CN103708448A - Atmospheric pressure controlled growth method for graphene - Google Patents
Atmospheric pressure controlled growth method for graphene Download PDFInfo
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- CN103708448A CN103708448A CN201410004425.XA CN201410004425A CN103708448A CN 103708448 A CN103708448 A CN 103708448A CN 201410004425 A CN201410004425 A CN 201410004425A CN 103708448 A CN103708448 A CN 103708448A
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Abstract
The invention discloses an atmospheric pressure controlled growth method for 1-3 layers of graphene. The method comprises the following steps: putting a metal base into an atmosphere containing a carbon source gas at atmospheric pressure, and obtaining one layer of graphene, two layers of graphene or three layers of graphene, which are completely covered on the overall metal base after the graphene passes through a nucleation stage, a nuclear growth stage and a complete coverage stage; controlling the number (one layer, two layers or three layers) of layers of graphene nucleation at the surface of the metal base by nucleation temperature, and then controlling large-area growth of the graphene on the surface of the metal base on the basis of the original number of layers by adjusting the total gas flow rate of the complete coverage stage. By adopting the atmospheric pressure controlled growth method provided by the invention, accurate control growth of the 1-3 layers of graphene can be achieved under an atmospheric pressure environment, the graphene is uniform in number of layers, and fewer in defects, and operation and large-scale production are facilitated. Therefore, the graphene obtained by the method is applicable to building of electronic devices such as a field effect transistor, a light emitting diode, a transparent electrode and the like.
Description
Technical field
The present invention relates to a kind of Graphene, preferably the normal pressure method for controllable growth of 1-3 layer graphene, belongs to nano material and technical field.
Background technology
Graphene is owing to having excellent carrier mobility (～20,000cm
2/ (V.S), be about 100 times of Si), in fields such as high speed transistor, high sensitive sensor, touch screen-device and high performance solar batteries, have broad application prospects.But the semipermanent mold structure that the energy band structure of single-layer graphene is Overlapping, does not therefore have band gap, cannot fully meet the necessary transistor of logical circuit " shutoff " function.Bernal type double-layer graphite alkene can be with and can pass through the continuously adjustable special property of longitudinal electric field due to it, is subject in recent years investigator's extensive concern.Traditional Bernal type Graphene generally obtains by tape stripping method, this kind of method inefficiency, and size is generally less than 100 μ m, is difficult to amplify produce and application.
Chemical vapor deposition (CVD) method since 2009 find to can be used for growing graphene, because its growth size is easy to amplify, advantages such as Graphene quality height and progressively become the main approach that obtains high-quality graphene.According to Korea S Cheng Jun shop (the Nature Nanotechnology. of university, 2010,5,722-726), they by CVD method can growth size under low pressure environment the Graphene individual layer of 30 inches, and by heat, release the auxiliary volume to volume transfer method of adhesive tape, successfully this Graphene is transferred to PET substrate and makes touch screen-device.But conventional CVD fado completes under low pressure environment, the growth restriction of Graphene is difficult to form multilayered structure in " self-limiting growth mechanism ", although the people such as XF.Duan find to expose Cu substrate by the upper source in Graphene growth substrate, and the Graphene fragment on Cu surface, upper source is transferred to Graphene surface, lower source and obtains Bernal type double-layer graphite alkene, but lower (the ACS Nano. of the method output, 2012,6,8241-8249).Although and the people such as JM.Tour have report to control Graphene at 1000 handkerchief left and right growing large-area Bernal type double-layer graphite alkene, the method is still low-pressure process, be difficult to meet actual production and application (ACS Nano., 2012,6,9790-9796).Therefore, a kind of can be under atmospheric pressure environment to the Graphene number of plies accurately controlled method seem particularly important.
Summary of the invention
The object of the present invention is to provide a kind of normal pressure method for controllable growth of 1-3 layer graphene.Principal feature of the present invention is under atmospheric pressure environment, controls the growth number of plies of substrate surface Graphene by growth temperature, then by total gas flow rate, controls multi-layer graphene in the coverage of substrate surface, finally obtains 1-3 layer graphene.Method provided by the present invention, controls accurately the number of plies of Graphene, and defect is few, and homogeneity is good, simple and easy to do.
The present invention is achieved through the following technical solutions:
A kind of chemical vapour deposition normal pressure method for controllable growth of 1-3 layer graphene, it is characterized in that, under normal pressure, metal base is placed under the atmosphere that contains carbon-source gas, Graphene is through nucleation stage, the nucleus growth stage, cover the stage completely, obtain being covered in completely the one deck in whole metal base, two-layer or three layer graphenes, wherein, by nucleation temperature, control the number of plies (one deck of described metal substrate surface Graphene nucleation, two-layer or three layers), by changing the described total gas flow rate that covers the stage completely, control again Graphene large area deposition on the basis of original number of plies of described metal substrate surface.
According to the present invention, described nucleation stage, refers to and in metal base, forms Graphene fragment.In the described nucleus growth stage, refer to and increase Graphene chip size.Describedly cover the stage completely, refer to Graphene large area deposition until cover full whole metal base completely.
According to the present invention, described nucleation stage is controlled Graphene in the nucleation number of plies of substrate surface by employing temperature, and by flow rate of carrier gas, controls carbon radicals and in the diffusion process of substrate surface, control the large area deposition of multi-layer graphene.
According to the present invention, described Graphene nucleation temperature, according to the different number of plies demands of Graphene, is specially single-layer graphene nucleation temperature 1000-1080 ℃, preferably 1000-1050 ℃; Double-layer graphite alkene nucleation temperature 950-990 ℃, preferably 960-980 ℃; The nucleation temperature of three layer graphenes is 890-940 ℃, preferably 900-930 ℃.Described nucleation time is preferably 10-20min.
According to the present invention, described nucleation stage, nucleus growth stage are identical with the temperature that covers the stage completely.
According to the present invention, the described total gas flow rate of total gas flow rate in stage lower than described nucleation or nucleus growth stage that cover completely.Different according to the Graphene growth number of plies, be specially, the total gas flow rate of single-layer graphene nucleation stage is 100-250sccm, and total gas flow rate of nucleus growth stage is 100-250sccm, and covering total gas flow rate of stage is completely 50-150sccm; During double-layer graphite alkene, the total gas flow rate of nucleation stage is 1500-2000sccm; Total gas flow rate of nucleus growth stage is 1500-2000sccm, and covering total gas flow rate of stage is completely 750-1000sccm; During three layer graphenes, the total gas flow rate of nucleation stage is 400-1000sccm, and total gas flow rate of nucleus growth stage is 400-1000sccm, and covering total gas flow rate of stage is completely 200-500sccm.
According to the present invention, total gas flow rate and the total gas flow rate of nucleation stage in described nucleus growth stage are identical or different, and more preferably, total gas flow rate in nucleus growth stage is identical with total gas flow rate of nucleation stage.
According to the present invention, described, cover the stage completely, the growth time of the completely attached full growth substrate of Graphene, different according to the Graphene growth number of plies, the growth time of the completely attached full growth substrate of single-layer graphene is 20-30min; The growth time of the completely attached full growth substrate of double-layer graphite alkene is 120-150min; The growth time of the completely attached full growth substrate of three layer graphenes is 180-210min.
According to the present invention, in aforesaid method, the concentration of described carbon-source gas is at nucleation stage, nucleus growth stage, increase successively in the covering stage completely, be the concentration of carbon-source gas in described Graphene nucleus growth stage higher than the concentration of Graphene nucleation stage carbon-source gas, described Graphene covers the concentration of carbon-source gas in stage completely higher than the concentration of the carbon-source gas in Graphene nucleus growth stage.
According to the present invention, in 1-3 layer graphene nucleation stage process, carbon-source gas concentration is 5-20ppm, and in 1-3 layer graphene nucleus growth phase process, carbon-source gas concentration is 10-40ppm; At 1-3 layer graphene, cover completely in phase process, carbon-source gas concentration is 20-80ppm.
According to the present invention, the concentration of described carbon-source gas can regulate by the flow of carbon-source gas.
Preferably, the invention provides a kind of 1-3 layer graphene chemical vapour deposition normal pressure method for controllable growth, it is characterized in that, under normal pressure, metal base is placed under the atmosphere that contains carbon-source gas, by nucleation temperature, control the number of plies (one deck, two-layer or three layers) (being nucleation stage) of described metal substrate surface Graphene nucleation, then increase carbon source concentration to increase Graphene chip size (being the nucleus growth stage), finally increase again carbon-source gas concentration, and reduce total gas flow rate simultaneously and make the completely attached full growth substrate (covering the stage completely) of Graphene.
According to the present invention, described in contain carbon-source gas atmosphere comprise carbon-source gas, rare gas element and hydrogen.Described carbon-source gas is such as being methane, acetylene, alcohol atmosphere etc.Described rare gas element is argon gas for example.At 1-3 layer graphene, cover the stage completely, preferably increase hydrogen and carbon-source gas concentration simultaneously, preferred, described density of hydrogen is 10000-50000ppm.
According to the present invention, described metal base is for example selected from least one in platinum, copper, nickel.Preferably copper substrate.
According to the present invention, two layers of preparing of described growth method or three layer graphenes are Bernal type Graphene.
According to the present invention, described growth method also comprises: before Graphene growth, first substrate is carried out to anneal containing under the rare gas element of hydrogen.Described anneal process is mainly used in removing substrate surface residual impurity and/or oxide compound.
According to the present invention, in above-mentioned anneal process, described in contain hydrogen rare gas element be preferably hydrogen-argon-mixed body, be for example 5% hydrogen-argon-mixed.Described total gas flow rate is preferably 300-500sccm, and described annealing temperature is preferably 900-1050 ℃, and the anneal time is preferably 0.5h.
According to the present invention, described growth method also comprises: before growing graphene, substrate is carried out to ultrasonic cleaning processing.Described ultrasonic power is preferably 40-100W, and ultrasonic time is preferably 5-20min.
According to the present invention, described ultrasonic cleaning is processed and is specifically comprised the steps:
(1) substrate is processed in organic solvent for ultrasonic, removed surperficial oil residues and/or zone of oxidation;
(2) step (1) gained sample is transferred to ultrasonic cleaning in water, dries up standby;
The preferred acetone of described organic solvent, ethanol or acetic acid etc., preferred, by substrate respectively at processing in acetone, ethanol and acetum.Described water is preferably deionized water.Preferably use N
2dry up substrate.
According to the present invention, described growth method comprises: under normal pressure, clean substrate is positioned under hydrogen-argon-mixed atmosphere and is heated up, anneal, then be adjusted to target temperature, pass into certain flow methane gas growing graphene fragment, then increase methane concentration to increase Graphene chip size, finally increase hydrogen and methane concentration simultaneously, and reduce total gas flow rate and make the completely attached full growth substrate of Graphene.
According to the present invention, described growth method specifically comprises the steps:
(1) metal base is processed in organic solvent for ultrasonic, removed surperficial oil residues and zone of oxidation;
(2) step (1) gained sample is transferred to deionized water for ultrasonic and cleans, dry up;
(3) metal base is positioned in silica tube, vacuumizes and remove residual air in tube furnace, and repeat to rinse several times with Ar;
(4) close vacuum pump, pass into hydrogen-argon-mixed adjusting intraductal pressure and get final product UNICOM's offgas duct to stink cupboard to normal atmosphere, heat up and make anneal;
(5) according to the demand of the Graphene number of plies, regulate tube furnace to target temperature, pass into certain flow methane gas and regulate total gas flow rate, control the Graphene nucleating growth time;
(6) in the situation that keeping total gas flow rate constant, increase concentration of methane gas, promote Graphene nucleus growth;
(7) further increase density of hydrogen and methane concentration, reduce total gas flow rate simultaneously, make Graphene cover full metal base completely;
(8) reduce rapidly silica tube temperature to room temperature, can obtain respectively individual layer, two layers or three layer graphenes in metal substrate surface.
One deck of preparing according to growth method of the present invention, two layers or three layer graphenes, structural integrity, defect is less.Prepared Graphene number of plies homogeneous is complete, and in single-layer graphene, individual layer ratio is greater than 99%, and in double-layer graphite alkene, double-deck ratio is greater than three stratum proportions in 90%, three layer graphene and is greater than 95%.
The invention has the advantages that, by nucleation temperature, can control Graphene in the nucleation number of plies of metal substrate surface, the total gas flow rate cover the stage by changing completely can be controlled the large-area homogeneity of multi-layer graphene and grow, can under atmospheric pressure environment, realize the accuracy controlling to 1-3 layer graphene, the number of plies ratio of Graphene can be controlled on 90%.And if it is constant to maintain all the time total gas flow rate in the preparation process of Graphene, cannot realize the large-area homogeneity growth of Graphene described above, defect is larger, the more difficult control of number of plies ratio of Graphene, for example in single-layer graphene, individual layer ratio is less than 90%.
Compared with the prior art, the present invention has following features:
(1) growing environment used in the present invention is atmospheric pressure environment, simple and easy to do, is easy to amplify produce.
(2) number of plies ratio that can accurately control Graphene by growth temperature and gas flow rate is on 90%, and Graphene defect is few, best in quality.
The prepared Graphene of the inventive method is applicable to construct electron device as field-effect transistor, sensor, transparency electrode etc.
Accompanying drawing explanation
Fig. 1-3 are respectively the scanning electron microscope (SEM) photograph of embodiment 1, embodiment 5, the initial pattern of embodiment 9 copper foil surface Graphene, and corresponding illustration is SEM shape appearance figure on a large scale.
Fig. 4 is the uv-visible absorption spectra that in embodiment 1, embodiment 5 and embodiment 9, Graphene is transferred to respectively quartz substrate.
Fig. 5 is that in embodiment 1, embodiment 5 and embodiment 9, Graphene is transferred to respectively SiO
2the single-point Raman spectrum of/Si substrate surface, and the Lorentz fit at 2D peak.
Fig. 6 is that the Raman face that embodiment 1 Graphene is transferred to SiO2/Si substrate surface is swept figure.
Fig. 7 is that the Raman face that embodiment 5 Graphenes are transferred to SiO2/Si substrate surface is swept figure.
Fig. 8 is that the Raman face that embodiment 9 Graphenes are transferred to SiO2/Si substrate surface is swept figure.
Fig. 9-11 are respectively the scanning electron microscope (SEM) photograph of the initial pattern of embodiment 2-4 copper foil surface Graphene.
Figure 12-14 are respectively the scanning electron microscope (SEM) photograph of the initial pattern of embodiment 6-8 copper foil surface Graphene.
Figure 15-17 are respectively the scanning electron microscope (SEM) photograph of the initial pattern of embodiment 10-12 copper foil surface Graphene.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto, and any improvement of making on basis of the present invention and invention are all within protection scope of the present invention.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, take methane gas as carbon source is at Copper Foil substrate surface growth single-layer graphene
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 900 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 1050 ℃, adjustments of gas flow velocity 200sccm, passes into low-concentration methane gas concentration and is about 5ppm growing graphene fragment, then increases concentration of methane gas to 10ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 20ppm, 10000ppm, adjusting total gas flow rate is 100sccm, growth time 20-30min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1000 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 1080 ℃, adjustments of gas flow velocity 100sccm, passes into low-concentration methane gas concentration and is about 20ppm growing graphene fragment, then increases concentration of methane gas to 40ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 80ppm, 50000ppm, adjusting total gas flow rate is 50sccm, growth time 20-30min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 3, take methane gas as carbon source is at Copper Foil substrate surface growth single-layer graphene
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 900 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 1040 ℃, adjustments of gas flow velocity 250sccm, passes into low-concentration methane gas concentration and is about 10ppm growing graphene fragment, then increases concentration of methane gas to 20ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 40ppm, 20000ppm, adjusting total gas flow rate is 120sccm, growth time 20-30min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 4, take methane gas as carbon source is at Copper Foil substrate surface growth single-layer graphene
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1050 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 1000 ℃, adjustments of gas flow velocity 150sccm, passes into low-concentration methane gas concentration and is about 15ppm growing graphene fragment, then increases concentration of methane gas to 30ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 60ppm, 40000ppm, adjusting total gas flow rate is 75sccm, growth time 20-30min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 5, take methane gas as carbon source is at Copper Foil substrate surface Growing Double-Layer Graphene
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 900 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 950 ℃, adjustments of gas flow velocity 1750sccm, passes into low-concentration methane gas concentration and is about 5ppm growing graphene fragment, then increases concentration of methane gas to 10ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 20ppm, 10000ppm, adjusting total gas flow rate is 850sccm, growth time 120-150min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 6, take methane gas as carbon source is at Copper Foil substrate surface Growing Double-Layer Graphene
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1000 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 980 ℃, adjustments of gas flow velocity 2000sccm, passes into low-concentration methane gas concentration and is about 20ppm growing graphene fragment, then increases concentration of methane gas to 40ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 80ppm, 50000ppm, adjusting total gas flow rate is 1000sccm, growth time 120-150min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 7, take methane gas as carbon source is at Copper Foil substrate surface Growing Double-Layer Graphene
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1050 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 960 ℃, adjustments of gas flow velocity 1500sccm, passes into low-concentration methane gas concentration and is about 10ppm growing graphene fragment, then increases concentration of methane gas to 25ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 50ppm, 30000ppm, adjusting total gas flow rate is 800sccm, growth time 120-150min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 8, take methane gas as carbon source is at Copper Foil substrate surface Growing Double-Layer Graphene
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1030 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 970 ℃, adjustments of gas flow velocity 2000sccm, passes into low-concentration methane gas concentration and is about 15ppm growing graphene fragment, then increases concentration of methane gas to 25ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 60ppm, 40000ppm, adjusting total gas flow rate is 950sccm, growth time 120-150min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 9, take methane gas as carbon source is at Copper Foil substrate surface three layer graphenes of growing
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 900 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 900 ℃, adjustments of gas flow velocity 600sccm, passes into low-concentration methane gas concentration and is about 5ppm growing graphene fragment, then increases concentration of methane gas to 10ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 20ppm, 10000ppm, adjusting total gas flow rate is 300sccm, growth time 180-210min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 10, take methane gas as carbon source is at Copper Foil substrate surface three layer graphenes of growing
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1050 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 940 ℃, adjustments of gas flow velocity 400sccm, passes into low-concentration methane gas concentration and is about 5ppm growing graphene fragment, then increases concentration of methane gas to 10ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 20ppm, 10000ppm, adjusting total gas flow rate is 200sccm, growth time 180-210min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 11, take methane gas as carbon source is at Copper Foil substrate surface three layer graphenes of growing
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1020 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 920 ℃, adjustments of gas flow velocity 1000sccm, passes into low-concentration methane gas concentration and is about 10ppm growing graphene fragment, then increases concentration of methane gas to 30ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 60ppm, 40000ppm, adjusting total gas flow rate is 500sccm, growth time 180-210min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 12, take methane gas as carbon source is at Copper Foil substrate surface three layer graphenes of growing
Preparation process is as follows:
(1) commercialization Copper Foil (Alfa, #13382) is cut into and needs size, be placed in successively acetone, ethanol and acetum ultrasonic clean, every group of 5-20min of ultrasonic time, finally cleans N with clear water
2dry up.
(2) Copper Foil is positioned in tube furnace silica tube, opens after vacuum pump extracts pipeline air and continue logical argon gas several times, fully eliminate remnant oxygen in system.Finally, by hydrogen-argon-mixed adjusting pipeline air pressure to one normal atmosphere, UNICOM's offgas duct is to atmosphere.
(3) rising furnace body temperature to 1000 ℃, cycle annealing is processed, and removes copper foil surface residual impurity and oxide compound.
(4) after annealing finishes, be warming up to 930 ℃, adjustments of gas flow velocity 400sccm, passes into low-concentration methane gas concentration and is about 15ppm growing graphene fragment, then increases concentration of methane gas to 25ppm, Graphene chip size is increased, finally further increase methane concentration and density of hydrogen respectively to 50ppm, 30000ppm, adjusting total gas flow rate is 200sccm, growth time 180-210min, makes the completely attached full whole metal base of Graphene.
(5) reduce rapidly furnace body temperature to room temperature, take out sample.
Embodiment 13
In embodiment 1-12, Graphene is transferred to respectively quartz substrate and SiO
2/ Si substrate.The number of plies of Graphene sample is confirmed by uv-visible absorption spectra and Raman spectrum.Wherein uv-visible absorption spectra completes in quartz substrate.Single-point Raman spectrum and Raman face are swept figure at SiO
2/ Si substrate surface obtains.
Fig. 1-3 are respectively the scanning electron microscope (SEM) photograph of embodiment 1, embodiment 5, the initial pattern of embodiment 9 copper foil surface Graphene.Fig. 9-11 are respectively the scanning electron microscope (SEM) photograph of the initial pattern of embodiment 2-4 copper foil surface Graphene.Figure 12-14 are respectively the scanning electron microscope (SEM) photograph of the initial pattern of embodiment 6-8 copper foil surface Graphene.Figure 15-17 are respectively the scanning electron microscope (SEM) photograph of the initial pattern of embodiment 10-12 copper foil surface Graphene.It shows, is optimized to after nuclear temperature and the total gas flow rate of growth, and the Graphene uniform surface of CVD method growth is smooth, inclusion-free and obviously damaged, and also Graphene can maintain good homogeneity on a large scale.In addition, nucleation temperature can affect the Graphene number of plies, and total gas flow rate of growing has very important impact for the Graphene coverage of the different numbers of plies.
Fig. 4 is the uv-visible absorption spectra that in embodiment 1, embodiment 5 and embodiment 9, Graphene is transferred to respectively quartz substrate.Wherein, the transparence of single-layer graphene sample is 97.7%, the transparence of double-layer graphite alkene sample is 95.4%, the transparence of three layer graphene samples is 93.6%, the absorbancy 2.3% of this and the every layer graphene of bibliographical information matches, and has proved that the Graphene number of plies that the inventive method obtains is evenly controlled.In addition, the uv-visible absorption spectra of embodiment 2-4 and embodiment's 1 is approximate, and the uv-visible absorption spectra of embodiment 6-8 and embodiment's 5 is approximate, and the uv-visible absorption spectra of embodiment 10-12 and embodiment's 9 is approximate.
Raman spectrum in Fig. 5, shows the I of 1-3 layer graphene sample
2D/ I
gratio is respectively 2.54,0.83 and 0.48, this and 1-3 layer graphene I
2D/ I
g theoretical ratio 2,0.8-1.2,0.5-0.8 match, proved that the sample that the method is grown is 1-3 layer Bernal type Graphene.
In Fig. 6-8, Raman face is swept result and is shown, prepared sample can be controlled the number of plies ratio of Graphene more than 90%, and homogeneity is good.
Claims (10)
1. the chemical vapour deposition normal pressure method for controllable growth of a 1-3 layer graphene, it is characterized in that, under normal pressure, metal base is placed under the atmosphere that contains carbon-source gas, Graphene is through nucleation stage, the nucleus growth stage, cover the stage completely, obtain being covered in completely the one deck in whole metal base, two-layer or three layer graphenes, wherein by nucleation temperature, control the number of plies of described metal substrate surface Graphene nucleation, that is: one deck, two-layer or three layers, the total gas flow rate that covers again the stage by changing is completely controlled Graphene large area deposition on the basis of original number of plies of described metal substrate surface.
2. normal pressure method for controllable growth according to claim 1, described Graphene nucleation temperature, according to the different number of plies demands of Graphene, is specially single-layer graphene nucleation temperature 1000-1080 ℃, preferably 1000-1050 ℃; Double-layer graphite alkene nucleation temperature 950-990 ℃; Preferred 960-980 ℃; The nucleation temperature of three layer graphenes is 890-940 ℃, preferably 900-930 ℃.
3. according to the normal pressure method for controllable growth described in claim 1-2 any one, the described total gas flow rate of total gas flow rate in stage lower than described nucleation or nucleus growth stage that cover completely, preferably, the total gas flow rate of described nucleation stage is identical with total gas flow rate of described nucleus growth stage, different according to the Graphene growth number of plies, be preferably, the total gas flow rate of single-layer graphene nucleation stage is 100-250sccm, total gas flow rate of nucleus growth stage is gas 100-250sccm, and covering total gas flow rate of stage is completely 50-150sccm; During double-layer graphite alkene, the total gas flow rate of nucleation stage is 1500-2000sccm; Total gas flow rate of nucleus growth stage is 1500-2000sccm, and covering total gas flow rate of stage is completely 750-1000sccm; During three layer graphenes, the total gas flow rate of nucleation stage is 400-1000sccm, and total gas flow rate of nucleus growth stage is 400-1000sccm, and covering total gas flow rate of stage is completely 200-500sccm.
4. according to the normal pressure method for controllable growth described in claim 1-3 any one, described, cover the stage completely, the growth time of the completely attached full growth substrate of Graphene, different according to the Graphene growth number of plies, the growth time of the completely attached full growth substrate of single-layer graphene is 20-30min; The growth time of the completely attached full growth substrate of double-layer graphite alkene is 120-150min; The growth time of the completely attached full growth substrate of three layer graphenes is 180-210min.
5. according to the normal pressure method for controllable growth described in claim 1-3 any one, described in contain carbon-source gas atmosphere comprise carbon-source gas, rare gas element and hydrogen, described carbon-source gas is such as being methane, acetylene, alcohol atmosphere etc.Described rare gas element is argon gas for example.
6. according to the normal pressure method for controllable growth described in claim 1-3 any one, it is characterized in that, the concentration of the carbon-source gas in described Graphene nucleus growth stage is higher than the concentration of Graphene nucleation stage carbon-source gas, and described Graphene covers the concentration of carbon-source gas in stage completely higher than the concentration of the carbon-source gas in Graphene nucleus growth stage.
7. normal pressure method for controllable growth according to claim 6, at first, in Graphene nucleation stage process, carbon-source gas concentration is 5-20ppm, afterwards, and in 1-3 layer graphene nucleus growth phase process, carbon-source gas concentration is 10-40ppm, finally, at 1-3 layer graphene, cover completely in phase process, carbon-source gas concentration is 20-80ppm.
8. according to the normal pressure method for controllable growth described in claim 6-7 any one, at 1-3 layer graphene, cover completely in phase process, increase hydrogen and carbon-source gas concentration simultaneously, preferred, described density of hydrogen is 10000-50000ppm.
9. according to the normal pressure method for controllable growth described in claim 1-8 any one, described metal base is selected from least one in platinum, copper, nickel, preferably copper substrate.
10. according to the normal pressure method for controllable growth described in claim 1-9 any one, described growth method also comprises: before Graphene growth, first substrate is carried out to anneal containing under the rare gas element of hydrogen, the described rare gas element that contains hydrogen is preferably hydrogen-argon-mixed body, be for example 5% hydrogen-argon-mixed, described gas flow rate is preferably 300-500sccm, and described annealing temperature is preferably 900-1050 ℃, and the anneal time is preferably 0.5h.
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