CN103643288B - A kind of preparation method of high-quality large-size monocrystal graphene - Google Patents
A kind of preparation method of high-quality large-size monocrystal graphene Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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Abstract
The present invention relates to graphene new material and chemical vapor deposition (CVD) technology of preparing thereof, the preparation method of a kind of high-quality large-size monocrystal graphene, be suitable to prepare high-quality large-size monocrystal graphene.Use chemical vapour deposition technique, with the metal such as copper, platinum as growing substrate, with Hydrocarbon as carbon source, in the presence of the carrier gas containing hydrogen, first metallic matrix is carried out heat treatment, and utilizes catalytic pyrolysis under carbon-source gas high temperature, grow single crystal graphene.Then being performed etching Graphene by regulation and control hydrogen and carbon source concentration, significantly reduce the distribution density of single crystal graphene, regulation reaction atmosphere makes its regrowth the most again, is so repeated several times, finally obtains high-quality large-size monocrystal graphene.Use the present invention can obtain high-quality inch level single crystal graphene, lay the foundation in the application of the photoelectric field such as nanometer electronic device, nesa coating, display and electrode of solar battery, gas sensor, thin film electronic device for it.
Description
Technical field:
The present invention relates to graphene new material and chemical vapor deposition (CVD) technology of preparing thereof, be specially one
The preparation method of high-quality large-size monocrystal graphene, is suitable to prepare high-quality large-size monocrystal graphene.
Background technology:
Graphene is tightly packed one-tenth bi-dimensional cellular shape crystal structure monolayer carbon atomic crystal, is to build other dimensions
The elementary cell of Carbon Materials (such as zero dimension fullerene, one-dimensional nano carbon pipe, three-dimensional graphite).This strict two
Dimension atomic crystal material has fabulous electricity, calorifics and mechanical property, such as: under room temperature, its electron mobility is high
Reach 200,000cm2/ V s, thermal conductivity is up to 5000W m-1·K-1, Young's modulus is up to 1TPa.Graphene is this
Excellent performance make its be expected multi-functional nanometer electronic device, nesa coating, composite, catalysis material,
The fields such as energy storage material, field emmision material, gas sensor and gas storage obtain extensively application.Therefore, certainly
After the seminar of Univ Manchester UK in 2004 obtains the Graphene of stable existence first, it just rapidly becomes
The study frontier that the fields such as material science, Condensed Matter Physics, chemistry are enlivened the most.
At present, the preparation of Graphene has a lot of method, including micromechanics stripping method, chemical stripping method, carborundum
Epitaxial growth method, chemical vapour deposition technique.Wherein, mechanical stripping method process is simple, and product quality is high, but only
Can obtain very small amount Graphene, efficiency is low, randomness is big；Surface of SiC epitaxial growth method can obtain large-area
Single-layer graphene, and quality is higher, but the method growth efficiency is low, poor controllability, and growth conditions is harsh,
Graphene is difficult to shift；Chemical stripping method causes the Graphene prepared to contain relatively due to the participation of Strong oxdiative process
Many defects, electric conductivity is poor, and the size of Graphene less (sheet footpath is mostly in micron dimension).CVD side
Method have simple, gained Graphene is of high quality, can realize large area deposition and be relatively easy to transfer to each
The advantage such as use on kind of matrix, therefore the method is widely used in preparing grapheme transistor and transparent conductive film,
It is increasingly becoming the main method preparing high-quality graphene at present.
But, Graphene mobility prepared by current CVD method is the most on the low side, generally between hundreds of to thousand of
cm2/ V s, its electric conductivity is also far below theoretical limit.The crystal boundary of Graphene and in-plane defects are generally considered leads
Cause one of major influence factors of mobility and electric conductivity reduction.But in CVD preparation process, due to graphite
The Enhancing Nucleation Density of alkene is wayward, the crystallite dimension of the Graphene of preparation generally hundreds of nanometer to hundreds of micron it
Between.And, Graphene easily produces defect in forming core and growth course.These are very the biggest have impact on migration
Rate and electric conductivity.Therefore, CVD method how is utilized to prepare the large-sized single crystal graphene of high-quality always
The difficult point of Graphene research field.
Summary of the invention:
It is an object of the invention to provide the preparation method of a kind of high-quality large-size monocrystal graphene, the method has
There are the advantages such as low cost, flow process are simple, controllability is good, therefore can be suitable to prepare high-quality large scale as one
The Perfected process of single crystal graphene.
The technical scheme is that
The invention provides the preparation method of a kind of high-quality large-size monocrystal graphene, the method uses chemistry gas
Phase deposition technique, in the presence of the carrier gas containing hydrogen, first carries out heat treatment, and profit to metallic matrix
With under carbon-source gas high temperature at metal base surface catalytic pyrolysis, grow single crystal graphene.Then by controlling
Hydrogen, carbon source concentration, perform etching the Graphene monocrystalline after growth, significantly reduces dividing of single crystal graphene
Cloth density so that it is every 10 square inches of numbers are reduced to 1～2, and this provides sky for growing large-size monocrystalline
Between, then regulation hydrogen and carbon source concentration make it regrow, and when the number of single crystal graphene becomes many, then enter
Row etching, the most repeatedly.After etching regrowth for several times, final acquisition high-quality large-size monocrystal graphite
Alkene.
In the present invention, metallic matrix used is noble metal or the metals such as copper, nickel such as the platinum of surfacing, ruthenium or iridium
Thin slice or thin film, purity be more than 99wt%, thickness be not less than 100nm, preferably 500nm～1 μm.
In the present invention, metallic matrix used need to be at one or more of acetone, ethyl lactate, water and ethanol
Middle respectively ultrasonic cleaning, the time is no less than 10 minutes, preferably 1 hour～2 hours.
In the present invention, metallic matrix used needs annealed heat treatment, and treatment temperature is 800 DEG C～1500 DEG C, excellent
Elect 900 DEG C～1100 DEG C as；Atmosphere is hydrogen (or mixed gas of hydrogen and the gas such as nitrogen or argon), its
Middle hydrogen mol ratio is not less than 1%, and flow velocity is not less than 10sccm；Annealing time is no less than 10 minutes.Preferably
, hydrogen mol ratio is 50～100%, and flow velocity is 300～700sccm；Annealing time is 8 hours～10
Hour.
In the present invention, use chemical vapour deposition technique prepare large-size monocrystal graphene, carbon source used be methane,
In the Hydrocarbon such as ethane, acetylene, ethylene, ethanol one or more, carrier be hydrogen (or
Hydrogen and the mixed gas of the gas such as nitrogen or argon), the purity of carbon source and carrier gas is all higher than 99%(volume),
Carbon source is 0.005～1 with the mol ratio of hydrogen, preferably 0.005～0.1.Growth temperature is 600 DEG C～1200
DEG C, preferably 900 DEG C～1100 DEG C.Growth time is not less than 20 minutes, preferably 30 minutes～1 hour.
In the present invention, lithographic method used, etching temperature is 600 DEG C～1200 DEG C, preferably 900 DEG C～1100
DEG C, etch period is not less than 10 seconds, preferably 30 seconds～2 minutes, and etching atmosphere is the mixed of carbon source and hydrogen
Close gas, carbon source used be in methane, ethane, acetylene, ethylene, ethanol Hydrocarbon one or
More than Zhong, carbon source is 0.005～0.1 with the mol ratio of hydrogen, preferably 0.01～0.05.
In the present invention, regrowth method used, regrowth temperature is 600 DEG C～1200 DEG C, preferably 900
DEG C～1100 DEG C, regrowth time be not less than 20 minutes, preferably 1 hour～100 hours.Regrowth atmosphere
For carbon source and the mixed gas of hydrogen, carbon source used is methane, ethane, acetylene, ethylene, ethanol nytron
In thing one or more.Carbon source is 0.005～0.5 with the mol ratio of hydrogen, preferably 0.01～0.5.
In the present invention, the cycle-index of growth-etching-regrowth be more than 1 time, preferably more than 3 times.
In the present invention, after growth terminates, metallic matrix need to be quickly cooled under the carrier containing hydrogen is protected
Less than 300 DEG C, preferably 100 DEG C～200 DEG C；Carrier gas is hydrogen and nitrogen or the mixed gas of argon, hydrogen
Mol ratio is not less than 1%, preferably 50～80%；Quickly the speed of cooling is not less than 10 DEG C/sec, preferably 30～
50 DEG C/sec.
In the present invention, (general range is 1 inch～4 to Graphene monocrystalline prepared by the method a size of inch level
Inch), its mobility is at 10000cm2V-1s-1Above, even up to 50000cm2V-1s-1(general model above
Enclose is 20000～50000cm2V-1s-1).
The feature of the present invention and providing the benefit that:
1, the present invention uses chemical vapour deposition technique, with the metal such as copper, platinum as growing substrate, with nytron
Thing is carbon source, in the presence of the carrier gas containing hydrogen, first metallic matrix is carried out heat treatment, and utilizes
At metal base surface catalytic pyrolysis under carbon-source gas high temperature, grow single crystal graphene.Then by controlling hydrogen
Gas, carbon source concentration, perform etching the Graphene monocrystalline after growth, significantly reduce the distribution of single crystal graphene
Density so that it is every 10 square inches of numbers are reduced to 1～2, and this provides space for growing large-size monocrystalline,
Then regulation hydrogen and carbon source concentration make it regrow, and when the number of single crystal graphene becomes many, then carve
Erosion, the most repeatedly.After etching regrowth for several times, finally obtain high-quality large-size monocrystal graphene.
2, present invention process flow process is simple, processing ease, low cost, and product quality height, size are big and uniform,
And can be expected to produce in a large number.
3, using the present invention can obtain inch level high quality single crystal Graphene, its mobility is up to 50000
cm2V-1s-1Above, for Graphene nanometer electronic device, nesa coating, display and electrode of solar battery,
The application of the photoelectric field such as gas sensor, thin film electronic device is laid a good foundation, and can be expected to obtain bigger chi
Very little silicon circle level Graphene monocrystalline.
Accompanying drawing illustrates:
Fig. 1 is the experimental provision schematic diagram of CVD growth single crystal graphene.In figure, 1 gas access；2 gold medals
Belong to matrix；3 thermocouples；4 gas outlets.
The large-size monocrystal graphene after outgrowth-etching-regrowth that Fig. 2 (A) grows with platinum for matrix
Stereoscan photograph；Fig. 2 (B) is the single crystal graphene after Fig. 2 (A) performs etching again；Fig. 2 (C) and
Fig. 2 (D) is that the Confocal laser-scanning microscopy Surface scan that Fig. 2 (B) Graphene is carried out characterizes, and sees embodiment 1.
The large scale after twice etching regrowth that Fig. 3 (A) and Fig. 3 (B) grows with platinum for matrix
The stereoscan photograph of single crystal graphene.Fig. 3 (C) and Fig. 3 (D) with platinum for matrix grow through three times
The stereoscan photograph of the large-size monocrystal graphene after etching regrowth, is shown in embodiment 6.
Fig. 4 is the Raman spectrum of large-size monocrystal graphene, and optical maser wavelength is 532 nanometers.
Fig. 5 (A) is to transfer to Si/SiO after growth on platinum2The field effect transistor that Graphene monocrystalline on matrix is made
Pipe, electrode is Ti/Au；Fig. 5 (B) is resistance and the grid electricity of the graphene field effect transistor recorded under room temperature
The relation of pressure；Fig. 5 (C) is voltage difference at resistance and grid voltage and the dirac point of graphene field effect transistor
Relation, the carrier mobility that can get single crystal graphene accordingly is 12800cm2/V.s。
Detailed description of the invention:
The present invention uses chemical vapour deposition technique, with the metal such as copper, platinum as growing substrate, with Hydrocarbon
For carbon source, in the presence of the carrier gas containing hydrogen, first metallic matrix is carried out heat treatment, and utilize carbon
At metal base surface catalytic pyrolysis under the gas high temperature of source, grow single crystal graphene.Then by control hydrogen,
Carbon source concentration, performs etching the Graphene monocrystalline after growth, significantly reduces the distribution density of single crystal graphene,
Making its number be reduced to several, this provides space for growing large-size monocrystalline, and then regulation hydrogen and carbon source are dense
Degree makes it regrow, and when the number of single crystal graphene becomes many, then performs etching, the most repeatedly.Through number
After secondary etching regrowth, finally obtain high-quality large-size monocrystal graphene.The present invention is used to be possible not only to obtain
Obtain inch level single crystal graphene, and owing to experienced by the process repeatedly etching regrowth, the defect of Graphene obtains
Having arrived reparation, quality is greatly improved.The preparation method of this high-quality large-size monocrystal graphene is it
In nanometer electronic device, nesa coating, display and electrode of solar battery, gas sensor, opto-electronic conversion
The application of the photoelectric field such as device, thin film electronic device lays the foundation.
It is described in further detail the present invention below by embodiment and accompanying drawing.
Embodiment 1
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is platinum) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Platinized platinum (thickness 180 μm, length × wide=20mm × 16mm) be put in acetone, water, ethanol carry out respectively ultrasonic
Clean 40 minutes.After cleaning completes, platinized platinum being put in high temperature furnace, anneal at 1100 DEG C 10h, makes single
Crystal grain reaches grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, after annealing
Platinized platinum be positioned over horizontal reacting furnace (boiler tube diameter 22 millimeters, reaction zone length 40 millimeters) middle section
(reaction zone has thermocouple to monitor furnace temperature in real time in this position)；In the atmosphere of hydrogen, it is heated to 1040 DEG C (add
In thermal process, hydrogen flow rate is 700 ml/min, programming rate 40 DEG C/min), heat treatment 10 minutes；Heat
(gas flow rate is respectively methane 3.7 ml/min, hydrogen to be passed through the mixed gas of methane and hydrogen after having processed
Gas 700 ml/min), start to grow Graphene, growth time is 30 minutes, grows methane stream after terminating
Amount is adjusted to 3.3 ml/min, and Graphene etches, and etch period is 12 minutes, and etching will after terminating
Methane flow is adjusted to 3.5 ml/min, and regrowth occurs in Graphene, and regrowth time is 7 minutes, afterwards
Methane flow is adjusted to 3.3 ml/min again, and Graphene etches, and etch period is 8 minutes.Etching
It is quickly cooled to less than 300 DEG C with the speed of 50 DEG C/sec after end, obtains high-quality approximation hexagon monocrystalline stone
Ink alkene (see figure 2).
Scanning electron microscope and resonance laser Raman spectroscopy Surface scan are observed and are shown, gained Graphene is high-quality
Mono-crystalline structures.No longer there is hexagonal holes in the middle of after etching, the forming core defect of gained single crystal graphene has been described
Repairing, graphene-structured is continuous whole without damaged, has better quality, and is monolayer.
Embodiment 2
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is platinum) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Platinized platinum (thickness 180 μm, length × wide=5cm × 5cm) be put in acetone, water, ethanol carry out respectively ultrasonic clearly
Wash 40 minutes.After cleaning completes, platinized platinum being put in high temperature furnace, anneal at 1100 DEG C 10h, makes single crystalline substance
Grain reaches grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, by after annealing
Platinized platinum is positioned over the (reaction of horizontal reacting furnace (boiler tube diameter 8cm, reaction zone length 15cm) middle section
District, has thermocouple to monitor furnace temperature in real time in this position)；The atmosphere of hydrogen is heated to 1040 DEG C (heated
In journey, hydrogen flow rate is 700 ml/min, programming rate 40 DEG C/min), heat treatment 10 minutes；Heat treatment
(gas flow rate is respectively methane 3.7 ml/min, hydrogen 700 to be passed through the mixed gas of methane and hydrogen after completing
Ml/min), start to grow Graphene, growth time is 30 minutes, and methane flow is regulated after terminating by growth
Being 3.3 ml/min, Graphene etches, and etch period is 12 minutes, etches methane stream after terminating
Amount is adjusted to 3.5 ml/min, and regrowth occurs in Graphene, and regrowth time is 7 minutes, the most again by first
Alkane Flow-rate adjustment is 3.3 ml/min, and Graphene etches, and etch period is 8 minutes.The most again by first
Alkane is adjusted to 3.5 ml/min, and regrowth time is 10 hours, regrowth terminate after with the speed of 50 DEG C/sec
It is quickly cooled to less than 300 DEG C, obtains high-quality large-size monocrystal graphene.
Scanning electron microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal knot
Structure, full-size is 1 inch, and graphene-structured is continuous whole without damaged, has a better quality, and all
For monolayer.Mobility is up to 30000cm2/V.s。
Embodiment 3
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is copper) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Copper sheet (thickness 25 μm, length × wide=5cm × 5cm) is put in acetone, water, ethanol and carries out ultrasonic cleaning respectively
40 minutes.After cleaning completes, copper sheet being put in high temperature furnace, anneal at 1083 DEG C 10h, makes single crystal grain
Reach grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, by the copper after annealing
Sheet be positioned over horizontal reacting furnace (boiler tube diameter 8cm, reaction zone length 15cm) middle section (reaction zone,
Thermocouple is had to monitor furnace temperature in real time in this position)；1040 DEG C it are heated to (in heating process in the atmosphere of hydrogen
Hydrogen flow rate is 700 ml/min, programming rate 40 DEG C/min), heat treatment 1 hour；After heat treatment completes
Be passed through methane and hydrogen mixed gas (gas flow rate be respectively methane 4.8 ml/min, hydrogen 700 milliliters/
Minute), starting to grow Graphene, growth time is 30 minutes, and growth turns off methane gas, graphite after terminating
Alkene etches, and etch period is 20 seconds, etches and methane flow is adjusted to after terminating 4.5 ml/min, stone
There is regrowth in ink alkene, and regrowth time is 1 hour, turns off methane gas the most again, and Graphene etches,
Etch period is 20 seconds.Methane is adjusted to 4.5 ml/min the most again, and growth time is 15 hours, then
Growth is quickly cooled to less than 300 DEG C with the speed of 50 DEG C/sec after terminating, and obtains high-quality large-size monocrystal graphite
Alkene.
Scanning electron microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal knot
Structure, full-size is 1.5 inch, and graphene-structured is continuous whole has better quality without damaged, and
It is monolayer.Mobility is up to 30000cm2/V.s。
Embodiment 4
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is platinum) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Platinized platinum (thickness 180 μm, length × wide=5cm × 5cm) be put in acetone, water, ethanol carry out respectively ultrasonic clearly
Wash 40 minutes.After cleaning completes, platinized platinum being put in high temperature furnace, anneal at 1100 DEG C 10h, makes single crystalline substance
Grain reaches grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, by after annealing
Platinized platinum is positioned over the (reaction of horizontal reacting furnace (boiler tube diameter 8cm, reaction zone length 15cm) middle section
District, has thermocouple to monitor furnace temperature in real time in this position)；The atmosphere of hydrogen is heated to 1060 DEG C (heated
In journey, hydrogen flow rate is 1000 ml/min, programming rate 40 DEG C/min), heat treatment 10 minutes；Heat treatment
(gas flow rate is respectively methane 4.5 ml/min, hydrogen 1000 to be passed through the mixed gas of methane and hydrogen after completing
Ml/min), start to grow Graphene, growth time is 30 minutes, and methane flow is regulated after terminating by growth
Being 3.5 ml/min, Graphene etches, and etch period is 1 minute, etches methane flow after terminating
Being adjusted to 4.0 ml/min, there is regrowth in Graphene, and regrowth time is 15 hours, after regrowth terminates
It is quickly cooled to less than 300 DEG C with the speed of 50 DEG C/sec, obtains high-quality large-size monocrystal graphene.
Scanning electron microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal knot
Structure, full-size is 1.5 inch, and graphene-structured is continuous whole has better quality without damaged, and
It is monolayer.
Embodiment 5
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is platinum) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Platinized platinum (thickness 180 μm, length × wide=5cm × 5cm) be put in acetone, water, ethanol carry out respectively ultrasonic clearly
Wash 40 minutes.After cleaning completes, platinized platinum being put in high temperature furnace, anneal at 1100 DEG C 10h, makes single crystalline substance
Grain reaches grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, by after annealing
Platinized platinum is positioned over the (reaction of horizontal reacting furnace (boiler tube diameter 8cm, reaction zone length 15cm) middle section
District, has thermocouple to monitor furnace temperature in real time in this position)；The atmosphere of hydrogen is heated to 1060 DEG C (heated
In journey, hydrogen flow rate is 1000 ml/min, programming rate 40 DEG C/min), heat treatment 10 minutes；Heat treatment
(gas flow rate is respectively methane 4.5 ml/min, hydrogen 1000 to be passed through the mixed gas of methane and hydrogen after completing
Ml/min), start to grow Graphene, growth time is 30 minutes, and methane flow is regulated after terminating by growth
Being 3.5 ml/min, Graphene etches, and etch period is 1 minute, etches methane flow after terminating
Being adjusted to 4.0 ml/min, there is regrowth in Graphene, and regrowth time is 2 hours, the most again by methane
Flow-rate adjustment is 3.5 ml/min, and Graphene etches, and etch period is 1 minute.The most again by methane
Being adjusted to 4.0 ml/min, regrowth time is 20 hours, and regrowth is fast with the speed of 50 DEG C/sec after terminating
Speed is cooled to less than 300 DEG C, obtains high-quality large-size monocrystal graphene.
Scanning electron microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal knot
Structure, full-size is 2 inch, and graphene-structured is continuous whole without damaged, has a better quality, and all
For monolayer.
Embodiment 6
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is platinum) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Platinized platinum (thickness 180 μm, length × wide=20mm × 16mm) be put in acetone, water, ethanol carry out respectively ultrasonic
Clean 40 minutes.After cleaning completes, platinized platinum being put in high temperature furnace, anneal at 1100 DEG C 10h, makes single
Crystal grain reaches grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, after annealing
Platinized platinum be positioned over horizontal reacting furnace (boiler tube diameter 22 millimeters, reaction zone length 40 millimeters) middle section
(reaction zone has thermocouple to monitor furnace temperature in real time in this position)；In the atmosphere of hydrogen, it is heated to 1060 DEG C (add
In thermal process, hydrogen flow rate is 1000 ml/min, programming rate 40 DEG C/min), heat treatment 10 minutes；Heat
(gas flow rate is respectively methane 4.5 ml/min, hydrogen to be passed through the mixed gas of methane and hydrogen after having processed
Gas 1000 ml/min), start to grow Graphene, growth time is 30 minutes, grows methane after terminating
Flow-rate adjustment is 3.5 ml/min, and Graphene etches, and etch period is 1 minute, and etching will after terminating
Methane flow is adjusted to 4.0 ml/min, and regrowth occurs in Graphene, and regrowth time is 2 hours, afterwards
Methane flow is adjusted to 3.5 ml/min again, and Graphene etches, and etch period is 1 minute.Afterwards
Methane is adjusted to 4.0 ml/min again, and regrowth time is 2 hours, is adjusted to by methane flow the most again
3.5 ml/min, Graphene etches, and etch period is 1 minute.The most again methane is adjusted to 4.0
Ml/min, regrowth time is 3 hours, and regrowth is quickly cooled to 300 with the speed of 50 DEG C/sec after terminating
Below DEG C, obtain high-quality large-size monocrystal graphene (see figure 3).
Scanning electron microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal knot
Structure, full-size is 3 millimeter, and graphene-structured is continuous whole without damaged, has a better quality, and all
For monolayer.Mobility is up to 40000cm2/V.s。
Embodiment 7
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is copper) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Copper sheet (thickness 25 μm, length × wide=15cm × 15cm) be put in acetone, water, ethanol carry out respectively ultrasonic clearly
Wash 40 minutes.After cleaning completes, copper sheet being put in high temperature furnace, anneal at 1083 DEG C 10h, makes single crystalline substance
Grain reaches grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, by after annealing
Copper sheet is positioned over the (reaction of horizontal reacting furnace (boiler tube diameter 8cm, reaction zone length 15cm) middle section
District, has thermocouple to monitor furnace temperature in real time in this position)；The atmosphere of hydrogen is heated to 1060 DEG C (heated
In journey, hydrogen flow rate is 700 ml/min, programming rate 40 DEG C/min), heat treatment 1 hour；Heat treatment is complete
(gas flow rate is respectively methane 4.3 ml/min, hydrogen 700 to be passed through the mixed gas of methane and hydrogen after one-tenth
Ml/min), start to grow Graphene, growth time is 30 minutes, and growth turns off methane gas after terminating,
Graphene etches, and etch period is 20 seconds, etches and methane flow is adjusted to after terminating 4.0 ml/min,
There is regrowth in Graphene, and regrowth time is 1 hour, turns off methane gas the most again, and Graphene is carved
Erosion, etch period is 20 seconds.Methane is adjusted to 4.0 ml/min the most again, and growth time is 2 hours,
Turning off methane gas the most again, Graphene etches, and etch period is 30 seconds.The most again methane is adjusted to
3.9 ml/min, growth time is 5 hours, turns off methane gas the most again, and Graphene etches, and carves
The erosion time is 50 seconds.Methane is adjusted to 3.8 ml/min the most again, and growth time is 10 hours, afterwards
Turning off methane gas again, Graphene etches, and etch period is 50 seconds.The most again methane is adjusted to 3.8
Ml/min, growth time is 20 hours, turns off methane gas the most again, and Graphene etches, etching
Time is 50 seconds.Methane is adjusted to 3.8 ml/min the most again, and growth time is 30 hours, the most again
Turning off methane gas, Graphene etches, and etch period is 50 seconds.Methane is adjusted to 3.8 millis the most again
Liter/min, growth time is 30 hours, and regrowth is quickly cooled to 300 DEG C with the speed of 50 DEG C/sec after terminating
Hereinafter, high-quality large-size monocrystal graphene is obtained.
Scanning electron microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal knot
Structure, full-size is 4 inch, and graphene-structured is continuous whole without damaged, has a better quality, and all
For monolayer.Mobility is up to 40000cm2/V.s。
Embodiment 8
As it is shown in figure 1, the present invention uses horizontal reacting furnace to grow Graphene, horizontal reacting furnace two ends are respectively
Being provided with gas access 1 and gas outlet 4, metallic matrix 2(the present embodiment is platinum) it is placed in horizontal reacting furnace height
Warm area, thermocouple 3 is positioned at horizontal reacting furnace high-temperature region, to monitor reaction temperature in real time.First, by polycrystalline
Platinized platinum (thickness 180 μm, length × wide=15cm × 15cm) be put in acetone, water, ethanol carry out respectively ultrasonic
Clean 40 minutes.After cleaning completes, platinized platinum being put in high temperature furnace, anneal at 1100 DEG C 10h, makes single
Crystal grain reaches grade (the single crystallite dimension of the present embodiment is specially 1mm～5mm).Then, after annealing
Platinized platinum to be positioned over horizontal reacting furnace (boiler tube diameter 8cm, reaction zone length 15cm) middle section (anti-
Answer district, have thermocouple to monitor furnace temperature in real time in this position)；1060 DEG C of (heating it are heated in the atmosphere of hydrogen
During hydrogen flow rate be 1000 ml/min, programming rate 40 DEG C/min), heat treatment 10 minutes；At Re
(gas flow rate is respectively methane 4.3 ml/min, hydrogen to be passed through the mixed gas of methane and hydrogen after having managed
1000 ml/min), start to grow Graphene, growth time is 30 minutes, and growth turns off methane after terminating
Gas, Graphene etches, and etch period is 30 seconds, and methane flow is adjusted to 4.1 in the least after terminating by etching
Liter/min, there is regrowth in Graphene, and regrowth time is 30 minutes, turns off methane gas, stone the most again
Ink alkene etches, and etch period is 30 seconds.Methane is adjusted to 4.0 ml/min the most again, during regrowth
Between be 2 hours, turn off methane gas the most again, Graphene etches, and etch period is 50 seconds.The most again
Methane is adjusted to 3.9 ml/min, and regrowth time is 5 hours, turns off methane gas, graphite the most again
Alkene etches, and etch period is 50 seconds.Methane is adjusted to 3.9 ml/min, regrowth time the most again
Being 20 hours, turn off methane gas the most again, Graphene etches, and etch period is 50 seconds.The most again
Methane is adjusted to 3.9 ml/min, and regrowth time is 30 hours, turns off methane gas, graphite the most again
Alkene etches, and etch period is 50 seconds.Methane is adjusted to 3.9 ml/min, regrowth time the most again
Being 30 hours, turn off methane gas the most again, Graphene etches, and etch period is 50 seconds.The most again
Methane is adjusted to 3.9 ml/min, and regrowth time is 30 hours, regrowth terminate after with 50 DEG C/sec
Speed is quickly cooled to less than 300 DEG C, obtains high-quality large-size monocrystal graphene.
Scanning electron microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal knot
Structure, full-size is 4 inch, and graphene-structured is continuous whole without damaged, has a better quality, and all
For monolayer.Mobility is up to 50000cm2/V.s。
As it is shown in figure 1, one end of gas access 1 is provided with multiple mass flowmenter in figure, optionally control
It is passed through the gases such as hydrogen, methane, ethylene, acetylene or argon.Liquid carbon source is (such as ethanol, methanol, benzene, first
Benzene or hexamethylene etc.) it is placed in Meng Shi wash bottle, brought into by the gaseous mixture bubbling of argon or argon with nitrogen etc..
As in figure 2 it is shown, the Graphene quality after outgrowth-etching-regrowth is intact, again after etching also
Middle hexagonal holes does not occurs, in conjunction with the sign of Raman spectrum Surface scan, may certify that the method can improve
The quality of Graphene.
As it is shown on figure 3, the stereoscan photograph of Graphene is it can be seen that use growth-etching-regeneration from platinum
Long method can incrementally increase the size of single crystal graphene, and the hexagonal shape of gained Graphene is constant,
Large scale is up to 3 millimeters.
As shown in Figure 4, from the Raman spectrum of Graphene it can be seen that use large scale graphite prepared by the method
Alkene monocrystalline is the 1340cm in monolayer, and Raman spectrum-1The intensity of (D mould) position is the lowest, illustrates that it has
The highest quality.
As it is shown in figure 5, use the carrier mobility of the single crystal graphene of the method growth up to 12800
cm2/ V.s, further demonstrates the high-quality of single crystal graphene.
Embodiment result shows, the present invention is proposed and performed etching Graphene by regulation and control hydrogen and carbon source concentration,
Significantly reducing the distribution density of single crystal graphene, this provides space for growing large-size monocrystalline, the most again
Regulation reaction atmosphere makes its regrowth, is so repeated several times, is finally obtained high-quality large-size monocrystal graphene.
The direction break through to promote Graphene application particularly nanometer electronic device, nesa coating, display and
The application in the fields such as film photoelectric functional device such as electrode of solar battery, gas sensor, integrated circuit has
Important strategic importance.
Claims (6)
1. the preparation method of a high-quality large-size monocrystal graphene, it is characterized in that: the method uses chemical vapour deposition technique, in the presence of the carrier gas containing hydrogen, first metallic matrix is carried out heat treatment, and utilize under methane gas high temperature at metal base surface catalytic pyrolysis, grow single crystal graphene；Then by controlling hydrogen, methane concentration, Graphene monocrystalline after growth is performed etching, significantly reduce the distribution density of single crystal graphene, its every 10 square inches of numbers are made to be reduced to 1～2, this provides space for growing large-size monocrystalline, and then regulation hydrogen and methane concentration make it regrow, when the number of single crystal graphene becomes many, perform etching again, the most repeatedly；After over etching regrowth, finally obtain high-quality large-size monocrystal graphene；
One of described growth, etching and regrowth process employing are following:
(1) mixed gas of methane and hydrogen it is passed through at 1040 DEG C, gas flow rate is respectively methane 3.7 ml/min, hydrogen 700 ml/min, start to grow Graphene, growth time is 30 minutes, grow and after terminating, methane flow is adjusted to 3.3 ml/min, Graphene etches, etch period is 12 minutes, etch and after terminating, methane flow is adjusted to 3.5 ml/min, there is regrowth in Graphene, and regrowth time is 7 minutes, and methane flow is adjusted to 3.3 ml/min the most again, Graphene etches, and etch period is 8 minutes；
(2) mixed gas of methane and hydrogen it is passed through at 1040 DEG C, gas flow rate is respectively methane 3.7 ml/min, hydrogen 700 ml/min, start to grow Graphene, growth time is 30 minutes, grow and after terminating, methane flow is adjusted to 3.3 ml/min, Graphene etches, etch period is 12 minutes, etch and after terminating, methane flow is adjusted to 3.5 ml/min, there is regrowth in Graphene, and regrowth time is 7 minutes, and methane flow is adjusted to 3.3 ml/min the most again, Graphene etches, and etch period is 8 minutes；Methane is adjusted to 3.5 ml/min the most again, and regrowth time is 10 hours；
(3) be passed through the mixed gas of methane and hydrogen at 1040 DEG C, gas flow rate is respectively methane 4.8 ml/min, hydrogen 700 ml/min, starts to grow Graphene, growth time is 30 minutes, growth turns off methane gas after terminating, and Graphene etches, and etch period is 20 seconds, etch and after terminating, methane flow is adjusted to 4.5 ml/min, there is regrowth in Graphene, and regrowth time is 1 hour, turns off methane gas the most again, Graphene etches, and etch period is 20 seconds；Methane is adjusted to 4.5 ml/min the most again, and growth time is 15 hours；
(4) mixed gas of methane and hydrogen it is passed through at 1060 DEG C, gas flow rate is respectively methane 4.5 ml/min, hydrogen 1000 ml/min, start to grow Graphene, growth time is 30 minutes, and methane flow is adjusted to 3.5 ml/min after terminating by growth, and Graphene etches, etch period is 1 minute, methane flow is adjusted to 4.0 ml/min after terminating by etching, and regrowth occurs in Graphene, and regrowth time is 15 hours；
(5) mixed gas of methane and hydrogen it is passed through at 1060 DEG C, gas flow rate is respectively methane 4.5 ml/min, hydrogen 1000 ml/min, start to grow Graphene, growth time is 30 minutes, grow and after terminating, methane flow is adjusted to 3.5 ml/min, Graphene etches, etch period is 1 minute, etch and after terminating, methane flow is adjusted to 4.0 ml/min, there is regrowth in Graphene, and regrowth time is 2 hours, and methane flow is adjusted to 3.5 ml/min the most again, Graphene etches, and etch period is 1 minute；Methane is adjusted to 4.0 ml/min the most again, and regrowth time is 20 hours；
(6) mixed gas of methane and hydrogen it is passed through at 1060 DEG C, gas flow rate is respectively methane 4.5 ml/min, hydrogen 1000 ml/min, start to grow Graphene, growth time is 30 minutes, grow and after terminating, methane flow is adjusted to 3.5 ml/min, Graphene etches, etch period is 1 minute, etch and after terminating, methane flow is adjusted to 4.0 ml/min, there is regrowth in Graphene, and regrowth time is 2 hours, and methane flow is adjusted to 3.5 ml/min the most again, Graphene etches, and etch period is 1 minute；Methane is adjusted to 4.0 ml/min the most again, and regrowth time is 2 hours, and methane flow is adjusted to 3.5 ml/min the most again, and Graphene etches, and etch period is 1 minute；Methane is adjusted to 4.0 ml/min the most again, and regrowth time is 3 hours；
(7) be passed through the mixed gas of methane and hydrogen at 1060 DEG C, gas flow rate is respectively methane 4.3 ml/min, hydrogen 700 ml/min, starts to grow Graphene, growth time is 30 minutes, growth turns off methane gas after terminating, and Graphene etches, and etch period is 20 seconds, etch and after terminating, methane flow is adjusted to 4.0 ml/min, there is regrowth in Graphene, and regrowth time is 1 hour, turns off methane gas the most again, Graphene etches, and etch period is 20 seconds；Methane is adjusted to 4.0 ml/min the most again, and growth time is 2 hours, turns off methane gas the most again, and Graphene etches, and etch period is 30 seconds；Methane is adjusted to 3.9 ml/min the most again, and growth time is 5 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.8 ml/min the most again, and growth time is 10 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.8 ml/min the most again, and growth time is 20 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.8 ml/min the most again, and growth time is 30 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.8 ml/min the most again, and growth time is 30 hours；
(8) be passed through the mixed gas of methane and hydrogen at 1060 DEG C, gas flow rate is respectively methane 4.3 ml/min, hydrogen 1000 ml/min, starts to grow Graphene, growth time is 30 minutes, growth turns off methane gas after terminating, and Graphene etches, and etch period is 30 seconds, etch and after terminating, methane flow is adjusted to 4.1 ml/min, there is regrowth in Graphene, and regrowth time is 30 minutes, turns off methane gas the most again, Graphene etches, and etch period is 30 seconds；Methane is adjusted to 4.0 ml/min the most again, and regrowth time is 2 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.9 ml/min the most again, and regrowth time is 5 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.9 ml/min the most again, and regrowth time is 20 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.9 ml/min the most again, and regrowth time is 30 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.9 ml/min the most again, and regrowth time is 30 hours, turns off methane gas the most again, and Graphene etches, and etch period is 50 seconds；Methane is adjusted to 3.9 ml/min the most again, and regrowth time is 30 hours.
2. according to the preparation method of the high-quality large-size monocrystal graphene described in claim 1, it is characterised in that: metallic matrix used is the platinum of surfacing, ruthenium, iridium, copper or the thin slice of nickel metal or thin film, and purity is more than 99 wt%, and thickness is not less than 100nm.
3. according to the preparation method of the high-quality large-size monocrystal graphene described in claim 1, it is characterised in that: metallic matrix used is ultrasonic cleaning respectively in one or more of acetone, ethyl lactate, water and ethanol, and the time is no less than 10 minutes.
4. according to the preparation method of the high-quality large-size monocrystal graphene described in claim 1, it is characterized in that: metallic matrix heat treatment used uses annealing, treatment temperature is 800 DEG C～1500 DEG C, atmosphere is hydrogen, or, atmosphere is hydrogen and nitrogen or the mixed gas of noble gas, and wherein hydrogen mol ratio is not less than 1%, flow velocity is not less than 10 sccm, and annealing time is no less than 10 minutes.
5. according to the preparation method of the high-quality large-size monocrystal graphene described in claim 1, it is characterised in that: the cycle-index of growth-etching-regrowth is more than 1 time.
6. according to the preparation method of the high-quality large-size monocrystal graphene described in claim 1; it is characterized in that: after growth terminates; metallic matrix is under the carrier containing hydrogen is protected; it is quickly cooled to less than 300 DEG C; in carrier gas, hydrogen mol ratio is not less than 1%, and quickly the speed of cooling is not less than 10 DEG C/sec.
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