CN103643288A - Preparation method of high-quality large-size monocrystal graphene - Google Patents
Preparation method of high-quality large-size monocrystal graphene Download PDFInfo
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Abstract
The invention relates to a novel graphene material and a chemical vapor deposition (CVD) preparation technology, and in particular relates to a preparation method of high-quality large-size monocrystal graphene, suitable for preparing high-quality large-size monocrystal graphene. The preparation method comprises the steps of: based on a chemical vapor deposition technology, in the presence of a carrier gas containing hydrogen, carrying out heat treatment on a metal substrate (copper, platinum and other metals) by taking a hydrocarbon compound as a carbon source, and carrying out catalytic cracking at a high temperature by virtue of the carbon source gas, so as to grow the monocrystal graphene; etching graphene by regulating concentrations of hydrogen and carbon source, so as to greatly reduce distribution density of the monocrystal graphene; and regulating a reaction atmosphere again to grow monocrystal graphene again, and carrying out the growth operations several times in the same way, so as to finally obtain the high-quality large-size monocrystal graphene. The high-quality inch-grade monocrystal graphene disclosed by the invention lays the foundation for application in a nano-electronic component, a transparent conductive film, a display, a solar cell electrode, a gas sensor, a thin-film electronic component and other photoelectric fields.
Description
Technical field:
The present invention relates to Graphene novel material and chemical vapor deposition (CVD) technology of preparing thereof, be specially a kind of preparation method of high quality large size single crystal Graphene, be suitable for preparing high quality large size single crystal Graphene.
Background technology:
Graphene is tightly packed one-tenth bi-dimensional cellular shape crystalline structure monolayer carbon atomic crystal, is the elementary cell that builds other dimension Carbon Materials (as zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).This strict two-dimentional atomic crystal material has fabulous electricity, calorifics and mechanical property, as: under room temperature, its electronic mobility is up to 200,000cm
2/ Vs, thermal conductivity is up to 5000Wm
-1k
-1, Young's modulus is up to 1TPa.The performance of this excellence of Graphene makes it be expected to obtain widespread use in fields such as multi-functional nanometer electronic device, nesa coating, matrix material, catalytic material, energy storage material, field emmision material, gas sensor and atmosphere storage.Therefore, from the study group of Univ Manchester UK in 2004, obtain first after the Graphene of stable existence, it just becomes rapidly the most active research forward positions, field such as Materials science, Condensed Matter Physics, chemistry.
At present, Graphene be prepared with a lot of methods, comprise micromechanics stripping method, chemical stripping method, silicon carbide epitaxial growth method, chemical Vapor deposition process.Wherein, mechanically peel method process is simple, and product quality is high, but can only obtain minute quantity Graphene, and efficiency is low, randomness is large; SiC surface 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, and Graphene is difficult to shift; Chemical stripping method is because the participation of strong oxidising process causes the Graphene of preparing to contain more defect, and electroconductibility is poor, and the size of Graphene less (sheet footpath is mostly in micron dimension).That CVD method has is simple, gained Graphene is of high quality, can realize large area deposition and be easy to transfer to and the advantage such as on various matrixes, use, therefore the method is widely used in preparing Graphene transistor and transparent conductive film, becomes gradually the main method of preparing high-quality graphene at present.
Yet the Graphene mobility that at present prepared by CVD method is generally on the low side, conventionally arrives several thousand cm between hundreds of
2/ Vs, its electroconductibility is also far below theoretical limit.The crystal boundary of Graphene and in-plane defects are generally considered one of major influence factors causing mobility and electroconductibility reduction.But in CVD preparation process, because the Enhancing Nucleation Density of Graphene is wayward, the grain-size of the Graphene of preparation arrives between hundreds of micron in hundreds of nanometer conventionally.And Graphene easily produces defect in forming core and process of growth.These are all very big has affected mobility and electroconductibility.Therefore, how to utilize CVD method to prepare the large-sized single crystal graphene of high quality is the difficult point of Graphene research field always.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of high quality large size single crystal Graphene, the method has the advantages such as cost is low, flow process is simple, controllability is good, therefore can be used as a kind of Perfected process that is suitable for preparing high quality large size single crystal Graphene.
Technical scheme of the present invention is:
The invention provides a kind of preparation method of high quality large size single crystal Graphene, the method adopts chemical vapour deposition technique, in the situation that the carrier gas that contains hydrogen exists, first metallic matrix is heat-treated, and utilize under carbon-source gas high temperature at metal base surface catalytic pyrolysis, grow single crystal graphene.Then by controlling hydrogen, carbon source concentration, Graphene monocrystalline after growth is carried out to etching, significantly reduce the distribution density of single crystal graphene, make its every 10 square inches of numbers be reduced to 1～2, this provides space for growing large-size monocrystalline, then regulates hydrogen and carbon source concentration that it is regrowed, when the number of single crystal graphene becomes many, carry out again etching, so repeatedly.After etching regrowth for several times, finally obtain high quality large size single crystal Graphene.
In the present invention, thin slice or the film of the metals such as the precious metals such as the platinum that metallic matrix used is surfacing, ruthenium or iridium or copper, nickel, purity is greater than 99wt%, and thickness is not less than 100nm, is preferably 500nm～1 μ m.
In the present invention, metallic matrix used need ultrasonic cleaning respectively in one or more of acetone, ethyl lactate, water and ethanol, and the time is no less than 10 minutes, is preferably 1 hour～2 hours.
In the present invention, metallic matrix used need be through annealing thermal treatment, and treatment temp is 800 ℃～1500 ℃, is preferably 900 ℃～1100 ℃; Atmosphere is hydrogen (or mixed gas of the gas such as hydrogen and nitrogen or argon gas), and wherein 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 hours.
In the present invention, adopt chemical Vapor deposition process to prepare large size single crystal Graphene, carbon source used be in the hydrocarbon polymers such as methane, ethane, acetylene, ethene, ethanol one or more, carrier is hydrogen (or mixed gas of the gas such as hydrogen and nitrogen or argon gas), the purity of carbon source and carrier gas is all greater than 99%(volume), the mol ratio of carbon source and hydrogen is 0.005～1, is preferably 0.005～0.1.Growth temperature is 600 ℃～1200 ℃, is preferably 900 ℃～1100 ℃.Growth time is not less than 20 minutes, is preferably 30 minutes～1 hour.
In the present invention, lithographic method used, etching temperature is 600 ℃～1200 ℃, be preferably 900 ℃～1100 ℃, etching time is not less than 10 seconds, is preferably 30 seconds～2 minutes, etching atmosphere is the mixed gas of carbon source and hydrogen, carbon source used be in methane, ethane, acetylene, ethene, ethanol hydrocarbon polymer one or more, the mol ratio of carbon source and hydrogen is 0.005～0.1, is preferably 0.01～0.05.
In the present invention, regrowth method used, regrowth temperature is 600 ℃～1200 ℃, is preferably 900 ℃～1100 ℃, the regrowth time is not less than 20 minutes, is preferably 1 hour～100 hours.Regrowth atmosphere is the mixed gas of carbon source and hydrogen, carbon source used be in methane, ethane, acetylene, ethene, ethanol hydrocarbon polymer one or more.The mol ratio of carbon source and hydrogen is 0.005～0.5, is preferably 0.01～0.5.
In the present invention, the cycle index of growth-etching-regrowth is greater than 1 time, is preferably more than 3 times.
In the present invention, after growth finishes, metallic matrix need be quickly cooled to below 300 ℃ under the carrier protection that contains hydrogen, is preferably 100 ℃～200 ℃; Carrier gas is the mixed gas of hydrogen and nitrogen or argon gas, and hydrogen mol ratio is not less than 1%, is preferably 50～80%; Cooling speed is not less than 10 ℃/sec fast, is preferably 30～50 ℃/sec.
In the present invention, Graphene monocrystalline prepared by the method is of a size of inch level (general range is 1 inch～4 inches), and its mobility is at 10000cm
2v
-1s
-1above, even can reach 50000cm
2v
-1s
-1(general range is 20000～50000cm above
2v
-1s
-1).
Feature of the present invention and beneficial effect are:
1, the present invention adopts chemical vapour deposition technique, the metals such as copper, platinum of take are growing substrate, take hydrocarbon polymer as carbon source, in the situation that the carrier gas that contains hydrogen exists, first metallic matrix is heat-treated, and utilize under carbon-source gas high temperature at metal base surface catalytic pyrolysis, grow single crystal graphene.Then by controlling hydrogen, carbon source concentration, Graphene monocrystalline after growth is carried out to etching, significantly reduce the distribution density of single crystal graphene, make its every 10 square inches of numbers be reduced to 1～2, this provides space for growing large-size monocrystalline, then regulates hydrogen and carbon source concentration that it is regrowed, when the number of single crystal graphene becomes many, carry out again etching, so repeatedly.After etching regrowth for several times, finally obtain high quality large size single crystal Graphene.
2, technical process of the present invention is simple, processing ease, and cost is low, and product quality is high, size is large and evenly, and can be expected to a large amount of production.
3, adopt the present invention can obtain inch level high quality single crystal Graphene, its mobility can reach 50000cm
2v
-1s
-1above, for Graphene is laid a good foundation in the application of the photoelectric fields such as nanometer electronic device, nesa coating, indicating meter and electrode of solar battery, gas sensor, thin film electronic device, and can be expected to obtain larger sized silicon circle level Graphene monocrystalline.
Accompanying drawing explanation:
Fig. 1 is the experimental installation schematic diagram of CVD method growing single-crystal Graphene.In figure, 1 gas inlet; 2 metallic matrixes; 3 thermopairs; 4 pneumatic outlets.
Fig. 2 (A) be take platinum and is the stereoscan photograph of large size single crystal Graphene after outgrowth-etching-regrowth of matrix growth; Fig. 2 (B) carries out the single crystal graphene after etching again for Fig. 2 (A); The burnt Raman spectrum face scanning of copolymerization that Fig. 2 (C) and Fig. 2 (D) carry out for Fig. 2 (B) Graphene characterizes, and sees embodiment 1.
Fig. 3 (A) and Fig. 3 (B) be take platinum and are the stereoscan photograph through the large size single crystal Graphene after twice etching regrowth of matrix growth.Fig. 3 (C) and Fig. 3 (D) be take platinum and are the stereoscan photograph through the large size single crystal Graphene after three etching regrowths of matrix growth, see embodiment 6.
Fig. 4 is the Raman spectrum of large size single crystal Graphene, and optical maser wavelength is 532 nanometers.
Fig. 5 (A) is for transferring to Si/SiO after growth on platinum
2the field-effect transistor that Graphene monocrystalline on matrix is made, electrode is Ti/Au; The resistance of graphene field effect transistor and the relation of grid voltage of Fig. 5 (B) for recording under room temperature; The relation of the resistance that Fig. 5 (C) is graphene field effect transistor and grid voltage and dirac point place voltage difference, the carrier mobility that can obtain accordingly single crystal graphene is 12800cm
2/ V.s.
Embodiment:
The present invention adopts chemical vapour deposition technique, the metals such as copper, platinum of take are growing substrate, take hydrocarbon polymer as carbon source, in the situation that the carrier gas that contains hydrogen exists, first metallic matrix is heat-treated, and utilize under carbon-source gas high temperature at metal base surface catalytic pyrolysis, grow single crystal graphene.Then by controlling hydrogen, carbon source concentration, Graphene monocrystalline after growth is carried out to etching, significantly reduce the distribution density of single crystal graphene, its number is reduced to several, this provides space for growing large-size monocrystalline, then regulates hydrogen and carbon source concentration that it is regrowed, when the number of single crystal graphene becomes many, carry out again etching, so repeatedly.After etching regrowth for several times, finally obtain high quality large size single crystal Graphene.Adopt the present invention not only can obtain inch level single crystal graphene, and owing to having experienced the process of etching regrowth repeatedly, the defect of Graphene has obtained reparation, quality is greatly improved.The preparation method of this high quality large size single crystal Graphene lays the foundation for its application at photoelectric fields such as nanometer electronic device, nesa coating, indicating meter and electrode of solar battery, gas sensor, photoelectric commutator, thin film electronic devices.
Below by embodiment and accompanying drawing, be described in further detail the present invention.
Embodiment 1
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is platinum) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline platinized platinum (thickness 180 μ m, length * wide=20mm * 16mm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, platinized platinum is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1100 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the platinized platinum after annealing is positioned over to horizontal Reaktionsofen (22 millimeters of boiler tube diameters, 40 millimeters of reaction zone length) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); In the atmosphere of hydrogen, be heated to 1040 ℃ (in heat-processed, hydrogen flow rate is 700 ml/min, 40 ℃/min of heat-up rates), thermal treatment 10 minutes; After completing, thermal treatment passes into the mixed gas (gas flow rate is respectively methane 3.7 ml/min, hydrogen 700 ml/min) of methane and hydrogen, start growing graphene, growth time is 30 minutes, after growth finishes, methane flow is adjusted to 3.3 ml/min, Graphene generation etching, etching time is 12 minutes, after etching finishes, methane flow is adjusted to 3.5 ml/min, there is regrowth in Graphene, the regrowth time is 7 minutes, again methane flow is adjusted to afterwards to 3.3 ml/min, Graphene generation etching, etching time is 8 minutes.Speed with 50 ℃/sec after etching finishes is quickly cooled to below 300 ℃, obtains high-quality approximate hexagon single crystal graphene (see figure 2).
Scanning electronic microscope and resonance laser Raman spectroscopy face scanning show, gained Graphene is high quality single crystal structure.In the middle of after etching, no longer include hexagonal holes, illustrate that the forming core defect of gained single crystal graphene is repaired, graphene-structured continuous whole, without breakage, has better quality, and is individual layer.
Embodiment 2
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is platinum) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline platinized platinum (thickness 180 μ m, length * wide=5cm * 5cm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, platinized platinum is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1100 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the platinized platinum after annealing is positioned over to horizontal Reaktionsofen (boiler tube diameter 8cm, reaction zone length 15cm) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); In the atmosphere of hydrogen, be heated to 1040 ℃ (in heat-processed, hydrogen flow rate is 700 ml/min, 40 ℃/min of heat-up rates), thermal treatment 10 minutes; After completing, thermal treatment passes into the mixed gas (gas flow rate is respectively methane 3.7 ml/min, hydrogen 700 ml/min) of methane and hydrogen, start growing graphene, growth time is 30 minutes, after growth finishes, methane flow is adjusted to 3.3 ml/min, Graphene generation etching, etching time is 12 minutes, after etching finishes, methane flow is adjusted to 3.5 ml/min, there is regrowth in Graphene, the regrowth time is 7 minutes, again methane flow is adjusted to afterwards to 3.3 ml/min, Graphene generation etching, etching time is 8 minutes.Methane is adjusted to afterwards to 3.5 ml/min, the regrowth time is 10 hours again, and the speed with 50 ℃/sec after regrowth finishes is quickly cooled to below 300 ℃, obtains high quality large size single crystal Graphene.
Scanning electronic microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal structure, and overall dimension is 1 inch of left and right, and graphene-structured continuous whole, without breakage, has better quality, and is individual layer.Mobility can reach 30000cm
2/ V.s.
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is copper) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline copper sheet (thickness 25 μ m, length * wide=5cm * 5cm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, copper sheet is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1083 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the copper sheet after annealing is positioned over to horizontal Reaktionsofen (boiler tube diameter 8cm, reaction zone length 15cm) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); In the atmosphere of hydrogen, be heated to 1040 ℃ (in heat-processed, hydrogen flow rate is 700 ml/min, 40 ℃/min of heat-up rates), thermal treatment 1 hour; After completing, thermal treatment passes into the mixed gas (gas flow rate is respectively methane 4.8 ml/min, hydrogen 700 ml/min) of methane and hydrogen, start growing graphene, growth time is 30 minutes, after growth finishes, turns off methane gas, Graphene generation etching, etching time is 20 seconds, after etching finishes, methane flow is adjusted to 4.5 ml/min, and regrowth appears in Graphene, the regrowth time is 1 hour, turn off again afterwards methane gas, Graphene generation etching, etching time is 20 seconds.Methane is adjusted to afterwards to 4.5 ml/min, growth time is 15 hours again, and the speed with 50 ℃/sec after regrowth finishes is quickly cooled to below 300 ℃, obtains high quality large size single crystal Graphene.
Scanning electronic microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal structure, and overall dimension is 1.5 inches of left and right, and graphene-structured continuous whole, without breakage, has better quality, and is individual layer.Mobility can reach 30000cm
2/ V.s.
Embodiment 4
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is platinum) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline platinized platinum (thickness 180 μ m, length * wide=5cm * 5cm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, platinized platinum is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1100 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the platinized platinum after annealing is positioned over to horizontal Reaktionsofen (boiler tube diameter 8cm, reaction zone length 15cm) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position), in the atmosphere of hydrogen, be heated to 1060 ℃ (in heat-processed, hydrogen flow rate is 1000 ml/min, 40 ℃/min of heat-up rates), thermal treatment 10 minutes, (gas flow rate is respectively methane 4.5 ml/min after thermal treatment completes, to pass into the mixed gas of methane and hydrogen, hydrogen 1000 ml/min), start growing graphene, growth time is 30 minutes, after growth finishes, methane flow is adjusted to 3.5 ml/min, Graphene generation etching, etching time is 1 minute, after etching finishes, methane flow is adjusted to 4.0 ml/min, there is regrowth in Graphene, the regrowth time is 15 hours, speed with 50 ℃/sec after regrowth finishes is quickly cooled to below 300 ℃, obtain high quality large size single crystal Graphene.
Scanning electronic microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal structure, and overall dimension is 1.5 inches of left and right, and graphene-structured continuous whole, without breakage, has better quality, and is individual layer.
Embodiment 5
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is platinum) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline platinized platinum (thickness 180 μ m, length * wide=5cm * 5cm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, platinized platinum is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1100 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the platinized platinum after annealing is positioned over to horizontal Reaktionsofen (boiler tube diameter 8cm, reaction zone length 15cm) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); In the atmosphere of hydrogen, be heated to 1060 ℃ (in heat-processed, hydrogen flow rate is 1000 ml/min, 40 ℃/min of heat-up rates), thermal treatment 10 minutes; After completing, thermal treatment passes into the mixed gas (gas flow rate is respectively methane 4.5 ml/min, hydrogen 1000 ml/min) of methane and hydrogen, start growing graphene, growth time is 30 minutes, after growth finishes, methane flow is adjusted to 3.5 ml/min, Graphene generation etching, etching time is 1 minute, after etching finishes, methane flow is adjusted to 4.0 ml/min, there is regrowth in Graphene, the regrowth time is 2 hours, again methane flow is adjusted to afterwards to 3.5 ml/min, Graphene generation etching, etching time is 1 minute.Methane is adjusted to afterwards to 4.0 ml/min, the regrowth time is 20 hours again, and the speed with 50 ℃/sec after regrowth finishes is quickly cooled to below 300 ℃, obtains high quality large size single crystal Graphene.
Scanning electronic microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal structure, and overall dimension is 2 inches of left and right, and graphene-structured continuous whole, without breakage, has better quality, and is individual layer.
Embodiment 6
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is platinum) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline platinized platinum (thickness 180 μ m, length * wide=20mm * 16mm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, platinized platinum is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1100 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the platinized platinum after annealing is positioned over to horizontal Reaktionsofen (22 millimeters of boiler tube diameters, 40 millimeters of reaction zone length) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); In the atmosphere of hydrogen, be heated to 1060 ℃ (in heat-processed, hydrogen flow rate is 1000 ml/min, 40 ℃/min of heat-up rates), thermal treatment 10 minutes; After completing, thermal treatment passes into the mixed gas (gas flow rate is respectively methane 4.5 ml/min, hydrogen 1000 ml/min) of methane and hydrogen, start growing graphene, growth time is 30 minutes, after growth finishes, methane flow is adjusted to 3.5 ml/min, Graphene generation etching, etching time is 1 minute, after etching finishes, methane flow is adjusted to 4.0 ml/min, there is regrowth in Graphene, the regrowth time is 2 hours, again methane flow is adjusted to afterwards to 3.5 ml/min, Graphene generation etching, etching time is 1 minute.Methane is adjusted to afterwards to 4.0 ml/min, the regrowth time is 2 hours again, methane flow is adjusted to afterwards to 3.5 ml/min again, Graphene generation etching, and etching time is 1 minute.Methane is adjusted to afterwards to 4.0 ml/min, the regrowth time is 3 hours again, and the speed with 50 ℃/sec after regrowth finishes is quickly cooled to below 300 ℃, obtains high quality large size single crystal Graphene (see figure 3).
Scanning electronic microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal structure, and overall dimension is 3 millimeter, and graphene-structured continuous whole, without breakage, has better quality, and is individual layer.Mobility can reach 40000cm
2/ V.s.
Embodiment 7
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is copper) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline copper sheet (thickness 25 μ m, length * wide=15cm * 15cm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, copper sheet is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1083 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the copper sheet after annealing is positioned over to horizontal Reaktionsofen (boiler tube diameter 8cm, reaction zone length 15cm) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); In the atmosphere of hydrogen, be heated to 1060 ℃ (in heat-processed, hydrogen flow rate is 700 ml/min, 40 ℃/min of heat-up rates), thermal treatment 1 hour; After completing, thermal treatment passes into the mixed gas (gas flow rate is respectively methane 4.3 ml/min, hydrogen 700 ml/min) of methane and hydrogen, start growing graphene, growth time is 30 minutes, after growth finishes, turns off methane gas, Graphene generation etching, etching time is 20 seconds, after etching finishes, methane flow is adjusted to 4.0 ml/min, and regrowth appears in Graphene, the regrowth time is 1 hour, turn off again afterwards methane gas, Graphene generation etching, etching time is 20 seconds.Methane is adjusted to afterwards to 4.0 ml/min, growth time is 2 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 30 seconds.Methane is adjusted to afterwards to 3.9 ml/min, growth time is 5 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.8 ml/min, growth time is 10 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.8 ml/min, growth time is 20 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.8 ml/min, growth time is 30 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.8 ml/min, growth time is 30 hours again, and the speed with 50 ℃/sec after regrowth finishes is quickly cooled to below 300 ℃, obtains high quality large size single crystal Graphene.
Scanning electronic microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal structure, and overall dimension is 4 inches of left and right, and graphene-structured continuous whole, without breakage, has better quality, and is individual layer.Mobility can reach 40000cm
2/ V.s.
Embodiment 8
As shown in Figure 1, the present invention adopts horizontal Reaktionsofen growing graphene, horizontal Reaktionsofen two ends are respectively equipped with gas inlet 1 and pneumatic outlet 4, metallic matrix 2(the present embodiment is platinum) be placed in horizontal Reaktionsofen high-temperature zone, thermopair 3 is positioned at horizontal Reaktionsofen high-temperature zone, to monitor in real time temperature of reaction.First, polycrystalline platinized platinum (thickness 180 μ m, length * wide=15cm * 15cm) is put into and in acetone, water, ethanol, carries out respectively ultrasonic cleaning 40 minutes.After cleaning completes, platinized platinum is put in High Temperature Furnaces Heating Apparatus, the 10h that anneals at 1100 ℃, makes single crystal grain reach grade (the single grain-size of the present embodiment is specially 1mm～5mm).Then, the platinized platinum after annealing is positioned over to horizontal Reaktionsofen (boiler tube diameter 8cm, reaction zone length 15cm) middle section (there is thermopair Real-Time Monitoring furnace temperature reaction zone in this position); In the atmosphere of hydrogen, be heated to 1060 ℃ (in heat-processed, hydrogen flow rate is 1000 ml/min, 40 ℃/min of heat-up rates), thermal treatment 10 minutes; After completing, thermal treatment passes into the mixed gas (gas flow rate is respectively methane 4.3 ml/min, hydrogen 1000 ml/min) of methane and hydrogen, start growing graphene, growth time is 30 minutes, after finishing, growth turns off methane gas, Graphene generation etching, etching time is 30 seconds, after etching finishes, methane flow is adjusted to 4.1 ml/min, there is regrowth in Graphene, the regrowth time is 30 minutes, turn off again afterwards methane gas, Graphene generation etching, etching time is 30 seconds.Methane is adjusted to afterwards to 4.0 ml/min, the regrowth time is 2 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.9 ml/min, the regrowth time is 5 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.9 ml/min, the regrowth time is 20 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.9 ml/min, the regrowth time is 30 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.9 ml/min, the regrowth time is 30 hours, turns off afterwards methane gas again again, Graphene generation etching, and etching time is 50 seconds.Methane is adjusted to afterwards to 3.9 ml/min, the regrowth time is 30 hours again, and the speed with 50 ℃/sec after regrowth finishes is quickly cooled to below 300 ℃, obtains high quality large size single crystal Graphene.
Scanning electronic microscope and resonance laser Raman spectroscopy are observed and are shown, gained Graphene is large size single crystal structure, and overall dimension is 4 inches of left and right, and graphene-structured continuous whole, without breakage, has better quality, and is individual layer.Mobility can reach 50000cm
2/ V.s.
As shown in Figure 1, in figure, one end of gas inlet 1 is provided with a plurality of mass flowmeters, optionally controls and passes into the gases such as hydrogen, methane, ethene, acetylene or argon gas.Liquid carbon source (as ethanol, methyl alcohol, benzene, toluene or hexanaphthene etc.) is placed in Meng Shi wash bottle, by the gas mixture bubbling of argon gas or argon gas and nitrogen etc., brings into.
As shown in Figure 2, the Graphene quality after outgrowth-etching-regrowth is intact, hexagonal holes in the middle of again not occurring after etching, and the sign in conjunction with the scanning of Raman spectrum face, can prove that this method can improve the quality of Graphene.
As shown in Figure 3, from platinum, the stereoscan photograph of Graphene can be found out, the method for employing growth-etching-regrowth can progressively increase the size of single crystal graphene, and the hexagonal shape of gained Graphene is constant, and overall dimension can reach 3 millimeters.
As shown in Figure 4, from the Raman spectrum of Graphene, can find out, the big size graphene monocrystalline that adopts the method to prepare is individual layer, and the 1340cm in Raman spectrum
-1the intensity of (D mould) position is very low, illustrates that it has very high quality.
As shown in Figure 5, adopt the carrier mobility of the single crystal graphene of the method growth can reach 12800cm
2/ V.s, has further proved the high quality of single crystal graphene.
Embodiment result shows, the present invention proposes by regulation and control hydrogen and carbon source concentration Graphene is carried out to etching, significantly reduce the distribution density of single crystal graphene, this provides space for growing large-size monocrystalline, again regulate afterwards reaction atmosphere to make its regrowth, so repeatedly for several times, finally obtained high quality large size single crystal Graphene.The breakthrough of this direction particularly has important strategic importance in the application in the fields such as film photoelectric functional device such as nanometer electronic device, nesa coating, indicating meter and electrode of solar battery, gas sensor, unicircuit to promoting the application of Graphene.
Claims (10)
1. the preparation method of a high quality large size single crystal Graphene, it is characterized in that: the method adopts chemical vapour deposition technique, in the situation that the carrier gas that contains hydrogen exists, first metallic matrix is heat-treated, and utilize under carbon-source gas high temperature at metal base surface catalytic pyrolysis, grow single crystal graphene; Then by controlling hydrogen, carbon source concentration, Graphene monocrystalline after growth is carried out to etching, significantly reduce the distribution density of single crystal graphene, make its every 10 square inches of numbers be reduced to 1～2, this provides space for growing large-size monocrystalline, then regulates hydrogen and carbon source concentration that it is regrowed, when the number of single crystal graphene becomes many, carry out again etching, so repeatedly; After over etching regrowth, finally obtain high quality large size single crystal Graphene; Graphene monocrystalline prepared by the method is of a size of 1～4 inch, and its mobility is 10000cm
2v
-1s
-1above.
2. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1, it is characterized in that: thin slice or the film of the platinum that metallic matrix used is surfacing, ruthenium, iridium, copper or nickel metal, purity is greater than 99wt%, and thickness is not less than 100nm.
3. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1, it is characterized 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 high quality large size single crystal Graphene claimed in claim 1, it is characterized in that: metallic matrix thermal treatment used adopts anneal, treatment temp is 800 ℃～1500 ℃, atmosphere is hydrogen, or atmosphere is the mixed gas of hydrogen and nitrogen or rare gas element, wherein hydrogen mol ratio is not less than 1%, flow velocity is not less than 10sccm, and annealing time is no less than 10 minutes.
5. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1, it is characterized in that: carbon source used be in methane, ethane, acetylene, ethene, ethanol hydrocarbon polymer one or more, carrier is hydrogen, or, carrier is the mixed gas of hydrogen and nitrogen or rare gas element, the bulk purity of carbon source and carrier gas is all greater than 99%, and the mol ratio of carbon source and hydrogen is 0.005～1.
6. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1, it is characterized in that: growth temperature is 600 ℃～1200 ℃, and growth time is not less than 20 minutes.
7. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1, it is characterized in that: etching temperature is 600 ℃～1200 ℃, and etching time is not less than 10 seconds, etching atmosphere is the mixed gas of carbon source and hydrogen; Carbon source used be in methane, ethane, acetylene, ethene, ethanol hydrocarbon polymer one or more; The mol ratio of carbon source and hydrogen is 0.005～0.1.
8. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1, it is characterized in that: regrowth temperature is 600 ℃～1200 ℃, and the regrowth time is not less than 20 minutes; The mol ratio of carbon source and hydrogen is 0.005～0.5.
9. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1, it is characterized in that: the cycle index of growth-etching-regrowth is greater than 1 time.
10. according to the preparation method of high quality large size single crystal Graphene claimed in claim 1; it is characterized in that: after growth finishes; metallic matrix is under the carrier protection that contains hydrogen; be quickly cooled to below 300 ℃; in carrier gas, hydrogen mol ratio is not less than 1%, and cooling speed is not less than 10 ℃/sec fast.
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