CN109023291A - A kind of graphene film and the preparation method and application thereof - Google Patents

A kind of graphene film and the preparation method and application thereof Download PDF

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CN109023291A
CN109023291A CN201810923236.0A CN201810923236A CN109023291A CN 109023291 A CN109023291 A CN 109023291A CN 201810923236 A CN201810923236 A CN 201810923236A CN 109023291 A CN109023291 A CN 109023291A
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hydrogen
flow
carbon source
graphene
substrate
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CN109023291B (en
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冯贺
田陆
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Hebei radium Technology Co.,Ltd.
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Beijing Radiboron Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0209—Pretreatment of the material to be coated by heating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only

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Abstract

The present invention relates to a kind of graphene film and preparation method and application, specific step is as follows for the preparation method: 1) substrate carries out physics removal of impurities and chemical subtraction respectively；2) substrate after removal of impurities is placed in CVD system, is made annealing treatment；3) substrate after annealing is placed in inert atmosphere, is passed through gasiform carbon source and hydrogen, carry out the growth of graphene；Wherein, the flow of the carbon source is 1~10sccm；The carbon source and the flow-rate ratio of the hydrogen are 1:5~100.The single layer or few layer graphene film of high quality can be made in preparation method of the present invention, and the speed of growth of graphene film is fast, can substantially reduce production cost, has pushed graphene in the extensive use in the fields such as display screen, electronic device and MEMS sensor.

Description

A kind of graphene film and the preparation method and application thereof
Technical field
The present invention relates to the technologies of preparing of graphene, and in particular to graphene film and its preparation of a kind of single layer or few layer Method and application.
Background technique
Graphene is the two-dimentional honeycomb lattice being arranged to make up in the form of sp2 hydridization by regular hexagon by single layer of carbon atom, The two-dimensional surface crystalline material of only one this atomic layer level thickness shows a series of superior characteristics, such as sub-micrometer scale Ballistic transport, high carrier mobility, excellent mechanical performance and thermal conductivity and good optical characteristics and chemistry are steady It is qualitative etc..As device size further reduces, graphene is expected to open the carbon-based integrated circuit of " rear silicon " epoch newly, in flexibility The fields such as electronic device, high-frequency element, memory, sensor, transparent conductive film, touch screen and energy storage device illustrate wide Application prospect.The carrier of new physics and new opplication is realized when the material of high quality, thus the material preparation of graphene also becomes Major issue in graphene research.
The method of preparation grapheme two-dimension material can be divided into two major classes " from top to bottom " and " from bottom to top " at present, from upper Lower preparation method such as micromechanics stripping method, chemical stripping method, laser ablation stripping method etc., the from bottom to top such as chemical gas of preparation method Mutually deposition (CVD), epitaxial growth method, molecular precursor synthetic method etc..Stripping method, which refers to, utilizes machinery, electrostatic, electromagnetism phase interaction Simple, practical, the effective method of one kind that firmly graphene is stripped out from high-quality graphene block materials.This method It is to prepare the prefered method of high-quality graphene at present, but be only applicable to scientific research, is not used to produce in batches.Chemical gaseous phase Deposition (CVD) is the main method of currently manufactured single crystal graphene and large-area polycrystalline graphene, and the quality of gained graphene is very Height, and be easily transferred to use on various matrixes, it is widely used in the electronics such as grapheme transistor, transparent conductive film or light Electronic device.CVD method has been increasingly becoming the main method for preparing high-quality graphene at present.
Summary of the invention
The purpose of the present invention is to provide the preparation method of a kind of single layer or the graphene film of few layer, the preparation methods Specifically comprise the following steps:
1) substrate successively carries out physics removal of impurities and chemical subtraction；
2) substrate after removal of impurities is placed in CVD system, is made annealing treatment；
3) substrate after annealing is placed in inert atmosphere, is passed through gasiform carbon source and hydrogen, carry out graphene Growth；Wherein, the flow of the carbon source is 1~10sccm；The carbon source and the flow-rate ratio of the hydrogen are 1:5~100.
The method that majority prepares graphene at present can not all be quickly obtained the graphene film of single layer or few layer；If wanting to obtain The graphene film of single layer or few layer, generallys use the lower carbon source of concentration and is slowly grown；This method not only growth time Long, cost is also very high.And the present invention is by the removal of impurities of the height of base material and the optimization of growth conditions, can quickly, The graphene thin layer of single layer or few layer is efficiently prepared.
For the present invention in such a way that physics cleans and chemical subtraction combines, the mode of re-optimization degeneration processing makes its institute It states base material and realizes smooth in micro-nano rank, the graphene single layer for growth single layer or few layer provides safeguard.
Wherein, the physics removal of impurities includes one of ultrasonic cleaning, mechanical grinding, polishing or a variety of；
Preferably, for the supersonic frequency that the ultrasonic cleaning specifically uses for 40~80KHz, ultrasonic time is 1~3 small When, temperature is 20~30 DEG C.
The mechanical grinding, the specific selection concentration of polishing are 0.3~0.5kg/cm2Aluminium oxide or silica suspension Liquid, time are 30~100min.
Preferably, after the physics removal of impurities, acetone, ethyl alcohol, water is respectively adopted and is cleaned.
Wherein, the chemical subtraction is respectively adopted is soaked selected from one of sulfuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid Bubble；
Preferably, for the concentration for the acid that the chemical subtraction uses for 1~18mol/L, the time of immersion is 1~5min；Its In, the time that strong acid impregnates is slightly shorter, and the time of acid soak on the weak side is slightly long.
Preferably, it after acid soak, adopts and is eluted with water.
Wherein, the temperature of the annealing is 600~1500 DEG C, and the time is 30~300min；
Preferably, the temperature of the annealing is 900~1050 DEG C, and the time is 30~120min；
Preferably, it is described annealing carry out under an inert atmosphere, in the inert atmosphere containing percent by volume be 1~ 20% hydrogen.
It is furthermore preferred that the hydrogen for being 15~20% containing percent by volume in the inert atmosphere.
Present invention further propose that the substrate is a kind of or several in metal foil Co, Ni, Fe, Cu, Pt, Au, Ag, Ir, Ru Kind alloy；
Or, the substrate is coated in metal foil Co, Ni, Fe, Cu, Pt, Au, Ag, Ir, Ru one or more of conjunctions using surface layer The ceramics of gold, quartz substrate；
Or, the substrate is metal carbides one or more of in Co, Ni, Fe, Cu, Pt, Au, Ag, Ir, Ru.
Wherein, above-mentioned different choice of the substrates, to annealing conditions, growth conditions, there are biggish differences；Actually answering In, need to select the conditions such as the corresponding temperature and time annealed, grown according to specific metal types.
The present invention most preferably uses copper foil, when which is copper foil, after carrying out physics removal of impurities and chemical subtraction, in conjunction with moving back Fire processing is easier to obtain the smooth of micro/nano level；And copper foil is used, optimize reasonable annealing, growth conditions, is easier to obtain single layer Film.
Present invention further propose that, the gasiform carbon source is from alkane, alkene, alkynes, benzene class or small molecular alcohol It is one or more；Preferably C1~C5Hydrocarbon gas, such as methane.
Present invention further propose that, the temperature of the growth is 600~1200 DEG C, and the time is no less than 15min；
Preferably, the temperature of the growth is 900~1000 DEG C, and the time is 100~150min.
Preferably, in the inert atmosphere of the growth, the hydrogen for being 1~10% containing percent by volume in the inert atmosphere Gas.
Preferably, the flow of the carbon source is 1~5sccm, the volume ratio (flow-rate ratio) of the hydrogen and carbon source is 5~ 100:1。
The present invention provides a kind of preferred embodiment, and specific step is as follows for the preparation method:
1) copper foil is first subjected to ultrasonic cleaning, then after carrying out mechanical grinding or polishing treatment, is placed in acid solution and impregnates, It is taken out after cleaning；
2) copper foil after cleaning is placed in CVD system, is passed through the inertia containing percent by volume for 15~20% hydrogen Gas, 900~1050 DEG C at a temperature of, make annealing treatment 30~120min；
3) substrate after annealing is placed in inert atmosphere, be passed through gasiform carbon source and hydrogen carry out 900~ At a temperature of 1000 DEG C, the growth time of graphene is 100~150min；
Wherein, the flow of the carbon source is 1~5sccm；The flow-rate ratio of hydrogen and carbon source is 5~100:1.
The present invention is respectively adopted physical method and chemical method and carries out height removal of impurities to the substrate of growth graphene, and right Substrate is made annealing treatment, and realizes that substrate is smooth in micro-nano rank, so that the nucleation site of graphene during the growth process is few, Single crystallization degree is high, and defect is few, it can be achieved that the single layer of high quality or the less growth of layer graphene.Moreover, when high concentration carbon source into When entering in reaction system, less nucleation site still can guarantee, and realize the fast-growth of graphene film, reduce life Cost is produced, has pushed graphene in the extensive use in the fields such as display screen, electronic device and MEMS sensor.
Detailed description of the invention
Fig. 1 is the picture of graphene film made from embodiment 1；
Fig. 2 is that graphene film made from embodiment 1 is transferred to the aobvious picture of the light in silicon base；
Fig. 3 is the Raman spectrum that the optical maser wavelength of graphene film made from embodiment 1 is 532nm；
Fig. 4 is the picture of graphene film made from comparative example 1.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in the concentrated sulfuric acid and impregnates 1min, uses deionized water It cleans；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1000 DEG C, keep the temperature 30min.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
As shown in Figure 1, the picture of the graphene film prepared using copper foil as substrate, it can be seen that bright copper foil illustrates to make Standby graphene film has good translucency.As shown in Fig. 2 and Fig. 3, light shows picture and Raman spectrum after graphene film transfer Analysis, the value at the peak 2D/G are greater than 2 and show that graphene is single layer, and without the presence at defect peak, illustrate to have obtained single layer stone height Quality graphene film.
Embodiment 2
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in concentrated nitric acid and impregnates 1min, uses deionized water It cleans；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1000 DEG C, keep the temperature 30min.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same single layer stone high-quality graphene film of same embodiment 1 can be obtained.
Embodiment 3
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in acetic acid and impregnates 5min, is washed with deionized water Only；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1000 DEG C, keep the temperature 30min.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same single layer stone high-quality graphene film of same embodiment 1 can be obtained
Embodiment 4
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in the HCl of 5mol/L and impregnates 2min, spends Ionized water is cleaned；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1000 DEG C, keep the temperature 30min.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same single layer stone high-quality graphene film of same embodiment 1 can be obtained.
Embodiment 5
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in phosphoric acid and impregnates 3min, is washed with deionized water Only；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1000 DEG C, keep the temperature 30min.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same single layer stone high-quality graphene film of same embodiment 1 can be obtained.
Embodiment 6
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to nickel foil, then by nickel foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in the concentrated sulfuric acid and impregnates 1min, uses deionized water It cleans；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1400 DEG C, keep the temperature 60min.
3) it growing: after isothermal holding, cooling the temperature to 1000 DEG C, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, Methane is passed through with the flow of 2sccm again, starts to grow graphene, stops being passed through methane, hydrogen flowing quantity adjustment after growing 120min For 2sccm, argon flow is adjusted to 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
Single layer stone high-quality graphene film can be obtained, quality is worse than embodiment 1.
Embodiment 7
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to platinized platinum, then by platinized platinum point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in the concentrated sulfuric acid and impregnates 1min, uses deionized water It cleans；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1100 DEG C, keep the temperature 200min.
3) it growing: after isothermal holding, cooling the temperature to 1000 DEG C, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, Methane is passed through with the flow of 2sccm again, starts to grow graphene, stops being passed through methane, hydrogen flowing quantity adjustment after growing 120min For 2sccm, argon flow is adjusted to 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
Single layer stone high-quality graphene film can be obtained, quality is worse than embodiment 1.
Embodiment 8
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to goldleaf, then by goldleaf point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in the concentrated sulfuric acid and impregnates 1min, uses deionized water It cleans；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 900 DEG C, keep the temperature 120min.
3) it grows: after isothermal holding, 1000 DEG C is warming up in 30min, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then methane is passed through with the flow of 2sccm, start to grow graphene, stops being passed through methane, hydrogen stream after growing 120min Amount is adjusted to 2sccm, and argon flow is adjusted to 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
Single layer stone high-quality graphene film can be obtained, quality is worse than embodiment 1.
Embodiment 9
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in the concentrated sulfuric acid and impregnates 1min, uses deionized water It cleans；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 100sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 20sccm again, heats up in 30min To 1000 DEG C, 30min is kept the temperature.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 120sccm, then with the flow of 5sccm It is passed through methane, starts to grow graphene, stops being passed through methane after growing 60min, hydrogen flowing quantity is adjusted to 10sccm, argon flow It is adjusted to 100sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same single layer stone high-quality graphene film of same embodiment 1 can be obtained.
Embodiment 10
The present embodiment provides a kind of preparation methods of graphene film, specifically comprise the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is placed in the concentrated sulfuric acid and impregnates 1min, uses deionized water It cleans；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 85sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 15sccm again, heats up in 30min To 1000 DEG C, 30min is kept the temperature.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 300sccm, then with the flow of 5sccm It is passed through methane, starts to grow graphene, stops being passed through methane after growing 60min, hydrogen flowing quantity is adjusted to 2sccm, argon flow It is adjusted to 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same single layer stone high-quality graphene film of same embodiment 1 can be obtained.
Comparative example 1
This comparative example provides a kind of preparation method of graphene film, specifically comprises the following steps:
1) it cleans: copper foil being respectively placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water, then is respectively placed in 1min is impregnated in the concentrated sulfuric acid, is washed with deionized water；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1000 DEG C, keep the temperature 30min.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
As shown in Figure 4, there is the phenomenon that Carbon deposition, graphene light transmission in the graphene film that copper foil surface is prepared Rate is poor, and the method cannot get single layer or few layer stone high-quality graphene film.
As shown in Figure 4, the picture of the graphene film prepared using copper foil as substrate can significantly observe copper foil surface Illustrate that the number of plies of graphene is more by atrament for the Carbon deposition formed during preparing graphene, it is second-rate.
Comparative example 2
This comparative example provides a kind of preparation method of graphene film, specifically comprises the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point It is not placed in acetone, ethyl alcohol, carries out ultrasonic cleaning 30min in ionized water；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 800 DEG C in 30min；It is passed through the hydrogen that flow is 2sccm again, is warming up in 30min 1000 DEG C, keep the temperature 30min.
3) grow: after isothermal holding, stopping is passed through argon gas, and hydrogen flowing quantity is adjusted to 12sccm, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same multilayer low quality graphene film of same comparative example 1 can be obtained.
Comparative example 3
This comparative example provides a kind of preparation method of graphene film, specifically comprises the following steps:
1) it cleans: using 0.5kg/cm2Aluminum oxide suspension carries out mechanical polishing 30min to copper foil, then by copper foil point Be not placed in acetone, ethyl alcohol, carry out ultrasonic cleaning 30min in ionized water, then be respectively placed in the concentrated sulfuric acid and impregnate 1min, spend from Sub- water is cleaned；
2) it anneals: the substrate after immersion is placed in CVD system, be evacuated to pressure less than after 1Pa, being passed through flow is Then the argon gas of 12sccm is warming up to 1000 DEG C in 60min.
3) grow: after isothermal holding, stopping is passed through argon gas, is passed through hydrogen with 12sccm flow, then logical with the flow of 2sccm Enter methane, start to grow graphene, stops being passed through methane after growing 120min, hydrogen flowing quantity is adjusted to 2sccm, argon flow tune Whole is 12sccm；Stop heating, is cooled to room temperature to get the graphene film.
The same multilayer low quality graphene film of same comparative example 1 can be obtained.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art 's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed Range.

Claims (10)

1. a kind of preparation method of graphene film, which is characterized in that specific step is as follows:
1) substrate successively carries out physics removal of impurities and chemical subtraction；
2) substrate after removal of impurities is placed in CVD system, is made annealing treatment；
3) substrate after annealing is placed in inert atmosphere, is passed through gasiform carbon source and hydrogen, carry out the life of graphene It is long；Wherein, the flow of the carbon source is 1~10sccm；The carbon source and the flow-rate ratio of the hydrogen are 1:5~100.
2. preparation method according to claim 1, which is characterized in that the substrate be metal foil Co, Ni, Fe, Cu, Pt, One or more of alloys in Au, Ag, Ir, Ru；
Or, the surface layer of the substrate is coated in metal foil Co, Ni, Fe, Cu, Pt, Au, Ag, Ir, Ru one or more of alloys；
Or, the substrate is metal carbides one or more of in Co, Ni, Fe, Cu, Pt, Au, Ag, Ir, Ru.
3. preparation method according to claim 1 or 2, which is characterized in that the physics removal of impurities includes ultrasonic cleaning, machine One of tool polishing, polishing are a variety of；
Preferably, the supersonic frequency that the ultrasonic cleaning specifically uses is 40~80KHz, and ultrasonic time is 1~3 hour, temperature Degree is 20~30 DEG C；
And/or the mechanical grinding or the specific selection concentration of polishing are 0.3~0.5kg/cm2Aluminium oxide or silica it is outstanding Supernatant liquid, time are 30~100min.
4. described in any item preparation methods according to claim 1~3, which is characterized in that the chemical subtraction, which uses, is selected from sulphur One of acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid a variety of are impregnated；
Preferably, for the concentration for the acid that the chemical subtraction uses for 1~18mol/L, the time of immersion is 1~5min.
5. preparation method according to any one of claims 1 to 4, which is characterized in that the temperature of the annealing is 600 ~1500 DEG C, the time is 30~300min；
Preferably, the temperature of the annealing is 900~1050 DEG C, and the time is 30~120min；
It is furthermore preferred that the degeneration processing carries out under an inert atmosphere, it is 1~20% that percent by volume is contained in the inert atmosphere Hydrogen.
6. described in any item preparation methods according to claim 1~5, which is characterized in that the gasiform carbon source is selected from alkane One of hydrocarbon, alkene, alkynes, benzene class or small molecular alcohol are a variety of.
7. described in any item preparation methods according to claim 1~6, which is characterized in that the temperature of the growth be 600~ 1200 DEG C, the time is not less than 15min；And/or the flow of the carbon source is 1~5sccm, the volume ratio of the hydrogen and carbon source For 5~100:1；
Preferably, the temperature of the growth is 900~1000 DEG C, and the time is 100~150min.
8. described in any item preparation methods according to claim 1~7, which is characterized in that specific step is as follows:
1) copper foil is first subjected to ultrasonic cleaning, then after carrying out mechanical grinding or polishing treatment, is placed in immersion treatment in acid solution, It is taken out after cleaning；
2) copper foil after cleaning is placed in CVD system, is passed through the inert gas containing percent by volume for 15~20% hydrogen, 900~1050 DEG C at a temperature of, make annealing treatment 30~120min；
3) substrate after annealing is placed in inert atmosphere, is passed through gasiform carbon source and hydrogen is carried out 900~1000 At a temperature of DEG C, the growth time of graphene is 100~150min；
Wherein, the flow of the carbon source is 1~5sccm；The flow-rate ratio of hydrogen and carbon source is 5~100:1.
9. graphene film made from any one of claim 1~8 preparation method.
10. application of the graphene film as claimed in claim 9 in display screen, electronic device and MEMS sensor.
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