is that graphene nano is brilliant, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 0.91, the transmitance of film at 550nm place is 95%, is bilayer graphene film.
Embodiment 3
(1) adopt 4cm × 4cm high purity quartz to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 1 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, nitrogen flow is 500sccm, and hydrogen flowing quantity is 50sccm, and annealing temperature is 1000 DEG C, and annealing time is 40min;
(3) the polycrystalline copper film-substrate after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 8 × 10
-4pa heated substrate to 450 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.The ratio passing into mass flow controller monitoring is afterwards the acetylene gas of 5% and the mixed gas of hydrogen, and with valve, growth air pressure is adjusted to 20Pa, opens heater supply and regulates tantalum wire temperature to 1600 DEG C, opening the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after 10min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by polycrystalline copper thin film corrosive, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue quartz substrate can be reused.After graphene film with PMMA is transferred to target substrate, in 55 DEG C of hot acetones, soak 1h, the PMMA of removing graphenic surface.
Prepared graphene film is that graphene nano is brilliant, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 0.91, the transmitance of film at 550nm place is 91%, is multi-layer graphene film.
Embodiment 4
(1) adopt 4cm × 4cm polished silicon slice to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 4 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, argon gas flow is 300sccm, and hydrogen flowing quantity is 50sccm, and annealing temperature is 1050 DEG C, and annealing time is 40min;
(3) the polycrystalline copper film-substrate after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 6 × 10
-4pa heated substrate to 350 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.The ratio passing into mass flow controller monitoring is afterwards the acetylene gas of 5% and the mixed gas of hydrogen, and with valve, growth air pressure is adjusted to 10Pa, open heater supply and regulate tantalum wire temperature to 1600 DEG C, by radio-frequency power supply power regulation to 100W, opening the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after growth 2min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by the polycrystalline copper thin film corrosive between polished silicon slice and Graphene, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue polished silicon slice can be reused.After the graphene film of band PMMA is transferred to target substrate, in 55 DEG C of hot acetones, soak 1h, the PMMA of removing graphenic surface.
The Raman collection of illustrative plates of prepared graphene film and transmitance collection of illustrative plates and Fig. 2 and Fig. 3 similar.Prepared Graphene is that graphene nano is brilliant, and Raman 2D peak fits to single Lorentz lorentz peak, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 0.87, the transmitance of film at 550nm place is 97.4%, is single-layer graphene film.
Embodiment 5
(1) adopt 4cm × 4cm high purity quartz to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 3 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, nitrogen flow is 300sccm, and hydrogen flowing quantity is 100sccm, and annealing temperature is 900 DEG C, and annealing time is 45min;
(3) the polycrystalline copper film-substrate after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 1 × 10
-4pa heated substrate to 400 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.Post-heating polystyrene to 180 DEG C, adopt mass flow controller to lead to Ar gas and the carbon-source gas of gasification and the blending ratio of hydrogen are adjusted to 5%, and growth air pressure is adjusted to 2Pa, open heater supply and regulate tungsten filament temperature to 2000 DEG C, opening the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after 2min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by polycrystalline copper thin film corrosive, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue quartz substrate can be reused.After graphene film with PMMA is transferred to target substrate, at 500 DEG C, be incubated 30min, the PMMA of removing graphenic surface.
The Raman collection of illustrative plates of prepared graphene film and the result of transmitance collection of illustrative plates and Fig. 2 and Fig. 3 similar.Prepared Graphene is that graphene nano is brilliant, and Raman 2D peak fits to single Lorentz lorentz peak, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 0.98, the transmitance of film is 97.3%, is single-layer graphene film.
Embodiment 6
(1) adopt 4cm × 4cm high purity quartz to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 2 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, nitrogen flow is 300sccm, and hydrogen flowing quantity is 100sccm, and annealing temperature is 1000 DEG C, and annealing time is 30min;
(3) the polycrystalline copper film-substrate after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 1 × 10
-4pa heated substrate to 350 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.Post-heating polystyrene to 230 DEG C, adopt mass flow controller to lead to Ar gas and the carbon-source gas of gasification and the blending ratio of hydrogen are adjusted to 5%, and growth air pressure is adjusted to 10Pa, open heater supply and regulate tungsten filament temperature to 1900 DEG C, by radio-frequency power supply power regulation to 50W, open the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after growth 6min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by the polycrystalline copper thin film corrosive between quartz substrate and Graphene, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue quartz substrate can be reused.Graphene film with PMMA is turned and adheres to after in glass substrate, at 500 DEG C, be incubated 30min, the PMMA of removing graphenic surface.
The Raman collection of illustrative plates of prepared graphene film and the result of transmitance collection of illustrative plates and Fig. 2 and Fig. 3 similar.Prepared Graphene is that graphene nano is brilliant, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 0.86, the transmitance of film is 95.1%, is bilayer graphene film.
Embodiment 7
(1) adopt 4cm × 4cm high purity quartz to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 4 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, argon gas flow is 300sccm, and hydrogen flowing quantity is 80sccm, and annealing temperature is 1050 DEG C, and annealing time is 60min;
(3) the polycrystalline copper film-substrate after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 6 × 10
-4pa heated substrate to 350 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.The ratio passing into mass flow controller monitoring is afterwards the acetylene gas of 5% and the mixed gas of hydrogen, and with valve, growth air pressure is adjusted to 10Pa, open heater supply and regulate tantalum wire temperature to 1900 DEG C, by radio-frequency power supply power regulation to 100W, substrate bias is adjusted to-100V, opens the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after growth 1min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by the polycrystalline copper thin film corrosive between quartz substrate and Graphene, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue quartz substrate can be reused.After the graphene film of band PMMA is transferred to target substrate, in 55 DEG C of hot acetones, soak 1h, the PMMA of removing graphenic surface.
The Raman collection of illustrative plates of prepared graphene film and transmitance collection of illustrative plates similar with Fig. 2 and Fig. 3, Graphene is graphene nano crystalline substance, and Raman 2D peak fits to single Lorentz lorentz peak, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 1.14, the transmitance of film at 550nm place is 97.6%, is single-layer graphene film.
Embodiment 8
(1) adopt 4cm × 4cm polished silicon slice to be substrate, after being used acetone, alcohol and deionized water ultrasonic cleaning, be placed in magnetron sputtering cavity.Vacuum tightness in chamber to be sputtered is evacuated to 6 × 10
-4pa, opens copper target (purity: radio frequency power source 99.99%) preheating 10 minutes; Start to control substrate frame and rotate (20r/min), pass into Ar gas 30sccm; Add radio-frequency voltage, make to produce aura between target and anode cap, the sputtering power arranging copper target is 150W, pre-sputtering 10 minutes, removes surface oxidation and contamination; Then open baffle plate and start deposit film, growth thickness is the Copper thin film of 5 μm; After growth terminates, baffle plate is closed rapidly, after closing vaccum-pumping equipment, take out sample.
(2) Copper thin film substrate is put into tube furnace and carry out normal pressure annealing at hydrogen and argon gas atmosphere; During annealing, nitrogen flow is 300sccm, and hydrogen flowing quantity is 100sccm, and annealing temperature is 1000 DEG C, and annealing time is 30min;
(3) the polycrystalline copper film-substrate after annealing is placed in HF CVD chamber, chamber vacuum degree is evacuated to 1 × 10
-4pa heated substrate to 350 DEG C, temperature rise rate is 10 DEG C/min.Substrate and filament distance 120mm, guarantee that in process of growth, filament temperature can not impact underlayer temperature.Post-heating polystyrene to 200 DEG C, adopt mass flow controller to lead to Ar gas and the carbon-source gas of gasification and the blending ratio of hydrogen are adjusted to 5%, and growth air pressure is adjusted to 10Pa, open heater supply and regulate tungsten filament temperature to 2100 DEG C, by radio-frequency power supply power regulation to 50W, substrate bias is adjusted to-800V, opens the growth that baffle plate carries out Graphene.Closing baffle plate, heater supply successively after growth 1min, take residual reaction gas away.Be cooled to after below 100 DEG C until substrate and open chamber sampling.
(4) at the graphene film surface spin coating one deck PMMA of growth in polycrystalline copper film-substrate, spin coating solution used is the PMMA solution of massfraction 10%, solvent is methyl-phenoxide, during spin coating, rotating speed is 3000r/min, then fallen by the polycrystalline copper thin film corrosive between polished silicon slice and Graphene, corrosive fluid is the ammonium persulfate aqueous solution of 30g/L.Residue polished silicon slice can be reused.Graphene film with PMMA is turned and adheres to after in glass substrate, at 500 DEG C, be incubated 30min, the PMMA of removing graphenic surface.
The Raman collection of illustrative plates of prepared graphene film and the result of transmitance collection of illustrative plates and Fig. 2 and Fig. 3 similar.Prepared Graphene is that graphene nano is brilliant, and Raman 2D peak fits to single Lorentz lorentz peak, the strength ratio (I at 2D peak and G peak
2D/ I
g) be 1.46, the transmitance of film is 97.4%, is single-layer graphene film.
Claims (6)
1. filament CVD low-temperature substrate prepares a method for graphene film, it is characterized in that comprising following process:
(1). first to substrate acetone, alcohol and deionized water ultrasonic cleaning, then be placed in magnetron sputtering cavity.After vacuum tightness in chamber to be sputtered is evacuated to background vacuum, to copper target pre-sputtering to remove surface oxidation and contamination.Then the Copper thin film of baffle plate deposit film 1-5 μm of thickness is opened;
(2). the Copper thin film substrate that step (1) obtains is put into tube furnace and anneals at hydrogen and inert gas atmosphere; During annealing, inert gas flow is 300sccm ~ 500sccm, and hydrogen flowing quantity is 50sccm ~ 100sccm, and annealing temperature is 900 DEG C ~ 1050 DEG C, and annealing time is 30min ~ 60min, obtains polycrystalline copper film-substrate;
(3). the polycrystalline copper film-substrate that step (2) obtains is put into the chamber of HF CVD equipment, Chamber vacuum degree is evacuated to 8 × 10
-4pa ~ 4 × 10
-4pa, and Heated Copper film-substrate to 350 DEG C ~ 450 DEG C of temperature; Pass into control ratio afterwards at the carbon-source gas of 2% ~ 5% and the mixed gas of hydrogen, and air pressure is adjusted to 2Pa ~ 20Pa, open heater supply and regulate filament temperature to 1400 DEG C ~ 2100 DEG C, be 0W ~ 100W by the power regulation of radio-frequency power supply, substrate bias is adjusted to 0V ~-800V, carry out the growth of Graphene, growth time is 1min ~ 10min;
(4). the graphene film that step (3) obtains is shifted; First at film surface spin coating one deck PMMA, spin coating solution used is the PMMA solution of massfraction 10%, and solvent is methyl-phenoxide, and during spin coating, rotating speed is 3000r/min.Then Copper thin film is eroded, then after the graphene film with PMMA is transferred to target substrate, the PMMA on removing surface.
2. a kind of filament CVD according to claim 1 prepares the method for graphene film in low-temperature substrate, it is characterized in that, the substrate described in step (1) is high purity quartz or polished silicon slice, and copper target purity is 99.99%.
3. a kind of filament CVD according to claim 1 prepares the method for graphene film in low-temperature substrate, it is characterized in that, the rare gas element described in step (2) is argon gas or nitrogen.
4. a kind of filament CVD according to claim 1 prepares the method for graphene film in low-temperature substrate, it is characterized in that, in step (3), the purity of acetylene is 99.999%, and the purity of polystyrene is 99.9%.
5. a kind of filament CVD according to claim 1 prepares the method for graphene film in low-temperature substrate, it is characterized in that, the filament in step (3) is tantalum wire or tungsten filament.
6. a kind of filament CVD according to claim 1 prepares the method for graphene film in low-temperature substrate, it is characterized in that, in step (4), the method for removing PMMA is hot acetone dissolution method or thermal degradation method.
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